CN101797512A - High-activity hydrocracking catalyst and preparation method thereof - Google Patents
High-activity hydrocracking catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 38
- 230000000694 effects Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 13
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 13
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- RJCRUVXAWQRZKQ-UHFFFAOYSA-N oxosilicon;silicon Chemical compound [Si].[Si]=O RJCRUVXAWQRZKQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 43
- 238000011156 evaluation Methods 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 16
- 230000008859 change Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- -1 phosphotungstic acid cesium salt Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
一种高活性加氢裂化催化剂及其制备方法，涉及一种多孔性固体催化剂及其制备方法。提供一种以正硅酸乙酯为氧化硅硅源，柠檬酸为络合剂的高活性加氢裂化催化剂及其制备方法。催化剂包括酸性组分、加氢组分及载体，酸性组分为磷钨酸铯盐，加氢组分为镍，载体为氧化硅；催化剂各组分按质量百分比含量为酸性组分10％～50％，加氢组分5％～10％，余量为载体。将按催化剂设定组分含量配制的水溶性镍盐、水溶性铯盐溶液分别加到络合剂水溶液中得溶液A；将按催化剂中氧化硅的设定含量计算所得的硅源加入到溶液A中得溶液B；将按催化剂的设定组分含量配制的杂多酸水溶液加入到溶液B中，蒸干溶液，干燥，将所得的固体焙烧，得催化剂。A high-activity hydrocracking catalyst and a preparation method thereof relate to a porous solid catalyst and a preparation method thereof. Provided is a highly active hydrocracking catalyst using ethyl orthosilicate as a silicon oxide silicon source and citric acid as a complexing agent and a preparation method thereof. The catalyst includes an acidic component, a hydrogenation component and a carrier. The acidic component is cesium phosphotungstate, the hydrogenation component is nickel, and the carrier is silicon oxide. The content of each component of the catalyst is 10% to 50%, 5% to 10% of the hydrogenation component, and the balance is the carrier. Add the water-soluble nickel salt and water-soluble cesium salt solutions prepared according to the set component content of the catalyst to the complexing agent aqueous solution to obtain solution A; add the silicon source calculated according to the set content of silicon oxide in the catalyst to the solution Solution B is obtained from A; the heteropolyacid aqueous solution prepared according to the set component content of the catalyst is added to the solution B, the solution is evaporated to dryness, dried, and the obtained solid is roasted to obtain the catalyst.
Description
Technical field
The present invention relates to a kind of porous solid catalyst and preparation method thereof, hydrocracking catalyst of especially a kind of long chain alkane and preparation method thereof.
Background technology
In petroleum refining industry, hydrocracking is the important process of being produced high-quality light-weight oil product by mink cell focus, is feedstock oil at high temperature, high pressure, faces a kind of conversion process of carrying out chemical reactions such as hydrogenation, desulfurization removing nitric, molecular skeleton rearrangement and cracking under the condition that hydrogen and catalyst exist.Hydrocracking process not only can be produced high grade light-end products, and liquid-phase product yield height.The core of hydrocracking technology is a catalyst, and hydrocracking catalyst is a kind of bifunctional catalyst, and it has acid function and hydrogenating function concurrently.U.S. Pat 5,536,687, US5,447,623 and European patent EP 0028938A1 in the acid function of involved hydrocracking catalyst mainly be to provide by molecular sieve, and hydrogenation component is selected Mo-Ni or W-Ni for use.And involved contain phosphorus heteropoly tungstic acid or silicotungstic heteropolyacid 20%～70%, hydrogenation component Ni, Co 5%～10%, the carrier of Chinese patent CN100450612C is that the catalyst of silica or aluminium oxide all has These characteristics.Contain molecular sieve hydrocracking catalyst and have acidity by force, the advantage that specific surface is big causes reactant and product diffusional resistance to increase but its shortcoming is a molecular sieve bore diameter for a short time, and the probability of second pyrolysis reaction increases.The hydrocracking catalyst that contains phosphotungstic acid has the acid strong and big advantage in aperture, but its shortcoming is the water-soluble height of phosphotungstic acid, more easily runs off in the use, and because it has highly acid, has increased the possibility of second pyrolysis reaction.
Summary of the invention
It is the silicon oxide silicon source with the ethyl orthosilicate that purpose of the present invention aims to provide a kind of, and citric acid is high-activity hydrocracking catalyst of complexing agent and preparation method thereof.
Described high-activity hydrocracking catalyst comprises acidic components, hydrogenation component and carrier, and acidic components are the phosphotungstic acid cesium salt, and hydrogenation component is a nickel, and carrier is a silica; Each component of catalyst content by mass percentage is acidic components 10%～50%, and hydrogenation component 5%～10%, surplus are carrier.
Cs and H in the composition of described phosphotungstic acid cesium salt
3PW
12O
40The mol ratio of (heteropoly acid) is 0.5～2.
The preparation method of described high-activity hydrocracking catalyst may further comprise the steps:
1) will be added to respectively in the complexing agent aqueous solution by water soluble nickel salt, the water-soluble cesiated salt solution that catalyst is set constituent content preparation, solution A;
2) will join in the step 1) solution A by the silicon source of the setting cubage gained of silica in the catalyst, solution B;
3) will join in the solution B by the heteropoly acid aqueous solution that the setting constituent content of catalyst is prepared, stir down with evaporate to dryness solution at 70～90 ℃, drying with the solid roasting of gained, gets high-activity hydrocracking catalyst.
In step 1), the temperature of described complexing agent aqueous solution can be 50～70 ℃, and the mol ratio of described complexing agent and nickel can be 1～3; Described water soluble nickel salt can be nickel nitrate or nickel acetate etc.; Described water-soluble cesium salt can be cesium carbonate or cesium nitrate etc.; Described complexing agent can be citric acid etc.
In step 2) in, described silicon source can be ethyl orthosilicate etc.
In step 3), the temperature of described drying can be 100～120 ℃, and the dry time can be 12～24h; The temperature of described roasting can be 300～500 ℃, and the time of roasting can be 3～6h; Described heteropoly acid can be phosphotungstic acid etc.
The evaluation of high-activity hydrocracking catalyst is as follows: in the reactor of under the room temperature normal pressure oxidation state hydrocracking catalyst being packed into, feed in the hydrogen exchange reactor and the air in the pipeline before and after the reactor, with reaction system progressively adherence pressure to the required pressure of hydrocracking reaction.The temperature that promotes beds behind the steady air current more gradually is to required catalyst reduction temperature, constant temperature 1～5h, bed temperature is adjusted to the required temperature of hydrocracking reaction, and hydrogen flowing quantity is adjusted to the required flow of hydrocracking reaction, progressively cut the reacted hydrocarbon raw material at last.
Above-mentioned hydrocracking reaction pressure, reaction temperature, hydrogen hydrocarbon volume ratio and hydrocarbon charging air speed are determined by the hydrocarbon feed character and the purpose product requirement of reaction.General reaction condition is: reaction pressure 1.0～10.0MPa, 270～400 ℃ of reaction temperatures, hydrogen hydrocarbon volume ratio 600～1800, liquid hydrocarbon feed volume space velocity 1.0～4.0h
-1Particularly sulfur content, purpose product requirement and hydrocracking reaction condition determine that reduction pressure is generally equal to hydrocracking reaction pressure to the reducing program of catalyst by the hydrocarbon feed character of reacting.In the ordinary course of things, the catalyst reduction temperature is 200～400 ℃, and the recovery time is 1～6h.Used reacted hydrocarbon raw material can be the employed various raw materials of common hydrocracking, comprise carbon atom number in the molecule greater than linear paraffin of 6 and composition thereof, and described linear paraffin and the other types organic matter mixture of organosulfur compound and organonitrogen compound particularly.
As acidic components, it forms simple with the phosphotungstic acid cesium salt in the present invention, and structure is determined, not only has the architectural feature of complex and metal oxide concurrently, presents acidity and oxidation-reduction quality, and its heat endurance is also higher, and is insoluble in water, is difficult for running off.In the Preparation of catalysts process, be the silica presoma, and the adding by the complexing agent citric acid, hydrogenation component can be disperseed better, help acidic components and hydrogenation component cooperates better with the ethyl orthosilicate.The catalyst method for making is easy, step is few, easy to implement.The catalytic performance that catalyst is applied to hydrocracking reaction is significantly higher than the catalyst of reference, and shows good sulphur-nitrogen resistant performance.
The specific embodiment
The present invention is further illustrated below by embodiment, and the used reacted hydrocarbon raw material of embodiment is the n-decane solution that contains 525ppm thiophene and 170ppm pyridine.
Hydrogenation cracking activity is represented by the conversion ratio of n-decane, and selectivity is designated as C by " the alkane molal quantity that contains 5 carbon atoms and 5 above carbon atoms in the product is divided by the product total mole number " expression
5 +Selectivity.This is because in general hydrocracking process, wishes more than pyrolysis product and the second pyrolysis product is few that when being the reacted hydrocarbon raw material with the n-decane, the alkane that contains 5 carbon atoms and 5 above carbon atoms in the product all is a pyrolysis product, so C
5 +Selectivity has characterized the relative quantity of a pyrolysis product in the product.
Embodiment 1: with 140ml concentration is 0.03molL
-1Cesium carbonate solution, 135ml concentration be 1molL
-1Nickel nitrate solution and 90ml concentration be 3molL
-1Citric acid solution be mixed with mixed solution, then add the 140ml ethyl orthosilicate, stir down 0.5h at 60 ℃, add the 50g phosphotungstic acid aqueous solution again, stir down with evaporate to dryness solution at 80 ℃, with gained solid oven dry 24h.With the oven dry after solids in muffle furnace with 2 ℃ of min
-1Speed rise to 400 ℃, constant temperature 4h makes 8%Ni-50%Cs
0.5H
2.5PW
12O
40/ SiO
2Catalyst, wherein the mol ratio of citric acid and nickel is 2.
Catalyst is packed in the reaction tube, feed hydrogen, volume space velocity is 1500h
-1, reaction system progressively adherence pressure to 2.0MPa, check air tight after, reaction system is warming up to 300 ℃, heating rate is 2 ℃ of min
-1, keep 1h, at stable hydrogen volume air speed 1500h
-1Following incision contains the n-decane liquid of 525ppm thiophene and 170ppm pyridine, and its mass space velocity is 2.92h
-1, begin collected specimens behind the reaction 1h, detect hydrogenation cracking activity and the selectivity of catalyst under reaction condition, the results are shown in Table 1.
Embodiment 2: in embodiment 1, change cesium carbonate solution into 280ml, ethyl orthosilicate changes 135ml into, and all the other are with embodiment 1, and the gained catalyst is 8%Ni-50%CsH
2PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 3: in embodiment 1, change cesium carbonate solution into 420ml, ethyl orthosilicate changes 130ml into, and all the other are with embodiment 1, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 4: in embodiment 1, change cesium carbonate solution into 560ml, ethyl orthosilicate changes 125ml into, and all the other are with embodiment 1, and the gained catalyst is 8%Ni-50%Cs
2HPW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 5: in embodiment 1, change cesium carbonate solution into 340ml, ethyl orthosilicate changes 175ml into, and phosphotungstic acid changes 40g into, and all the other are with embodiment 1, and the gained catalyst is 8%Ni-40%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 6: in embodiment 1, change cesium carbonate solution into 255ml, ethyl orthosilicate changes 215ml into, and phosphotungstic acid changes 30g into, and all the other are with embodiment 1, and the gained catalyst is 8%Ni-30%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 7: in embodiment 1, change cesium carbonate solution into 170ml, ethyl orthosilicate changes 255ml into, and phosphotungstic acid changes 20g into, and all the other are with embodiment 1, and the gained catalyst is 8%Ni-20%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 8: in embodiment 1, change cesium carbonate solution into 85ml, ethyl orthosilicate changes 300ml into, and phosphotungstic acid changes 10g into, and all the other are with embodiment 1, and the gained catalyst is 8%Ni-10%Cs
1.5H
1.5HPW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 9: in embodiment 3, change nickel nitrate solution into 85ml, ethyl orthosilicate changes 145ml into, and all the other are with embodiment 3, and the gained catalyst is 5%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 10: in embodiment 3, change nickel nitrate solution into 170ml, ethyl orthosilicate changes 120ml into, and all the other are with embodiment 3, and the gained catalyst is 10%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 11: in embodiment 3, change cesium carbonate solution into cesium nitrate solution, all the other are with embodiment 3, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 12: in embodiment 3, change nickel nitrate solution into nickel acetate solution, all the other are with embodiment 3, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 13: in embodiment 3, change sintering temperature into 350 ℃, all the other are with embodiment 3, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2-350.
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 14: in embodiment 3, change sintering temperature into 450 ℃, all the other are with embodiment 3, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2-450.
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 15: in embodiment 3, change citric acid solution into 45ml, all the other are with embodiment 3, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2, wherein the mol ratio of citric acid and nickel is 1.
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Embodiment 16: in embodiment 3, change citric acid solution into 135ml, all the other are with embodiment 3, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2, wherein the mol ratio of citric acid and nickel is 3.
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Comparative Examples 1: in embodiment 3, change cesium carbonate solution into 420ml, do not add citric acid solution, all the other are with embodiment 3, and the gained catalyst is 8%Ni-50%Cs
1.5H
1.5PW
12O
40/ SiO
2
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Comparative Examples 2: in embodiment 1, do not add cesium carbonate solution, all the other are with embodiment 1, and the gained catalyst is 8%Ni-50%H
3PW
12O
40/ SiO
2This catalyst does not contain the Cs element.
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.
Comparative Examples 3: the method preparation that catalyst is provided according to patent CN1393521, this catalyst contains molecular sieve.
The evaluation of catalyst is with embodiment 1, and the selectivity of conversion ratio and crackate the results are shown in Table 1.The result shows that its catalytic activity and sulphur-nitrogen resistant performance all are lower than catalyst provided by the invention.
The hydrogenation cracking activity of each routine catalyst of table 1. and selectivity
| Embodiment/Comparative Examples | N-decane conversion ratio (%) | ??C 5 +Selectivity (%) |
| Embodiment 1 | ??42.3 | ??82.5 |
| Embodiment 2 | ??61.4 | ??82.6 |
| Embodiment 3 | ??80.0 | ??83.4 |
| Embodiment 4 | ??71.3 | ??84.6 |
| Embodiment 5 | ??79.1 | ??84.6 |
| Embodiment 6 | ??77.2 | ??85.0 |
| Embodiment 7 | ??65.5 | ??86.5 |
| Embodiment 8 | ??48.3 | ??86.7 |
| Embodiment 9 | ??69.5 | ??78.7 |
| Embodiment 10 | ??75.5 | ??82.1 |
| Embodiment 11 | ??70.5 | ??78.1 |
| Embodiment/Comparative Examples | N-decane conversion ratio (%) | ??C 5 +Selectivity (%) |
| Embodiment 12 | ??74.6 | ??79.2 |
| Embodiment 13 | ??72.2 | ??82.1 |
| Embodiment 14 | ??67.0 | ??80.7 |
| Embodiment 15 | ??66.0 | ??81.2 |
| Embodiment 16 | ??68.4 | ??89.9 |
| Comparative Examples 1 | ??19.1 | ??76.1 |
| Comparative Examples 2 | ??37.3 | ??80.4 |
| Comparative Examples 3 | ??26.7 | ??78.9 |
Claims (10)
Priority Applications (1)
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| CN102335621A (en) * | 2011-07-15 | 2012-02-01 | 厦门大学 | Heteropolyacid-containing aromatics hydrogenation catalyst and preparation method thereof |
| CN102451721A (en) * | 2010-10-26 | 2012-05-16 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application and hydrogenation refining method |
| CN103100392A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103100423A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN104646043A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for preparing hydrocracking catalyst by sol-gel method |
| CN104646059A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Heteropolyacid cesium salt-containing hydrocracking catalyst, and preparation and application thereof |
| RU2603776C1 (en) * | 2015-11-05 | 2016-11-27 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Method of hydrocracking hydrocarbon material |
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| CN102451721B (en) * | 2010-10-26 | 2013-11-06 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof as well as hydrofining method |
| CN102335621A (en) * | 2011-07-15 | 2012-02-01 | 厦门大学 | Heteropolyacid-containing aromatics hydrogenation catalyst and preparation method thereof |
| CN103100392A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN103100392B (en) * | 2011-11-09 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| CN103861647B (en) * | 2012-12-10 | 2016-01-20 | 中国石油天然气股份有限公司 | Hydrocracking catalyst containing heteropoly acid and application thereof |
| KR101472498B1 (en) * | 2013-04-04 | 2014-12-15 | 고려대학교 산학협력단 | A method for preparing light oil from extra heavy oil using cesium substituted heteropolyacid catalyst and method for regenerating the catalyst |
| CN104646043A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for preparing hydrocracking catalyst by sol-gel method |
| CN104646059A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Heteropolyacid cesium salt-containing hydrocracking catalyst, and preparation and application thereof |
| RU2603776C1 (en) * | 2015-11-05 | 2016-11-27 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Method of hydrocracking hydrocarbon material |
| CN107297224A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN107297224B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN109926093A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN109926093B (en) * | 2017-12-15 | 2021-10-08 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN108067285A (en) * | 2017-12-22 | 2018-05-25 | 安徽工业大学 | A kind of preparation method and applications of solvent-free high activity loading type metalNicatalyst |
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