Title of Invention	" PREPARATION OF SYNGAS FOR ACETIC ACID SYNTHESIS BY PARTIAL OXIDATION OF METHANOL FEEDSTOCK"
Abstract	(54) Title: PREPARATION OF SYNGAS FOR ACETIC ACID SYNTHESIS BY PARTIAL OXIDATION OF METHANOL FEED STOCK (57) Abstract: A method for the production of syngas from methanol feedstock is disclosed, The methanol feed (110) is supplied to a partial oxidation reactor (112) with oxygen (I I4)and optionally steam(116) to yield a mixed stream (118) of hydrogen, carbon monoxide,and carbon dioxide. The carbon dioxide (122) is separated out and the hydrogen and carbon monoxide mixture (124) is fed to a cold box (126) where it is separated into hydrogen-rich and carbon monoxide-rich streams (130, 128). The separated carbon dioxide (122) can be recycled buck to the partial oxidation reactor (112) as a temperature moderator if desired. The carbon monoxide-rich stream (128) can be reacted with methanol (134) in an acetic acid synthesis unit (132) by a conventional process to produce acetic acid (136) or an acetic acid precursor. Optionally, an ammonia synthesis unit (144) and/or vinyl acetate monomer

Title of Invention

" PREPARATION OF SYNGAS FOR ACETIC ACID SYNTHESIS BY PARTIAL OXIDATION OF METHANOL FEEDSTOCK"

Abstract

(54) Title: PREPARATION OF SYNGAS FOR ACETIC ACID SYNTHESIS BY PARTIAL OXIDATION OF METHANOL FEED STOCK (57) Abstract: A method for the production of syngas from methanol feedstock is disclosed, The methanol feed (110) is supplied to a partial oxidation reactor (112) with oxygen (I I4)and optionally steam(116) to yield a mixed stream (118) of hydrogen, carbon monoxide,and carbon dioxide. The carbon dioxide (122) is separated out and the hydrogen and carbon monoxide mixture (124) is fed to a cold box (126) where it is separated into hydrogen-rich and carbon monoxide-rich streams (130, 128). The separated carbon dioxide (122) can be recycled buck to the partial oxidation reactor (112) as a temperature moderator if desired. The carbon monoxide-rich stream (128) can be reacted with methanol (134) in an acetic acid synthesis unit (132) by a conventional process to produce acetic acid (136) or an acetic acid precursor. Optionally, an ammonia synthesis unit (144) and/or vinyl acetate monomer

Full Text	BACKGROUND OF THE INVENTION [0001] This invention generally relates to a method for the process for making hydrogen and carbon monoxide by partial oxidation reforming of a lower alcohol, e.g., methanol, and more particularly to a process for making acetic acid from a methanol feedstock and carbon monoxide obtained by partial oxidation of methanol. [0002] In recent years, methanol production has increased in countries with high gas production due the development of high capacity plants utilizing high yield processes, for example, the Mega-methanol technology. Market conditions sin different locations can often result in relatively low methanol ;prices (in the case of an oversupply) and relatively high natural gas prices (in the case of a shortage), due generally to excessive usage in the heating of buildings and homes, and as well as high usage in power plants. For example, in chemical plants where syngas is produced for the purpose of extracting CO for the synthesis of acetic acid, high costs can make natural gas cost prohibitive as a feedstock. [0003] The primary raw materials in acetic acid manufacture are carbon monoxide (CO) and methanol. By retrofitting existing methanol plants to include acetic acid synthesis units, it is possible to eliminate the step of importing methanol for the synthesis of acetic acid, instead producing methanol in situ for the acetic acid synthesis. The retrofit of existing methanol plants for the manufacture of acetic acid is known in the art. Representative references disclosing this and similar processes include US Pat. Nos. 6,232,352 to Vidalin, 6,274,096 to Thiebaut et al, and 6,353,133 to Thiebaut et al, each of which is hereby incorporated by reference. [0004] In US Pat. No. 3,920,717, Marion discloses a continuous process for the production of methanol from solid and/or liquid hydrocarbon material in a catalyst free reaction zone using a partial oxidation reactor. In US Pat. No. 4,006,099, Marion et al. disclose improved combustion efficiency in the non-catalytic partial oxidation of liquid hydrocarbonaceous materials in a doublefannulus-type burner. In US Pat. Nos. 4,081,253 and 4,110,359, Marion discloses a method for producing synthesis gas, substantially comprising H2 and CO and having a mole ratio (H2/CO) of about 0.5 to 1.9 by partial oxidation of a hydrocarbonaceous fuel with substantially pure oxygen. [0005] The use of partial oxidation reactors for the reforming of natural gas. feedstock to syngas is well known in the art. Representative references disclosing partial oxidation reactors for the production of Syngas include US Pat. No. 2,896,927 to Nagle et al; US Pat. No. 3,920,717 to Marion; US Pat. No. 3,929,429 to Croucih; and US Pat. No. 4,081,253 to Marion, each of which is hereby incorporated herein by reference. i[0006] The manufacture of hydrogen from methanol using a methanol reforming catalyst alone or in conjunction with; a hydrogen-generating shift reactor is known in the art. Representative references [disclosing this and similar processes include US Pat. No. 4,175,115 to Ball et al; USJPat. No. 4,316,880 to Jockel et al; US Pat. No. 4,780,300 to Yokoyama; and US Pat. No. 6,171,574 to Juda, each of whichlis hereby incorporated herein by reference. [0007] The manufacture of acetic acid from carbon monoxide and methanol using a carbonylation catalyst is well known in the art, as demonstrated by representative references disclosing this and other similar processes including US Pat. No. 1,961,736 to Carlin et al; US Pat. No.; 3,769,329 to Paulik et al; US Pat. No. 5,155,261 to Marston et al; US Pat. No. 5;672,743 to Garland et al; US Pat. No. 5,728,871 to Joensen et al; US Pat. No. 5,817,869 to Hinnenkamp et al; US Pat. Nos. 5,877,347 and 5,877,348 to Ditzel et al; US Pat. No. 5,883,289 to Denis et al; and US Pat. No. 5,883,295 to Sunley et al, each of which is hereby incorporated by reference i herein. [0008] The primary raw materials for vinyl acetate monomer (VAM) manufacture are ethylene, acetic acid and oxygen. Carbon dioxide is produced as ian undesirable byproduct in the reaction and must be removed from the recycled ethylene. A significant expense of new production capacity for syngas, methanol, acetic acid and acetic acid derivatives such as VAM, is the capital cost of the necessary equipment. Other significant expenses include the operating costs, including the cost of raw materials. It would be desirable if these capital and operating costs could be reduced. [0009] As far as applicant is aware, there is no disclosure in the prior art for supplying a methanol feedstock to a partial oxidation reactor to produce hydrogen and carbon monoxide for the synthesis of acetic acid. Further, as far as applicant is aware, there is no disclosure in the prior art for modifying existing methanol plants haying partial oxidation reactors to reform a lower alcohol, e.g. methanol, in the presence of carbon dioxide, oxygen, steam or a combination thereof. SUMMARY OF THE INVENTION [0010] The present invention is directed to a method for the preparation of syngas from the partial oxidation of methanol for use when the costs of methanol feedstock are low relative to the costs of natural gas, and more particularly to a method for the preparation of acetic acid from methanol and CO, where the CO is separated from syngas produced by the partial oxidation of a methanol feedstock. . [0011] The present invention provides, in one embodiment, a method for preparing a hydrogen-rich stream and a carbon monoxide-rich stream. The method includes the steps of (a) reacting a methanol feed stream and an oxygen rich stream, and optionally a temperature moderator, in a partial oxidation reactor to produce a syngas stream, (b) separating the syngas stream into a carbon dioxide rich stream and a mixed stream containing hydrogen/carbon monoxide, and (c) separating the mixed stream into a hydrogen-rich stream and a carbon monoxide-rich stream. The method can further include the step of vaporizing the methanol feed stream before supplying to the partial oxidation reactor. The temperature moderator can be selected from steam, carbon dioxide, nitrogen, cooled and recycled effluent, or mixtures thereof. The temperature moderator can be a carbon dioxide-rich stream recycled from the reactor effluent. The partial oxidation reactor can be catalyst-free and operated at a temperature between 1100° and 2000°C. Preferably, the partial oxidation reactor can be operated at a temperature between 1300° and 1500°C. The method can further include reacting a portion of the methanol feed stream with the carbon monoxide rich stream to produce acetic acid. The method can further include the steps of providing a nitrogen stream from an air separation unit, and supplying the nitrogen stream and the hydrogen-rich stream to an ammonia synthesis unit to produce ammonia. The method can further include the steps of providing an ethylene stream, and supplying the ethylene stream, oxygen, and acetic acid to a vinyl acetate monomer synthesis unit to produce vinyl acetate monomer. The oxygen supplied to the partial oxidation reactor and to the vinyl acetate monomer synthesis unit can he provided by a single air separation unit. . [0012] The present invention provides, in another embodiment, a method for i converting an original methanol plant to a converted plant for the synthesis of acetic acid. The method includes the steps of (a) providing the original methanol plant ' . having at least one partial oxidation reactor fori converting a hydrocarbon to a syngas stream containing hydrogen, carbon monoxide and carbon dioxide; and a methanol synthesis loop for converting hydrogen and carbon monoxide from the syngas stream to methanol, (b) providing for supplying at least a portion of a methanol feedstock stream, oxygen from an air separation unit and optionally, a temperature moderator, to the at least one partial oxidation reactor, (c) installing a first separation unit for separating a carbon dioxide-rich stream and a mixed hydrogen/carbon monoxide stream from the syngas effluent, (d) installing a second separation unit for separating a hydrogen-rich stream and a carbon monoxide rich stream from the mixed stream, (e) installing an acetic acid synthesis unit, (f) providing for supplying the carbon monoxide-rich stream from the second separation unit and a portion of the methanol feedstock stream to the acetic acid synthesis unit; and (g) installing isolation valves for isolating the methanol synthesis loop from jthe remainder of the converted plant. The methanol feedstock can be vaporized prior to being supplied to the partial oxidation reactor. The method can further include the steps of (h) installing an ammonia synthesis unit for reacting a hydrogen-rich stream and nitrogen to form ammonia, (i) providing for supplying at least a portion of the hydrogen-rich stream from the separation unit to the ammonia synthesis unit; and (j) providing a nitrogen stream from the air separation unit to the ammonia synthesis unit. The method can further include the steps of installing a vinyl acetate monomer synthesis unit for reacting ethylene, oxygen, and acetic acid to; form vinyl acetate monomer, providing for supplying at least a portion of the oxygen from an air separation unit to the vinyl acetate monomer synthesis unit; and producing a carbon dioxide-rich stream in the vinyl acetate monomer synthesis unit. The method can further include recycling the carbon dioxide-rich stream to the partial oxidation reactor. [0013] In another embodiment, the present invention provides a method for preparing hydrogen, carbon monoxide and acetic acid from methanol. The method includes the steps of (a) supplying a vaporized methanol feed stream, an oxygen-rich stream, and optionally, a temperature moderator, to a catalyst-free partial oxidation reactor to form a syngas stream comprising hydrogen, carbon monoxide and carbon dioxide, (b) separating a carbon dioxide-rich stream and a mixed hydrogen/carbon monoxide stream from the syngas stream, (c) separating a hydrogen-rich stream and a carbon monoxide-rich stream from the mixed stream, and (d) reacting the carbon monoxide-rich stream with methanol in an acetic acid synthesis unit to produce acetic acid. The method can further include the step: of recycling at least a portion of the carbon dioxide-rich stream to the catalyst free partial oxidation reactor as a temperature moderator. BRIEF DESCRIPTION OF THE Accompanying DRAWINGS [0014] Fig. 1 is a simplified overall block flow diagram of one embodiment ;of the present invention for the production of hydrogen and carbon monoxide from methanol. [0015] Fig. 2 is a simplified overall block flow diagram for the plant of Fig. l, wherein an acetic acid reactor has been added for the synthesis of acetic acid. [0016] Fig. 3 is a simplified overall block flow diagram for the plant of Fig 2, wherein an ammonia synthesis reactor has been added for the synthesis of ammonia.) [0017] Fig. 4 is a simplified overall block diagram for the plant of Fig. \|2, wherein a vinyl- acetate monomer reactor has been added for the synthesis of vinyl i acetate monomer. [0018] Fig. 5 is a simplified overall block diagram for the plant of Fig.3, wherein a vinyl acetate monomer reactor has been added for the synthesis of vinyl acetate monomer. [0019] Fig. 6 is a simplified overall block flow diagram for an alternate embodiment of the present invention for the: production of hydrogen and carbon monoxide from methanol wherein carbon dioxide is separated and recycled to the reactor. [0020] Fig. 7 is a simplified overall block flow diagram for the plant of Fig. 6, wherein an acetic acid reactor has been added for the synthesis of acetic acid. [0021] Fig. 8 is a simplified overall block flow diagram for the plant of Fig.i7, wherein an ammonia reactor has been added, for the synthesis of ammonia. . [0022] Fig. 9 is a simplified overall block diagram for the plant of Fig; 7, wherein a vinyl acetate monomer reactor has been added for the synthesis of vinyl acetate monomer. [0023] Fig 10 is a simplified overall block diagram for the plant of Fig 8, wherein a vinyl acetate monomer reactor has been added for the synthesis of vinyl acetate monomer. DESCRIPTION OF THE INVENTION [0024] Detailed embodiments of the present invention are disclosed herein. However, it is understood that the disclosed embodiments are merely exemplary, of the invention, which can be embodied in various forms, Specific structural and functional details disclosed herein are not intended to be limiting, but merely illustrations that can be modified within the scope of the attached claims. ' [0025] The plant for the process of reforming methanol in a partial oxidation reactor to produce syngas can be a new plant, or it is preferably the retrofit of an existing methanol plant which includes at least one partial oxidation reactor. [0026] The present invention provides a solution to the problems associated . with the production of syngas from natural gas when the costs of natural gas are high. When such economic conditions exist, plants designed for methanol and acetic acid synthesis can be reconfigured for the production of acetic acid using existing methanol stock as feed to the reactor, instead of natural gas. [0027] The conversion of methanol to carbon monoxide and hydrogen is shown generally by the following reactions: i If desired, carbon monoxide production can be increased via the reverse shift reaction (shown below) where carbon dioxide and hydrogen combine to form carbon monoxide and water. : ' i [0028] Referring to Fig. 1, a process is provided for the partial oxidation of a methanol feedstock stream to produce a syngas stream which can be separated into hydrogen (H2) and carbon monoxide (CO) streams for further use. A methanol stream 110 is supplied to a catalyst-free partial oxidation (POX) reactor 112 of an existing methanol synthesis plant, where it lis combined with oxygen 114 and optionally steam 116. The methanol stream 110 is preferably a pre-existing purified feedstock or a commercial methanol product which has been purified by distillation or another conventional process. The oxygen 114 is obtained from an air separation unit (ASU) 111, which is supplied with compressed air. Steam 116 can preferably be provided by pre-existing facilities. Nitrogen and excess oxygen (not shown) provided by ASU 111 can be provided to controls. [0029] If oxygen feedstock 114 is not limited, the methanol feedstock 110 can be supplied to the reactor at room temperature.; If supplies of oxygen 114 are limited, however, the methanol feedstock 110 can be preheated and/or vaporized (not shown) prior to supplying to the POX reactor 112. When room temperature methanol 110 is supplied to the partial oxidation reactor 112 with an excess of oxygen 114, hydrogen content in the syngas effluent 118 is reduced. [0030] POX reactor 112 can produce a syngas effluent 118 consisting of H2, CO and C02. The effluent 118 is generally [cleaner than syngas produced from a natural gas feed as much of the impurities were removed during synthesis of the methanol feed stream 110. Effluent 118, after cooling, can be fed to C02 separation unit 120 which produces a C02-rich stream 122 and a mixed CO/H2 stream 124 essentially free of C02. The C02-rich stream 122 can be vented and the mixed CO/H2 stream 124 can be supplied to separation unit 126. [0031] Separation unit 126 preferably includes molecular sieves and a conventional cold box. The separation unit 126 splits the mixed stream 124 into at least a CO-rich stream 128 and an H2-rich stream 130, but can also include minor amounts of one or more residual or tail gas streams of mixed H2 and CO which can be used as fuel or exported (not shown). The CO-rich stream 128 and H2-rich stream 130 can be supplied to alternate processes, such as, for example, acetic acid synthesis units or ammonia synthesis units, respectively, which are further discussed below. [0032] As shown in Fig. 2, CO-rich stream 128 can be supplied to an acetic acid synthesis unit 132 where it is combined with a methanol stream 134, which can be obtained from the same feedstock that supplies the POX reactor 112. The acetic acid synthesis unit 132 can employ manufacturing equipment and methodology well known and/or commercially available to those! skilled in the art to form acetic acid 136 from CO via stream 128 and methanol via stream 134, such as, for example, from one or more of the acetic acid manufacturing patents mentioned above. For example, a conventional BP/Monsanto process can be employed, or an improved BP/Monsanto process employing BP-Cativa technology (iridium catalyst), Celanese low water technology (rhodium-lithium acetate catalyst), Millennium low water technology (rhodium-phosphorous oxide catalyst) and/or dual process methanol carbonylation- methyl formate isomerization. The reaction generally comprises reacting methanol, methyl formate, or a combination thereof; in the presence of a reaction mixture comprising carbon monoxide, water, a solvent and a catalyst system comprising at least one halogenated promoter and at least one compound of rhodium, iridium, or a combination thereof. [0033] The reaction mixture for the acetic acid synthesis preferably has a water content of less than 20 weight percent more preferably between approximately 14 and 15 weight percent. When the reaction comprises low water carbonylation, ithe water content in the reaction mixture is preferably from abbut 2 to about 8 weight percent. When the reaction comprises methyl formate isomerization or a combination i. of isomerization and methanol carbonylation, the reaction mixture preferably contains a nonzero quantity of water up to 2 weight percent. [0034] As shown in Fig. 3, the process can optionally include an ammonia ■ i' synthesis unit 144, designed to take advantage of the H2 from the syngas stream 118 and nitrogen from the ASU 111. All or a portion of hydrogen stream 130 from the CO/H2 separation unit 126 is reacted with ah N2 stream 142 from the air separation unit to form ammonia collected in stream 146. Ammonia output from the synthesis unit 144 can be increased by increasing hydrogen feed, br by adding a second ammonia synthesis unit (not shown). [0035] As shown in Fig. 4, the process) can optionally include a vinyl acetate ■ :\| monomer (VAM) synthesis unit 156. A portion of the acetic acid from line 136 can be fed via line 150 to an the VAM synthesis unit 156 where it can be reacted with ethylene 152 via line 154 and at least a portionjof the oxygen 113 from air separation unit 111. A liquid product stream 158 is processed via conventional VAM distillation unit 160 to produce essentially pure (commercial specification) VAM via line 162. Carbon dioxide produced as a byproduct of the VAM synthesis can be separated from the reactor effluent gases via a conventional C02 removal system (not shown) and recycled to the POX reactor 112 via line 164. [0036] VAM production can be mainly achieved by the acetoxylation of i ethylene according to the reaction: The main by-product C02 is formed by the reaction ■ i Selectivity for the process yields approximately 7-8% C02 by mass. Typically, a VAM plant producing approximately 100,000 metric tons per year (MTY) of VAM requires approximately 35,000 MTY of ethylene and produces between 5,000 and 10,000 MTY of C02. [0037] As shown in Fig. 5, a vinyl acetate synthesis unit 156 can be added to. j, the existing acetic acid synthesis unit 132 and ammonia synthesis unit 144 for optimal usage of the syngas stream. The VAM synthesis unit 156 can be supplied with a portion of the acetic acid product stream 136j via line 1501 for the synthesis of !the monomer. Crude VAM exits the VAM synthesis unit 156 via line 158 and enters a distillation unit 160 to produce a product stream 162. Carbon dioxide produced as a byproduct of the VAM synthesis can be separated from the reactor effluent gases via a conventional C02 removal system (not shown) and recycled to the POX reactor 112 via line 164. [0038] As shown in Fig. 6, all or a portion of the carbon dioxide 222 produced and separated from the syngas effluent 218 and recycled to the POX reactor 212. A methanol stream 210 is supplied to the partial oxidation (POX) reactor 212 of an existing methanol synthesis plant, where it is combined with oxygen 214 and carbon dioxide 222. The methanol stream 210 is preferably a pre-existing methanol feedstock which has been previously purified by distillation; or another conventional process (not shown). The oxygen 214 is obtained from pre-existing air separation unit (ASU) 211, which is fed with air compressed. Carbon dioxide 222 can be produced in the reformation of the methanol 210 and can be recycled to the reactor 212 feed. ![0039] POX reactor 212 can produce a syngas effluent 218 consisting of H2, CO and C02. The effluent 218 is generally cleaner than syngas produced from a natural gas feed as much of the impurities are removed during synthesis of the feedstock. Effluent 218, after cooling, can be fed to C02 separation unit 220 which produces a C02-rich stream 222 and a mixed\|CO/H2 stream 224 essentially free of C02. The C02-rich stream 222 can be recycled to the POX reactor 212 and the mixed CO/H2 stream 224 is supplied to separation unit 226. Recycle of the C02-rich stream to the POX reactor can increase CO production between approximately 5-10% and decrease hydrogen production between approximately 3-8%. When the C02 is recycled to the POX reactor, for a given production rate, the methanol feed requirement is thus reduced. [0040] Separation unit 226 preferably includes molecular sieves andj a conventional cold box. The separation unit 226 splits the stream 224 into at least a CO-rich stream 228 and an H2-rich stream 230, but can also include minor amounts of one or more residual or tail gas streams of mixed H2 and CO which can be used as fuel, recycled to the reactor, or exported (not shwn). [0041] As shown in Fig. 7, CO-rich stream 228 can be combined with a stoichiometric amount of the methanol feedstock 234 to yield acetic acid 236, by a synthetic process which has been described aove. As show in Fig. 8, the H2-rich stream 230 can be reacted with nitrogen 242 from ASU 240 in an ammonia synthesis unit 244 to yield ammonia product 246. Alternatively, all or a portion of the H2-rich stream can be supplied as fuel or exported to an alternate process (not shown). [0042] As shown in Fig. 9, the process can optionally include a vinyl acetate monomer (VAM) synthesis unit 256. A portion of the acetic acid from line 236 can be fed via line 250 to an the VAM synthesis unit 256 where rt is reacted with ethylene 252 via line 254 and at least a portion of the oxygen 213 from air separation unit 211. A liquid product stream 258 can be processed via conventional VAM distillation unit 260 to produce essentially pure (commercial specification) VAM via line 262. Carbon dioxide produced as a byproduct of the! VAM synthesis can be separated from the reactor effluent gases via a conventional C02 removal system (not shown) and recycled, to the POX reactor 212 via line 264. [0043] As shown in Fig. 10, a vinyl acetate synthesis unit 256 can be added to the existing acetic acid synthesis unit 232 and ammonia synthesis unit 244 for optimal usage of the syngas stream. VAM synthesis unit 256 can be supplied with a portion of the acetic acid product stream 236 via line 250, ethylene 252 via line 254, and oxygen from the ASU 211 via line 213. Crude VAM exits the VAM synthesis unit 256 via line 258 and enters a distillation unit 260 to produce a product stream 262. Carbon dioxide produced as a byproduct of the VAM synthesis can be separated from the reactor effluent gases via a conventional C02 removal system (not shown) and recycled to the POX reactor 212 via line 264. , [0044] Utilities (not shown), which typically include the steam system, cooling water, compressed air and the like, can be supplied from a pre-existing methanol plant and can be used to supply an associated processes, such as, for example, acetic acid and ammonia synthesis units, as well. Steam generated by waste heat recovery from the acetic acid synthesis unit 132 and/or any other associated integrated unit, can be used to drive or supply steam to water pumps (not shown), ASU compressor 111, POX reactor 112, C02 removal unit 12:0, and the like. [0045] The partial oxidation reactors can be unpacked, free-flow, rion .catalytic gas generators to which preheated hydrocarbon and oxygen are supplied. Optionally, a temperature moderator can be supplied to the reactor as well. The partial oxidation reactor effluent is then quenched or cooled, and optionally cleaned to remove soot and other particulate impuritids, and can be further processed; or separated for additional downstream uses. When hydrogen gas is the desired end product, such as, for example, for ammonia synthesis reactors, high and low temperature shift converters can be employed to convert CO and steam to hydrogen and C02. Where carbon monoxide is the desired end product, such as, for example, for acetic acid synthesis reactors, any C02 can be removed and recycled to the reactor to increase CO production, or reverse shift reabtors can be employed to convert C02 and H2 to CO and H2O. [0046] When the partial oxidation reactor is from ;a pre-existing methanol plant, the burner can be adjusted for operation for use with a methanol feedstock. The partial oxidation reactor temperature can be maintained from 1100°- 2000°C ( 2000°- 3600°F), preferably from 1300°- 1500°C ( 240!o°- 2700°F). The reactor pressure can be maintained at between 2 and 6 MPa, preferably approximately 4 MPa. [0047] The production of syngas from liquid and solid carbon materials can often result in the presence of many unwanted! impurities, such as for example, CO2, S02, COS, CH4, Ar, N2, H20 and NH3. Typically, when natural gas is used as the feedstock for the production of syngas, a desulfurizing/saturation unit with a catalyst bed, such as, for example, nickel/molybdenum catalyst can be used to remove sulfur . from feed prior to supplying to the reactor. Because the natural gas used in,the synthesis of the methanol has already desulfurized and the methanol product ihas already been purified by distillation or another conventional purification process, many of the undesired impurities normally present from synthesis with natural gas are effectively eliminated from the syngas product. [0048] The effluent from the partial oxidation has a molar ratio of H2-C02 to CO+C02 (referred to in the present specification as the R ratio" (H2- C02)/(CO+C02)), which can be optimized for the production of CO. Generally, for the production of methanol, an R ratio of approximately 2.0 is desired. For the ' synthesis of syngas high in CO, the H2 to CO ratio can range from 1.5 to 3, and preferably between 1.5 and 2. [0049] Suitable temperature moderators, to control the reaction conditions, can be added to the reaction zone and can include H20, CO2, and N2 from the air : \| separation unit, flue gas, cooled and recycled effluent gas, arid mixtures thereof. The need for a temperature moderator is generally driven by the carbon:hydrogen ratio of the hydrocarbon feed and the presence of free oxygen. Preferably, the temperature moderator can include a portion of C02 cooled and separated from the partial oxidation reactor effluent and recycled back to the reactor feed. When steam is used as the temperature moderator, control of the flow rate can limit or prevent the production of soot in the reactor. [0050] The C02 removal unit separates the effluent stream into a C02-rich and a C02-lean stream using conventional C02 separation equipment and methodology, such as, for example, a.bsorption stripping with a solvent such as water, methanol, generally aqueous alkanolamines such as ethanolamine, diethanolamine, methyldiethanolamine and the like, aqueous alkali carbonates such as sodium and potassium carbonates, and the like. Such C02 absorption-stripping processes :are commercially available under the trade designations Girbotol, Sulfinol, Rectisol, Purisol, Fluor, BASF (aMDEA) and the like. [0051] The C02-lean stream contains primarily CO and hydrogen and can be separated in a CO separation unit into CO-rich and hydrogen-rich streams. The separation unit can comprise any equipment and/or methodologies known in the art for separating the CO and hydrogen mixture into relatively pure CO and hydrogen streams, such as, for example, semi-permeable membranes, cryogenic fractionation, or the like. Cryogenic fractional distillation! is preferred, land can include simple partial condensation without any columns, optionally with a pressure swing absorption (PSA) unit and a hydrogen recycle (compressor , or methane wash. Partial condensation with columns is typically sufficient for obtaining CO and hydrogen of sufficient purity for acetic acid and ammonia production, respectively, keeping the equipment and operating costs to a minimum; The PSA unit and hydrogen recycle compressor can be added for increasing the hydrogen purity and CO production rates if desired. For the manufacture of acetic acid, the CO stream preferably contains less than 1000 ppm hydrogen and less than 2 mole percent nitrogen plus methane. For ammonia production, the hydrogen stream which is sent to a nitrogen wash unit (not shown) preferably contains at least 80 mol% hydrogen, and more preferably contains at least 95 mol% hydrogen. [0052] Example 1. A methanol feedstock stream is supplied to a partial oxidation reactor for the recovery of hydrogen! and carbon monoxide. The methanol stream is supplied at a rate of 1438 kmoles/hour, where it is combined with 719 kmoles/hour of oxygen and 884 kmoles/hour of steam. The partial oxidation reactor is operated at approximately 1300CC (2372 °F) and 4 MPa, producing a syrigas effluent stream. Carbon dioxide can be removed from the syngas stream, producing a carbon dioxide-rich stream and a carbon dioxide-lean stream of carbon monoxide and hydrogen. The carbon dioxide-rich stream can be vented or collected. The carbon dioxide-lean stream can be supplied to a cold bbx where the component hydrogen and carbon monoxide are separated, yielding 1045 kmoles/hour of carbon monoxide and 1812 kmoles/hour of hydrogen. [0053] Example 2. A methanol feedstock stream is fed to a partial oxidation reactor for recovery of hydrogen and carbon monoxide. The methanol stream is supplied at a rate of 1438 kmoles/hour, where it is combined with 719 kmoles/hour of oxygen, 350 kmoles/hour of steam, and 296 kmoles/hour of carbon dioxide recycled from the reactor effluent. The partial oxidation reactor operates at approximately 1400°C (2552°F) and 4 MPa, producing a syngas effluent stream. Carbon dioxide is removed from the syngas stream by known means, producing a carbon dioxide-rich stream and a carbon dioxide-lean stream of carbon monoxide and hydrogen. The carbon dioxide-rich stream is recycled to the partial oxidation reactor at a rate of 296 kmoles/hour. The carbon dioxide-lean stream is supplied to a cold box where the components are separated, yielding 1045 kmoles/hour of carbon monoxide and 1812 kmoles/hour of hydrogen. [0054] Example 3. The production of acetic acid from a plant having the operating conditions of Example 1. A stoichiometric amount of methanol (1045 kmoles/hour) is added to the carbon monoxide-rich stream (1045 kmoles/hour) in an acetic acid synthesis unit to produce approximately 1045 kmoles/hour of acetic acid. [0055] Example 4. The production of acetic acid from a plant having; the operating conditions of Example 2. A stoichiometric amount of methanol (1:134 . . kmoles/hour) is added to the carbon monoxide-rich stream (1134 kmoles/hour) infan acetic acid synthesis unit to produce approximately 1134 kmoles/hour of acetic acid. [0056J The invention is described above in reference to specific examples land embodiments. The metes and bounds of the invention are not to be limited by the foregoing disclosure, which is illustrative only, but should be determined in accordance with the full scope and spirit; of the appended claims. Various modifications will be apparent to those skilled in the art in view of the description and examples. It is intended that all such variations within the scope and spirit of the appended claims be embraced thereby. WE CLAIM: 1. A method for preparing a hydrogen-rich stream and a carbon monoxide-rich stream, comprising: reacting a methanol feed stream and oxygen, and optionally a temperature moderator, in a partial oxidation reactor to produce a syngas stream, wherein the partial oxidation reactor is catalyst-free and operated at a temperature between 1100° and 2000°C; separating the syngas stream into a carbon dioxide rich stream and a mixed stream containing hydrogen/carbon monoxide; and separating the mixed stream into a hydrogen-rich stream and a carbon monoxide-rich stream. 2. The method as claimed in claim 1, wherein the methanol feed stream supplied to the partial oxidation reactor is vaporized. 3. The method as claimed in claim 1, wherein the temperature moderator is selected from steam, carbon dioxide, nitrogen, cooled and recycled effluent, or mixtures thereof. 4. The method as claimed in claim 1, wherein the temperature moderator is a carbon dioxide- rich stream recycled from the reactor effluent. 5. The method as claimed in claim 1, wherein the partial oxidation reactor is operated at a pressure between 2 and 6 MPa. 6. The method as claimed in claim 1, wherein the partial oxidation reactor is operated at a temperature between 1300° and 1500°C. 7. The method as claimed in claim 1, wherein a portion of the methanol feed stream is reacted with the carbon monoxide rich stream to produce acetic acid. 8. The method as claimed in claim 1, which involves: providing a nitrogen stream from an air separation unit, and supplying the nitrogen stream and the hydrogen-rich stream to an ammonia synthesis unit to produce ammonia. 9. The method as claimed in claim 7, which involves: providing an ethylene stream; and supplying the ethylene stream, oxygen, and acetic acid to a vinyl acetate monomer synthesis unit to produce vinyl acetate monomer. 10. The method as claimed in claim 9, wherein the oxygen supplied to the partial oxidation reactor and to the vinyl acetate monomer synthesis unit is provided by a single air separation unit. 11. A method for converting an original methanol plant to a converted plant for the synthesis of acetic acid, the method comprising the steps of: providing the original methanol plant having at least one partial oxidation reactor for converting a hydrocarbon to a syngas stream containing hydrogen, carbon monoxide and carbon dioxide; and a methanol synthesis loop for converting hydrogen and carbon monoxide from the syngas stream to methanol; providing for supplying at least a portion of a methanol feedstock stream, oxygen from an air separation unit and optionally, a temperature moderator, to the at least one partial oxidation reactor, wherein the partial oxidation reactor is catalyst-free and is operated at a temperature between 1100° and 2000°C; installing a first separation unit for separating a carbon dioxide-rich stream and a mixed hydrogen/carbon monoxide stream from the syngas effluent; installing a second separation unit for separating a hydrogen-rich stream and a carbon monoxide rich stream from the mixed stream; installing an acetic acid synthesis unit; providing for supplying the carbon monoxide-rich stream from the second separation unit and a portion of the methanol feedstock stream to the acetic acid synthesis unit; and installing isolation valves for isolating the methanol synthesis loop from the remainder of the converted plant. 12. The method as claimed in claim 11, wherein the methanol feedstock is vaporized for supply to the partial oxidation reactor. 13. The method as claimed in claim 11, which involves: installing an ammonia synthesis unit for reacting a hydrogen-rich stream and nitrogen to form ammonia; providing for supplying at least a portion of the hydrogen-rich stream from the separation unit to the ammonia synthesis unit; and providing a nitrogen stream from the air separation unit to the ammonia synthesis unit. 14. The method as claimed in claim 11, which involves: installing a vinyl acetate monomer synthesis unit for reacting ethylene, oxygen, and acetic acid to form vinyl acetate monomer; providing for supplying at least a portion of the oxygen from an air separation unit to the vinyl acetate monomer synthesis unit; and producing a carbon dioxide-rich stream in the vinyl acetate monomer synthesis unit. 15. The method as claimed in claim 14, wherein the carbon dioxide-rich stream is recycled to the partial oxidation reactor. 16. A method for preparing hydrogen, carbon monoxide and acetic acid from methanol, comprising the steps of: supplying a vaporized methanol feed stream, oxygen, and optionally, a temperature moderator, to a partial oxidation reactor to form a syngas stream comprising hydrogen, carbon monoxide and carbon dioxide, wherein the partial oxidation reactor is catalyst-free and operated at a temperature between 1100° and 2000°C; separating a carbon dioxide-rich stream and a mixed hydrogen/carbon monoxide stream from the syngas stream; separating a hydrogen-rich stream and a carbon monoxide-rich stream from the mixed stream; and reacting the carbon monoxide-rich stream with methanol in an acetic acid synthesis unit to produce acetic acid. 17. The method as claimed in claim 12, wherein at least a portion of the carbon dioxide-rich stream is recycled to the partial oxidation reactor as a temperature moderator. 18. The method as claimed in claim 17, wherein the temperature moderator is steam. ABSTRACT (54) Title: PREPARATION OF SYNGAS FOR ACETIC ACID SYNTHESIS BY PARTIAL OXIDATION OF METHANOL FEED STOCK (57) Abstract: A method for the production of syngas from methanol feedstock is disclosed, The methanol feed (110) is supplied to a partial oxidation reactor (112) with oxygen (I I4)and optionally steam(116) to yield a mixed stream (118) of hydrogen, carbon monoxide,and carbon dioxide. The carbon dioxide (122) is separated out and the hydrogen and carbon monoxide mixture (124) is fed to a cold box (126) where it is separated into hydrogen-rich and carbon monoxide-rich streams (130, 128). The separated carbon dioxide (122) can be recycled buck to the partial oxidation reactor (112) as a temperature moderator if desired. The carbon monoxide-rich stream (128) can be reacted with methanol (134) in an acetic acid synthesis unit (132) by a conventional process to produce acetic acid (136) or an acetic acid precursor. Optionally, an ammonia synthesis unit (144) and/or vinyl acetate monomer

Full Text

BACKGROUND OF THE INVENTION
[0001] This invention generally relates to a method for the process for making
hydrogen and carbon monoxide by partial oxidation reforming of a lower alcohol,
e.g., methanol, and more particularly to a process for making acetic acid from a
methanol feedstock and carbon monoxide obtained by partial oxidation of methanol.
[0002] In recent years, methanol production has increased in countries with
high gas production due the development of high capacity plants utilizing high yield

processes, for example, the Mega-methanol technology. Market conditions sin

different locations can often result in relatively low methanol ;prices (in the case of an
oversupply) and relatively high natural gas prices (in the case of a shortage), due
generally to excessive usage in the heating of buildings and homes, and as well as
high usage in power plants. For example, in chemical plants where syngas is
produced for the purpose of extracting CO for the synthesis of acetic acid, high costs
can make natural gas cost prohibitive as a feedstock.
[0003] The primary raw materials in acetic acid manufacture are carbon
monoxide (CO) and methanol. By retrofitting existing methanol plants to include

acetic acid synthesis units, it is possible to eliminate the step of importing methanol
for the synthesis of acetic acid, instead producing methanol in situ for the acetic acid
synthesis. The retrofit of existing methanol plants for the manufacture of acetic acid

is known in the art. Representative references disclosing this and similar processes
include US Pat. Nos. 6,232,352 to Vidalin, 6,274,096 to Thiebaut et al, and 6,353,133

to Thiebaut et al, each of which is hereby incorporated by reference.

[0004] In US Pat. No. 3,920,717, Marion discloses a continuous process for

the production of methanol from solid and/or liquid hydrocarbon material in a catalyst
free reaction zone using a partial oxidation reactor. In US Pat. No. 4,006,099, Marion
et al. disclose improved combustion efficiency in the non-catalytic partial oxidation of
liquid hydrocarbonaceous materials in a doublefannulus-type burner. In US Pat. Nos.

4,081,253 and 4,110,359, Marion discloses a method for producing synthesis gas,

substantially comprising H2 and CO and having a mole ratio (H2/CO) of about 0.5 to
1.9 by partial oxidation of a hydrocarbonaceous fuel with substantially pure oxygen.
[0005] The use of partial oxidation reactors for the reforming of natural gas.
feedstock to syngas is well known in the art. Representative references disclosing
partial oxidation reactors for the production of Syngas include US Pat. No. 2,896,927
to Nagle et al; US Pat. No. 3,920,717 to Marion; US Pat. No. 3,929,429 to Croucih;

and US Pat. No. 4,081,253 to Marion, each of which is hereby incorporated herein by
reference.
i[0006] The manufacture of hydrogen from methanol using a methanol

reforming catalyst alone or in conjunction with; a hydrogen-generating shift reactor is
known in the art. Representative references [disclosing this and similar processes
include US Pat. No. 4,175,115 to Ball et al; USJPat. No. 4,316,880 to Jockel et al; US
Pat. No. 4,780,300 to Yokoyama; and US Pat. No. 6,171,574 to Juda, each of whichlis
hereby incorporated herein by reference.

[0007] The manufacture of acetic acid from carbon monoxide and methanol

using a carbonylation catalyst is well known in the art, as demonstrated by
representative references disclosing this and other similar processes including US Pat.
No. 1,961,736 to Carlin et al; US Pat. No.; 3,769,329 to Paulik et al; US Pat. No.
5,155,261 to Marston et al; US Pat. No. 5;672,743 to Garland et al; US Pat. No.

5,728,871 to Joensen et al; US Pat. No. 5,817,869 to Hinnenkamp et al; US Pat. Nos.
5,877,347 and 5,877,348 to Ditzel et al; US Pat. No. 5,883,289 to Denis et al; and US
Pat. No. 5,883,295 to Sunley et al, each of which is hereby incorporated by reference
i
herein.
[0008] The primary raw materials for vinyl acetate monomer (VAM)
manufacture are ethylene, acetic acid and oxygen. Carbon dioxide is produced as ian
undesirable byproduct in the reaction and must be removed from the recycled
ethylene. A significant expense of new production capacity for syngas, methanol,

acetic acid and acetic acid derivatives such as VAM, is the capital cost of the
necessary equipment. Other significant expenses include the operating costs,
including the cost of raw materials. It would be desirable if these capital and

operating costs could be reduced.
[0009] As far as applicant is aware, there is no disclosure in the prior art for
supplying a methanol feedstock to a partial oxidation reactor to produce hydrogen and

carbon monoxide for the synthesis of acetic acid. Further, as far as applicant is aware,
there is no disclosure in the prior art for modifying existing methanol plants haying
partial oxidation reactors to reform a lower alcohol, e.g. methanol, in the presence of
carbon dioxide, oxygen, steam or a combination thereof.
SUMMARY OF THE INVENTION
[0010] The present invention is directed to a method for the preparation of

syngas from the partial oxidation of methanol for use when the costs of methanol

feedstock are low relative to the costs of natural gas, and more particularly to a
method for the preparation of acetic acid from methanol and CO, where the CO is
separated from syngas produced by the partial oxidation of a methanol feedstock. .

[0011] The present invention provides, in one embodiment, a method for
preparing a hydrogen-rich stream and a carbon monoxide-rich stream. The method
includes the steps of (a) reacting a methanol feed stream and an oxygen rich stream,
and optionally a temperature moderator, in a partial oxidation reactor to produce a
syngas stream, (b) separating the syngas stream into a carbon dioxide rich stream and
a mixed stream containing hydrogen/carbon monoxide, and (c) separating the mixed
stream into a hydrogen-rich stream and a carbon monoxide-rich stream. The method
can further include the step of vaporizing the methanol feed stream before supplying
to the partial oxidation reactor. The temperature moderator can be selected from
steam, carbon dioxide, nitrogen, cooled and recycled effluent, or mixtures thereof.
The temperature moderator can be a carbon dioxide-rich stream recycled from the
reactor effluent. The partial oxidation reactor can be catalyst-free and operated at a
temperature between 1100° and 2000°C. Preferably, the partial oxidation reactor can
be operated at a temperature between 1300° and 1500°C. The method can further

include reacting a portion of the methanol feed stream with the carbon monoxide rich
stream to produce acetic acid. The method can further include the steps of providing
a nitrogen stream from an air separation unit, and supplying the nitrogen stream and
the hydrogen-rich stream to an ammonia synthesis unit to produce ammonia. The
method can further include the steps of providing an ethylene stream, and supplying
the ethylene stream, oxygen, and acetic acid to a vinyl acetate monomer synthesis unit
to produce vinyl acetate monomer. The oxygen supplied to the partial oxidation
reactor and to the vinyl acetate monomer synthesis unit can he provided by a single
air separation unit. .
[0012] The present invention provides, in another embodiment, a method for
i
converting an original methanol plant to a converted plant for the synthesis of acetic

acid. The method includes the steps of (a) providing the original methanol plant
'
.
having at least one partial oxidation reactor fori converting a hydrocarbon to a syngas

stream containing hydrogen, carbon monoxide and carbon dioxide; and a methanol

synthesis loop for converting hydrogen and carbon monoxide from the syngas stream

to methanol, (b) providing for supplying at least a portion of a methanol feedstock
stream, oxygen from an air separation unit and optionally, a temperature moderator, to
the at least one partial oxidation reactor, (c) installing a first separation unit for
separating a carbon dioxide-rich stream and a mixed hydrogen/carbon monoxide
stream from the syngas effluent, (d) installing a second separation unit for separating

a hydrogen-rich stream and a carbon monoxide rich stream from the mixed stream, (e)

installing an acetic acid synthesis unit, (f) providing for supplying the carbon
monoxide-rich stream from the second separation unit and a portion of the methanol
feedstock stream to the acetic acid synthesis unit; and (g) installing isolation valves
for isolating the methanol synthesis loop from jthe remainder of the converted plant.
The methanol feedstock can be vaporized prior to being supplied to the partial
oxidation reactor. The method can further include the steps of (h) installing an
ammonia synthesis unit for reacting a hydrogen-rich stream and nitrogen to form
ammonia, (i) providing for supplying at least a portion of the hydrogen-rich stream
from the separation unit to the ammonia synthesis unit; and (j) providing a nitrogen
stream from the air separation unit to the ammonia synthesis unit. The method can
further include the steps of installing a vinyl acetate monomer synthesis unit for
reacting ethylene, oxygen, and acetic acid to; form vinyl acetate monomer, providing
for supplying at least a portion of the oxygen from an air separation unit to the vinyl
acetate monomer synthesis unit; and producing a carbon dioxide-rich stream in the

vinyl acetate monomer synthesis unit. The method can further include recycling the
carbon dioxide-rich stream to the partial oxidation reactor.
[0013] In another embodiment, the present invention provides a method for
preparing hydrogen, carbon monoxide and acetic acid from methanol. The method

includes the steps of (a) supplying a vaporized methanol feed stream, an oxygen-rich
stream, and optionally, a temperature moderator, to a catalyst-free partial oxidation
reactor to form a syngas stream comprising hydrogen, carbon monoxide and carbon

dioxide, (b) separating a carbon dioxide-rich stream and a mixed hydrogen/carbon
monoxide stream from the syngas stream, (c) separating a hydrogen-rich stream and a
carbon monoxide-rich stream from the mixed stream, and (d) reacting the carbon
monoxide-rich stream with methanol in an acetic acid synthesis unit to produce acetic
acid. The method can further include the step: of recycling at least a portion of the
carbon dioxide-rich stream to the catalyst free partial oxidation reactor as a
temperature moderator.

BRIEF DESCRIPTION OF THE Accompanying DRAWINGS
[0014] Fig. 1 is a simplified overall block flow diagram of one embodiment ;of
the present invention for the production of hydrogen and carbon monoxide from
methanol.
[0015] Fig. 2 is a simplified overall block flow diagram for the plant of Fig. l,
wherein an acetic acid reactor has been added for the synthesis of acetic acid.
[0016] Fig. 3 is a simplified overall block flow diagram for the plant of Fig 2,
wherein an ammonia synthesis reactor has been added for the synthesis of ammonia.)
[0017] Fig. 4 is a simplified overall block diagram for the plant of Fig. |2,
wherein a vinyl- acetate monomer reactor has been added for the synthesis of vinyl
i
acetate monomer.

[0018] Fig. 5 is a simplified overall block diagram for the plant of Fig.3,
wherein a vinyl acetate monomer reactor has been added for the synthesis of vinyl

acetate monomer.

[0019] Fig. 6 is a simplified overall block flow diagram for an alternate
embodiment of the present invention for the: production of hydrogen and carbon
monoxide from methanol wherein carbon dioxide is separated and recycled to the
reactor.
[0020] Fig. 7 is a simplified overall block flow diagram for the plant of Fig. 6,
wherein an acetic acid reactor has been added for the synthesis of acetic acid.
[0021] Fig. 8 is a simplified overall block flow diagram for the plant of Fig.i7,
wherein an ammonia reactor has been added, for the synthesis of ammonia.
.
[0022] Fig. 9 is a simplified overall block diagram for the plant of Fig; 7,
wherein a vinyl acetate monomer reactor has been added for the synthesis of vinyl
acetate monomer.

[0023] Fig 10 is a simplified overall block diagram for the plant of Fig 8,
wherein a vinyl acetate monomer reactor has been added for the synthesis of vinyl
acetate monomer.
DESCRIPTION OF THE INVENTION
[0024] Detailed embodiments of the present invention are disclosed herein.
However, it is understood that the disclosed embodiments are merely exemplary, of
the invention, which can be embodied in various forms, Specific structural and
functional details disclosed herein are not intended to be limiting, but merely

illustrations that can be modified within the scope of the attached claims.
'
[0025] The plant for the process of reforming methanol in a partial oxidation

reactor to produce syngas can be a new plant, or it is preferably the retrofit of an

existing methanol plant which includes at least one partial oxidation reactor.
[0026] The present invention provides a solution to the problems associated
.

with the production of syngas from natural gas when the costs of natural gas are high.
When such economic conditions exist, plants designed for methanol and acetic acid
synthesis can be reconfigured for the production of acetic acid using existing
methanol stock as feed to the reactor, instead of natural gas.
[0027] The conversion of methanol to carbon monoxide and hydrogen is

shown generally by the following reactions:
i
If desired, carbon monoxide production can be increased via the reverse shift reaction
(shown below) where carbon dioxide and hydrogen combine to form carbon
monoxide and water.
: ' i
[0028] Referring to Fig. 1, a process is provided for the partial oxidation of a
methanol feedstock stream to produce a syngas stream which can be separated into
hydrogen (H2) and carbon monoxide (CO) streams for further use. A methanol

stream 110 is supplied to a catalyst-free partial oxidation (POX) reactor 112 of an
existing methanol synthesis plant, where it lis combined with oxygen 114 and
optionally steam 116. The methanol stream 110 is preferably a pre-existing purified
feedstock or a commercial methanol product which has been purified by distillation or
another conventional process. The oxygen 114 is obtained from an air separation unit
(ASU) 111, which is supplied with compressed air. Steam 116 can preferably be
provided by pre-existing facilities. Nitrogen and excess oxygen (not shown) provided
by ASU 111 can be provided to controls.

[0029] If oxygen feedstock 114 is not limited, the methanol feedstock 110 can
be supplied to the reactor at room temperature.; If supplies of oxygen 114 are limited,
however, the methanol feedstock 110 can be preheated and/or vaporized (not shown)
prior to supplying to the POX reactor 112. When room temperature methanol 110 is

supplied to the partial oxidation reactor 112 with an excess of oxygen 114, hydrogen
content in the syngas effluent 118 is reduced.
[0030] POX reactor 112 can produce a syngas effluent 118 consisting of H2,
CO and C02. The effluent 118 is generally [cleaner than syngas produced from a
natural gas feed as much of the impurities were removed during synthesis of the
methanol feed stream 110. Effluent 118, after cooling, can be fed to C02 separation
unit 120 which produces a C02-rich stream 122 and a mixed CO/H2 stream 124

essentially free of C02. The C02-rich stream 122 can be vented and the mixed
CO/H2 stream 124 can be supplied to separation unit 126.
[0031] Separation unit 126 preferably includes molecular sieves and a

conventional cold box. The separation unit 126 splits the mixed stream 124 into at
least a CO-rich stream 128 and an H2-rich stream 130, but can also include minor
amounts of one or more residual or tail gas streams of mixed H2 and CO which can
be used as fuel or exported (not shown). The CO-rich stream 128 and H2-rich stream

130 can be supplied to alternate processes, such as, for example, acetic acid synthesis
units or ammonia synthesis units, respectively, which are further discussed below.

[0032] As shown in Fig. 2, CO-rich stream 128 can be supplied to an acetic
acid synthesis unit 132 where it is combined with a methanol stream 134, which can

be obtained from the same feedstock that supplies the POX reactor 112. The acetic
acid synthesis unit 132 can employ manufacturing equipment and methodology well
known and/or commercially available to those! skilled in the art to form acetic acid

136 from CO via stream 128 and methanol via stream 134, such as, for example, from
one or more of the acetic acid manufacturing patents mentioned above. For example,
a conventional BP/Monsanto process can be employed, or an improved BP/Monsanto
process employing BP-Cativa technology (iridium catalyst), Celanese low water
technology (rhodium-lithium acetate catalyst), Millennium low water technology
(rhodium-phosphorous oxide catalyst) and/or dual process methanol carbonylation-
methyl formate isomerization. The reaction generally comprises reacting methanol,
methyl formate, or a combination thereof; in the presence of a reaction mixture
comprising carbon monoxide, water, a solvent and a catalyst system comprising at
least one halogenated promoter and at least one compound of rhodium, iridium, or a
combination thereof.
[0033] The reaction mixture for the acetic acid synthesis preferably has a
water content of less than 20 weight percent more preferably between approximately
14 and 15 weight percent. When the reaction comprises low water carbonylation, ithe
water content in the reaction mixture is preferably from abbut 2 to about 8 weight
percent. When the reaction comprises methyl formate isomerization or a combination
i.
of isomerization and methanol carbonylation, the reaction mixture preferably contains

a nonzero quantity of water up to 2 weight percent.
[0034] As shown in Fig. 3, the process can optionally include an ammonia
■ i'
synthesis unit 144, designed to take advantage of the H2 from the syngas stream 118

and nitrogen from the ASU 111. All or a portion of hydrogen stream 130 from the
CO/H2 separation unit 126 is reacted with ah N2 stream 142 from the air separation
unit to form ammonia collected in stream 146. Ammonia output from the synthesis
unit 144 can be increased by increasing hydrogen feed, br by adding a second
ammonia synthesis unit (not shown).

[0035] As shown in Fig. 4, the process) can optionally include a vinyl acetate
■ :|
monomer (VAM) synthesis unit 156. A portion of the acetic acid from line 136 can
be fed via line 150 to an the VAM synthesis unit 156 where it can be reacted with
ethylene 152 via line 154 and at least a portionjof the oxygen 113 from air separation
unit 111. A liquid product stream 158 is processed via conventional VAM distillation
unit 160 to produce essentially pure (commercial specification) VAM via line 162.
Carbon dioxide produced as a byproduct of the VAM synthesis can be separated from
the reactor effluent gases via a conventional C02 removal system (not shown) and
recycled to the POX reactor 112 via line 164.

[0036] VAM production can be mainly achieved by the acetoxylation of
i
ethylene according to the reaction:

The main by-product C02 is formed by the reaction
■ i
Selectivity for the process yields approximately 7-8% C02 by mass. Typically, a

VAM plant producing approximately 100,000 metric tons per year (MTY) of VAM

requires approximately 35,000 MTY of ethylene and produces between 5,000 and
10,000 MTY of C02.
[0037] As shown in Fig. 5, a vinyl acetate synthesis unit 156 can be added to.
j,
the existing acetic acid synthesis unit 132 and ammonia synthesis unit 144 for optimal
usage of the syngas stream. The VAM synthesis unit 156 can be supplied with a
portion of the acetic acid product stream 136j via line 1501 for the synthesis of !the

monomer. Crude VAM exits the VAM synthesis unit 156 via line 158 and enters a

distillation unit 160 to produce a product stream 162. Carbon dioxide produced as a
byproduct of the VAM synthesis can be separated from the reactor effluent gases via a

conventional C02 removal system (not shown) and recycled to the POX reactor 112

via line 164.
[0038] As shown in Fig. 6, all or a portion of the carbon dioxide 222 produced
and separated from the syngas effluent 218 and recycled to the POX reactor 212. A
methanol stream 210 is supplied to the partial oxidation (POX) reactor 212 of an

existing methanol synthesis plant, where it is combined with oxygen 214 and carbon
dioxide 222. The methanol stream 210 is preferably a pre-existing methanol
feedstock which has been previously purified by distillation; or another conventional
process (not shown). The oxygen 214 is obtained from pre-existing air separation unit
(ASU) 211, which is fed with air compressed. Carbon dioxide 222 can be produced

in the reformation of the methanol 210 and can be recycled to the reactor 212 feed.
![0039] POX reactor 212 can produce a syngas effluent 218 consisting of H2,
CO and C02. The effluent 218 is generally cleaner than syngas produced from a

natural gas feed as much of the impurities are removed during synthesis of the
feedstock. Effluent 218, after cooling, can be fed to C02 separation unit 220 which
produces a C02-rich stream 222 and a mixed|CO/H2 stream 224 essentially free of
C02. The C02-rich stream 222 can be recycled to the POX reactor 212 and the
mixed CO/H2 stream 224 is supplied to separation unit 226. Recycle of the C02-rich
stream to the POX reactor can increase CO production between approximately 5-10%

and decrease hydrogen production between approximately 3-8%. When the C02 is
recycled to the POX reactor, for a given production rate, the methanol feed
requirement is thus reduced.
[0040] Separation unit 226 preferably includes molecular sieves andj a
conventional cold box. The separation unit 226 splits the stream 224 into at least a
CO-rich stream 228 and an H2-rich stream 230, but can also include minor amounts

of one or more residual or tail gas streams of mixed H2 and CO which can be used as
fuel, recycled to the reactor, or exported (not shwn).
[0041] As shown in Fig. 7, CO-rich stream 228 can be combined with a
stoichiometric amount of the methanol feedstock 234 to yield acetic acid 236, by a
synthetic process which has been described aove. As show in Fig. 8, the H2-rich

stream 230 can be reacted with nitrogen 242 from ASU 240 in an ammonia synthesis
unit 244 to yield ammonia product 246. Alternatively, all or a portion of the H2-rich
stream can be supplied as fuel or exported to an alternate process (not shown).
[0042] As shown in Fig. 9, the process can optionally include a vinyl acetate
monomer (VAM) synthesis unit 256. A portion of the acetic acid from line 236 can
be fed via line 250 to an the VAM synthesis unit 256 where rt is reacted with ethylene
252 via line 254 and at least a portion of the oxygen 213 from air separation unit 211.

A liquid product stream 258 can be processed via conventional VAM distillation unit
260 to produce essentially pure (commercial specification) VAM via line 262.
Carbon dioxide produced as a byproduct of the! VAM synthesis can be separated from
the reactor effluent gases via a conventional C02 removal system (not shown) and
recycled, to the POX reactor 212 via line 264.
[0043] As shown in Fig. 10, a vinyl acetate synthesis unit 256 can be added to

the existing acetic acid synthesis unit 232 and ammonia synthesis unit 244 for optimal

usage of the syngas stream. VAM synthesis unit 256 can be supplied with a portion

of the acetic acid product stream 236 via line 250, ethylene 252 via line 254, and

oxygen from the ASU 211 via line 213. Crude VAM exits the VAM synthesis unit

256 via line 258 and enters a distillation unit 260 to produce a product stream 262.

Carbon dioxide produced as a byproduct of the VAM synthesis can be separated from
the reactor effluent gases via a conventional C02 removal system (not shown) and

recycled to the POX reactor 212 via line 264. ,

[0044] Utilities (not shown), which typically include the steam system,

cooling water, compressed air and the like, can be supplied from a pre-existing
methanol plant and can be used to supply an associated processes, such as, for
example, acetic acid and ammonia synthesis units, as well. Steam generated by waste
heat recovery from the acetic acid synthesis unit 132 and/or any other associated
integrated unit, can be used to drive or supply steam to water pumps (not shown),
ASU compressor 111, POX reactor 112, C02 removal unit 12:0, and the like.
[0045] The partial oxidation reactors can be unpacked, free-flow, rion
.catalytic gas generators to which preheated hydrocarbon and oxygen are supplied.

Optionally, a temperature moderator can be supplied to the reactor as well. The
partial oxidation reactor effluent is then quenched or cooled, and optionally cleaned to

remove soot and other particulate impuritids, and can be further processed; or

separated for additional downstream uses. When hydrogen gas is the desired end

product, such as, for example, for ammonia synthesis reactors, high and low
temperature shift converters can be employed to convert CO and steam to hydrogen
and C02. Where carbon monoxide is the desired end product, such as, for example,
for acetic acid synthesis reactors, any C02 can be removed and recycled to the reactor

to increase CO production, or reverse shift reabtors can be employed to convert C02
and H2 to CO and H2O.
[0046] When the partial oxidation reactor is from ;a pre-existing methanol
plant, the burner can be adjusted for operation for use with a methanol feedstock. The
partial oxidation reactor temperature can be maintained from 1100°- 2000°C ( 2000°-
3600°F), preferably from 1300°- 1500°C ( 240!o°- 2700°F). The reactor pressure can
be maintained at between 2 and 6 MPa, preferably approximately 4 MPa.

[0047] The production of syngas from liquid and solid carbon materials can

often result in the presence of many unwanted! impurities, such as for example, CO2,
S02, COS, CH4, Ar, N2, H20 and NH3. Typically, when natural gas is used as the
feedstock for the production of syngas, a desulfurizing/saturation unit with a catalyst
bed, such as, for example, nickel/molybdenum catalyst can be used to remove sulfur

.
from feed prior to supplying to the reactor. Because the natural gas used in,the
synthesis of the methanol has already desulfurized and the methanol product ihas
already been purified by distillation or another conventional purification process,
many of the undesired impurities normally present from synthesis with natural gas are
effectively eliminated from the syngas product.
[0048] The effluent from the partial oxidation has a molar ratio of H2-C02 to
CO+C02 (referred to in the present specification as the R ratio" (H2-
C02)/(CO+C02)), which can be optimized for the production of CO. Generally, for
the production of methanol, an R ratio of approximately 2.0 is desired. For the
'
synthesis of syngas high in CO, the H2 to CO ratio can range from 1.5 to 3, and
preferably between 1.5 and 2.
[0049] Suitable temperature moderators, to control the reaction conditions,
can be added to the reaction zone and can include H20, CO2, and N2 from the air

: |
separation unit, flue gas, cooled and recycled effluent gas, arid mixtures thereof. The
need for a temperature moderator is generally driven by the carbon:hydrogen ratio of

the hydrocarbon feed and the presence of free oxygen. Preferably, the temperature

moderator can include a portion of C02 cooled and separated from the partial
oxidation reactor effluent and recycled back to the reactor feed. When steam is used

as the temperature moderator, control of the flow rate can limit or prevent the
production of soot in the reactor.

[0050] The C02 removal unit separates the effluent stream into a C02-rich
and a C02-lean stream using conventional C02 separation equipment and
methodology, such as, for example, a.bsorption stripping with a solvent such as water,
methanol, generally aqueous alkanolamines such as ethanolamine, diethanolamine,
methyldiethanolamine and the like, aqueous alkali carbonates such as sodium and
potassium carbonates, and the like. Such C02 absorption-stripping processes :are
commercially available under the trade designations Girbotol, Sulfinol, Rectisol,
Purisol, Fluor, BASF (aMDEA) and the like.
[0051] The C02-lean stream contains primarily CO and hydrogen and can be
separated in a CO separation unit into CO-rich and hydrogen-rich streams. The
separation unit can comprise any equipment and/or methodologies known in the art
for separating the CO and hydrogen mixture into relatively pure CO and hydrogen
streams, such as, for example, semi-permeable membranes, cryogenic fractionation,
or the like. Cryogenic fractional distillation! is preferred, land can include simple
partial condensation without any columns, optionally with a pressure swing
absorption (PSA) unit and a hydrogen recycle (compressor , or methane wash. Partial
condensation with columns is typically sufficient for obtaining CO and hydrogen of
sufficient purity for acetic acid and ammonia production, respectively, keeping the
equipment and operating costs to a minimum; The PSA unit and hydrogen recycle
compressor can be added for increasing the hydrogen purity and CO production rates
if desired. For the manufacture of acetic acid, the CO stream preferably contains less
than 1000 ppm hydrogen and less than 2 mole percent nitrogen plus methane. For
ammonia production, the hydrogen stream which is sent to a nitrogen wash unit (not

shown) preferably contains at least 80 mol% hydrogen, and more preferably contains
at least 95 mol% hydrogen.

[0052] Example 1. A methanol feedstock stream is supplied to a partial
oxidation reactor for the recovery of hydrogen! and carbon monoxide. The methanol
stream is supplied at a rate of 1438 kmoles/hour, where it is combined with 719
kmoles/hour of oxygen and 884 kmoles/hour of steam. The partial oxidation reactor
is operated at approximately 1300CC (2372 °F) and 4 MPa, producing a syrigas
effluent stream. Carbon dioxide can be removed from the syngas stream, producing a

carbon dioxide-rich stream and a carbon dioxide-lean stream of carbon monoxide and

hydrogen. The carbon dioxide-rich stream can be vented or collected. The carbon
dioxide-lean stream can be supplied to a cold bbx where the component hydrogen and
carbon monoxide are separated, yielding 1045 kmoles/hour of carbon monoxide and
1812 kmoles/hour of hydrogen.
[0053] Example 2. A methanol feedstock stream is fed to a partial oxidation
reactor for recovery of hydrogen and carbon monoxide. The methanol stream is
supplied at a rate of 1438 kmoles/hour, where it is combined with 719 kmoles/hour of
oxygen, 350 kmoles/hour of steam, and 296 kmoles/hour of carbon dioxide recycled

from the reactor effluent. The partial oxidation reactor operates at approximately
1400°C (2552°F) and 4 MPa, producing a syngas effluent stream. Carbon dioxide is
removed from the syngas stream by known means, producing a carbon dioxide-rich
stream and a carbon dioxide-lean stream of carbon monoxide and hydrogen. The
carbon dioxide-rich stream is recycled to the partial oxidation reactor at a rate of 296
kmoles/hour. The carbon dioxide-lean stream is supplied to a cold box where the

components are separated, yielding 1045 kmoles/hour of carbon monoxide and 1812

kmoles/hour of hydrogen.
[0054] Example 3. The production of acetic acid from a plant having the
operating conditions of Example 1. A stoichiometric amount of methanol (1045

kmoles/hour) is added to the carbon monoxide-rich stream (1045 kmoles/hour) in an
acetic acid synthesis unit to produce approximately 1045 kmoles/hour of acetic acid.
[0055] Example 4. The production of acetic acid from a plant having; the
operating conditions of Example 2. A stoichiometric amount of methanol (1:134

. .
kmoles/hour) is added to the carbon monoxide-rich stream (1134 kmoles/hour) infan
acetic acid synthesis unit to produce approximately 1134 kmoles/hour of acetic acid.
[0056J The invention is described above in reference to specific examples land
embodiments. The metes and bounds of the invention are not to be limited by the
foregoing disclosure, which is illustrative only, but should be determined in
accordance with the full scope and spirit; of the appended claims. Various

modifications will be apparent to those skilled in the art in view of the description and
examples. It is intended that all such variations within the scope and spirit of the
appended claims be embraced thereby.

WE CLAIM:
1. A method for preparing a hydrogen-rich stream and a carbon monoxide-rich stream,
comprising:
reacting a methanol feed stream and oxygen, and optionally a temperature moderator, in a
partial oxidation reactor to produce a syngas stream, wherein the partial oxidation reactor
is catalyst-free and operated at a temperature between 1100° and 2000°C;
separating the syngas stream into a carbon dioxide rich stream and a mixed stream containing
hydrogen/carbon monoxide; and
separating the mixed stream into a hydrogen-rich stream and a carbon monoxide-rich stream.
2. The method as claimed in claim 1, wherein the methanol feed stream supplied to the partial
oxidation reactor is vaporized.
3. The method as claimed in claim 1, wherein the temperature moderator is selected from
steam, carbon dioxide, nitrogen, cooled and recycled effluent, or mixtures thereof.
4. The method as claimed in claim 1, wherein the temperature moderator is a carbon dioxide-
rich stream recycled from the reactor effluent.
5. The method as claimed in claim 1, wherein the partial oxidation reactor is operated at a
pressure between 2 and 6 MPa.
6. The method as claimed in claim 1, wherein the partial oxidation reactor is operated at a
temperature between 1300° and 1500°C.
7. The method as claimed in claim 1, wherein a portion of the methanol feed stream is reacted
with the carbon monoxide rich stream to produce acetic acid.
8. The method as claimed in claim 1, which involves:
providing a nitrogen stream from an air separation unit, and

supplying the nitrogen stream and the hydrogen-rich stream to an ammonia synthesis unit to
produce ammonia.
9. The method as claimed in claim 7, which involves:
providing an ethylene stream; and
supplying the ethylene stream, oxygen, and acetic acid to a vinyl acetate monomer synthesis
unit to produce vinyl acetate monomer.
10. The method as claimed in claim 9, wherein the oxygen supplied to the partial oxidation
reactor and to the vinyl acetate monomer synthesis unit is provided by a single air separation unit.
11. A method for converting an original methanol plant to a converted plant for the synthesis of
acetic acid, the method comprising the steps of:
providing the original methanol plant having
at least one partial oxidation reactor for converting a hydrocarbon to a syngas stream
containing hydrogen, carbon monoxide and carbon dioxide; and
a methanol synthesis loop for converting hydrogen and carbon monoxide from the
syngas stream to methanol;
providing for supplying at least a portion of a methanol feedstock stream, oxygen from an air
separation unit and optionally, a temperature moderator, to the at least one partial
oxidation reactor, wherein the partial oxidation reactor is catalyst-free and is operated at a
temperature between 1100° and 2000°C;
installing a first separation unit for separating a carbon dioxide-rich stream and a mixed
hydrogen/carbon monoxide stream from the syngas effluent;
installing a second separation unit for separating a hydrogen-rich stream and a carbon
monoxide rich stream from the mixed stream;
installing an acetic acid synthesis unit;

providing for supplying the carbon monoxide-rich stream from the second separation unit and
a portion of the methanol feedstock stream to the acetic acid synthesis unit; and
installing isolation valves for isolating the methanol synthesis loop from the remainder of the
converted plant.
12. The method as claimed in claim 11, wherein the methanol feedstock is vaporized for supply
to the partial oxidation reactor.
13. The method as claimed in claim 11, which involves:
installing an ammonia synthesis unit for reacting a hydrogen-rich stream and nitrogen to form
ammonia;
providing for supplying at least a portion of the hydrogen-rich stream from the separation unit
to the ammonia synthesis unit; and
providing a nitrogen stream from the air separation unit to the ammonia synthesis unit.
14. The method as claimed in claim 11, which involves:
installing a vinyl acetate monomer synthesis unit for reacting ethylene, oxygen, and acetic
acid to form vinyl acetate monomer;
providing for supplying at least a portion of the oxygen from an air separation unit to the vinyl
acetate monomer synthesis unit; and
producing a carbon dioxide-rich stream in the vinyl acetate monomer synthesis unit.
15. The method as claimed in claim 14, wherein the carbon dioxide-rich stream is recycled to
the partial oxidation reactor.
16. A method for preparing hydrogen, carbon monoxide and acetic acid from methanol,
comprising the steps of:

supplying a vaporized methanol feed stream, oxygen, and optionally, a temperature
moderator, to a partial oxidation reactor to form a syngas stream comprising hydrogen,
carbon monoxide and carbon dioxide, wherein the partial oxidation reactor is catalyst-free
and operated at a temperature between 1100° and 2000°C;
separating a carbon dioxide-rich stream and a mixed hydrogen/carbon monoxide stream from
the syngas stream;
separating a hydrogen-rich stream and a carbon monoxide-rich stream from the mixed stream;
and
reacting the carbon monoxide-rich stream with methanol in an acetic acid synthesis unit to
produce acetic acid.
17. The method as claimed in claim 12, wherein at least a portion of the carbon dioxide-rich
stream is recycled to the partial oxidation reactor as a temperature moderator.
18. The method as claimed in claim 17, wherein the temperature moderator is steam.

ABSTRACT
(54) Title: PREPARATION OF SYNGAS FOR ACETIC ACID SYNTHESIS BY PARTIAL OXIDATION OF METHANOL
FEED STOCK

(57) Abstract: A method for the production of syngas from methanol feedstock is disclosed, The methanol feed (110) is supplied
to a partial oxidation reactor (112) with oxygen (I I4)and optionally steam(116) to yield a mixed stream (118) of hydrogen, carbon
monoxide,and carbon dioxide. The carbon dioxide (122) is separated out and the hydrogen and carbon monoxide mixture (124)
is fed to a cold box (126) where it is separated into hydrogen-rich and carbon monoxide-rich streams (130, 128). The separated
carbon dioxide (122) can be recycled buck to the partial oxidation reactor (112) as a temperature moderator if desired. The carbon
monoxide-rich stream (128) can be reacted with methanol (134) in an acetic acid synthesis unit (132) by a conventional process to
produce acetic acid (136) or an acetic acid precursor. Optionally, an ammonia synthesis unit (144) and/or vinyl acetate monomer

" PREPARATION OF SYNGAS FOR ACETIC ACID SYNTHESIS BY PARTIAL OXIDATION OF METHANOL FEEDSTOCK"

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