CN102397796A - Steeping solution and method for preparing catalyst by adopting steeping solution - Google Patents

Steeping solution and method for preparing catalyst by adopting steeping solution Download PDF

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CN102397796A
CN102397796A CN2010102766695A CN201010276669A CN102397796A CN 102397796 A CN102397796 A CN 102397796A CN 2010102766695 A CN2010102766695 A CN 2010102766695A CN 201010276669 A CN201010276669 A CN 201010276669A CN 102397796 A CN102397796 A CN 102397796A
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maceration extract
acid
catalyst
concentration
extract according
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CN102397796B (en
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毛以朝
李明丰
辛靖
聂红
董建伟
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a steeping solution and a method for preparing a catalyst by adopting the steeping solution. The steeping solution contains a compound containing VIB family metals, an organic acid salt containing VIII family metals, inorganic acid and an organic additive, wherein the concentration of the organic additive in the steeping solution is 1-150 g/L; and counted by the compound, the concentration of the compound containing VIB family metals is 100-1,100 g/L, the concentration of the organic acid salt containing VIII family metals is 10-800 g/L, and the concentration of the inorganic acid is 1-100 g/L. When the steeping solution provided by the invention is used for preparing a hydrogenation catalyst, the performance of the hydrogenation catalyst is improved, and the hydrogenation catalytic activity of heavy aromatic hydrocarbon is remarkably raised particularly.

Description

A kind of maceration extract and adopt this maceration extract to prepare the method for catalyst
Technical field
The present invention relates to a kind of maceration extract and adopt this maceration extract to prepare the method for catalyst, particularly a kind of preparation hydrogenation catalyst is used maceration extract, and adopts this maceration extract to prepare the method for catalyst.
Background technology
Hydrogenation catalyst is a kind of catalyst of extensive use in the petroleum refining process, and it in use has high hydrogenation activity, and this high hydrogenation activity generally derives from the metal component with group vib and VIII family in the periodic table of elements.In order further to improve the hydrogenation activity of catalyst, generally achieve the goal through improving method for preparing catalyst.For example, improve of the dispersion of VIII family metal, thereby improve hydrogenation activity at carrier surface through adding organic complex.
For example; CN 1175481A discloses a kind of co-impregnated solution that is used to prepare hydrocracking catalyst; It consists of: 25-65g WO3/100ml solution, 3-20g NiO/100ml solution, wherein also contain a kind of organic acid or ammonium salt at least, and content is 0.5-15g/100ml solution.
In the maceration extract of preparation hydrogenation class catalyst, add organic acid or ammonium salt, favourable to the performance that improves and improve catalyst.But find that in application this type of catalyst is wherein the aromatic hydrogenation performance of hydrocracking catalyst particularly, still is apparent not enough like the high active of hydrogenation catalysis to heavy arene.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of new hydrogenation catalyst for preparing with maceration extract and adopt this maceration extract to prepare the method for catalyst on the basis of existing technology.
The invention provides a kind of preparation hydrogenation catalyst and use maceration extract; Contain the compound of group vib metal, the acylate that contains VIII family metal, inorganic acid and organic additive, wherein, the concentration of organic additive is 1-150g/L in the said maceration extract; In oxide; The compound concentrations that contains the group vib metal is 100-1100g/L, and the concentration that contains the acylate of VIII family metal is 10-800g/L, and the concentration of inorganic acid is 1-100g/L.
The present invention also provides a kind of hydrogenization catalyst preparation method, comprises catalyst carrier is contacted with maceration extract with the preparation hydrogenation catalyst, carries out drying afterwards, and wherein, it is aforementioned maceration extract provided by the invention that said preparation hydrogenation catalyst uses maceration extract.
Compared with prior art, when adopting maceration extract provided by the invention to prepare catalyst, can obviously improve the hydrogenation activity of catalyst, especially improve the high active of hydrogenation catalysis of catalyst towards heavy matter aromatic hydrocarbons.
The specific embodiment
According to maceration extract provided by the invention, wherein, the concentration of organic additive is 1-150g/L in the said maceration extract; Be preferably 5-100g/L, to change thing, the concentration that contains the group vib metallic compound is 100-1100g/L; Be preferably 300-800g/L, the concentration that contains the acylate of VIII family metal is 10-800g/L, is preferably 150-600/L; The concentration of inorganic acid is 1-100g/L, is preferably 8-70g/L.
According to maceration extract provided by the invention, wherein, said organic additive can be water miscible arbitrarily and can make the organic matter of aqueous solution surface tension reduction.The example of this type organic additive as: the alcohol and/or the weight average molecular weight that are selected from C1-C8 are the polyethylene glycol of 120-4000; Under the preferable case, said water-soluble organic additive is to be selected from the polyethylene glycol that methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerine, butanols, amylalcohol, hexanol, octanol, the pure and mild weight average molecular weight of methyl cyclohexane are 200-1000 one or more.In a special preferred implementation; Said organic additive is that weight average molecular weight is the polyethylene glycol of 300-500 and the mixture of glycerine, and the polyethylene glycol that further is preferably glycerine and weight average molecular weight and is 300-500 is with 1: 0.1-100, further be preferably 1: the mixture of the mol ratio of 1-10.
Said VIII family metal is selected from base metal wherein, for example can be in nickel, cobalt and the iron one or more, is preferably nickel.The acylate of the said VIII of containing family metal is selected from their water soluble salt.For example, said acylate is selected from one or more in formates, acetate, oxalate, citrate and the tartrate that contains VIII family metal.Said inorganic acid is selected from a kind of in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid or several.
Said group vib metal is preferably molybdenum and/or tungsten; Wherein, The described compound that contains the group vib metal is selected from one or more in their water soluble compound; For example, one or more in molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates and the metatungstate, one or more in the preferred ammonium molybdate, ammonium paramolybdate, ammonium metatungstate wherein.
According to maceration extract provided by the invention, under the condition that is enough to said each component is water-soluble and mixing, the present invention has no particular limits the preparation method of said maceration extract.
According to hydrogenization catalyst preparation method provided by the invention, wherein, the consumption of said maceration extract preferably satisfies every liter of said maceration extract dipping 900-3300 gram carrier and further preferably satisfies every liter of said maceration extract dipping 1000-1400 gram carrier.
Said carrier is selected from the various carriers that are suitable for preparing hydrogenation class catalyst.For example, said carrier can be aluminium oxide, silica gel, silica-alumina, molecular sieve and their mixture of moulding or not moulding.
According to said hydrogenization catalyst preparation method provided by the invention, the method for wherein said drying and condition are conventional method and condition, and under the preferable case, described drying condition is included in 50-200 ℃ and descended dry 1-48 hour.
Below through embodiment the present invention is described further.
Embodiment 1-6 explains dipping solution provided by the invention, the preparation of this maceration extract and adopt this maceration extract to prepare the method for hydrogenation catalyst.
Embodiment 1
(1) dipping solution and preparation thereof
117.6 gram basic nickel carbonates (are given birth to catalyst Co., Ltd available from Yixing City Shen, Jiangsu; NiO content is 51 weight %) and the citric acid (available from upright chemical industry Co., Ltd of Tianjin unit, analyzing pure) and 40g nitric acid (Beijing Chemical Plant the analyzes pure) mixing of 150 grams; To wherein adding 600ml water; Stirring is warming up to 95 ℃, and under this temperature constant temperature 1 hour, thereby make the citric acid nickel aqueous solution.Then; With 756 the gram ammonium metatungstate (available from Sichuan Zigong Hard Alloy Foundry company; Tungsten oxide content is 82 weight %) be added in the said citric acid nickel aqueous solution; The glycerine (Beijing Chemical Plant analyzes pure) and the water that add 4 grams afterwards again are settled to 1000ml, thereby make the dipping solution A1 of hydrogenation catalyst.
(2) preparation catalyst carrier
The LAY molecular sieve of getting contents on dry basis and be 450 grams is (available from catalyst Chang Ling branch company of China Petrochemical Corp.; Parameter be
Figure BSA00000262866600041
with brilliant bag) with contents on dry basis be that the 600 SB powder that restrain are (available from Sasol company; Water content is 25 weight %) mix; Extruded moulding is 1.6 millimeters cylinder bars; Carry out drying then, and 580 ℃ of following roastings 3 hours, thereby make molecular sieve carrier B1.
(3) preparation hydrogenation catalyst
Made among the dipping solution A1 of the hydrogenation catalyst that the molecular sieve carrier B 1 that makes in 200 grams steps (2) makes dipping 40 minutes in 150 milliliters step (1), and under 180 ℃, carried out drying 2 hours then, thereby make catalyst C1.
Embodiment 2
(1) dipping solution and preparation thereof
117.6 gram basic nickel carbonates (are given birth to catalyst Co., Ltd available from Yixing City Shen, Jiangsu; NiO content is 51 weight %) and the citric acid (available from upright chemical industry Co., Ltd of Tianjin unit, analyzing pure) and 5g sulfuric acid (Beijing Chemical Plant the analyzes pure) mixing of 150 grams; To wherein adding 600ml water; Stirring is warming up to 95 ℃, and under this temperature constant temperature 1 hour, thereby make the citric acid nickel aqueous solution.Then; With 756 the gram ammonium metatungstate (available from Sichuan Zigong Hard Alloy Foundry company; Tungsten oxide content is 82 weight %) be added in the said citric acid nickel aqueous solution, add the ethanol (Beijing Chemical Plant analyzes pure) of 99 grams afterwards again; And water is settled to 1000ml, thereby makes the dipping solution A2 of hydrogenation catalyst.
(2) preparation hydrogenation catalyst
Made among the dipping solution A2 of the hydrogenation catalyst that 200 gram embodiment carrier B 1 make dipping 120 minutes in 150 milliliters step (1), and under 120 ℃, carried out drying 2 hours then, thereby make catalyst C2.
Embodiment 3
(1) dipping solution and preparation thereof
138 gram basic nickel carbonates (are given birth to catalyst Co., Ltd available from Yixing City Shen, Jiangsu; NiO content is 51 weight %) and citric acid (available from upright chemical industry Co., Ltd of Tianjin unit, analyzing pure) mixing and the 20g phosphoric acid (Beijing Chemical Plant analyzes pure) of 170 grams; To wherein adding 600ml water; Stirring is warming up to 95 ℃, and under this temperature constant temperature 1 hour, thereby make the citric acid nickel aqueous solution.Then; With 488 the gram ammonium metatungstate (available from Sichuan Zigong Hard Alloy Foundry company; Tungsten oxide content is 82 weight %) be added in the said citric acid nickel aqueous solution, add the tert-butyl alcohol (Beijing Chemical Plant analyzes pure) of 15 grams afterwards again; And water is settled to 1000ml, thereby makes the dipping solution A3 of hydrogenation catalyst.
(2) preparation catalyst carrier
The LAY molecular sieve of getting contents on dry basis and be 450 grams is (available from catalyst Chang Ling branch company of China Petrochemical Corp.; Parameter be
Figure BSA00000262866600051
with brilliant bag) with contents on dry basis be that the 600 CL powder that restrain are (available from catalyst Chang Ling branch company; Water content is 22 weight %) mix; Extruded moulding is 1.8 millimeters cylinder bars; Carry out drying then, and 600 ℃ of following roastings 3 hours, thereby make molecular sieve carrier B3.
(3) preparation hydrogenation catalyst
Made among the dipping solution A3 of the hydrogenation catalyst that 200 gram embodiment carrier B 3 make dipping 120 minutes in 170 milliliters step (1), and under 120 ℃, carried out drying 2 hours then, thereby make catalyst C3.
Embodiment 4
(1) dipping solution and preparation thereof
78 gram basic nickel carbonates (are given birth to catalyst Co., Ltd available from Yixing City Shen, Jiangsu; NiO content is 51 weight %) and ethanedioic acid (Beijing Chemical Plant the analyzes pure) mixing and the 80g nitric acid (Beijing Chemical Plant analyzes pure) of 94 grams; To wherein adding 600ml water; Stirring is warming up to 95 ℃, and under this temperature constant temperature 1 hour, thereby make the ethanedioic acid nickel aqueous solution.Then; With 609 the gram ammonium metatungstate (available from Sichuan Zigong Hard Alloy Foundry company; Tungsten oxide content is 82 weight %) be added in the said ethanedioic acid nickel aqueous solution, add the ethylene glycol (, analyzing pure) of 20 grams afterwards again available from Tianjin chemical reagent Co., Ltd; And water is settled to 1000ml, thereby makes the dipping solution A4 of hydrogenation catalyst.
(2) preparation hydrogenation catalyst
Made among the dipping solution A3 of the hydrogenation catalyst that 200 gram embodiment 3 carrier B 3 make dipping 120 minutes in 170 milliliters step (1), and under 200 ℃, carried out drying 1 hour then, thereby make catalyst C4.
Embodiment 5
(1) dipping solution and preparation thereof
170 gram basic nickel carbonates (are given birth to catalyst Co., Ltd available from Yixing City Shen, Jiangsu; NiO content is 51 weight %) and formic acid (Beijing Chemical Plant the analyzes pure) mixing and the 20g phosphoric acid (Beijing Chemical Plant analyzes pure) of 241 grams; To wherein adding 600ml water; Stirring is warming up to 95 ℃, and under this temperature constant temperature 1 hour, thereby make the nickel formate aqueous solution.Then with 939 the gram ammonium metatungstate (available from Sichuan Zigong Hard Alloy Foundry company; Tungsten oxide content is 82 weight %) be added in the said lemon nickel formate aqueous solution; The weight average molecular weight that adds 20 grams afterwards again is that 800 polyethylene glycol are (available from Tianjin chemical reagent Co., Ltd; Analyze pure), and water is settled to 1000ml, thus make the dipping solution A5 of hydrogenation catalyst.
(2) preparation catalyst carrier
The LAY molecular sieve of getting contents on dry basis and be 450 grams is (available from catalyst Chang Ling branch company of China Petrochemical Corp.; Parameter be with brilliant bag) with contents on dry basis be that the 600 SD powder that restrain are (available from Shandong Aluminum Co., Ltd; Water content is 22 weight %) mix; Extruded moulding is 2.0 millimeters cylinder bars; Carry out drying then, and 500 ℃ of following roastings 6 hours, thereby make molecular sieve carrier B5.
(3) preparation hydrogenation catalyst
Made among the dipping solution A3 of the hydrogenation catalyst that 200 gram embodiment carrier B 5 make dipping 120 minutes in 120 milliliters step (1), and under 120 ℃, carried out drying 2 hours then, thereby make catalyst C3.
Embodiment 6
(1) dipping solution and preparation thereof
117.6 gram basic nickel carbonates (are given birth to catalyst Co., Ltd available from Yixing City Shen, Jiangsu; NiO content is 51 weight %) and the citric acid (available from upright chemical industry Co., Ltd of Tianjin unit, analyzing pure) and 15g phosphoric acid (Beijing Chemical Plant the analyzes pure) mixing of 150 grams; To wherein adding 600ml water; Stirring is warming up to 95 ℃, and under this temperature constant temperature 1 hour, thereby make the citric acid nickel aqueous solution.Then, the ammonium metatungstate (available from Sichuan Zigong Hard Alloy Foundry company, tungsten oxide content is 82 weight %) with 756 grams is added in the said citric acid nickel aqueous solution; The glycerine that adds 25 grams afterwards again is (available from the Beijing Chemical Plant; Analyze pure) and the mixture of polyethylene glycol (available from Tianjin chemical reagent Co., Ltd, weight average molecular weight is 300-500, analyzes pure) (mixing mol ratio is 1: 5); And water is settled to 1000ml, thereby makes the dipping solution A6 of hydrogenation catalyst.
(2) preparation hydrogenation catalyst
Made among the dipping solution A6 of the hydrogenation catalyst that 200 gram embodiment carrier B 1 make dipping 240 minutes in 150 milliliters step (1), and under 170 ℃, carried out drying 4 hours then, thereby make catalyst C6.
Comparative Examples 1
(1) dipping solution of preparation hydrogenation catalyst
With 413 the gram ammonium metatungstate (available from the Sichuan Zigong Hard Alloy Foundry; Tungsten oxide content is 82 weight %) and the nickel nitrate (available from Beijing Yili Fine Chemicals Co., Ltd., nickel oxide content is 25.4 weight %) of 164 grams add in the entry, stir and to be warming up to dissolving fully; (chemical industry Co., Ltd is found by unit available from Tianjin to the citric acid that wherein adds 10 grams; Analyze pure), and water is settled to 540ml, thus make the dipping solution DA1 of hydrogenation catalyst.
(2) preparation hydrogenation catalyst
Method according to embodiment 1 prepares catalyst carrier and hydrogenation catalyst, and different is to replace the dipping solution A1 of hydrogenation catalyst with the dipping solution DA1 of the hydrogenation catalyst that makes in the above-mentioned steps (1), thereby makes hydrogenation catalyst DC1.
Comparative Examples 2
Prepare the dipping solution and the hydrogenation catalyst of hydrogenation catalyst according to the method for Comparative Examples 1, different is citric acid wherein to be replaced to the glycerine (available from the Beijing Chemical Plant, analyzing pure) of 10 grams, thereby make hydrogenation catalyst DC2.
Hydrogenation catalyst performance is estimated
Hydrogenation catalyst C1 is broken into the particle that diameter is the 2-3 millimeter; In one 30 milliliters fixed bed reactors, load RN-32 catalyst (available from catalyst Chang Ling branch company of China Petrochemical Industry) earlier, the particle of the said catalyst C1 that in next 30 milliliters fixed bed reactors, packs into again.
Before reaction, under hydrogen atmosphere, down the catalyst bed of above-mentioned two fixed reactors was carried out presulfurization 25 hours with the kerosene of the carbon disulfide that contains 2 weight % at 360 ℃, (density is 0.8875g/ml to feed the heavy arene raw material then; Boiling range is 291-438 ℃, and boiling range is the ingredients constitute 95 weight % greater than 350 ℃, and S content is 1.9 weight %; N content is 305ppm) react; Reaction temperature is 355 ℃, and hydrogen partial pressure is 6.4 MPas, and liquid hourly space velocity rate (LHSV) is 1.0h -1, hydrogen-oil ratio (volume) is 700.
Under 350 ℃, the oil content that obtains through above-mentioned reaction is distilled; In the oil content with said acquisition<and 350 ℃ of cuts account in the said heavy arene raw material>and the percentage of 350 ℃ of cuts recently estimates the hydrocracking conversion ratio of said heavy arene; To through obtain after the said distillation>350 ℃ of cuts carry out the analysis of tail oil BMCI value, wherein, BMCI value employing document (woods generation ruler of great talent and bold vision volume; " petroleum refining engineering " the 3rd edition; Petroleum industry publishing house, 2007, the 74 pages) the middle definition of putting down in writing; And the BMCI value can characterize the high active of hydrogenation catalysis of hydrogenation catalyst to heavy arene indirectly, and the low more hydrogenation catalyst that shows of tail oil BMCI value is high more to the high active of hydrogenation catalysis of heavy arene.Hydrocracking conversion ratio that records (being conversion ratio) and BMCI value are as shown in table 1 below.
Adopt said hydrogenation catalyst C2-C6 and DC1-DC2 to replace said hydrogenation catalyst C1 to carry out above-mentioned experiment respectively, to estimate the performance of said hydrogenation catalyst.Conversion ratio that records respectively and BMCI value are as shown in table 1 below.
Table 1
Hydrogenation catalyst Conversion ratio (%) The BMCI value
DC1 46.4 13.3
DC2 47.1 13.1
C1 50.1 11.5
C2 50.3 11.4
C3 48.6 11.9
C4 50.2 11.3
C5 51.2 11.1
C6 54.2 10.6
Can know that by the data shown in the table 1 with respect to Comparative Examples 1 and 2, the hydrogenation catalyst of embodiment 1-6 preparation has the conversion ratio of obvious raising and the BMCI value of reduction to heavy arene.This shows that the hydrogenation catalyst that adopts the dipping solution of hydrogenation catalyst provided by the invention to make has the high active of hydrogenation catalysis of obvious raising to heavy arene.

Claims (14)

1. maceration extract; Contain the compound of group vib metal, the acylate that contains VIII family metal, inorganic acid and organic additive, wherein, the concentration of organic additive is 1-150g/L in the said maceration extract; In oxide; The compound concentrations that contains the group vib metal is 100-1100g/L, and the concentration that contains the acylate of VIII family metal is 10-800g/L, and the concentration of inorganic acid is 1-100g/L.
2. maceration extract according to claim 1; It is characterized in that; The concentration of said organic additive is 5-100g/L; The said compound concentrations that contains the group vib metal is 300-800g/L, and the concentration of the acylate of the said VIII of containing family metal is 150-600g/L, and the concentration of inorganic acid is 8-70g/L.
3. maceration extract according to claim 1 and 2 is characterized in that, said organic additive is selected from one or more in the alcohol of C1-C8 and/or the polyethylene glycol that weight average molecular weight is 120-4000.
4. maceration extract according to claim 3; It is characterized in that; The alcohol of said C1-C8 is selected from one or more in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerine, butanols, amylalcohol, hexanol, octanol, the methyl cyclohexanol, and it is among the 200-1000 one or more that said polyethylene glycol is selected from weight average molecular weight.
5. maceration extract according to claim 4 is characterized in that, said organic additive is selected from glycerine and weight average molecular weight is the mixture of the polyethylene glycol of 300-500.
6. maceration extract according to claim 5 is characterized in that, in the mixture of said glycerine and polyethylene glycol, the mol ratio of glycerine and polyethylene glycol is 1: 0.1-100.
7. maceration extract according to claim 6 is characterized in that, the mol ratio of said glycerine and polyethylene glycol is 1: 1-10.
8. maceration extract according to claim 1 is characterized in that, said VIII family metal is selected from one or more in nickel, cobalt and the iron, and the acylate of the said VIII of containing family metal is selected from one or more in their water soluble salt.
9. maceration extract according to claim 1 is characterized in that, said VIII family metal is a nickel, and said acylate is selected from one or more in formates, acetate, oxalate, citrate and the tartrate that contains VIII family metal.
10. maceration extract according to claim 1; It is characterized in that; Said group vib metal is molybdenum and/or tungsten, and the said compound that contains the group vib metal is selected from least a in molybdic acid, para-molybdic acid, molybdate, paramolybdate, wolframic acid, metatungstic acid, ethyl metatungstic acid, tungstates and the metatungstate.
11. maceration extract according to claim 1 is characterized in that, said inorganic acid is selected from a kind of in hydrochloric acid, nitric acid, sulfuric acid, the phosphoric acid or several.
12. a hydrogenization catalyst preparation method comprises catalyst carrier is contacted with maceration extract with the preparation hydrogenation catalyst, carries out drying afterwards, it is characterized in that said maceration extract is any described maceration extract among the claim 1-10.
13. method according to claim 12 is characterized in that, the consumption of said maceration extract satisfies every liter of said maceration extract dipping 900-3300 gram carrier.
14. method according to claim 12 is characterized in that, the consumption of said maceration extract satisfies every liter of said maceration extract dipping 1000-1400 gram carrier.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107486251A (en) * 2016-06-12 2017-12-19 中国石油化工股份有限公司 A kind of hydrogenation catalyst preparation method and hydrogenation catalyst obtained by this method

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CN1448488A (en) * 2002-04-04 2003-10-15 中国石油化工股份有限公司 Catalyst for hydrorefining petroleum waxes and its prep.
CN1854261A (en) * 2005-04-29 2006-11-01 中国石油化工股份有限公司 Hydrogenation cracking catalyst composition

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Publication number Priority date Publication date Assignee Title
US5215955A (en) * 1991-10-02 1993-06-01 Chevron Research And Technology Company Resid catalyst with high metals capacity
CN1393517A (en) * 2001-07-02 2003-01-29 中国石油化工股份有限公司 Process for preparing hydrocatalyst
CN1448488A (en) * 2002-04-04 2003-10-15 中国石油化工股份有限公司 Catalyst for hydrorefining petroleum waxes and its prep.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107486251A (en) * 2016-06-12 2017-12-19 中国石油化工股份有限公司 A kind of hydrogenation catalyst preparation method and hydrogenation catalyst obtained by this method
CN107486251B (en) * 2016-06-12 2019-12-27 中国石油化工股份有限公司 Preparation method of hydrogenation catalyst and hydrogenation catalyst prepared by same

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