Title of Invention	A CATALYTIC CONVERSION PROCESS FOR PRODUCING LIGHT OLEFINS WITH A HIGH YIELD FROM PETROLEUM HYDROCARBONS
Abstract	A catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons, which comprises the steps of contacting a pre-heated petroleum hydrocarbons feedstock with a catalyst which comprises phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor^ and converting under the catalytic conversion conditions to produce reaction effluent and a spent catalyst, separating the resulted reaction effluent and spent catalyst^ further separating said reaction effluent into liquid products and gaseous products comprising ethylene and propylene; stripping the spent catalyst by steam; regenerating the stripped catalyst by contacting the spent catalyst with oxygen- containing gas and burning off coke; and recycling the regenerated catalyst to reactor for reuse.

Title of Invention

A CATALYTIC CONVERSION PROCESS FOR PRODUCING LIGHT OLEFINS WITH A HIGH YIELD FROM PETROLEUM HYDROCARBONS

Abstract

A catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons, which comprises the steps of contacting a pre-heated petroleum hydrocarbons feedstock with a catalyst which comprises phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor^ and converting under the catalytic conversion conditions to produce reaction effluent and a spent catalyst, separating the resulted reaction effluent and spent catalyst^ further separating said reaction effluent into liquid products and gaseous products comprising ethylene and propylene; stripping the spent catalyst by steam; regenerating the stripped catalyst by contacting the spent catalyst with oxygen- containing gas and burning off coke; and recycling the regenerated catalyst to reactor for reuse.

Full Text	A catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons Technical field The present invention relates to a catalytic conversion process of petroleum hydrocarbons, in particular, to a catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons. Background of present invention The conventional process for producing gaseous olefins from petroleum hydrocarbons is steam cracking process, wherein the feedstocks are light hydrocarbons comprising natural gas, naphtha and light gas oil and so on. The supply of light hydrocarbons was limited as crude oil becomes heavier Thus, more attentions are paid to processes for producing gaseous olefins from heavy hydrocarbons. Such processes, for example, include thermal cracking process of heavy hydrocarbons by using inert soUd materials such as quartz or coke as heat carriers, and thermo-catalytic cracking process of heavy hydrocarbons by using alkali metal oxides or alkalme earth metal oxides as catalyst. The reaction temperatures in such processes are both greater than SOO'^Co Recently the processes for producing gaseous olefins from petroleum hydrocarbons have been described in various publications, wherein using solid acidic catalysts in certain reactor style and under certain operation conditions. For example, JP 60-222,428 discloses a process using ZSM-5 as a catalyst and C^ to Css paraffinic hydrocarbons as feedstock. The process is carried out at a reaction temperature of between 600 to 750°C, with 30wt% yield for Cj to C4 olefins, US Patent No, 3,758,403 disclosed that a catalyst comprising both ZSM-5 zeolite and large pore zeolite (e.g. X type or Y type) as active components in a ratio of 1:10 - 3:1 raised octane number of gasoUne while increasing yield of total propylene and butylenes to about 10wt%. It has been reported in US Patent No. 5,318,696 that the catalyst comprising large pore zeolite and medium pore zeolite in ratio of SiOj/AljOj being less than 30 can be used to produce high octane gasoline, and to increase the yield of gaseous olefins, especially propylene. Said medium pore zeolite is in the form of MFI structure. US Patent No. 4,980,053 disclosed the catalyst comprising mixture of ZSM-5 zeolite and Y type zeolite as active components can be used to increase octane number of gasoline in products and to increase yield of light olefins in reaction temperature of 500 -- 650^:. And light olefins are mainly consisting of propylene and butylene. It has been reported in prior art that the process for modifying zeolite having a structure of pentasil to increase the selectivity to the reaction product. For example, phosphorus and/or metal ion can be incorporated into zeolite having a structure of pentasil (such as ZSM-5) to adjust the adsorption and catalysis properties of the zeolite. It has been reported in US Patent No. 4,365,104 that the process for modifying ZSM-S zeolite by using phosphorus and magnesium, for the purpose of using modified zeolite to the isomerization of xylene to increase selectivity to xylene. The incorporation of phosphorus and magnesium is to increase the shape selectivity of zeolite. However, both acidity of molecular sieve and hydrocarbons conversion reactivity of zeolite after modification are decreased. It has been reported in US Patent No, 5,236,880 that the incorporation of group VEIIB metals, preferably nickel into zeolite in the ratio of SiOj to AI2O3 being greater than 5. Said zeolite is in the form of MFI or MEL structure. The catalyst disclosed in US Patent No. 5,236,880 can be used to increase the conversion of paraffinic hydrocarbons, to increase aromatics content in gasoline fraction, to increase octane number of gasoUne in products and yield of gasoline. A catalyst comprising both phosphorus and rare earth-containing silica rich zeolite having a Stracture of pentasil as active component has been disclosed in US Patent No. 5,380,690 and China patent publication 1,093,101A respectively. The catalyst has stronger hydrothermal stability. The conversion obtained by using said catalyst is higher than that obtained by using the catalyst comprising HZSM-5 zeolite as active component by 4-7wt% in the reaction temperature of SSO'C, Similarly, the yield of C2-C4 olefin is higher by 4 - 5wt%. A combination process of catalytic cracking with dehydrogenation has been disclosed in US Patent No. 5,414,181. The spent catalyst is regenerated after the catalytic cracking reaction is completed. The regenerated catalyst is deposited with carbon derived from coke precursor and then C2-C10 alkane is dehydrogenated to produce olefins. It has been disclosed in US Patent No. 6,106,697 that a process for selectively producing Cj-C4 olefin by using vacuum gas oil or residual oil as feedstock and using two-stage reactor to carry out catalytic cracking reaction. Vacuum gas oil or residual oil feedstock is fed into the first stage reactor. The feedstock is contacted with large pore zeolite catalyst under conventional catalytic cracking conditions to carry out catalytic cracking reaction to produce various products with different boiling ranges, including gasoline fractions. The gasoline fractions produced in the first reactor are fed into the second reactor and contacted with medium pore zeolite catalyst in the reaction temperature of 500-650X:;, the catalyst/oil ratio of 4-10:1, and the oil vapor partial pressure of 70-280 kPa. As a result, C2-C4 olefins are produced. It has been reported in China patent pubUcation No. 1,255,474A a catalytic cracking process for producing light olefms from lower alkane. The process comprises contaaing C4-C6 alkane with a silica rich zeolite catalyst being modified by one of the elements selected from the group consisting of alkali metal, alkaline earth metal and group VIII transition metal and having a structure of pentasil, wherein the catalyst comprises rare earth and phosphorus. The reaction is carried out in temperature of 450 - 580X and weight hourly space velocity of 5-300 hour \ The alkali metal is preferably potassium, alkaline earth metal is preferably barium and group VIII transition metal is preferably iron or nickel. It has been disclosed in US patent publication 2003/0006168Al that a catalytic cracking process for producing light olefins with a high yield from heavy oil. The process comprises the steps of contacting the heavy oil with a catalyst mixture, consisting of 60 to 95 % by weight of a base cracking catalyst containing an USY type molecular sieve and less than 0.5 % by weight of rare earth metal oxide, and 5 to 40 % by weight of an additive containing a shape-selective zeolite; the oil and the catalyst are contacted m a downer reactor, and are contacted under conditions so that the reaction zone outlet temperature is in the range of 580-630°C, the catalyst/oil ratio is in the range of 15-40 and the contact time is in the range of 0.1-1.0 seconds. Said process can be used to improve yield of light olefins, for example, the yield of propylene can be about 20 % by weight. It has been disclosed in EP 0,922,744A1 that a process for producing LPG and light olefms with a high yield under the reaction conditions of weight hourly space velocity in the range of 40-120h'\ catalyst/oil ratio in the range of 15-25, riser outlet temperature in the range of 530-600^C, reaction pressure in the range of 1.0-4.0Kg/cm^g and steam for dilution and quenching of hydrocarbon in the range of 3-50% by weight of the feedstock. The catalyst used in said process comprises 1-6% by weight of USY zeolite, 8-25% by weight of shape-selective zeolite, 0-8% by weight of bottoms selective cracking active component, 0-1% by weight of rare earth component and 60-91% by weight of non-acidic component & binder. The yield of LPG obtained by the process can be about 40-65% by weight. The selectivity of propylene and butylenes in LPG are about 40% and 45% by weight respectively. The carbon content in the regenerated catalyst is typically required to be less than 0,1 % by weight and preferably be less than 0.05 % by weight during the catalytic crack process for the purpose of restoring cracking activity of catalyst. As discussed above, the process for producing light olefins with a high yield by using phosphorus-containing silica rich zeolite having a structure of pentasil as active component has not been described in the prior art, wherein said silica rich zeolite has also been modified with group VIII transition metals, although the processes such as in which silica rich zeolite having a structure of pentasil being used as one of the active components in the catalyst have been disclosed. Disclosure of present invention The object of present invention is to overcome the disadvantages that are related to the prior art and to provide a catalytic conversion process using a catalyst comprising phosphorus and transition metals modified silica rich zeolite having a structure of pentasil for producing light olefms with a high yield so that more raw materials in petrochemical industry will be produced. Other objects and advantages will be more apparent in view of following detailed description. In the process of the present invention, pre-heated petroleum hydrocarbons are contacted with a catalyst which comprises phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor, and are catalytically converted under given operating conditions to produce reaction effluent and a spent catalyst. The reaction effluents and spent catalyst are separated by a rapid gas-soUd separator. The reaction effluents are further separated to obtain ethylene and propylene containing gaseous products and liquid products, and the spent catalyst is removed to a stripper. After stripping, the catalyst is directed to a regenerator, where it is contacted with an oxygen-containing gas and regenerated, the hot regenerated catalyst is recycled to the reactor for reuse. More particularly, in the process of the present invention, pre-heated petroleum hydrocarbons are contacted with a catalyst which comprises phosphorus and transition metal modified silica rich zeolite havmg a structure of pentasil in a riser or a fluidized bed reactor at the reaction temperature in the range of 500-700°C, reaction pressure in the range of 150-400 kPa, weight hourly space velocity in the range of 1-200 hour^ catalyst to feedstock ratio by weight in the range of 5-40:1 and steam to feedstock ratio by weight in the range of 0,05-1:1 and catalytically converted. After being stripped and separated from the reaction products, the spent catalyst, having been deposited with coke, is transferred to a regenerator by burning the coke deposited on the catalyst, and returning the catalyst to the reactor Light olefms, gasoline, diesel, bottoms and other saturated hght hydrocarbons are obtained by the separation thereof from the reaction products. Feedstock and product The petroleum hydrocarbons used in present invention as feedstock can be selected from the group consisting of gasoline, atmospheric gas oil, vacuum gas oil, atmospheric residual oil, vacuum residual oil and mixtures thereof Crude oil also may be directly used. The injection of said feedstock can be either single-site injection or multi-site injection. The term "single-site injection' as used herein means that the petroleum hydrocarbons can be injected into a reactor through the feeding nozzle(s) located in a same elevation. There may be just one feeding nozzle or several feeding nozzles in a reactor. The term *multi-site injection" as used herein means that the petroleum hydrocarbons can be injected into a reactor through the feeding nozzles located in different elevations. The process according to present invention can be utilized to obtain gaseous products comprising ethylene and propylene and liquid products comprising gasoline and diesel, wherein the yield of ethylene can be about 5-25% by weight and the yield of propylene can be about 21-26% by weight. Catalyst In the process according to present invention, the catalyst comprises 0-70% by weight of clay, 5-99% by weight of inorganic oxides and 1-50% by weight of zeolite, all based on total weight of the catalyst. The zeolite comprises 75-100% by weight of silica rich zeolite having a structure of pentasil and 0-25% by weight of Y type zeolite, wherein said silica rich zeolite having a structure of pentasil is modified with both phosphorous and transition metal M, with an anhydrous formula of (0-0.3)Na2O-(0.3-5)Al2O3-(1.0-10)P2O5'(07-15)M,Oy ■(0-10)RE2O3-(70-98)SiO2 based on the mass of oxides. In the formula, element M is at least one element selected from the group consisting of Fe, Co, Ni, Cu, Zn, Mo and Mn. And RE represents rare earth elements, x represents valence of oxygen and y represents valence of transition metal, x is equal to 1 and y is a value of the valence of transition metal divided by 2 provided that the valence of transition metal is an even number. It is preferably that said phosphorus and transition metal M modified silica rich zeolite having a structure of pentasil has an anhydrous formula of either (0-0.2)Na2O»(0.9-5)Al2O3'(l,5-7)PA-(0.9-10)M,Oy (82-92)Si02, or (0-0.2)Na2O The transition metal M have the function of dehydrogenation, and are preferably at least two elements or more selected from the group consisting of Fe, Co, Ni, Cu, Zn, Mo and Mn, more preferably selected from the group consisting of Fe, Co and Ni, and the most preferably are Fe and Ni. The clay comprised in the catalyst according to present invention can be natural source or synthesized source. The clay can be any conventional one used as matrix of cracking catalyst in the art, which can be optionally subjected to various chemical and/or physical treatments. Examples of such clays are, but not limited to, kaoUn or kaolin polyhydrate and the like. The inorganic oxides comprised in the catalyst according to present invention can be selected from the group consisting of amorphous SiO^'AlaOa, AI2O3 and/or SiOj. The Y type zeoUte comprised in the catalyst according to present invention can be prepared by usmg various chemical and/or physical methods. Such methods include, for example, hydrothermal method, chemical treatment method (such as treated by EDTA acid, by ammonium jfluorosilicate to extract aluminum and reinforce silicon, and SiCl4 gas phase process) or the combination thereof Y type zeolite optionally contains rare earth elements. The rare earth element-containing Y type zeolite is referred as rare earth hydrogen Y (REHY) or rare earth ultra-stable Y (REUSY). In general, the preparation of said silica rich zeolite having a structure of pentasil includes the steps of ammonium exchange, modification by phosphorus and metals, and calcination. The ammonium exchange can be as follows: sodium type silica rich zeolite having a structure of pentasil and optionally comprising rare earth elements obtained by conventional crystallization is exchanged in a ratio of zeolite; ammonium salt: H2O in 1:(0.1-1);(5-10) by weight in a temperature from room temperature to lOO'C for a period of 0,3-1 hour and then filtered, wherein template agent should be initially removed if an organic template agent has been used during the synthesis of sodium type zeoUte. Said ammonium sah can be conventional inorganic one in the art and can be selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate or the mixture thereof. The modification by phosphorus and metals can be carried out by impregnation or ion exchange methods. The impregnation methods may include, for example, as follows: a. ammonium exchanged zeolite is mixed homogeneously with a pre-calculated amount of aqueous solution containing phosphorus compound in a temperature from room temperature to 95 C J dried, then calcined in a temperature of 400-800 "C, and then mixed homogeneously with a pre-calculated amount of aqueous solution containing transition metal M compound in a temperature from room temperature to 95 C and dried. b. ammonium exchanged zeolite is mixed homogeneously with a pre-calculated amount of aqueous solution containing phosphorus compound in a temperature from room temperature to 95 €, dried, and then mixed homogeneously with a pre-calculated amount of aqueous solution containing transition metal M compound in a temperature from room temperature to 95 C, and dried. The order for impregnating into said aqueous solutions can be reversed. c. ammonium exchanged zeolite is mixed homogeneously with pre-calculated amounts of aqueous solution mixture containbg phosphorus and transition metal M compounds in a temperature from room temperature to 95 "C, and then dried. The ion exchange method can be as follows: ammonium exchanged zeolite is mixed homogeneously with a pre-calculated amount of aqueous solution containing phosphorus compound in a temperature from room temperature to 95X1!, dried, then calcined in a temperature of 400-800'C, and then mixed homogeneously with a pre-calculated amount of aqueous solution containing transition metal M compound in a ratio of solid to liquid of l:(5-20), mixed in a temperature of 80-95 X: under pH 4-7 for 2-3 hours and then filtered. The exchange can be repeated for several times The phosphorus compound containing aqueous solution can be the aqueous solution of the phosphoric acid, aluminum phosphate, ammonium hydrogen phosphate, ammonium biphosphate, ammonium phosphate and the mixture thereof The transition metal M compound containing aqueous solution can be the aqueous solution of chloride, nitrate, sulfate or carbonate of the transition metal M, for example, but not be limited to, iron sulfate, ferrous sulfate, iron nitrate, iron chloride, ferrous chloride, cobalt sulfate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel sulfate, nickel chloride and the like. The catalyst according to present invention can be prepared by the steps of mixing the precursor of inorganic oxides such as pseudo-boehmite, alumina sol, silica sol or its mixture, and silica-alumina sol or gel with kaolin polyhydrate in a pre-determined ratio; formulating a slurry with the solid content of 10-50 wt% by adding de-cationizcd water and then homogeneously mixed, adjusting and maintaining the pH value of the slurry to 2-4 by using an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, adding alumina sol after aging statically at temperature of 20-80C for 0-2 hours, mixing for 0.5-1.5 hours, adding into it pre- calculated amounts of both silica rich zeolite having a structure of pentasii and Y type zeolite, homogenizing, spray drying, washing off the free sodium ion and drying. Other matters In the process according to present invention, it is preferred that the petroleum hydrocarbons are contacted with hot catalyst havmg a carbon content of 0-0.5% by weight, preferably 0.05-0,45% by weight in a riser or fluidized bed reactor More preferably the carbon content is in the range of 0.1-0.3 % by weight. The catalyst comprises phosphorus and transition metal M modified silica rich zeolite having a structure of pentasiL The catalytic conversion reaction is carried out subsequently The carbon-containing catalyst as described above can be prepared by controlling the regenerate condition of the spent catalyst. In another word, the spent catalyst is regenerated in regenerator by using the part combustion operation. Alternatively, the carbon-containing catalyst can be prepared by contacting the regenerated catalyst with light hydrocarbons enriched by olefins in a pre-reactor before said regenerated catalyst is recycled to reactor. The pre-reactor as used herein can be either a second riser or fluidized bed reactor other than the reactor for catalytic conversion of petroleum hydrocarbons, or a portion zone in the reactor for catalytic conversion, for e^cample, the reaction zone on the bottom of riser reactor In the process according to present invention, it is preferable to strip the regenerated catalyst with steam and/or light hydrocarbons enriched by methane to remove non-hydrocarbon gaseous impurities absorbed on or carried by the catalyst, and then recycle the catalyst to reactor The examples as described follows will fiirther illustrate the process according to present invention, but not intend to limitmg present invention in any way. The catalysts used in the examples and comparative Examples respectively are as follows. Examples Catalyst A is one of the catalysts being prepared according to present invention, which comprises 18% silica rich zeolite having a structure of pentasil, 27% aluminum oxide and the balance being kaolin, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 2.4% phosphorus oxide, 3.8% rare earth oxide, and 1.5% iron oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 30. Catalyst B is another one of the catalysts being prepared according to present invention, which comprises 18% silica rich zeolite havmg a structure of pentasiL, 27% aluminum oxide and the balance being kaolin, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 4.1% phosphorus oxide, L0% iron oxide and 1.0% nickel oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60. Catalyst C is another one of the catalysts being prepared according to present invention, which comprises 15% silica rich zeolite having a structure of pentasil, 5% REHY zeohte, 20% aluminum oxide, 6% amorphous aluminum silicate and the balance being kaolin, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 2.1% phosphorus oxide and 1.0% iron oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60. Catalyst D is another one of the catalysts being prepared according to present invention, which comprises 15% silica rich zeolite having a structure of pentasil, 5% REHY zeolite, 20% aluminum oxide, 6% amorphous aluminum silicate and the balance being kaolm, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 2.1% phosphorus oxide, 1.0% iron oxide and 0.6% nickel oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60. Comparative catalyst A is prepared by similar formulation and method as that described for catalyst A, except the silica rich zeolite having a structure of pentasil comprises 2.4% phosphorus oxide and 3.8% rare earth oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 30. Comparative catalyst B is prepared by similar formulation and method as that described for catalyst B, except the silica rich zeolite having a structure of pentasil comprises 4.1% phosphorus oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60. Comparative catalyst C is prepared by similar formulation and method as that described for catalyst C, except the silica rich zeolite having a structure of pentasil is HZSM-5 zoelite with a mole ratio of silica to alumina being 60. Example 1 The example illustrates that ethylene and propylene are produced by the process according to present invention in which catalyst A comprising silica rich zeolite having a structure of pentasil is used, wherein the zeolite has been modified by phosphorus, rare earth and iron. A catalytic conversion reaction is carried out in a bench-scale fixed-fluidized bed reactor with vacuum gas oil feedstock having density of 0.873 and boiling-range of 350- 540°C, under operation conditions of reaction temperature of 700C, catalyst/oil ratio of 25:1, steam/oil ratio of 0.5:1 and weight hourly space velocity of 10 h 'V The results axe shown in table 1, Comparative example 1 The comparative example illustrates the use of comparative catalyst A comprising phosphorus and rare earth modified sihca rich zeolite having a structure of pentasil. The feedstock and operation conditions are both same to that described in example 1. The results are shown in table 1. The example illustrates that ethylene and propylene are produced by the process according to present invention in which catalyst B comprising silica rich zeolite having a structure of pentasilis is used, wherein the zeolite has been modified by phosphorus, iron and nickel, A catalytic conversion reaction is carried out in a bench-scale fixed-fluidized bed reactor with vacuum gas oil feedstock having density of 0.873 and boiling-range of 350 - 540°C, under operation conditions of reaction temperature of 620'C, catalyst/oil ratio of 15; 1, steam/oil ratio of 0.4:1 and weight hourly space velocity of 150 h '\ The results are shown in table 2. Comparative example 2 The comparative example illustrates the use of comparative catalyst B comprising phosphorus modified silica rich zeolite having a structure of pentasil. The feedstock and operation conditions are both same to that described in example 2. The results are shown in table 2. Example 3 The example illustrates that ethylene and propylene are produced by the process according to present invention in which catalyst C comprising both silica rich zeolite having a structure of pentasil and REUSY zeolite is used, wherein the silica rich zeolite has been modified by phosphorus and iron. Further, catalyst D comprising both silica rich zeolite having a structure of pentasil and REUSY zeolite is used, whereui the silica rich zeolite has been modified by phosphorus^ iron and nickel Catalytic conversion reactions are carried out in a bench-scale fixed-fluidized bed reactor with vacuum gas oil feedstock having density of 0.873 and boiling-range of 350"'540'C, under operation condition of reaction temperature of SSO^C, catalyst/oil ratio of 10:1, steam/oil ratio of 0.3; 1 and weight hourly space velocity of 250 h '\ The results are shown in table 3. Comparative example 3 The comparative example illustrates the use of comparative catalyst C comprising both ZSM-5 zeolite and REUSY zeolite. The feedstock and operation conditions are both same to that described in example 3. The results are shown in table 3. Example 4 The example illustrates that the catalytic conversion of petroleum hydrocarbons to produce light olefins in fluidi^ed bed reactor by using the process according to present invention. A catalytic conversion reaction is carried out in a pilot fluidized bed reactor operated in the continuous reaction-regeneration mode with catalyst A and paraffin-based atmospheric residual oil feedstock having density of 0.896. The hot regenerated catalyst is contacted \vith a portion of C4 fraction which have been recycled to the pre-lifting zone located in the bottom of fluidized bed reactor in elevated temperature so that about 0,18 % by weight of carbon is deposited onto the catalyst. The coke-deposited catalyst is contacted with feedstock which has been heated to about 350°C by means of pre-heated oven in the fluidized bed reactor under the conditions of reactor bed temperature of 580'C, pressure of 200kPa, weight hourly space velocity of 4 h"\ catalyst/oil ratio of 15:1 and steam/oil ratio of 0,25: L The reaction effluents and spent catalyst are transferred to a gas-soHd separator through reactor outlet. The reaction effluents and spent catalyst are rapidly separated between each other in the gas-sohd separator The reaction effluents are further separated into gaseous products comprising ethylene and propylene, C4 fraction, gasoline, diesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam. The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The regenerated catalyst is recycled to the pre-lifting zone located in the bottom of fluidized bed reactor in which catalyst is contacted with C4 fraction to deposit the catalyst with coke. The coke-deposited catalyst is contacted with feedstock and the reaction is continued. The resuhs are shown in table 4. Comparative example 4 The comparative example illustrates that the production of light olefins by using the process disclosed in the art under same operation conditions to that described in example 4. A catalytic conversion reaction is carried out in a pilot fluidized bed reactor operated in the continuous reaction-regeneration mode with comparative catalyst A and paraflBn-based atmospheric residual oil feedstock having density of 0,896. The reaction is in single pass operation mode. Regenerated catalyst is contacted with feedstock which has been heated to about dSO'^C by means of pre-heated oven in the fluidized bed reactor under the conditions of reaaor bed temperature of 580°C, pressure of 200kPa, weight hourly space velocity of 4 h'\ catalyst/oil ratio of 15:1 and steam/oil ratio of 0.25:1. The reaction effluents and spent catalyst are transferred to a gas-solid separator through reactor outlet. The reaction eflEluents and catalyst are rapidly separated between each other in the gas-sohd separator. The reaction effluents are further separated into Ught gaseous products comprising ethylene and propylene, C4 fraction, gasoline, diesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam. The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The resulted regenerated catalyst has a carbon content of less than 0.05 % by weight. The regenerated catalyst is recycled to fluidized bed reactor and the reaction is continued. The results are shown in table 4. Example 5 The example illustrates that the catalytic conversion of petroleum hydrocarbons to produce light olefins in riser reactor by using the process according to present invention, A catalytic conversion reaction is carried out in a pilot riser reactor operated in the continuous reaction-regeneration mode with catalyst C and paraffm-based atmospheric residual oil feedstock having density of 0.896. The reaction-regeneration is in a part combustion regeneration operation mode. The resulted regenerated catalyst has a carbon content of 0.2 % by weight. The steps comprise contacting the coke-deposited catalyst with feedstock which has been heated lo about 350°C by means of pre-heated oven in the reactor under the conditions of reactor outlet temperature of 650'C, pressure of 250 kPa, reaction time of 5 seconds, catalyst/oil ratio of 25:1 and steam/oil ratio of 0.5:1. The reaction effluents and spent catalyst are transferred to a gas-solid separator through reactor outlet. The reaction effluents and catalyst are rapidly separated between each other in the gas-solid separator The reaction effluents are ftirther separated into gaseous products, gasoline, diesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam, The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The carbon content in the regenerated catalyst is adjusted to 0.2 wt % by controlling regenerate temperature and air rate. The coke-deposited regenerated catalyst is recycled into reactor. The results are shown in table 5. Comparative example 5 The comparative example illustrates that the production of light olefins by using the process disclosed in the art under same operation conditions to that described in example 5. A catalytic conversion reaction is carried out in a pilot riser reactor operated in the continuous reaction-regeneration mode with comparative catalyst C and paraffin-based atmospheric residual oil feedstock having density of 0,896, The reaction is in a foil combustion regeneration operation mode. Regenerated catalyst is contacted with feedstock which has been heated to about 350'C by means of pre-heated oven in the reactor under the conditions of reactor outlet temperature of 650C, pressure of 250 kPa, reaction time of 5 seconds, catalyst/oil ratio of 25:1 and steam/oil ratio of 0.5:1. The reaction effluents and spent catalyst are transferred to a gas-soUd separator through reactor outlet. The reaction effluents and catalyst are rapidly separated between each other in the gas-solid separator. The reaction effluents are further separated into gaseous products, gasoline, dtesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam. The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The resulted regenerated catalyst has a carbon content of less than 0.05 % by weight. The regenerated catalyst is recycled into reactor. The resuhs are shown in table 5, It can be seen from the results cited in tables 1-5, the yield of total gaseous olefins according to the process of present inveution ts greater than that according to the process of comparative examples, especially the yield of ethylene and propylene. What is claimed is K. Pcatalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons, which comprises the steps of contacting a pre-heated petroleum hydrocarbons feedstock with a catalyst which comprises phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor^ and converting under the catalj^ic conversion conditions to produce reaction eflfluent and a spent catalyst, separating the resulted reaction effluent and spent catalyst, further separating said reaction effluent into liquid products and gaseous products comprising ethylene and propylene; stripping the spent catalyst by steam; regenerating the stripped catalyst by contacting the spent catalyst with oxygen- containing gas and burning off coke; and recycling the regenerated catalyst to reactor for reuse. 2> A process according to claim 1, being characterized by said process is carried out under catalytic conversion conditions of reaction temperature in the range of 500-700 X^, reaction pressure in the range of 150-400 kPa, weight hourly space velocity in the range of 1-200 hour\ catalyst to feedstock ratio by weight in the range of 5-40:1 and steam to feedstock ratio by weight in the range of 0.05-1:1. 3 s A process according to claim 2, bemg characterized by said process is carried out under catalytic conversion conditions of reaction temperature in the range of 550-650 "C, weight hourly space velocity in the range of 4-180 hour \ catalyst to feedstock ratio by weight in the range of 10-30:1 and steam to feedstock ratio by weight in the range of 0.1-0.5:1. 4> A process according to claim 1, being characterized by said petroleum hydrocarbons feedstock is selected fi:om the group consisting of gasoline, atmospheric gas oil, vacuum gas oil, atmospheric residual oil, vacuum residual oil, crude oil and the mixture thereof; and the injection of said petroleum hydrocarbons can be either single-site injection or multi^site injection. 5> A process according to claim 1, being characterized by said phosphorus and transition metal modified silica rich zeolite having a structure of pentasil has an anhydrous formula of (0-0.3)Na5O-(0.3-5)A)2O3 6s A process according to claim 5, being characterized by said phosphorus and transition metal modified silica rich zeolite having a structure of pentasil has an anhydrous formula of either (0-0.2)Na^O-(0.9-5)Al2O3-(1.5-7)P2O5-(0.9-10)M,Oy '(82-92)Si02 based on the mass of oxides, or (0-0.2)NaiO-(0.9-5)Al2O3'(l-5-7)PA'(0.9"10)M,Oy •(0.540)REjO3'(82-92)SiOj based on the mass of oxides, wherein M, x and y are as defined in claim 5, 7. A process according to claim 5, being characterized by said element M are at least two elements or more selected from the group consisting of Fe, Co, Ni, Cu, Zn, Mo and Mn. 8^ A process according to claim 7, being characterized by said element M are at least two elements or more selected from the group consisting of Fe, Co and Ni. 9. A process according to claim 8, being characterized by said element M are Fe and Ni. 10. A process according to claim 1, being characterized by said petroleum hydrocarbons feedstock is contacted with said catalyst comprising phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor, wherein said catalyst has a carbon content of 0 " 0.5 % by weight, 11 > A process according to claim 10, being characterized by said petroleum hydrocarbons feedstock is contacted with said catalyst comprising phosphorus and transition metal modified silica rich zeohte having a structure of pentasil in a riser or a fluidized bed reactor, wherein said catalyst has a carbon content of 0.05 ~ 0.45 % by weight. 12H A process according to claim 11, being characterised by said petroleum hydrocarbons feedstock is contacted with said catalyst comprising phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor, wherein said catalyst has a carbon content of 0.1 ~ 0.3 % by weight. 13. A process according to claim 12, being characterized by said catalyst comprising phosphorus and transition metal modified silica rich zeolite having a structure of pentasil is obtained by regenerating the spent catalyst m a regenerator which operates in a part combustion mode, wherein said catalyst has a carbon content of 0.1 - 0.3 % by weight, 14 s A process according to claim 12, being characterized by said catalyst comprising phosphorus and transition metal modified silica rich zeolite having a structure of pentasil is obtained by contacting the regenerated catalyst with light hydrocarbons enriched by olefins in a pre-reactor before said regenerated catalyst is recycled to reactor, wherein said catalyst has a carbon content of 0.1 - 0,3 % by weight. 15s A process according to claim 14, being characterized by said pre-reactor is either a second riser or fluidized bed reactor other than the reactor for catalytic conversion of petroleum hydrocarbons, or a portion zone in the reactor for catalytic conversion of petroleum hydrocarbons. 16. A process according to claim 1, being characterized by said regenerated catalyst is stripped with steam and/or with light hydrocarbons enriched by methane to remove non-hydrocarbon gaseous impurities absorbed on and/or carried by the catalyst, and then the catalyst is recycled for reuse. 17. A catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons, substantially as herein described with reference to the accompanying drawings.

Full Text

A catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons
Technical field
The present invention relates to a catalytic conversion process of petroleum hydrocarbons, in particular, to a catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons.
Background of present invention
The conventional process for producing gaseous olefins from petroleum hydrocarbons is steam cracking process, wherein the feedstocks are light hydrocarbons comprising natural gas, naphtha and light gas oil and so on. The supply of light hydrocarbons was limited as crude oil becomes heavier Thus, more attentions are paid to processes for producing gaseous olefins from heavy hydrocarbons. Such processes, for example, include thermal cracking process of heavy hydrocarbons by using inert soUd materials such as quartz or coke as heat carriers, and thermo-catalytic cracking process of heavy hydrocarbons by using alkali metal oxides or alkalme earth metal oxides as catalyst. The reaction temperatures in such processes are both greater than SOO'^Co
Recently the processes for producing gaseous olefins from petroleum hydrocarbons have been described in various publications, wherein using solid acidic catalysts in certain reactor style and under certain operation conditions. For example, JP 60-222,428 discloses a process using ZSM-5 as a catalyst and C^ to Css paraffinic hydrocarbons as feedstock. The process is carried out at a reaction temperature of between 600 to 750°C, with 30wt% yield for Cj to C4 olefins, US Patent No, 3,758,403 disclosed that a catalyst comprising both ZSM-5 zeolite and large pore

zeolite (e.g. X type or Y type) as active components in a ratio of 1:10 - 3:1 raised octane number of gasoUne while increasing yield of total propylene and butylenes to about 10wt%.
It has been reported in US Patent No. 5,318,696 that the catalyst comprising large pore zeolite and medium pore zeolite in ratio of SiOj/AljOj being less than 30 can be used to produce high octane gasoline, and to increase the yield of gaseous olefins, especially propylene. Said medium pore zeolite is in the form of MFI structure.
US Patent No. 4,980,053 disclosed the catalyst comprising mixture of ZSM-5 zeolite and Y type zeolite as active components can be used to increase octane number of gasoline in products and to increase yield of light olefins in reaction temperature of 500 -- 650^:. And light olefins are mainly consisting of propylene and butylene.
It has been reported in prior art that the process for modifying zeolite having a structure of pentasil to increase the selectivity to the reaction product. For example, phosphorus and/or metal ion can be incorporated into zeolite having a structure of pentasil (such as ZSM-5) to adjust the adsorption and catalysis properties of the zeolite.
It has been reported in US Patent No. 4,365,104 that the process for modifying ZSM-S zeolite by using phosphorus and magnesium, for the purpose of using modified zeolite to the isomerization of xylene to increase selectivity to xylene. The incorporation of phosphorus and magnesium is to increase the shape selectivity of zeolite. However, both acidity of molecular sieve and hydrocarbons conversion reactivity of zeolite after modification are decreased.
It has been reported in US Patent No, 5,236,880 that the incorporation of group VEIIB metals, preferably nickel into zeolite in the ratio of SiOj to AI2O3 being greater than 5. Said zeolite is in the form of MFI or MEL structure. The catalyst disclosed in US Patent No. 5,236,880 can be used to increase the conversion of paraffinic hydrocarbons, to increase aromatics content in gasoline fraction, to increase octane number of gasoUne in products and yield of gasoline.

A catalyst comprising both phosphorus and rare earth-containing silica rich zeolite having a Stracture of pentasil as active component has been disclosed in US Patent No. 5,380,690 and China patent publication 1,093,101A respectively. The catalyst has stronger hydrothermal stability. The conversion obtained by using said catalyst is higher than that obtained by using the catalyst comprising HZSM-5 zeolite as active component by 4-7wt% in the reaction temperature of SSO'C,
Similarly, the yield of C2-C4 olefin is higher by 4 *- 5wt%.
A combination process of catalytic cracking with dehydrogenation has been disclosed in US Patent No. 5,414,181. The spent catalyst is regenerated after the catalytic cracking reaction is completed. The regenerated catalyst is deposited with carbon derived from coke precursor and then C2-C10 alkane is dehydrogenated to produce olefins.
It has been disclosed in US Patent No. 6,106,697 that a process for selectively producing Cj-C4 olefin by using vacuum gas oil or residual oil as feedstock and using two-stage reactor to carry out catalytic cracking reaction. Vacuum gas oil or residual oil feedstock is fed into the first stage reactor. The feedstock is contacted with large pore zeolite catalyst under conventional catalytic cracking conditions to carry out catalytic cracking reaction to produce various products with different boiling ranges, including gasoline fractions. The gasoline fractions produced in the first reactor are fed into the second reactor and contacted with medium pore zeolite catalyst in the reaction temperature of 500-650X:;, the catalyst/oil ratio of 4-10:1, and the oil vapor partial pressure of 70-280 kPa. As a result, C2-C4 olefins are produced.
It has been reported in China patent pubUcation No. 1,255,474A a catalytic cracking process for producing light olefms from lower alkane. The process comprises contaaing C4-C6 alkane with a silica rich zeolite catalyst being modified by one of the elements selected from the group consisting of alkali metal, alkaline earth metal and group VIII transition metal and having a structure of pentasil, wherein the catalyst comprises rare earth and phosphorus. The reaction is

carried out in temperature of 450 - 580X and weight hourly space velocity of 5-300 hour \ The alkali metal is preferably potassium, alkaline earth metal is preferably barium and group VIII transition metal is preferably iron or nickel.
It has been disclosed in US patent publication 2003/0006168Al that a catalytic cracking process for producing light olefins with a high yield from heavy oil. The process comprises the steps of contacting the heavy oil with a catalyst mixture, consisting of 60 to 95 % by weight of a base cracking catalyst containing an USY type molecular sieve and less than 0.5 % by weight of rare earth metal oxide, and 5 to 40 % by weight of an additive containing a shape-selective zeolite; the oil and the catalyst are contacted m a downer reactor, and are contacted under conditions so that the reaction zone outlet temperature is in the range of 580-630°C, the catalyst/oil ratio is in the range of 15-40 and the contact time is in the range of 0.1-1.0 seconds. Said process can be used to improve yield of light olefins, for example, the yield of propylene can be about 20 % by weight.
It has been disclosed in EP 0,922,744A1 that a process for producing LPG and light olefms with a high yield under the reaction conditions of weight hourly space velocity in the range of 40-120h'\ catalyst/oil ratio in the range of 15-25, riser outlet temperature in the range of 530-600*^C, reaction pressure in the range of 1.0-4.0Kg/cm^g and steam for dilution and quenching of hydrocarbon in the range of 3-50% by weight of the feedstock. The catalyst used in said process comprises 1-6% by weight of USY zeolite, 8-25% by weight of shape-selective zeolite, 0-8% by weight of bottoms selective cracking active component, 0-1% by weight of rare earth component and 60-91% by weight of non-acidic component & binder. The yield of LPG obtained by the process can be about 40-65% by weight. The selectivity of propylene and butylenes in LPG are about 40% and 45% by weight respectively.
The carbon content in the regenerated catalyst is typically required to be less than 0,1 % by weight and preferably be less than 0.05 % by weight during the catalytic crack process for the

purpose of restoring cracking activity of catalyst.
As discussed above, the process for producing light olefins with a high yield by using phosphorus-containing silica rich zeolite having a structure of pentasil as active component has not been described in the prior art, wherein said silica rich zeolite has also been modified with group VIII transition metals, although the processes such as in which silica rich zeolite having a structure of pentasil being used as one of the active components in the catalyst have been disclosed.
Disclosure of present invention
The object of present invention is to overcome the disadvantages that are related to the prior art and to provide a catalytic conversion process using a catalyst comprising phosphorus and transition metals modified silica rich zeolite having a structure of pentasil for producing light olefms with a high yield so that more raw materials in petrochemical industry will be produced. Other objects and advantages will be more apparent in view of following detailed description.
In the process of the present invention, pre-heated petroleum hydrocarbons are contacted with a catalyst which comprises phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor, and are catalytically converted under given operating conditions to produce reaction effluent and a spent catalyst. The reaction effluents and spent catalyst are separated by a rapid gas-soUd separator. The reaction effluents are further separated to obtain ethylene and propylene containing gaseous products and liquid products, and the spent catalyst is removed to a stripper. After stripping, the catalyst is directed to a regenerator, where it is contacted with an oxygen-containing gas and regenerated, the hot regenerated catalyst is recycled to the reactor for reuse.
More particularly, in the process of the present invention, pre-heated petroleum hydrocarbons are contacted with a catalyst which comprises phosphorus and transition metal

modified silica rich zeolite havmg a structure of pentasil in a riser or a fluidized bed reactor at the reaction temperature in the range of 500-700°C, reaction pressure in the range of 150-400 kPa, weight hourly space velocity in the range of 1-200 hour^ catalyst to feedstock ratio by weight in the range of 5-40:1 and steam to feedstock ratio by weight in the range of 0,05-1:1 and catalytically converted. After being stripped and separated from the reaction products, the spent catalyst, having been deposited with coke, is transferred to a regenerator by burning the coke deposited on the catalyst, and returning the catalyst to the reactor Light olefms, gasoline, diesel, bottoms and other saturated hght hydrocarbons are obtained by the separation thereof from the reaction products.
Feedstock and product
The petroleum hydrocarbons used in present invention as feedstock can be selected from the group consisting of gasoline, atmospheric gas oil, vacuum gas oil, atmospheric residual oil, vacuum residual oil and mixtures thereof Crude oil also may be directly used. The injection of said feedstock can be either single-site injection or multi-site injection. The term "single-site injection' as used herein means that the petroleum hydrocarbons can be injected into a reactor through the feeding nozzle(s) located in a same elevation. There may be just one feeding nozzle or several feeding nozzles in a reactor. The term **multi-site injection" as used herein means that the petroleum hydrocarbons can be injected into a reactor through the feeding nozzles located in different elevations.
The process according to present invention can be utilized to obtain gaseous products comprising ethylene and propylene and liquid products comprising gasoline and diesel, wherein the yield of ethylene can be about 5-25% by weight and the yield of propylene can be about 21-26% by weight.

Catalyst
In the process according to present invention, the catalyst comprises 0-70% by weight of clay, 5-99% by weight of inorganic oxides and 1-50% by weight of zeolite, all based on total weight of the catalyst. The zeolite comprises 75-100% by weight of silica rich zeolite having a structure of pentasil and 0-25% by weight of Y type zeolite, wherein said silica rich zeolite having a structure of pentasil is modified with both phosphorous and transition metal M, with an anhydrous formula of (0-0.3)Na2O-(0.3-5)Al2O3-(1.0-10)P2O5'(07-15)M,Oy ■(0-10)RE2O3-(70-98)SiO2 based on the mass of oxides. In the formula, element M is at least one element selected from the group consisting of Fe, Co, Ni, Cu, Zn, Mo and Mn. And RE represents rare earth elements, x represents valence of oxygen and y represents valence of transition metal, x is equal to 1 and y is a value of the valence of transition metal divided by 2 provided that the valence of transition metal is an even number. It is preferably that said phosphorus and transition metal M modified silica rich zeolite having a structure of pentasil has an anhydrous formula of either (0-0.2)Na2O»(0.9-5)Al2O3'(l,5-7)PA-(0.9-10)M,Oy *(82-92)Si02, or (0-0.2)Na2O The transition metal M have the function of dehydrogenation, and are preferably at least two elements or more selected from the group consisting of Fe, Co, Ni, Cu, Zn, Mo and Mn, more preferably selected from the group consisting of Fe, Co and Ni, and the most preferably are Fe and
Ni.
The clay comprised in the catalyst according to present invention can be natural source or synthesized source. The clay can be any conventional one used as matrix of cracking catalyst in the art, which can be optionally subjected to various chemical and/or physical treatments. Examples of such clays are, but not limited to, kaoUn or kaolin polyhydrate and the like.

The inorganic oxides comprised in the catalyst according to present invention can be selected from the group consisting of amorphous SiO^'AlaOa, AI2O3 and/or SiOj.
The Y type zeoUte comprised in the catalyst according to present invention can be prepared by usmg various chemical and/or physical methods. Such methods include, for example, hydrothermal method, chemical treatment method (such as treated by EDTA acid, by ammonium jfluorosilicate to extract aluminum and reinforce silicon, and SiCl4 gas phase process) or the combination thereof Y type zeolite optionally contains rare earth elements. The rare earth element-containing Y type zeolite is referred as rare earth hydrogen Y (REHY) or rare earth ultra-stable Y (REUSY).
In general, the preparation of said silica rich zeolite having a structure of pentasil includes the steps of ammonium exchange, modification by phosphorus and metals, and calcination.
The ammonium exchange can be as follows: sodium type silica rich zeolite having a structure of pentasil and optionally comprising rare earth elements obtained by conventional crystallization is exchanged in a ratio of zeolite; ammonium salt: H2O in 1:(0.1-1);(5-10) by weight in a temperature from room temperature to lOO'C for a period of 0,3-1 hour and then filtered, wherein
template agent should be initially removed if an organic template agent has been used during the synthesis of sodium type zeoUte. Said ammonium sah can be conventional inorganic one in the art and can be selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium sulfate or the mixture thereof.
The modification by phosphorus and metals can be carried out by impregnation or ion exchange methods.
The impregnation methods may include, for example, as follows:
a. ammonium exchanged zeolite is mixed homogeneously with a pre-calculated amount of aqueous solution containing phosphorus compound in a temperature from room temperature to 95

*C J dried, then calcined in a temperature of 400-800 "C, and then mixed homogeneously with a pre-calculated amount of aqueous solution containing transition metal M compound in a temperature from room temperature to 95 *C and dried.
b. ammonium exchanged zeolite is mixed homogeneously with a pre-calculated amount of
aqueous solution containing phosphorus compound in a temperature from room temperature to 95
*€, dried, and then mixed homogeneously with a pre-calculated amount of aqueous solution
containing transition metal M compound in a temperature from room temperature to 95 *C, and
dried. The order for impregnating into said aqueous solutions can be reversed.
c. ammonium exchanged zeolite is mixed homogeneously with pre-calculated amounts of
aqueous solution mixture containbg phosphorus and transition metal M compounds in a
temperature from room temperature to 95 "C, and then dried.
The ion exchange method can be as follows: ammonium exchanged zeolite is mixed homogeneously with a pre-calculated amount of aqueous solution containing phosphorus compound in a temperature from room temperature to 95X1!, dried, then calcined in a temperature
of 400-800'C, and then mixed homogeneously with a pre-calculated amount of aqueous solution containing transition metal M compound in a ratio of solid to liquid of l:(5-20), mixed in a temperature of 80-95 X: under pH 4-7 for 2-3 hours and then filtered. The exchange can be repeated for several times The phosphorus compound containing aqueous solution can be the aqueous solution of the phosphoric acid, aluminum phosphate, ammonium hydrogen phosphate, ammonium biphosphate, ammonium phosphate and the mixture thereof The transition metal M compound containing aqueous solution can be the aqueous solution of chloride, nitrate, sulfate or carbonate of the transition metal M, for example, but not be limited to, iron sulfate, ferrous sulfate, iron nitrate, iron

chloride, ferrous chloride, cobalt sulfate, cobalt nitrate, cobalt chloride, nickel nitrate, nickel sulfate, nickel chloride and the like.
The catalyst according to present invention can be prepared by the steps of mixing the precursor of inorganic oxides such as pseudo-boehmite, alumina sol, silica sol or its mixture, and silica-alumina sol or gel with kaolin polyhydrate in a pre-determined ratio; formulating a slurry with the solid content of 10-50 wt% by adding de-cationizcd water and then homogeneously mixed, adjusting and maintaining the pH value of the slurry to 2-4 by using an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid, adding alumina sol after aging statically at temperature of 20-80*C for 0-2 hours, mixing for 0.5-1.5 hours, adding into it pre-
calculated amounts of both silica rich zeolite having a structure of pentasii and Y type zeolite, homogenizing, spray drying, washing off the free sodium ion and drying.
Other matters
In the process according to present invention, it is preferred that the petroleum hydrocarbons are contacted with hot catalyst havmg a carbon content of 0-0.5% by weight, preferably 0.05-0,45% by weight in a riser or fluidized bed reactor More preferably the carbon content is in the range of 0.1-0.3 % by weight. The catalyst comprises phosphorus and transition metal M modified silica rich zeolite having a structure of pentasiL The catalytic conversion reaction is carried out subsequently The carbon-containing catalyst as described above can be prepared by controlling the regenerate condition of the spent catalyst. In another word, the spent catalyst is regenerated in regenerator by using the part combustion operation. Alternatively, the carbon-containing catalyst can be prepared by contacting the regenerated catalyst with light hydrocarbons enriched by olefins in a pre-reactor before said regenerated catalyst is recycled to reactor. The pre-reactor as used herein can be either a second riser or fluidized bed reactor other than the reactor for catalytic

conversion of petroleum hydrocarbons, or a portion zone in the reactor for catalytic conversion, for e^cample, the reaction zone on the bottom of riser reactor
In the process according to present invention, it is preferable to strip the regenerated catalyst with steam and/or light hydrocarbons enriched by methane to remove non-hydrocarbon gaseous impurities absorbed on or carried by the catalyst, and then recycle the catalyst to reactor
The examples as described follows will fiirther illustrate the process according to present invention, but not intend to limitmg present invention in any way. The catalysts used in the examples and comparative Examples respectively are as follows.
Examples
Catalyst A is one of the catalysts being prepared according to present invention, which comprises 18% silica rich zeolite having a structure of pentasil, 27% aluminum oxide and the balance being kaolin, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 2.4% phosphorus oxide, 3.8% rare earth oxide, and 1.5% iron oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 30.
Catalyst B is another one of the catalysts being prepared according to present invention, which comprises 18% silica rich zeolite havmg a structure of pentasiL, 27% aluminum oxide and the balance being kaolin, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 4.1% phosphorus oxide, L0% iron oxide and 1.0% nickel oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60.
Catalyst C is another one of the catalysts being prepared according to present invention, which comprises 15% silica rich zeolite having a structure of pentasil, 5% REHY zeohte, 20% aluminum oxide, 6% amorphous aluminum silicate and the balance being kaolin, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 2.1% phosphorus

oxide and 1.0% iron oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60.
Catalyst D is another one of the catalysts being prepared according to present invention, which comprises 15% silica rich zeolite having a structure of pentasil, 5% REHY zeolite, 20% aluminum oxide, 6% amorphous aluminum silicate and the balance being kaolm, based on total weight of catalyst. Silica rich zeolite having a structure of pentasil comprises 2.1% phosphorus oxide, 1.0% iron oxide and 0.6% nickel oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60.
Comparative catalyst A is prepared by similar formulation and method as that described for catalyst A, except the silica rich zeolite having a structure of pentasil comprises 2.4% phosphorus oxide and 3.8% rare earth oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 30.
Comparative catalyst B is prepared by similar formulation and method as that described for catalyst B, except the silica rich zeolite having a structure of pentasil comprises 4.1% phosphorus oxide based on total weight of zeolite, with a mole ratio of silica to alumina being 60.
Comparative catalyst C is prepared by similar formulation and method as that described for catalyst C, except the silica rich zeolite having a structure of pentasil is HZSM-5 zoelite with a mole ratio of silica to alumina being 60.
Example 1
The example illustrates that ethylene and propylene are produced by the process according to present invention in which catalyst A comprising silica rich zeolite having a structure of pentasil is used, wherein the zeolite has been modified by phosphorus, rare earth and iron.

A catalytic conversion reaction is carried out in a bench-scale fixed-fluidized bed reactor with vacuum gas oil feedstock having density of 0.873 and boiling-range of 350- 540°C, under operation conditions of reaction temperature of 700*C, catalyst/oil ratio of 25:1, steam/oil ratio of 0.5:1 and weight hourly space velocity of 10 h 'V The results axe shown in table 1,
Comparative example 1
The comparative example illustrates the use of comparative catalyst A comprising phosphorus and rare earth modified sihca rich zeolite having a structure of pentasil. The feedstock and operation conditions are both same to that described in example 1. The results are shown in table 1.

The example illustrates that ethylene and propylene are produced by the process according to present invention in which catalyst B comprising silica rich zeolite having a structure of pentasilis is used, wherein the zeolite has been modified by phosphorus, iron and nickel,
A catalytic conversion reaction is carried out in a bench-scale fixed-fluidized bed reactor with vacuum gas oil feedstock having density of 0.873 and boiling-range of 350 - 540°C, under operation conditions of reaction temperature of 620'C, catalyst/oil ratio of 15; 1, steam/oil ratio of

0.4:1 and weight hourly space velocity of 150 h '\ The results are shown in table 2.
Comparative example 2
The comparative example illustrates the use of comparative catalyst B comprising phosphorus modified silica rich zeolite having a structure of pentasil. The feedstock and operation conditions are both same to that described in example 2. The results are shown in table 2.

Example 3
The example illustrates that ethylene and propylene are produced by the process according to present invention in which catalyst C comprising both silica rich zeolite having a structure of pentasil and REUSY zeolite is used, wherein the silica rich zeolite has been modified by phosphorus and iron. Further, catalyst D comprising both silica rich zeolite having a structure of pentasil and REUSY zeolite is used, whereui the silica rich zeolite has been modified by phosphorus^ iron and nickel
Catalytic conversion reactions are carried out in a bench-scale fixed-fluidized bed reactor with vacuum gas oil feedstock having density of 0.873 and boiling-range of 350"'540'*C, under
operation condition of reaction temperature of SSO^C, catalyst/oil ratio of 10:1, steam/oil ratio of 0.3; 1 and weight hourly space velocity of 250 h '\ The results are shown in table 3.
Comparative example 3
The comparative example illustrates the use of comparative catalyst C comprising both ZSM-5 zeolite and REUSY zeolite. The feedstock and operation conditions are both same to that described in example 3. The results are shown in table 3.

Example 4
The example illustrates that the catalytic conversion of petroleum hydrocarbons to produce light olefins in fluidi^ed bed reactor by using the process according to present invention.
A catalytic conversion reaction is carried out in a pilot fluidized bed reactor operated in the continuous reaction-regeneration mode with catalyst A and paraffin-based atmospheric residual oil feedstock having density of 0.896. The hot regenerated catalyst is contacted \vith a portion of C4 fraction which have been recycled to the pre-lifting zone located in the bottom of fluidized bed reactor in elevated temperature so that about 0,18 % by weight of carbon is deposited onto the

catalyst. The coke-deposited catalyst is contacted with feedstock which has been heated to about
350°C by means of pre-heated oven in the fluidized bed reactor under the conditions of reactor bed
temperature of 580'C, pressure of 200kPa, weight hourly space velocity of 4 h"\ catalyst/oil ratio of 15:1 and steam/oil ratio of 0,25: L The reaction effluents and spent catalyst are transferred to a gas-soHd separator through reactor outlet. The reaction effluents and spent catalyst are rapidly separated between each other in the gas-sohd separator The reaction effluents are further separated into gaseous products comprising ethylene and propylene, C4 fraction, gasoline, diesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam. The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The regenerated catalyst is recycled to the pre-lifting zone located in the bottom of fluidized bed reactor in which catalyst is contacted with C4 fraction to deposit the catalyst with coke. The coke-deposited catalyst is contacted with feedstock and the reaction is continued. The resuhs are shown in table 4.
Comparative example 4
The comparative example illustrates that the production of light olefins by using the process disclosed in the art under same operation conditions to that described in example 4.
A catalytic conversion reaction is carried out in a pilot fluidized bed reactor operated in the continuous reaction-regeneration mode with comparative catalyst A and paraflBn-based atmospheric residual oil feedstock having density of 0,896. The reaction is in single pass operation mode. Regenerated catalyst is contacted with feedstock which has been heated to about dSO'^C by means of pre-heated oven in the fluidized bed reactor under the conditions of reaaor bed temperature of 580°C, pressure of 200kPa, weight hourly space velocity of 4 h'\ catalyst/oil ratio

of 15:1 and steam/oil ratio of 0.25:1. The reaction effluents and spent catalyst are transferred to a gas-solid separator through reactor outlet. The reaction eflEluents and catalyst are rapidly separated between each other in the gas-sohd separator. The reaction effluents are further separated into Ught gaseous products comprising ethylene and propylene, C4 fraction, gasoline, diesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam. The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The resulted regenerated catalyst has a carbon content of less than 0.05 % by weight. The regenerated catalyst is recycled to fluidized bed reactor and the reaction is continued. The results are shown in table 4.

Example 5
The example illustrates that the catalytic conversion of petroleum hydrocarbons to produce light olefins in riser reactor by using the process according to present invention,
A catalytic conversion reaction is carried out in a pilot riser reactor operated in the continuous reaction-regeneration mode with catalyst C and paraffm-based atmospheric residual oil feedstock having density of 0.896. The reaction-regeneration is in a part combustion regeneration operation mode. The resulted regenerated catalyst has a carbon content of 0.2 % by weight. The steps comprise contacting the coke-deposited catalyst with feedstock which has been heated lo

about 350°C by means of pre-heated oven in the reactor under the conditions of reactor outlet temperature of 650'C, pressure of 250 kPa, reaction time of 5 seconds, catalyst/oil ratio of 25:1 and steam/oil ratio of 0.5:1. The reaction effluents and spent catalyst are transferred to a gas-solid separator through reactor outlet. The reaction effluents and catalyst are rapidly separated between each other in the gas-solid separator The reaction effluents are ftirther separated into gaseous products, gasoline, diesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam, The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The carbon content in the regenerated catalyst is adjusted to 0.2 wt % by controlling regenerate temperature and air rate. The coke-deposited regenerated catalyst is recycled into reactor. The results are shown in table 5.
Comparative example 5
The comparative example illustrates that the production of light olefins by using the process disclosed in the art under same operation conditions to that described in example 5.
A catalytic conversion reaction is carried out in a pilot riser reactor operated in the continuous reaction-regeneration mode with comparative catalyst C and paraffin-based atmospheric residual oil feedstock having density of 0,896, The reaction is in a foil combustion regeneration operation mode. Regenerated catalyst is contacted with feedstock which has been heated to about 350'C by means of pre-heated oven in the reactor under the conditions of reactor outlet temperature of 650*C, pressure of 250 kPa, reaction time of 5 seconds, catalyst/oil ratio of
25:1 and steam/oil ratio of 0.5:1. The reaction effluents and spent catalyst are transferred to a gas-soUd separator through reactor outlet. The reaction effluents and catalyst are rapidly separated between each other in the gas-solid separator. The reaction effluents are further separated into

gaseous products, gasoline, dtesel, bottoms and the like. The spent catalyst is forwarded to stripper by the action of gravity, and hydrocarbon products absorbed onto the spent catalyst are stripped from catalyst particles by using steam. The stripped spent catalyst is transferred to a regenerator in which catalyst is contacted with hot air to regenerate. The resulted regenerated catalyst has a carbon content of less than 0.05 % by weight. The regenerated catalyst is recycled into reactor. The resuhs are shown in table 5,

It can be seen from the results cited in tables 1-5, the yield of total gaseous olefins according to

the process of present inveution ts greater than that according to the process of comparative examples, especially the yield of ethylene and propylene.

What is claimed is
K. Pcatalytic conversion process for producing light olefins with a high yield from
petroleum hydrocarbons, which comprises the steps of contacting a pre-heated petroleum hydrocarbons feedstock with a catalyst which comprises phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor^ and converting under the catalj^ic conversion conditions to produce reaction eflfluent and a spent catalyst, separating the resulted reaction effluent and spent catalyst, further separating said reaction effluent into liquid products and gaseous products comprising ethylene and propylene; stripping the spent catalyst by steam; regenerating the stripped catalyst by contacting the spent catalyst with oxygen- containing gas and burning off coke; and recycling the regenerated catalyst to reactor for reuse.
2> A process according to claim 1, being characterized by said process is carried out under catalytic conversion conditions of reaction temperature in the range of 500-700 X^, reaction
pressure in the range of 150-400 kPa, weight hourly space velocity in the range of 1-200 hour\ catalyst to feedstock ratio by weight in the range of 5-40:1 and steam to feedstock ratio by weight in the range of 0.05-1:1.
3 s A process according to claim 2, bemg characterized by said process is carried out under catalytic conversion conditions of reaction temperature in the range of 550-650 "C, weight hourly
space velocity in the range of 4-180 hour \ catalyst to feedstock ratio by weight in the range of 10-30:1 and steam to feedstock ratio by weight in the range of 0.1-0.5:1.
4> A process according to claim 1, being characterized by said petroleum hydrocarbons feedstock is selected fi:om the group consisting of gasoline, atmospheric gas oil, vacuum gas oil, atmospheric residual oil, vacuum residual oil, crude oil and the mixture thereof; and the injection of said petroleum hydrocarbons can be either single-site injection or multi^site injection.

5> A process according to claim 1, being characterized by said phosphorus and transition
metal modified silica rich zeolite having a structure of pentasil has an anhydrous formula of (0-0.3)Na5O-(0.3-5)A)2O3 6s A process according to claim 5, being characterized by said phosphorus and transition
metal modified silica rich zeolite having a structure of pentasil has an anhydrous formula of either (0-0.2)Na^O-(0.9-5)Al2O3-(1.5-7)P2O5-(0.9-10)M,Oy '(82-92)Si02 based on the mass of oxides, or (0-0.2)NaiO-(0.9-5)Al2O3'(l-5-7)PA'(0.9"10)M,Oy •(0.540)REjO3'(82-92)SiOj based on the mass of oxides, wherein M, x and y are as defined in claim 5,
7. A process according to claim 5, being characterized by said element M are at least two elements or more selected from the group consisting of Fe, Co, Ni, Cu, Zn, Mo and Mn.
8^ A process according to claim 7, being characterized by said element M are at least two elements or more selected from the group consisting of Fe, Co and Ni.
9. A process according to claim 8, being characterized by said element M are Fe and Ni.
10. A process according to claim 1, being characterized by said petroleum hydrocarbons
feedstock is contacted with said catalyst comprising phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor, wherein said catalyst has a carbon content of 0 " 0.5 % by weight,
11 > A process according to claim 10, being characterized by said petroleum hydrocarbons feedstock is contacted with said catalyst comprising phosphorus and transition metal modified silica rich zeohte having a structure of pentasil in a riser or a fluidized bed reactor, wherein said

catalyst has a carbon content of 0.05 ~ 0.45 % by weight.
12H A process according to claim 11, being characterised by said petroleum hydrocarbons
feedstock is contacted with said catalyst comprising phosphorus and transition metal modified silica rich zeolite having a structure of pentasil in a riser or a fluidized bed reactor, wherein said catalyst has a carbon content of 0.1 ~ 0.3 % by weight.
13. A process according to claim 12, being characterized by said catalyst comprising
phosphorus and transition metal modified silica rich zeolite having a structure of pentasil is obtained by regenerating the spent catalyst m a regenerator which operates in a part combustion mode, wherein said catalyst has a carbon content of 0.1 - 0.3 % by weight,
14 s A process according to claim 12, being characterized by said catalyst comprising
phosphorus and transition metal modified silica rich zeolite having a structure of pentasil is obtained by contacting the regenerated catalyst with light hydrocarbons enriched by olefins in a pre-reactor before said regenerated catalyst is recycled to reactor, wherein said catalyst has a carbon content of 0.1 - 0,3 % by weight.
15s A process according to claim 14, being characterized by said pre-reactor is either a
second riser or fluidized bed reactor other than the reactor for catalytic conversion of petroleum hydrocarbons, or a portion zone in the reactor for catalytic conversion of petroleum hydrocarbons.
16. A process according to claim 1, being characterized by said regenerated catalyst is
stripped with steam and/or with light hydrocarbons enriched by methane to remove non-hydrocarbon gaseous impurities absorbed on and/or carried by the catalyst, and then the catalyst is recycled for reuse.

17. A catalytic conversion process for producing light olefins with a high yield from petroleum hydrocarbons, substantially as herein described with reference to the accompanying drawings.

Documents:

616-CHE-2004 EXAMINATION REPORT REPLY RECEIVED 04-10-2012.pdf

616-CHE-2004 AMENDED PAGES OF SPECIFICATION 01-08-2013.pdf

616-CHE-2004 AMENDED CLAIMS 01-08-2013.pdf

616-CHE-2004 EXAMINATION REPORT REPLY RECEIVED. 01-08-2013.pdf

616-CHE-2004 FORM-3 01-08-2013.pdf

616-CHE-2004 OTHER PATENT DOCUMENT 01-08-2013.pdf

616-CHE-2004 OTHERS 01-08-2013.pdf

616-CHE-2004 POWER OF ATTORNEY 01-08-2013.pdf

616-che-2004-abstract.pdf

616-che-2004-claims.pdf

616-che-2004-correspondnece-others.pdf

616-che-2004-description(complete).pdf

616-che-2004-form 1.pdf

616-che-2004-form 3.pdf

616-che-2004-form 5.pdf

616-che-2004-other documents.pdf

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Patent Number

257009

Indian Patent Application Number

616/CHE/2004

PG Journal Number

35/2013

Publication Date

30-Aug-2013

Grant Date

26-Aug-2013

Date of Filing

28-Jun-2004

Name of Patentee

CHINA PETROLEUM & CHEMICAL CORPORATION

Applicant Address

6A, HUIXIN DONG STREET, CHAOYANG DISTRICT, BEIJING 100029, CHINA.

Inventors:

#	Inventor's Name	Inventor's Address
1	XIE, CHAOGANG	18 XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING 100083, CHINA.
2	LONG, JUN	18 XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING 100083, CHINA.
3	ZHANG, JIUSHUN	18 XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING 100083, CHINA.
4	LI, ZAITING	18 XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING 100083, CHINA.
5	WANG, XIEQING	18 XUEYUAN ROAD, HAIDIAN DISTRICT, BEIJING 100083, CHINA.

PCT International Classification Number

C07C 4/02

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	03147977.4	2003-06-30	China
2	03147978.2	2003-06-30	China