Title of Invention	A PROCESS FOR SUPPRESSING THE FORMATION OF SOLID CARBON DURING CATALYTIC STEAM REFORMING OF A CARBONACEOUS FEEDSTOCK
Abstract	(A process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock) The present invention relates to a process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock by contacting the feedstock with a supported nickel catalyst further comprising gold on the nickel surface, the gold being present in an amount of 0.01% to 30% by weight, calculated on the amount of nickel in the catalyst.

Title of Invention

A PROCESS FOR SUPPRESSING THE FORMATION OF SOLID CARBON DURING CATALYTIC STEAM REFORMING OF A CARBONACEOUS FEEDSTOCK

Abstract

(A process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock) The present invention relates to a process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock by contacting the feedstock with a supported nickel catalyst further comprising gold on the nickel surface, the gold being present in an amount of 0.01% to 30% by weight, calculated on the amount of nickel in the catalyst.

Full Text	The present invention is related to a process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock. In particular, the present invention involves a gold containing nickel reforming catalyst for use in the steam reforming of a hydrocarbon feedstock. In the known processes for the production of hydrogen and/or carbon monoxide rich gases, a mixture of hydrocarbons and steam and/or carbon dioxide is passed at elevated temperature and pressure through a reactor packed with a catalyst, mainly consisting of nickel as the active catalytic component. Hydrocarbon feedstocks suitable for steam reforming are for instance natural gas, refinery off gases, propane, naphtha and liquefied petroleum gases. Taking methane as an example, the reactions which take place can be represented by the following equations: In addition to the reforming reactions (1) and (2), certain carbon forming reactions may occur as follows: The carbon thereby formed is detrimental in several ways. It decreases the activity of the catalyst by blocking its active sites. Carbon formation may further cause spalling and pulverization of the catalyst particles, resulting in increasing pressure drop over the catalyst bed and hence discontinuation of the reforming operation due to clogging of the reactor. It is well known to prevent carbon formation by increasing the steam to hydrocarbon ratio in the process gas or by reducing the molecular weight of the feedstock to reduce the potential for carbon formation. However, increased steam to hydrocarbon ratio will lead to reduced yields of CO by shifting more carbon monox¬ide over to carbon dioxide. Thus, in order to maintain CO/H2-production at the desired production rate, larger amounts of catalyst and feedstock are required, which depreciate the economy of the reforming process. Various attempts have been made to overcome carbon deposition without affecting the optimum steam to hydrocar¬bon ratio. A method of preventing carbon formation during the reforming process for the preparation of reducing gases with a high reduction potential is mentioned in GB patent No. 2,015,027. By the disclosed process a feed gas rich in methane is reformed over a supported nickel catalyst in the presence of 2 to 10 ppm by volume sulphur or sulphur com¬pounds in the feed. Thereby, the presence of sulphur coun¬teracts carbon formation and ensures satisfactory reforming activity of the catalyst to form carbon monoxide and hydro¬gen. Furthermore, several catalysts giving decreased carbon deposition have been suggested in the past. In gen¬eral, the prior art catalysts having a suppression effect upon carbon deposition mainly consist of nickel with alkali promoter. Disadvantages of the alkali promoted catalysts are low activity and the mobility of the alkali metals, which cause migration and evaporation of the alkali promo¬ter during the operation of the catalyst. Catalysts free of alkali metals are suggested in US Patent No. 3,926,583, by which a nickel, iron or cobalt reforming catalyst is prepared by reducing a precursor com¬prising an intimate mixture of magnesium aluminum spinel with a mixed solid phase of the oxides of nickel, iron or cobalt and in US Patent No. 3,791,993, disclosing a nickel, iron or cobalt, magnesium oxide reforming catalyst. Other promoters have been suggested in the art. US Patent No. 4,060,498 mentions a steam reforming process with a silver promoted nickel catalyst on a heat resistant oxide carrier. Furthermore, EP Patent No. 470,626 states the effect of Group IVa and Va metals suppressing the carbon formation. Amounts between 0.1 to 3 0% by weight calculated on the amount of metallic nickel, of germanium, tin, lead, arsenic, antimony and bismuth are included in the nickel containing catalyst. Elements from Group lb are not included in this patent, and in the literature, it is stated that addition of gold has no effect neither on carbon formation nor on the reforming activity (Mono and bi-metallic catalysts for steam reforming, Ph.D. Thesis by Isar-Ul Hague, University of New South Wales, 1990) . Recent STM studies (L.P. Nielsen et. al., Phys. Rev. Lett. 71 (1993) 754} have shown that gold may form an alloy in the surface of a nickel single crystal although these two elements are immiscible in the bulk. Furthermore, calculations using the density functional theory, predicts that addition of small amounts of gold will alter the reac¬tivity of the neighbouring nickel atoms (P. Kratzer et al., J. Chem. Phys. 105 (13) (1996) 5595) . Molecular beam studies of single crystals of nickel promoted with small amounts of gold have confirmed this (P. M. Holmblad et. al., J. Chem. Phys. 104 (1996) 7289). Thus, it is the main object of this invention to prevent carbon deposition in the steam reforming of hydro¬carbons . We have now observed that addition of small amounts of gold to a nickel containing catalyst provides a catalyst with suppressed carbon deposition during steam reforming of hydrocarbons. Though gold decreases the catalytic activity of the nickel catalyst, the catalyst still provide suffi¬cient activity for the steam reforming. EXAFS confirms that the gold is located at the nickel surface (Annual Report from HASYLAE, 1996} . Based on the above observation, a broad embodiment of the invention is directed towards a process for cata-lytically steam reforming of a carbonaceous feedstock with¬out carbon formation, wherein carbon forming reactions occurring during the steam reforming are substantially reduced by contacting the feedstock with a supported nickel catalyst further including gold in an amount of 0.01% to 3 0% by weight calculated on the amount of nickel in the catalyst. The amount of gold incorporated in the catalyst will depend on the nickel surface area. The gold containing nickel catalyst may be prepared by coimpregnation or sequentially impregnation of the car¬rier material with solutions containing a soluble nickel salt and a salt of the gold promoter. Suitable salts include chlorides, nitrates, carbonates, acetates or oxala¬tes. Carrier materials are conveniently selected from the group of alumina, magnesia, titania, silica, zirconia, beryllia, thoria, lanthania, calcium oxide and compounds or mixtures thereof. Preferred materials comprise alumina, calcium aluminates and magnesium aluminum spinel. The pro¬moted catalyst, thus obtained, can be used in the produc¬tion of hydrogen and/or carbon monoxide rich gases by steam reforming of methane or higher hydrocarbons. The hydrogen and/or carbon monoxide rich gases obtained may be used in many processes, hydrogen. Hydrogen is used worldwide in refineries, while mixtures of hydrogen and carbon monoxide are for instance employed in the syn¬thesis of oxygenated hydrocarbons and synthetic fuels. An important use of hydrogen-rich gas is in the preparation of ammonia and methanol. The nickel-gold catalyst are typically arranged as fixed bed in a top feeded tubular reforming reactor. Depending on the process conditions, the potential for carbon formation will typically be highest at the top layer in tube. Thus, it may be sufficient to arrange the nickel-gold catalyst as a layer in the upper portion of a fixed bed of conventional nickel steam reforming catalyst. Thereby, the nickel-gold catalyst layer preferably constitutes 5% to 50% of the catalyst bed. Accordingly, the present invention provides a process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock by contacting the feedstock with a supported nickel catalyst comprising gold on the nickel surface, the gold being present in an amount of 0.01% to 30% by weight, calculated on the amount of nickel in the catalyst. The invention will be further described in the following Examples. Example 1 Steam reforming activity. A series of nickel/gold catalyst samples containing 17% by weight of nickel and containing varying contents of gold were prepared by sequential impregnations of a spinel carrier with nickel nitrate and goldtetramminnitrate, [Au (NH3)4] (NO3)3s-Before the impregnation with the gold precursor, the nickel nitrate was decomposed. After drying the catalyst pellets were loaded in a reactor and activated during heating to 350°C in flowing hydrogen at atmospheric pressure. The activities obtained at SSO^C are shown in Table 1. The steam reforming activity was determined under the following conditions: Table 1 Steam reforming activity at 550°C. As apparent from Table 1, there is a minor decrease in. steam reforming activity for the gold containing nickel catalysts compared to the pure nickel catalyst. Example 2 TGA measurements The rates of carbon deposition on the reforming catalysts during steam reforming of butane prepared under Example 1 were measured gravimetrically for various values of temperature between 450°C to 550°C. The temperature was increased by 0.5°C/min. A conventional experimental set-up comprising a heated reactor tube associated with an on-line microbalance was used for the measurement. One catalyst pellet (0.1 g) was placed on the basket suspended from one arm of the microbalance. The total flow rate and the con¬centration of the feed stream passed over the catalyst pel¬let is given below: Total flow rate = 21,82 Nl/h Butane = 3,76 vol % Steam = 22,91 vol % Hydrogen = 4,58 vol % Nitrogen = 68,74 vol V The rate of carbon formation at the above con¬ditions is depicted in Fig,1 showing the amount of carbon (µg carbon/g catalyst 100) at different temperatures (°C • 1000) deposited on: Cat. 2, prepared under Example 1; in comparison to the conventional nickel reforming cata¬lyst, also prepared under Example 1. As apparent from the Fig., the catalyst according to the invention provides a highly improved resistance to carbon formation during steam reforming. WE CLAIM: 1. A process for suppressing the formation of solid carbon during catalyic steam reforming of a carbonaceous feedstock by contacting the feedstock with a supported nickel catalyst comprising gold on the nickel surface, the gold being present in an amount of 0.01% to 30% by weight, calculated on the amount of nickel in the catalyst. 2. The process as claimed in claim 1, wherein the amount of gold is between 0.01% and 10% by weight calculated on the total catalyst weight. 3. The process as claimed in claim 1, wherein the gold containing nickel catalyst is arranged as a top layer in a fixed bed of a conventional nickel steam reforming catalyst. 4. The process as claimed in claim 3, wherein the top layer constitutes between 5% and 50% of the total catalyst bed. 5. A process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock substantially as herein described and exemplified.

Full Text

The present invention is related to a process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock. In particular, the present invention involves a gold containing nickel reforming catalyst for use in the steam reforming of a hydrocarbon feedstock.
In the known processes for the production of hydrogen and/or carbon monoxide rich gases, a mixture of hydrocarbons and steam and/or carbon dioxide is passed at elevated temperature and pressure through a reactor packed with a catalyst, mainly consisting of nickel as the active catalytic component.
Hydrocarbon feedstocks suitable for steam reforming are for instance natural gas, refinery off gases, propane, naphtha and liquefied petroleum gases. Taking methane as an example, the reactions which take place can be represented by the following equations:

In addition to the reforming reactions (1) and (2), certain carbon forming reactions may occur as follows:

The carbon thereby formed is detrimental in several ways. It decreases the activity of the catalyst by blocking its active sites. Carbon formation may further cause spalling and pulverization of the catalyst particles, resulting in increasing pressure drop over the catalyst bed and hence discontinuation of the reforming operation due to clogging of the reactor.

It is well known to prevent carbon formation by increasing the steam to hydrocarbon ratio in the process gas or by reducing the molecular weight of the feedstock to reduce the potential for carbon formation.
However, increased steam to hydrocarbon ratio will lead to reduced yields of CO by shifting more carbon monox¬ide over to carbon dioxide. Thus, in order to maintain CO/H2-production at the desired production rate, larger amounts of catalyst and feedstock are required, which depreciate the economy of the reforming process.
Various attempts have been made to overcome carbon deposition without affecting the optimum steam to hydrocar¬bon ratio.
A method of preventing carbon formation during the reforming process for the preparation of reducing gases with a high reduction potential is mentioned in GB patent No. 2,015,027. By the disclosed process a feed gas rich in methane is reformed over a supported nickel catalyst in the presence of 2 to 10 ppm by volume sulphur or sulphur com¬pounds in the feed. Thereby, the presence of sulphur coun¬teracts carbon formation and ensures satisfactory reforming activity of the catalyst to form carbon monoxide and hydro¬gen.
Furthermore, several catalysts giving decreased carbon deposition have been suggested in the past. In gen¬eral, the prior art catalysts having a suppression effect upon carbon deposition mainly consist of nickel with alkali promoter. Disadvantages of the alkali promoted catalysts are low activity and the mobility of the alkali metals, which cause migration and evaporation of the alkali promo¬ter during the operation of the catalyst.
Catalysts free of alkali metals are suggested in US Patent No. 3,926,583, by which a nickel, iron or cobalt reforming catalyst is prepared by reducing a precursor com¬prising an intimate mixture of magnesium aluminum spinel with a mixed solid phase of the oxides of nickel, iron or

cobalt and in US Patent No. 3,791,993, disclosing a nickel, iron or cobalt, magnesium oxide reforming catalyst. Other promoters have been suggested in the art. US Patent No. 4,060,498 mentions a steam reforming process with a silver promoted nickel catalyst on a heat resistant oxide carrier. Furthermore, EP Patent No. 470,626 states the effect of Group IVa and Va metals suppressing the carbon formation. Amounts between 0.1 to 3 0% by weight calculated on the amount of metallic nickel, of germanium, tin, lead, arsenic, antimony and bismuth are included in the nickel containing catalyst.
Elements from Group lb are not included in this patent, and in the literature, it is stated that addition of gold has no effect neither on carbon formation nor on the reforming activity (Mono and bi-metallic catalysts for steam reforming, Ph.D. Thesis by Isar-Ul Hague, University of New South Wales, 1990) .
Recent STM studies (L.P. Nielsen et. al., Phys. Rev. Lett. 71 (1993) 754} have shown that gold may form an alloy in the surface of a nickel single crystal although these two elements are immiscible in the bulk. Furthermore, calculations using the density functional theory, predicts that addition of small amounts of gold will alter the reac¬tivity of the neighbouring nickel atoms (P. Kratzer et al., J. Chem. Phys. 105 (13) (1996) 5595) . Molecular beam studies of single crystals of nickel promoted with small amounts of gold have confirmed this (P. M. Holmblad et. al., J. Chem. Phys. 104 (1996) 7289).
Thus, it is the main object of this invention to prevent carbon deposition in the steam reforming of hydro¬carbons .
We have now observed that addition of small amounts of gold to a nickel containing catalyst provides a catalyst with suppressed carbon deposition during steam reforming of hydrocarbons. Though gold decreases the catalytic activity

of the nickel catalyst, the catalyst still provide suffi¬cient activity for the steam reforming. EXAFS confirms that the gold is located at the nickel surface (Annual Report from HASYLAE, 1996} .
Based on the above observation, a broad embodiment of the invention is directed towards a process for cata-lytically steam reforming of a carbonaceous feedstock with¬out carbon formation, wherein carbon forming reactions occurring during the steam reforming are substantially reduced by contacting the feedstock with a supported nickel catalyst further including gold in an amount of 0.01% to 3 0% by weight calculated on the amount of nickel in the catalyst.
The amount of gold incorporated in the catalyst will depend on the nickel surface area.
The gold containing nickel catalyst may be prepared by coimpregnation or sequentially impregnation of the car¬rier material with solutions containing a soluble nickel salt and a salt of the gold promoter. Suitable salts include chlorides, nitrates, carbonates, acetates or oxala¬tes.
Carrier materials are conveniently selected from the group of alumina, magnesia, titania, silica, zirconia, beryllia, thoria, lanthania, calcium oxide and compounds or mixtures thereof. Preferred materials comprise alumina, calcium aluminates and magnesium aluminum spinel. The pro¬moted catalyst, thus obtained, can be used in the produc¬tion of hydrogen and/or carbon monoxide rich gases by steam reforming of methane or higher hydrocarbons.
The hydrogen and/or carbon monoxide rich gases obtained may be used in many processes, hydrogen. Hydrogen is used worldwide in refineries, while mixtures of hydrogen and carbon monoxide are for instance employed in the syn¬thesis of oxygenated hydrocarbons and synthetic fuels. An important use of hydrogen-rich gas is in the preparation of ammonia and methanol.

The nickel-gold catalyst are typically arranged as fixed bed in a top feeded tubular reforming reactor. Depending on the process conditions, the potential for carbon formation will typically be highest at the top layer in tube. Thus, it may be sufficient to arrange the nickel-gold catalyst as a layer in the upper portion of a fixed bed of conventional nickel steam reforming catalyst. Thereby, the nickel-gold catalyst layer preferably constitutes 5% to 50% of the catalyst bed.
Accordingly, the present invention provides a process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock by contacting the feedstock with a supported nickel catalyst comprising gold on the nickel surface, the gold being present in an amount of 0.01% to 30% by weight, calculated on the amount of nickel in the catalyst.
The invention will be further described in the following Examples. Example 1 Steam reforming activity.
A series of nickel/gold catalyst samples containing 17% by weight of nickel and containing varying contents of gold were prepared by sequential impregnations of a spinel carrier with nickel nitrate and goldtetramminnitrate, [Au (NH3)4] (NO3)3s-Before the impregnation with the gold precursor, the nickel nitrate was decomposed. After drying the catalyst pellets were loaded in a reactor and activated during heating to 350°C in flowing hydrogen at atmospheric pressure.

The activities obtained at SSO^C are shown in Table 1.
The steam reforming activity was determined under the following conditions:

Table 1
Steam reforming activity at 550°C.

As apparent from Table 1, there is a minor decrease in. steam reforming activity for the gold containing nickel catalysts compared to the pure nickel catalyst.
Example 2
TGA measurements
The rates of carbon deposition on the reforming catalysts during steam reforming of butane prepared under Example 1 were measured gravimetrically for various values of temperature between 450°C to 550°C. The temperature was increased by 0.5°C/min. A conventional experimental set-up comprising a heated reactor tube associated with an on-line microbalance was used for the measurement. One catalyst pellet (0.1 g) was placed on the basket suspended from one arm of the microbalance. The total flow rate and the con¬centration of the feed stream passed over the catalyst pel¬let is given below:
Total flow rate = 21,82 Nl/h
Butane = 3,76 vol %
Steam = 22,91 vol %
Hydrogen = 4,58 vol %
Nitrogen = 68,74 vol V

The rate of carbon formation at the above con¬ditions is depicted in Fig,1 showing the amount of carbon (µg carbon/g catalyst 100) at different temperatures (°C • 1000) deposited on:
Cat. 2, prepared under Example 1;
in comparison to the conventional nickel reforming cata¬lyst, also prepared under Example 1.
As apparent from the Fig., the catalyst according to the invention provides a highly improved resistance to carbon formation during steam reforming.

WE CLAIM:
1. A process for suppressing the formation of solid carbon during catalyic steam
reforming of a carbonaceous feedstock by contacting the feedstock with a
supported nickel catalyst comprising gold on the nickel surface, the gold being
present in an amount of 0.01% to 30% by weight, calculated on the amount of
nickel in the catalyst.
2. The process as claimed in claim 1, wherein the amount of gold is between
0.01% and 10% by weight calculated on the total catalyst weight.
3. The process as claimed in claim 1, wherein the gold containing nickel catalyst
is arranged as a top layer in a fixed bed of a conventional nickel steam
reforming catalyst.
4. The process as claimed in claim 3, wherein the top layer constitutes between 5% and 50% of the total catalyst bed.
5. A process for suppressing the formation of solid carbon during catalytic steam reforming of a carbonaceous feedstock substantially as herein described and exemplified.

Documents:

1234-mas-1998 abstract duplicate.pdf

1234-mas-1998 abstract.pdf

1234-mas-1998 claims duplicate.pdf

1234-mas-1998 claims.pdf

1234-mas-1998 correspondence others.pdf

1234-mas-1998 correspondence po.pdf

1234-mas-1998 description (complete) duplicate.pdf

1234-mas-1998 description (complete).pdf

1234-mas-1998 drawing.pdf

1234-mas-1998 form-19.pdf

1234-mas-1998 form-2.pdf

1234-mas-1998 form-26.pdf

1234-mas-1998 form-4.pdf

1234-mas-1998 form-6.pdf

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Patent Number

200755

Indian Patent Application Number

1234/MAS/1998

PG Journal Number

8/2007

Publication Date

23-Feb-2007

Grant Date

01-Jun-2006

Date of Filing

08-Jun-1998

Name of Patentee

HALDOR TOPSOE A/S

Applicant Address

NYMOLLEVEJ 55, DK-2800 LYNGBY,

Inventors:

#	Inventor's Name	Inventor's Address
1	JENS HYLDTOFT	HESSELRODVEJ 7, DK-2980 KOKKEDAL
2	JENS KEHLET NORSKOV	RUSTENBORGVEJ 6, DK-2800 LYNGBY,
3	BJERNE STEFFEN CLAUSEN	HOBJERGVEJ 14, TROROD, DK-2950 VEDBAEK

PCT International Classification Number

C01B3/40

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0683/97	1997-06-10	Denmark