Coking dry gas hydrogenation catalyst and preparation method thereof

Abstract

The invention relates to the technical field of catalytic hydrogenation, and particularly discloses a coking dry gas hydrogenation catalyst and a preparation method thereof. The coking dry gas hydrogenation catalyst comprises the following components in percentage by mass: 1.0%-18.0% of WO3, 1.0%-10.0% of MoO3, 0.5%-7.0% of NiO, 0.1%-4.0% of CoO, 61%-94.1% of a coking dry gas hydrogenation catalyst carrier and the balance of a catalyst organic auxiliary agent. Compared with the prior art, the method provided by the invention solves the problems that the content of impurities such as oxygen, sulfur, CO and CO2 in the coking dry gas is high, the influence of impurities in the conventional hydrogenation reaction on the reaction is avoided, and the self-limitation that light hydrocarbon hydrogenation is concentrated, exothermic is strong and deep hydrogenation is difficult due to low catalyst activity is avoided, and solves the problem that the existing catalyst is relatively poor in activity.

Description

Technical Field

[0001] This invention relates to the field of catalytic hydrogenation technology, and in particular to a coking dry gas hydrogenation catalyst and its preparation method. Background Technology

[0002] With changes in ethylene demand and ethylene production feedstocks, ethylene production capacity has continued to grow. However, due to limited new global ethylene capacity and the commissioning of new plants for polyethylene and other derivatives, the ethylene market supply remains tight. Regarding ethylene feedstocks, although the composition of global ethylene feedstocks has remained relatively stable for many years, primarily consisting of naphtha and light hydrocarbons, recent years have seen a trend towards diversification due to varying resource availability and changes in feedstock markets across countries. Using low-carbon alkanes as ethylene feedstocks is one such trend. Coking gas, due to its high content of impurities such as oxygen, sulfur, CO, and CO2, has limited applications beyond fuel and hydrogen production.

[0003] The composition of coking gas feedstock shows that low-chain saturated hydrocarbons such as methane and ethane are the main components, and they hardly react during hydrogenation due to the low reaction temperature. Olefins are the main components reacting during hydrogenation in coking gas, but in reality, these light hydrocarbons contain not only certain amounts of alkenes and dienes, but also substances such as CO. X Various impurities, such as O2, H2S, extractants, and acid inhibitors, cannot be directly used as ethylene cracking feedstock and need to be removed during hydrogenation. However, conventional hydrogenation methods cannot produce qualified ethylene cracking feedstock due to the significant impact of impurities on the reaction and the inherent limitations of light hydrocarbon hydrogenation—which is characterized by concentrated, strongly exothermic reactions and difficulty in deep hydrogenation. Therefore, specialized catalysts with high olefin saturation activity and strong resistance to impurities at low temperatures are crucial for converting coking dry gas into high-quality ethylene feedstock.

[0004] CN114797855A belongs to the field of catalyst technology, disclosing a coking dry gas hydrogenation catalyst, its catalyst support, and related preparation methods and applications. The preparation steps of the catalyst support are as follows: first, kneading a solution containing lanthanum and cerium salts with the support raw materials; second, subjecting the kneaded product obtained in the first step to a first drying, first calcination, and roasting; third, contacting the product obtained in the second step with an aqueous solution of alkali metal hydroxide; and fourth, subjecting the product obtained in the third step to a second drying and second calcination. The coking dry gas hydrogenation catalyst prepared using the catalyst support of this invention exhibits high selectivity.

[0005] CN110270382A discloses a hydrophobically modified coking dry gas hydrogenation catalyst, its preparation method, and its application. The preparation method includes: preparing an active component solution containing ammonia complex ions of Group VIII and / or Group IB metals; placing a TiO2-Al2O3 composite oxide support into the above active component solution for impregnation and drying to obtain a catalyst precursor; contacting the catalyst precursor with a carrier gas carrying a silane modifier to complete the hydrophobic modification treatment; and then heating the hydrophobically modified catalyst precursor in a hydrogen atmosphere to obtain the coking dry gas hydrogenation catalyst. This invention utilizes multiple ammonia molecules complexed on the surface of Group VIII and / or Group IB metals to achieve spatial occupancy, thereby regulating the subsequent hydrophobic modification process, ultimately obtaining a coking dry gas hydrogenation catalyst whose catalytic activity is not reduced due to the active sites being covered by the silane modifier.

[0006] While existing technologies have solved the problem of impurities such as CO and CO2 affecting the hydrogenation of coking dry gas to produce ethylene cracking feedstock, the problem of poor activity and stability of existing catalysts still needs to be addressed. Improving the catalyst's resistance to impurities and water resistance is the simplest and most effective approach. Summary of the Invention

[0007] In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a coking dry gas hydrogenation catalyst and its preparation method.

[0008] In hydrogenation reactions, fluctuations in water content caused by feedstocks and reaction products affect catalyst activity, stability, and the smooth operation of the unit. Simultaneously, the polymerization and coking of unsaturated hydrocarbons on the catalyst surface also impairs its activity, lifespan, and unit operation. Therefore, it is necessary to improve the water resistance and anti-coking properties of coking dry gas hydrogenation catalysts.

[0009] This invention employs a core support grafted with hyperbranched polyetheramine, which is then encapsulated with polycaprolactone to obtain the catalyst's organic auxiliary agent. The core support provides more active sites, and its porous structure acts as a "nanoreactor" for the active metal, thereby improving metal dispersion. The support can anchor the active metal through coordination or hydroxyl groups. The hyperbranched polyetheramine reacts with the acidic hydroxyl groups of the support, inhibiting olefin polymerization. After calcination, the hyperbranched polyetheramine forms a nitrogen-doped carbon layer, thus maintaining metal dispersion. The polycaprolactone forms a long-chain alkyl group, retaining its hydrophobicity.

[0010] This invention loads active components W, Mo, Ni, and Co, along with organic additives, onto alumina. The additives ensure uniform dispersion of the active metal on the alumina support, while the organic additives weaken the metal-alumina interaction. The addition of organic additives increases the surface active groups of the catalyst, facilitating the anchoring of the active metal and thus improving the dispersion of the active metal. The use of a four-component metal composition of W, Mo, Ni, and Co further enhances the catalyst's activity. This invention addresses the limitations of high impurity content (oxygen, sulfur, CO, CO2, etc.) in coking dry gas, avoiding the influence of impurities on the reaction in conventional hydrogenation reactions, and the inherent limitation of low catalyst activity leading to concentrated, strongly exothermic hydrogenation of light hydrocarbons, hindering deep hydrogenation. It solves the problem of poor activity in existing catalysts.

[0011] To achieve the above objectives, the present invention provides a coking dry gas hydrogenation catalyst, which, based on mass fraction, contains 1.0% to 18.0% WO3, 1.0% to 10.0% MoO3, 0.5% to 7.0% NiO, 0.1% to 4.0% CoO, 61% to 94.1% hydrogenation catalyst support, and the balance being organic catalyst additives.

[0012] The preparation method of the catalyst organic auxiliary includes the following steps: ZIF-8 was dispersed in 5 times its mass of water, hyperbranched polyethyleneimine was added, the pH was adjusted to weakly alkaline after heating, and the mixture was stirred for 1-3 hours for grafting. Then, a toluene solution of polycaprolactone and dibutyltin dilaurate were added, and the mixture was heated and stirred for another 1-3 hours for coating. After centrifugation, washing, and drying, the catalyst organic additive was obtained.

[0013] Furthermore, the temperature range for the heating is 80~120℃.

[0014] Furthermore, the mass ratio of ZIF-8 to hyperbranched polyethyleneimine, polycaprolactone, and dibutyltin dilaurate is 1:0.7~0.8:1~2:0.01~0.02.

[0015] Furthermore, the toluene solution of the polycaprolactone is 40-50 wt%.

[0016] Furthermore, the WO3 content is preferably 6.0% to 16.0%.

[0017] Furthermore, the MoO3 content is preferably 3.0% to 8.0%.

[0018] Furthermore, the NiO content is preferably 2% to 6.0%.

[0019] Furthermore, the CoO content is preferably 0.5% to 3.0%.

[0020] Preferably, the method for preparing the catalyst organic auxiliary includes the following steps: SBA-15 was added to 10 times its mass of a 10wt% KH-550 ethanol solution and stirred at 70-80℃ for 1-2 hours for amination. After drying, it was dispersed in 5 times its mass of dilute hydrochloric acid and stirred at 80-90℃ for 1-3 hours under weak acidity to graft it onto hyperbranched polyethyleneimine. Then, 40-50wt% of a toluene solution of polycaprolactone and dibutyltin dilaurate were added, and the temperature was further raised to 110-120℃ and stirred for 1-3 hours for coating. After centrifugation, washing, and drying, the catalyst organic additive was obtained. The mass ratio of SBA-15 to KH-550, hyperbranched polyethyleneimine, polycaprolactone, and dibutyltin dilaurate was 1:0.1-0.2:0.7-0.8:1-2:0.01-0.02.

[0021] More preferably, the method for preparing the catalyst organic auxiliary includes the following steps: MIL-101(Cr) was dispersed in 5 times its weight of a 50wt% ethanol aqueous solution. Hyperbranched polyethyleneimine was added, and the temperature was raised to 80-90℃. The pH was adjusted to weakly acidic, and the mixture was stirred for 1-3 hours for grafting. Then, 40-50wt% of a toluene solution of polycaprolactone and dibutyltin dilaurate were added. The temperature was raised to 110-120℃ and stirred for 1-3 hours for coating. After centrifugation, washing, and drying, the catalyst organic additive was obtained. The mass ratio of MIL-101(Cr) to hyperbranched polyethyleneimine, polycaprolactone, and dibutyltin dilaurate was 1:0.7-0.8:1-2:0.01-0.02.

[0022] A method for preparing a coking dry gas hydrogenation catalyst includes the following steps: By loading active components such as W, Mo, Ni, and Co, along with organic additives, onto a hydrogenation catalyst support, a coking dry gas hydrogenation catalyst is obtained.

[0023] Furthermore, the loading method generally adopts impregnation, followed by drying and calcination. The drying process is carried out at 100~120℃ for 1~5 hours and calcination is carried out at 400~550℃ for 1~5 hours.

[0024] Furthermore, the coking dry gas hydrogenation catalyst has a pore volume of 0.3~1.0 mL / g and a specific surface area of ​​300~550 m². 2 / g.

[0025] The beneficial effects of this invention are: This invention loads active components W, Mo, Ni, and Co, along with organic additives, onto alumina. The additives ensure uniform dispersion of the active metal on the alumina support, while the organic additives weaken the metal-alumina interaction. The addition of organic additives increases the surface active groups of the catalyst, facilitating the anchoring of the active metal and thus improving the dispersion of the active metal. The use of a four-component metal composition of W, Mo, Ni, and Co further enhances the catalyst's activity. This invention addresses the limitations of high impurity content (oxygen, sulfur, CO, CO2, etc.) in coking dry gas, avoiding the influence of impurities on the reaction in conventional hydrogenation reactions, and the inherent limitation of low catalyst activity leading to concentrated, strongly exothermic hydrogenation of light hydrocarbons, hindering deep hydrogenation. It solves the problem of poor activity in existing catalysts. Detailed Implementation

[0026] ZIF-8, model: KAR-F01, particle size: 50~200nm, pore size: 0.8~1.8nm, is sourced from Guangdong Carbon Language New Materials Co., Ltd.

[0027] SBA-15, pore size: 6~13nm, is from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0028] MIL-101(Cr), model: KAR-F39, particle size: 100~200nm, pore size: 2.9~3.4nm, sourced from Guangdong Carbon Language New Materials Co., Ltd.

[0029] The alumina support has a total acid content of 0.5 mmol / g, a Lewis acid content of 0.55 mmol / g, a pore volume of 0.4 mL / g, and a specific surface area of ​​400 m². 2 / g. Hyperbranched polyethyleneimine, Mw=10000g / mol, derived from Alfa Aesar.

[0030] Polycaprolactone, brand name: N-500CESU, is sourced from Shenzhen Guanghua Weiye.

[0031] Example 1

[0032] A method for preparing a coking dry gas hydrogenation catalyst includes the following steps: Add 9g of catalyst organic promoter to 134mL of water, then add 26.4g of ammonium metatungstate, 19.2g of molybdenum trioxide, 25.3g of nickel nitrate, and 12.7g of cobalt nitrate. After stirring evenly, adjust the solution volume to 200mL and store it in a sealed container. Place 200g of alumina support in a spray impregnation boiler. Under rotating conditions, spray 156mL of the prepared solution into the alumina support in the boiler in a mist manner. After rotating for 30min, let it stand for 18h, dry it at 110℃ for 3h, and then calcine it at 500℃ for 3h with a temperature increase of 3℃ / min to obtain the coking dry gas hydrogenation catalyst.

[0033] The preparation method of the catalyst organic auxiliary includes the following steps: ZIF-8 was dispersed in 5 times its weight of water, hyperbranched polyethyleneimine was added, the temperature was raised to 80℃ and the pH was adjusted to 9. Grafting was carried out by stirring for 2 hours. Then, 45wt% of polycaprolactone in toluene solution and dibutyltin dilaurate were added. The temperature was raised to 120℃ and stirred for 2 hours for coating. After centrifugation, washing and drying, the catalyst organic additive was obtained. The mass ratio of ZIF-8 to hyperbranched polyethyleneimine, polycaprolactone and dibutyltin dilaurate was 1:0.75:1.5:0.015.

[0034] Example 2

[0035] It is basically the same as Example 1, except that the preparation method of the catalyst organic auxiliaries is different; The preparation method of the catalyst organic auxiliary includes the following steps: SBA-15 was added to 10 times its mass of a 10wt% KH-550 ethanol solution and stirred at 75℃ for 2h for amination. After drying, it was dispersed in 5 times its mass of 0.1mol / L dilute hydrochloric acid and stirred at pH 6.5 and 85℃ for 2h for grafting with hyperbranched polyethyleneimine. Then, 45wt% polycaprolactone in toluene solution and dibutyltin dilaurate were added, and the temperature was raised to 120℃ and stirred for 2h for coating. After centrifugation, washing, and drying, the catalyst organic additive was obtained. The mass ratio of SBA-15 to KH-550, hyperbranched polyethyleneimine, polycaprolactone, and dibutyltin dilaurate was 1:0.2:0.75:1.5:0.015.

[0036] Example 3

[0037] It is basically the same as Example 1, except that the preparation method of the catalyst organic auxiliaries is different; The preparation method of the catalyst organic auxiliary includes the following steps: MIL-101(Cr) was dispersed in 5 times its weight of a 50wt% ethanol aqueous solution. Hyperbranched polyethyleneimine was added, and the temperature was raised to 85℃. The pH was adjusted to 5.8, and the mixture was stirred for 2 hours for grafting. Then, 45wt% polycaprolactone in toluene solution and dibutyltin dilaurate were added. The temperature was raised to 120℃ and stirred for 2 hours for coating. After centrifugation, washing, and drying, the catalyst organic additive was obtained. The mass ratio of MIL-101(Cr) to hyperbranched polyethyleneimine, polycaprolactone, and dibutyltin dilaurate was 1:0.75:1.5:0.015.

[0038] Compare with Example 1

[0039] A method for preparing a coking dry gas hydrogenation catalyst includes the following steps: Add 9g of oxalic acid to 134mL of water, then add 26.4g of ammonium metatungstate, 19.2g of molybdenum trioxide, 25.3g of nickel nitrate, and 12.7g of cobalt nitrate. After stirring evenly, adjust the solution volume to 200mL and store it in a sealed container. Place 200g of alumina support in a spray-impregnation boiler. Under rotating conditions, spray 156mL of the prepared solution into the alumina support in the boiler in a mist manner. After rotating for 30min, let it stand for 18h, dry it at 110℃ for 3h, and then calcine it at 500℃ for 3h at a rate of 3℃ / min to obtain the coking dry gas hydrogenation catalyst.

[0040] Compare with Example 2

[0041] A method for preparing a coking dry gas hydrogenation catalyst includes the following steps: Add 9g of oxalic acid to 134mL of water, then add 26.7g of ammonium metatungstate, 19.4g of molybdenum trioxide, 25.7g of nickel nitrate, and 12.8g of cobalt nitrate. After stirring evenly, adjust the solution volume to 200mL and store it in a sealed container. Place 200g of alumina support in a spray-impregnation boiler. Under rotating conditions, spray 156mL of the prepared solution into the alumina support in the boiler in a mist manner. After rotating for 30min, let it stand for 18h, dry it at 110℃ for 3h, and then calcine it at 500℃ for 3h at a rate of 3℃ / min to obtain the coking dry gas hydrogenation catalyst.

[0042] Compare with Example 3

[0043] A method for preparing a coking dry gas hydrogenation catalyst includes the following steps: Add 9g of oxalic acid to 134mL of water, then add 23.5g of ammonium metatungstate, 20.0g of molybdenum trioxide, 23.0g of nickel nitrate, and 16.5g of cobalt nitrate. After stirring evenly, adjust the solution volume to 200mL and store it in a sealed container. Place 200g of alumina support in a spray-impregnation boiler. Under rotating conditions, spray 156mL of the prepared solution into the alumina support in the boiler in a mist manner. After rotating for 30min, let it stand for 18h, dry it at 110℃ for 3h, and then calcine it at 500℃ for 3h at a rate of 3℃ / min to obtain the coking dry gas hydrogenation catalyst.

[0044] Compare with Example 4

[0045] A method for preparing a coking dry gas hydrogenation catalyst includes the following steps: Add 9g of oxalic acid to 134mL of water, then add 48.0g of ammonium metatungstate, 20.3g of molybdenum trioxide, 16.8g of nickel nitrate, and 10.1g of cobalt nitrate. After stirring evenly, adjust the solution volume to 200mL and store it in a sealed container. Place 200g of alumina support in a spray-impregnation boiler. Under rotating conditions, spray 156mL of the prepared solution into the alumina support in the boiler in a mist manner. After rotating for 30min, let it stand for 18h, dry it at 110℃ for 3h, and then calcine it at 500℃ for 3h at a rate of 3℃ / min to obtain the coking dry gas hydrogenation catalyst.

[0046] Test Example 1

[0047] The catalysts prepared in the examples and control examples were tested for pore volume and specific surface area. The specific results are shown in Table 1.

[0048] Table 1 .

[0049] As shown in Table 1, compared to the control example, the catalysts in the examples have larger pore volumes and specific surface areas. This is likely because the core support provides more active sites, enabling the pore structure to act as a nanoreactor for the active metal, thereby improving metal dispersion. The macropore volume or micropore / cage structure of the core support enhances the subsequent alumina structure, resulting in varying degrees of improvement in both pore volume and specific surface area. Hyperbranched polyetheramine is grafted onto the macropore surface of the support, and polycaprolactone is then used for coating. After calcination, the hyperbranched polyetheramine forms a nitrogen-doped carbon layer to maintain metal dispersion, while the polycaprolactone forms a long-chain alkyl group that retains its hydrophobicity. Through molecular size control and dynamic coating, pore blockage is avoided, carbon deposition is prevented, and water resistance is improved.

[0050] Compared to Example 1, Example 3 has a larger pore volume and specific surface area. This is because MIL-101(Cr) has a cage-like structure with a large pore volume, which acts as a buffer space during calcination, better accommodating polycaprolactone decomposition products and reducing pore blockage. The high pore volume can better delay the aggregation of metal sulfides. In contrast, the microporous structure of ZIF-8 in Example 1 is more prone to collapse after calcination, but its skeleton can still maintain a high specific surface area. In Example 2, the large pore size of SBA-15 can resist sintering deformation and retain a large pore volume, but its wall thickness and specific surface area loss are relatively large.

[0051] Test Example 2

[0052] The catalysts prepared in the examples and comparative examples were used for the selective hydrogenation reaction of butadiene. During the reaction, water was injected into the catalyst bed by pump at a rate of 3 ml per 24 h. After 600 h of stable operation, the amount of coke was analyzed by a carbon-sulfur analyzer, and the yield of saturated alkanes after catalysis was calculated.

[0053] Table 2 .

[0054] In hydrogenation reactions, the water content of the feedstock and the water produced in the reaction can fluctuate, affecting the activity, stability, and smooth operation of the catalyst. At the same time, the polymerization and coking of unsaturated hydrocarbons on the catalyst surface can also damage its activity, lifespan, and the operation of the equipment.

[0055] As shown in Table 2, this invention loads active components W, Mo, Ni, and Co, along with organic additives, onto an alumina support for the coking dry gas hydrogenation catalyst. The additives ensure uniform dispersion of the active metal on the alumina support, while the organic additives weaken the metal-support interaction. The addition of organic additives increases the surface active groups of the catalyst, which is beneficial for anchoring the active metal and thus improving the dispersion of the active metal. The use of a four-component metal composition of W, Mo, Ni, and Co also enhances the catalyst activity. This invention addresses the limitations of high impurity content (oxygen, sulfur, CO, CO2, etc.) in coking dry gas, avoiding the influence of impurities on the reaction in conventional hydrogenation reactions, and the inherent limitation of low catalyst activity leading to concentrated, strongly exothermic hydrogenation of light hydrocarbons, which hinders deep hydrogenation. It solves the problem of poor activity in existing catalysts.

[0056] The catalysts in the examples exhibit higher activity and less carbon deposition compared to the control examples. This is because the core support is grafted with hyperbranched polyetheramine and then encapsulated with polycaprolactone to obtain the catalyst's organic promoter. The core support provides more active sites, and its pore structure can act as a nanoreactor for the active metal, thereby improving metal dispersion. The support can anchor the active metal through coordination or hydroxyl groups. The hyperbranched polyetheramine reacts with the acidic hydroxyl groups of the support, inhibiting olefin polymerization. After calcination, the hyperbranched polyetheramine forms a nitrogen-doped carbon layer, thus maintaining metal dispersion. The polycaprolactone forms long-chain alkyl groups while retaining hydrophobicity. The improved microporous structure of MIL-101 in Example 3 enhances selectivity, and the cage-like cavity accelerates product diffusion, thereby inhibiting secondary dehydrogenation, resulting in a significant increase in yield and reduced carbon deposition. The micropores in Example 1 only reduce excessive hydrogenation, while Example 2, due to its large pore size, has a slightly higher carbon deposition due to weaker barrier properties for colloidal molecules.

[0057] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning, or limited experimentation on the basis of existing technology should be within the scope of protection defined by the claims.

Claims

1. A catalyst for hydrogenating coking dry gas, characterized in that, Based on mass fraction, the content of WO3 is 1.0%~18.0%, the content of MoO3 is 1.0%~10.0%, the content of NiO is 0.5%~7.0%, the content of CoO is 0.1%~4.0%, the catalyst support for coking dry gas hydrogenation is 61%~94.1%, and the balance is organic additives for the catalyst.

2. The coking dry gas hydrogenation catalyst as described in claim 1, characterized in that, The preparation method of the catalyst organic auxiliary includes the following steps: ZIF-8 was dispersed in 5 times its mass of water, hyperbranched polyethyleneimine was added, the pH was adjusted to weakly alkaline after heating, and the mixture was stirred for 1-3 hours for grafting. Then, a toluene solution of polycaprolactone and the catalyst were added, and the mixture was heated and stirred for another 1-3 hours for coating. After centrifugation, washing, and drying, the catalyst organic auxiliary was obtained.

3. The coking dry gas hydrogenation catalyst as described in claim 2, characterized in that, The temperature range for the heating is 80~120℃.

4. The coking dry gas hydrogenation catalyst as described in claim 2, characterized in that, The mass ratio of ZIF-8 to hyperbranched polyethyleneimine and polycaprolactone is 1:0.7~0.8:1~2.

5. The coking dry gas hydrogenation catalyst as described in claim 2, characterized in that, The toluene solution of polycaprolactone is 40-50 wt%.

6. The coking dry gas hydrogenation catalyst as described in claim 1, characterized in that, The WO3 content is 6.0%~16.0%.

7. The coking dry gas hydrogenation catalyst as described in claim 1, characterized in that, The MoO3 content is 3.0%~8.0%.

8. The coking dry gas hydrogenation catalyst as described in claim 1, characterized in that, The NiO content is 2% to 6.0%.

9. The coking dry gas hydrogenation catalyst as described in claim 1, characterized in that, The CoO content is 0.5% to 3.0%.

10. A method for preparing a coking dry gas hydrogenation catalyst as described in any one of claims 1 to 9, characterized in that, Includes the following steps: By loading the active components W, Mo, Ni, and Co, along with organic catalyst additives, onto a hydrogenation catalyst support, a coking dry gas hydrogenation catalyst is obtained.