CN102188976A - Technical application of nickel catalyst in selective hydrogenation of cracked gasoline - Google Patents
Technical application of nickel catalyst in selective hydrogenation of cracked gasoline Download PDFInfo
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- CN102188976A CN102188976A CN2011100797960A CN201110079796A CN102188976A CN 102188976 A CN102188976 A CN 102188976A CN 2011100797960 A CN2011100797960 A CN 2011100797960A CN 201110079796 A CN201110079796 A CN 201110079796A CN 102188976 A CN102188976 A CN 102188976A
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Abstract
The invention discloses a curing nickel catalyst and an application thereof in selective hydrogenation of cracked gasoline. Based on the crystal lattice characteristics of hydrotalcite, a layered hydrotalcite precursor is synthesized on the surface of the inner holes of a carrier, and a high-dispersion Ni/Al2O3 catalyst is obtained by roasting at high temperature and reducing; the catalyst is provided with the metal nickel with higher hydrogenation activity, and the metal nickel is evenly loaded in a high-dispersion state on the carrier; when the catalyst is applied to hydrogenation reaction of cracked gasoline, the isoprene and alkylene arene components in the cracked gasoline are converted into monoolefine and alkyl aromatics; and the catalyst is suitable for the hydrogenation of C5-C9 hydrocarbon compound middle fraction and full fraction cracked gasoline, and has good activity and selectivity.
Description
Technical field
The invention belongs to catalyst preparation technical field, particularly a kind of vulcanization type nickel catalyst is applied to the drippolene selective hydrogenation.
Background technology
Drippolene is the important by-products of ethylene industry, and output is the 25-30% of ethylene production capacity approximately.Because of it is rich in aromatic hydrocarbons and high-octane alkene, so can also can only behind one-stage hydrogenation, obtain good gasoline mediation component as the important source of aromatic hydrocarbons extracting behind two-stage hydrogenation.Along with increasing substantially of China's ethylene yield, the quantity of drippolene is also in continuous increase.In order to effectively utilize valuable natural resources, adopt the selective hydrogenation technology to improve product property, improve the output of gasoline and aromatic hydrocarbons, significant to the economic benefit that improves ethylene unit.
Drippolene C from the cracker by-product
6-C
8Cut and C
5-C
9Recyclable benzene,toluene,xylene in the cut, most producers adopt one section Pd/Al
2O
3Catalyst, two sections Co-Mo/Al
2O
3Catalyst system carries out two sections selective hydrogenations, and last extracting goes out benzene, toluene and dimethylbenzene.Other has some producers to adopt Pd/Al
2O
3Catalyst carries out the selective hydrogenation of so-called full cut, to produce motor petrol.The purpose of drippolene selective hydrogenation just is to make wherein diolefin and alkyl alkenyl arene to generate corresponding monoolefine and alkylaromatic hydrocarbon by hydrogenation reaction.
Support type high dispersion metal catalyst is widely used in the catalytic reactions such as dehydrogenation, hydrogenation and reformation, is a most important class catalyst in petroleum refining and the petrochemical process.Metal supported catalyst is made of carrier and metallic compound cooperation usually, and carrier is made up of its skeleton and dentate.Load type metal catalyst also has load type metal compound catalyst, support type monometallic complex compound catalyst, load type metal bunch complex compound catalyst, load type double-metal complex compound catalyst etc. accordingly.Studies show that in recent years, load type metal catalyst have the advantage of inorganic matter heterogeneous catalysis and metal organic complex homogeneous catalyst concurrently, and it not only has characteristics such as higher activity and selectivity, and recycles and reuses good stability easily.
Traditional load type metal catalyst adopts immersion process for preparing, and it is that the porous carrier oxide be impregnated in the solution that contains metal active constituent, obtains catalyst sample through last handling process again after the drying.Use the immersion process for preparing catalyst, be subjected to the influence of dipping solution surface tension and solvation effect at drying stage, the metal active constituent presoma often is deposited on carrier surface with the form of aggregation, and roasting process subsequently is difficult to break this high concentration class; In addition, can not form strong interaction between dipping back reactive metal species and the carrier, high-temperature roasting causes metallic migration gathering easily and forms big metal grain.More than the generation of two kinds of phenomenons directly cause catalyst activity component bad dispersibility, and then have influence on the performance of catalyst and the repeatability of preparation.Therefore, at present people are being devoted to study other method and are preparing the high-dispersion loading type metallic catalyst.
In recent years, the method for preparing the high-dispersion loading type metallic catalyst both at home and abroad mainly contains ion-exchange, chemical grafting, ion beam implantation and chemical deposition etc.
Metal Ni has very high activity as active component to hydrogenation reaction, as the common preparation method of catalyst is to carry out co-precipitation or with its salt solution impregnation porous carrier, carry out roasting and reduction then and obtain catalyst sample with its esters and other metallic salt.But active component Ni is difficult for high degree of dispersion in the preparation process of these methods, and easily causes the coalescence of metal Ni crystallite in follow-up high-temperature process and reduction process, thereby further reduces the metal dispersity of catalyst surface, influences the catalytic activity of catalyst.
Hydrotalcite (LDHs) is the layered inorganic material that a class has special construction, and it is caused more and more that as Application of Catalyst people pay attention to.Result of study shows that divalence is close with the trivalent metal ion radius to be the necessary condition that forms LDHs, because of Ni
2+The radius of ion and Mg
2+Be more or less the same Ni
2+Ion can replace Mg
2+Preparation has the LDHs of rock-steady structure.If utilize the aluminium source of porous aluminium oxide bore area, the synthetic NiAlLDHs of original position can make Ni on the one hand in the hole
2+High degree of dispersion on the LDHs laminate is at the catalyst that can obtain the Ni high degree of dispersion after follow-up roasting and reduction processing; On the other hand, other metallic element of formation LDHs will be transformed into corresponding oxide and play co-catalyst and interleaving agent after high-temperature roasting is handled.
Summary of the invention
Solved by the inventionly be that the catalyst activity that uses in the drippolene selective hydrogenation is low, the problem of poor selectivity, decentralization difference, purpose is to provide a kind of vulcanization type nickel catalyst, is applied to the drippolene selective hydrogenation.
The preparation method of vulcanization type nickel catalyst of the present invention is: 1). at first utilize common houghite preparation methods-hydrothermal synthesis method in-situ preparing on carrier to go out layered di-hydroxyl composite metal oxidate, it is the houghite precursor, can pass through the modulation concentration of metal ions, prepare the different houghite precursor of load capacity; 2). after roasting, obtain the houghite catalyst precarsor; 3). liquid phase sulphurized catalyst precursor in Rotary Evaporators obtains the vulcanization type nickel catalyst.
Its concrete preparation process is as follows:
A, 3-10g is joined in the 100-1000ml mixing salt solution through 450-950 ℃ of roasting 4-6 hour aluminium oxide, dropwise add the dilute ammonia solution of 1-5wt% while stirring, regulator solution pH value is between 7-8; Place 50-90 ℃ water bath chader then, frequency of oscillation is 100-200 time/min, hydrothermal crystallizing 12-36 hour, promptly goes out houghite at the alumina surface growth in situ;
B, outwell supernatant liquid, aluminium oxide to the pH value that spends deionised water surface in situ growth houghite is 7-8, in vacuum drying chamber 50-180 ℃ dry 12-24 hour, through 450-600 ℃ of roasting 4-6 hour, obtain the houghite catalyst precarsor;
C, 3-8g is transferred in the Rotary Evaporators through 450-600 ℃ of roasting 4-6 hour houghite catalyst precarsor, vacuumizes 30-1200min earlier, add the vulcanizing agent of 10-50ml again through the alkane dilution, rotary evaporation in vacuo to the alkane volatilization fully;
D, repetition C step 1-5 time, drying promptly gets the vulcanization type nickel catalyst.
Described mixing salt solution is nickel nitrate and NH
4NO
3Mixed solution, nickel nitrate and NH
4NO
3The molar ratio scope be 1: 10-1: 3, nickel ion concentration is 0.05-0.35mol/l.
Described vulcanizing agent is meant liquid sulfur-containing compound, is specially in dimethyl sulfide, dimethyl disulfide, n-butyl mercaptan, the di-t-butyl thioether one or several; Alkane is specially toluene and/or normal heptane; The quality percentage composition of sulphur is 2.5-50% after the alkane dilution.
The vulcanization type nickel catalyst of above-mentioned preparation is applied to the drippolene selective hydrogenation, and the concrete operations step is:
A. the vulcanization type nickel catalyst is diluted with 60-80 order SiC, the mass ratio of vulcanization type nickel catalyst and SiC is 1: 2-2: 1, in hydrogen medium, reduce under 300-500 ℃ of temperature then, reduction pressure is 0.3-1.5MPa, recovery time is 1-4h, logical nitrogen cools to reaction temperature, uses for reaction;
B. drippolene selective hydrogenation process conditions: reaction temperature is 50-80 ℃, and reaction pressure is 1.5-3.0MPa, and the drippolene air speed is 3-5h
-1, hydrogen-oil ratio is (80-200): 1, and drippolene contacts with the vulcanization type nickel catalyst that step a reduces after handling, and selective hydrogenation takes place.
The present invention is by means of the properties of crystal lattice of hydrotalcite, at Al
2O
3The carrier bore area synthesizes stratiform houghite (LDHs) presoma NiAlLDHs/Al
2O
3, after high-temperature roasting and reduction, obtain the Ni/Al of high dispersive
2O
3Catalyst; The metallic nickel that has higher hydrogenation activity in this catalyst with the state uniform load of high dispersive on carrier, this catalyst is applied in the pyrolysis gasoline hydrogenation reaction, make diolefin and alkylene aromatic component in the drippolene change into monoolefine and alkylaromatic hydrocarbon, this catalyst is applicable to C
5-C
9Hydrocarbon compound midbarrel and full-cut fraction pyrolysis gasoline hydrogenation have good activity and selectivity.
Description of drawings
Fig. 1 is catalyst temperature programmed reduction figure, and a is preparation embodiment 1 gained vulcanization type nickel catalyst, and b is comparative example's gained catalyst, and c is preparation embodiment 3 gained vulcanization type nickel catalysts.
The specific embodiment
Preparation embodiment 1
A: take by weighing 8.72gNi (NO
3)
26H
2O and 14.55gNH
4NO
3Be dissolved in the 200mL deionized water, be made into mixing salt solution; And then take by weighing 6g through 6 hours alumina globule of 800 ℃ of roastings, join in the above-mentioned mixing salt solution; Dropwise add the dilute ammonia solution of 2wt% while stirring, regulator solution pH value is 7.25; Place 70 ℃ water bath chader then, frequency of oscillation is 140 times/min, and hydrothermal crystallizing 24 hours gets supernatant liquid and lower floor's light green color bead, promptly grows houghite at the alumina globule surface in situ;
B: detect supernatant liquid and contain unnecessary Ni hardly
2+Outwell supernatant liquid, spend deionised water lower floor light green color bead to neutral, be transferred to vacuum drying chamber, drying is 12 hours under 70 ℃, promptly gets the houghite catalyst precarsor in 4 hours through 500 ℃ of roastings;
C: 5g is transferred in the Rotary Evaporators through 4 hours houghite catalyst precarsor of 500 ℃ of roastings, vacuumize 40min earlier, add the dimethyl sulfide of 20mL through the normal heptane dilution then, wherein the quality percentage composition of sulphur is 10%, and rotary evaporation in vacuo is complete to the normal heptane volatilization;
D, repetition C step sulfidation 2 times, drying promptly gets the vulcanization type nickel catalyst.
Preparation embodiment 2
A: with example 1;
B: with example 1;
C: 5g is transferred in the Rotary Evaporators through 4 hours houghite catalyst precarsor of 500 ℃ of roastings, vacuumize 40min earlier, add the dimethyl disulfide of 20mL through the normal heptane dilution then, wherein the quality percentage composition of sulphur is 7.5%, and rotary evaporation in vacuo is complete to the normal heptane volatilization;
D: repeat C step sulfidation 2 times, drying promptly gets the vulcanization type nickel catalyst.
Preparation embodiment 3
A: take by weighing 4.65gNi (NO
3)
26H
2O and 7.76gNH
4NO
3Be dissolved in the deionized water, be made into mixing salt solution; And then take by weighing 6g through 5 hours alumina globule of 650 ℃ of roastings, join in the above-mentioned mixing salt solution; Dropwise add the dilute ammonia solution of preprepared 2wt% while stirring, regulator solution pH value is 7.25, and last liquor capacity keeps 200mL; Place 50 ℃ water bath chader then, maintain the temperature at 50 ℃, frequency of oscillation is 140 times/min, and hydrothermal crystallizing 24 hours gets supernatant liquid and lower floor's light green color bead, promptly grows houghite at the alumina globule surface in situ;
B: detect supernatant liquid and contain unnecessary Ni hardly
2+Outwell supernatant liquid, spend deionised water lower floor light green color bead to neutral, be transferred to vacuum drying chamber, drying is 12 hours under 70 ℃, promptly gets the houghite catalyst precarsor in 4 hours through 500 ℃ of roastings;
C: 5g is transferred in the Rotary Evaporators through 4 hours houghite catalyst precarsor of 500 ℃ of roastings, vacuumize 40min earlier, add the dimethyl disulfide of 20mL through the normal heptane dilution then, wherein the quality percentage composition of sulphur is 10%, and rotary evaporation in vacuo to normal heptane volatilizees fully;
D: repeat C step sulfidation 2 times, drying promptly gets the vulcanization type nickel catalyst.
Preparation embodiment 4
A: with example 3;
B: with example 3;
C: 5g is transferred in the Rotary Evaporators through 4 hours houghite catalyst precarsor of 500 ℃ of roastings, vacuumize 40min earlier, add the dimethyl disulfide of 20mL through the normal heptane dilution then, wherein the quality percentage composition of sulphur is 8.5%, and rotary evaporation in vacuo to normal heptane volatilizees fully;
D: repeat C step sulfidation 2 times, drying promptly gets the vulcanization type nickel catalyst.
The comparative example:
The tradition infusion process:
A: take by weighing 6g through 6 hours alumina globule of 800 ℃ of roastings, place 50ml, the Ni (NO of concentration 0.15mol/L
3)
2In the aqueous solution, under 70 ℃ temperature, till evaporation 30-60min is extremely substantially anhydrous; Temperature is increased to 90 ℃, continues evaporation 30min, so that moisture further removes; Evaporation back sample dry 24h in 70 ℃ of baking ovens obtained catalyst precarsor in 4 hours through 500 ℃ of roastings then;
B: the 5g catalyst precarsor is transferred in the Rotary Evaporators, vacuumizes 40min earlier, add the dimethyl disulfide of 20mL through the normal heptane dilution then, wherein the quality percentage composition of sulphur is 8.5%, and rotary evaporation in vacuo to normal heptane volatilizees fully;
C: repeat B step sulfidation 2 times, drying promptly gets sulfurized hydrogenation catalyst.
Application Example 1
Getting the present invention and prepare each 2g of catalyst that makes among embodiment 4 and the comparative example, weight 60-80 order SiC such as use to dilute, is 0.5MPa at Hydrogen Vapor Pressure, and temperature is that 500 ℃ and hydrogen flowing quantity are reduction two hours under the condition of 50ml/min; Logical nitrogen cools to reaction temperature, uses for reaction;
Drippolene selective hydrogenation process conditions: reaction temperature is 60 or 80 ℃, and Hydrogen Vapor Pressure is 2.5MPa, is the drippolene analogies with normal heptane and styrene mixture, and styrene-content is 4.7wt%, and drippolene analogies air speed is 3h
-1, hydrogen-oil ratio is 200: 1, the drippolene analogies contact with catalyst, react, and make diolefin and alkylene aromatic component in the drippolene analogies change into monoolefine and alkylaromatic hydrocarbon.Identical nickel content, under the identical situation of reaction time, hydrogenation result such as following table:
Application Example 2
Getting the present invention and prepare each 4g of catalyst that makes among embodiment 4 and the comparative example, weight 60-80 order SiC such as use to dilute, is 0.5MPa at Hydrogen Vapor Pressure, and temperature is that 500 ℃ and hydrogen flowing quantity are reduction two hours under the condition of 50ml/min; Logical nitrogen cools to reaction temperature, uses for reaction;
Drippolene selective hydrogenation process conditions: reaction temperature is 70 or 80 ℃, and Hydrogen Vapor Pressure is 2.5MPa, and drippolene analogies air speed is 3h
-1, hydrogen-oil ratio is 200: 1; The drippolene analogies are 50wt% normal heptane, 35wt% toluene, 10wt% styrene, 3.5wt%1-hexene and 1.5wt%1, the mixture of 7-octadiene; The drippolene analogies contact with catalyst, react, and make diolefin and alkylene aromatic component in the drippolene analogies change into monoolefine and alkylaromatic hydrocarbon.The hydrogenation result is as shown in the table, and wherein toluene does not have conversion ratio, and the ethylo benzene conversion ratio is 100%.
Application Example 3
Drippolene with Liaoyang petrochemical industry olefin plant is a raw material, and reaction pressure is that 2.8MPa, inlet temperature are that 40-110 ℃, raw material air speed are 3.5h
-1, hydrogen to oil volume ratio is 150, the vulcanization type nickel catalyst that preparation embodiment 4 is made has carried out the evaluation test of long period hydrogenation.Hydrogenated products diene value is all the time less than 2.0gI as a result
2/ 100g oil, product quality satisfy industrial requirement fully.Through the stability test of 1000h, this activity of such catalysts descends less, shows that this catalyst has higher activity, selectivity and stability.
The catalyst temperature programmed reduction is measured, and the result is as follows:
Fig. 1 is catalyst temperature programmed reduction figure, how the TP5000 of power instrument company production earlier measures with adsorbing on the instrument in Tianjin, a is preparation embodiment 1 gained vulcanization type nickel catalyst, and b is comparative example's gained catalyst, and c is preparation embodiment 3 gained vulcanization type nickel catalysts.As can be seen from Figure, the highest reduction temperature of curve a is 572 ℃, and the highest reduction temperature of curve b is 548 ℃, and the highest reduction temperature of curve c is 559 ℃.Maximum reduction temperature is high more shows the difficult more reduction of species, so the difficult reduction of the resulting catalyst of infusion process that the catalyst that the in-situ method that the embodiment of the invention is used makes comparison is used than embodiment.This is owing to interaction between atoms in the catalyst species of in-situ method preparation causes greatly.
Claims (5)
1. a vulcanization type nickel catalyst is characterized in that, its concrete preparation process is as follows:
A, 3-10g is joined in the 100-1000ml mixing salt solution through 450-950 ℃ of roasting 4-6 hour aluminium oxide, dropwise add the dilute ammonia solution of 1-5wt% while stirring, regulator solution pH value is between 7-8; Place 50-90 ℃ water bath chader then, frequency of oscillation is 100-200 time/min, hydrothermal crystallizing 12-36 hour, promptly goes out houghite at the alumina surface growth in situ;
B, outwell supernatant liquid, aluminium oxide to the pH value that spends deionised water surface in situ growth houghite is 7-8, in vacuum drying chamber 50-180 ℃ dry 12-24 hour, through 450-600 ℃ of roasting 4-6 hour, obtain the houghite catalyst precarsor;
C, 3-8g is transferred in the Rotary Evaporators through 450-600 ℃ of roasting 4-6 hour houghite catalyst precarsor, vacuumizes 30-1200min earlier, add the vulcanizing agent of 10-50ml again through the alkane dilution, rotary evaporation in vacuo to the alkane volatilization fully;
D, repetition C step 1-5 time, drying promptly gets the vulcanization type nickel catalyst.
2. a kind of vulcanization type nickel catalyst according to claim 1 is characterized in that described mixing salt solution is nickel nitrate and NH
4NO
3Mixed solution, nickel nitrate and NH
4NO
3The molar ratio scope be 1: 10-1: 3, nickel ion concentration is 0.05-0.35mol/l.
3. a kind of vulcanization type nickel catalyst according to claim 1 is characterized in that described vulcanizing agent is meant liquid sulfur-containing compound, is specially in dimethyl sulfide, dimethyl disulfide, n-butyl mercaptan, the di-t-butyl thioether one or several; Alkane is specially toluene and/or normal heptane; The quality percentage composition of sulphur is 2.5-50% after the alkane dilution.
4. a kind of vulcanization type nickel catalyst according to claim 1 is characterized in that, is applied to the drippolene selective hydrogenation.
5. a kind of vulcanization type nickel catalyst according to claim 4 is characterized in that, described drippolene selective hydrogenation concrete operations step is:
A. the vulcanization type nickel catalyst is diluted with 60-80 order SiC, the mass ratio of vulcanization type nickel catalyst and SiC is 1: 2-2: 1, in hydrogen medium, reduce under 300-500 ℃ of temperature then, reduction pressure is 0.3-1.5MPa, recovery time is 1-4h, logical nitrogen cools to reaction temperature, uses for reaction;
B. drippolene selective hydrogenation process conditions: reaction temperature is 50-80 ℃, and reaction pressure is 1.5-3.0MPa, and the drippolene air speed is 3-5h
-1, hydrogen-oil ratio is (80-200): 1, and drippolene contacts with the vulcanization type nickel catalyst that step a reduces after handling, and selective hydrogenation takes place.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698757A (en) * | 2012-05-31 | 2012-10-03 | 中国石油化工股份有限公司 | Cracking C9 hydrogenation catalyst and preparation method thereof |
| CN103223342A (en) * | 2013-05-22 | 2013-07-31 | 北京化工大学 | Preparation method and application of eggshell-type nickel-based catalyst |
| CN110237843A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of nickel catalyst and its preparation method and application |
| CN114433095A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
| CN114433092A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Pre-sulfurization method of hydrogenation catalyst, obtained pre-sulfurization hydrogenation catalyst and application |
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| CN101884924A (en) * | 2009-05-15 | 2010-11-17 | 中国石油天然气股份有限公司 | High-dispersion nickel catalyst and preparation method and application thereof |
| CN102029158A (en) * | 2010-10-13 | 2011-04-27 | 北京化工大学 | Sulfurizing type hydrogenation catalyst material and preparation method thereof |
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2011
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| US6540908B1 (en) * | 1999-04-08 | 2003-04-01 | Akzo Nobel N.V. | Process for sulfiding a hydrotreating catalyst comprising an organic compound comprising n and carbonyl |
| CN101884924A (en) * | 2009-05-15 | 2010-11-17 | 中国石油天然气股份有限公司 | High-dispersion nickel catalyst and preparation method and application thereof |
| CN102029158A (en) * | 2010-10-13 | 2011-04-27 | 北京化工大学 | Sulfurizing type hydrogenation catalyst material and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698757A (en) * | 2012-05-31 | 2012-10-03 | 中国石油化工股份有限公司 | Cracking C9 hydrogenation catalyst and preparation method thereof |
| CN103223342A (en) * | 2013-05-22 | 2013-07-31 | 北京化工大学 | Preparation method and application of eggshell-type nickel-based catalyst |
| CN110237843A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of nickel catalyst and its preparation method and application |
| CN114433095A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
| CN114433092A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Pre-sulfurization method of hydrogenation catalyst, obtained pre-sulfurization hydrogenation catalyst and application |
| CN114433092B (en) * | 2020-10-20 | 2024-01-30 | 中国石油化工股份有限公司 | Pre-sulfiding method of hydrogenation catalyst, obtained pre-sulfiding hydrogenation catalyst and application |
| CN114433095B (en) * | 2020-10-20 | 2024-05-03 | 中国石油化工股份有限公司 | Nickel catalyst and preparation method and application thereof |
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Application publication date: 20110921 |