CN100450612C - Heteropoly acid containing hydrocracking catalyst and its preparation method - Google Patents
Heteropoly acid containing hydrocracking catalyst and its preparation method Download PDFInfo
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- CN100450612C CN100450612C CNB2006101417578A CN200610141757A CN100450612C CN 100450612 C CN100450612 C CN 100450612C CN B2006101417578 A CNB2006101417578 A CN B2006101417578A CN 200610141757 A CN200610141757 A CN 200610141757A CN 100450612 C CN100450612 C CN 100450612C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 31
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 3
- 239000011147 inorganic material Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 15
- 239000001257 hydrogen Substances 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 30
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 21
- 230000008859 change Effects 0.000 description 10
- 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 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- -1 hydrogen hydrocarbon Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a hydrocracking catalyst which contains heteropoly acid, with large diameter and high activity. Wherein, it comprises heteropoly acid, hydrogen component and carrier; the carrier is porous thermal-resistant inorganic material; the heteropoly acid is H3PW12O40 .nH2O, H3PMo12O40 .nH2O, H4SiW12O40 .nH2O or H4SiMo12O40 ..nH2O; the hydrogen component is transition metal element; the heteropoly acid is 20-70%, the hydrogen component is 1-20% and the left is carrier. And the production comprises: selecting inorganic thermal-resistant particle carrier as catalyst carrier, preparing the metal salt water solution of hydrogen component, emerging said carrier, drying the separated solid, baking; preparing heteropoly acid water solution; drying and baking the solid.
Description
Technical field
The present invention relates to the hydrocracking catalyst and the preparation method of long chain alkane.
Background technology
In petroleum refining industry, hydrocracking is the important process process of being produced the high-quality light-weight oil product by mink cell focus, and its technological core is a catalyst system therefor.Hydrocracking catalyst is a kind of bifunctional catalyst, has acid function and hydrogenating function concurrently.The acid function of used typical hydrocracking catalyst mainly is to be provided by molecular sieve now, and hydrogenation component is selected Mo-Ni or W-Ni for use.For example U.S. Pat 5,536, and 687, US5,447,623 and US5,350,501; European patent EP 0028938A1; Chinese patent CN1389545A and CN2393521A all relate to hydrocracking catalyst and preparation method thereof.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, distributes for apparent reactivity and product and brings negative effect.
Summary of the invention
Purpose of the present invention is intended to cause reactant and product diffusional resistance to increase for a short time at the existing molecular sieve bore diameter that contains the molecular sieve hydrocracking catalyst existence, bring problems such as negative effect for the distribution of apparent reactivity and product, highly active hydrocracking catalyst in a kind of large aperture and preparation method thereof is provided.
The hydrocracking catalyst that contains heteropoly acid of the present invention consist of heteropoly acid, hydrogenation component and carrier.Described heteropoly acid is H
3PW
12O
40NH
2O, H
3PMo
12O
40NH
2O, H
4SiW
12O
40NH
2O or H
4SiMo
12O
40NH
2O, the particularly H of Keggin structure
3PW
12O
40NH
2O or H
3PMo
12O
40NH
2The heteropoly acid H that O heteropoly acid, especially heat endurance are high
3PW
12O
40NH
2O.Described hydrogenation component can be selected transition metals such as Ni, Co for use, preferred Ni.Carrier is heat-resisting inorganic material of porous such as SiO
2Or aluminium oxide, preferred SiO
2Each components contents of catalyst is a heteropoly acid 20%～70% by mass percentage, and is preferred 40%～60%, and hydrogenation component (in simple substance) is 1%～20%, preferred 5%～10%, and surplus is a carrier.
The preparation method of the hydrocracking catalyst that contains heteropoly acid of the present invention is as follows:
1) selects inorganic heat proof material particulate vector such as SiO by the catalytic component proportioning
2Or aluminium oxide is as catalyst carrier, according to the aqueous metal salt of the constituent content preparation hydrogenation component of catalyst, with this solution impregnating carrier 2～12h;
2) solids after the liquid-solid separation is dried 3～8h down at 80～150 ℃, again in 350～450 ℃ of following roasting 4～8h;
3) according to the constituent content preparation heteropoly acid aqueous solution of catalyst, by the prepared solids of step 2, leave standstill 2～12h with this solution impregnation; At 80～150 ℃ of following oven dry 3～8h, again through 350～450 ℃ of roasting 4～8h, last catalyst.
Catalyst carries out presulfurization before using, and its pre-vulcanization process is the CS with 5/95 (volume ratio)
2/ H
2As sulfiding gas, flow velocity 40～70mlmin
-1, vulcanize 3～8h down at 300～500 ℃.Then switch and feed hydrogen, reaction system progressively adherence pressure to the required pressure of hydrocracking reaction, promote the temperature of beds more gradually to the required temperature of hydrocracking reaction after hydrogen flowing quantity is stable, and hydrogen flowing quantity transferred to the required flow of hydrocracking reaction, progressively cut the reacted hydrocarbon raw material again after stable.
In the aforesaid operations process, hydrocracking reaction pressure, reaction temperature, hydrogen hydrocarbon volume ratio and hydrocarbon charging air speed are determined by hydrocarbon feed character, purpose product requirement and the catalyst performance of reaction.Be generally: reaction pressure 1.0～10.0MPa, 270～400 ℃ of reaction temperatures, hydrogen hydrocarbon volume ratio 600～1800, hydrocarbon feed volume air speed 1.0～4.0h
-1
The present invention selects for use composition comparatively simple, and structure is determined, not only has the architectural feature of complex and metal oxide concurrently, presents acidity and oxidation-reduction quality, and the also good heteropoly acid of its heat endurance is to provide acid function.Catalyst can be used for big molecule linear paraffin and contains for example hydrocracking and the hydroisomerizing reaction of various oil products of hydrocarbon mixture of big molecule linear paraffin.Its hydrogenation cracking activity is higher than the similar catalyst that contains molecular sieve.
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 of in hydrocracking process, wishes that pyrolysis product is many and the second pyrolysis product is few, and 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.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
1) preliminary treatment of carrier: with the carrier specific surface is 380m
2G
-1SiO
2Particle soaks 4h in dilute acid soln, be washed till neutrality with distilled water, and dry 5h under 80～120 ℃ is in 550 ℃ of roasting 4h.Final sizing 40～60 purpose SiO
2Standby.
2) Preparation of Catalyst: the carrier S iO that 80g is above-mentioned
2Placing 600ml concentration is 0.5molL
-1Nickel nitrate solution, leave standstill 12h, then in 120 ℃ of following oven dry 5h.With the oven dry after solids in muffle furnace with 10 ℃ of min
-1Speed rise to 400 ℃, constant temperature 5h.Baked catalyst soakage in the phosphotungstic acid aqueous solution that contains 86g, is left standstill behind the 10h at 100 ℃ of dry 5h down, then at 430 ℃ of following roasting 4h.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.
3) appreciation condition: with the catalyst of preparation at the CS of 5/95 (volume ratio)
2/ H
2As vulcanizing 4h in 300 ℃ under the sulfiding gas.After sulfuration finishes, cut into hydrogen, stablize laggard n-decane at hydrogen flow rate, reaction process condition sees Table 2.Hydrocracking conversion ratio and the product of evaluate catalysts under reaction condition distributes.The n-decane conversion ratio reaches 65.7%, crackate C
5+ selectivity reach 73.2%.(seeing Table 3)
Embodiment 2
In embodiment 1, with preparation process 2) in the 86g phosphotungstic acid to change the 37g phosphotungstic acid into be the cost example.The results are shown in Table 3.
Embodiment 3
In embodiment 1, with preparation process 2) in phosphotungstic acid content to change the 70g phosphotungstic acid into be the cost example.The results are shown in Table 3.
Embodiment 4
In embodiment 3, with preparation process 2) in load phosphotungstic acid after sintering temperature change 380 ℃ into, i.e. cost example.
Embodiment 5
In embodiment 1, with preparation process 2) in the 86g phosphotungstic acid change the 86g phosphomolybdic acid into, i.e. cost example.
Embodiment 6
In embodiment 1, with preparation process 2) in the 86g phosphotungstic acid change the 86g silico-tungstic acid into, i.e. cost example.
Embodiment 7
In embodiment 1, with preparation process 2) in the 86g phosphotungstic acid change the 86g silicomolybdic acid into, i.e. cost example.
Embodiment 8
In embodiment 1, with preparation process 2) in the 0.5molL of 600ml
-1Nickel nitrate solution change 300ml into, i.e. cost example.
Embodiment 9
In embodiment 1, with preparation process 2) in the 0.5molL of 600ml
-1Nickel nitrate solution change 600ml nickel oxalate solution, i.e. cost example into.
Embodiment 10
1) preliminary treatment of carrier: with the carrier specific surface is 300m
2G
-1Aluminium oxide standby behind 600 ℃ of roasting 4h.
2) Preparation of Catalyst: it is 0.5molL that the alumina catalyst support that 80g is above-mentioned places 600ml concentration
-1Nickel nitrate solution, leave standstill 3～12h, then in 120 ℃ of following oven dry 5h.With the oven dry after solids in muffle furnace with 10 ℃ of min
-1Speed rise to 400 ℃, constant temperature 5h.Baked catalyst soakage in containing the 86g phosphotungstic acid aqueous solution, is left standstill behind the 10h at 100 ℃ of dry 5h down, then at 440 ℃ of following roasting 4h.The chemical composition of institute's controlling catalyst, the heteropoly acid thing is listed in table 1 mutually.
3) appreciation condition: with the catalyst of preparation at the CS of 5/95 (volume ratio)
2/ H
2As vulcanizing 4h in 300 ℃ under the sulfiding gas.After sulfuration finishes, cut into hydrogen, stablize laggard n-decane at hydrogen flow rate.Estimating hydrocracking conversion ratio and the product of each catalyst under reaction condition distributes.(selectivity of gained conversion ratio and crackate sees Table 3)
Embodiment 11
In embodiment 1, with preparation process 2) in the 0.5molL of 600ml
-1Nickel nitrate solution change the cobalt nitrate solution of 600ml, i.e. cost example into.
Embodiment 12
In embodiment 10, with preparation process 2) in the 0.5molL of 600ml
-1Nickel nitrate solution change the cobalt nitrate solution of 600ml, i.e. cost example into.
Comparative example 1
The method preparation that this routine catalyst is provided according to patent CN1389545A.Raw materials used and the reaction process condition of evaluation of catalyst activity sees Table 2.Estimate the CS of catalyst system therefor in 5/95 (volume ratio)
2/ H
2As vulcanizing 4h in 300 ℃ under the sulfiding gas.After sulfuration finishes, cut into hydrogen, stablize laggard n-decane in hydrogen gas speed.Estimating hydrocracking conversion ratio and the product of each catalyst under reaction condition distributes.The result is a n-decane conversion ratio 31.7%, C
5+ selectivity 77.3%.
By the selectivity (seeing Table 3) of gained conversion ratio and crackate as can be seen: adopt institute of the present invention controlling catalyst under same reaction condition and close selective conditions, higher hydrogenation cracking activity to be arranged.
The physico-chemical property of each routine catalyst of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Heteropoly acid have a phase | The Keggin structure | The Keggin structure | The Keggin structure | The Keggin structure |
| Chemical composition | ||||
| Used heteropoly acid, Wt% | 60 | 30 | 50 | 50 |
| Used carrier, Wt% | 26 | 56 | 36 | 36 |
| Ni，Wt％ | 10 | 10 | 10 | 10 |
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Heteropoly acid have a phase | The Keggin structure | The Keggin structure | The Keggin structure | The Keggin structure |
| Chemical composition | ||||
| Used heteropoly acid, Wt% | 60 | 60 | 50 | 50 |
| Used carrier, Wt% | 26 | 26 | 36 | 43 |
| Ni，Wt％ | 10 | 10 | 10 | 5 |
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Heteropoly acid have a phase | The Keggin structure | The Keggin structure | The Keggin structure | The Keggin structure |
| Chemical composition | ||||
| Used heteropoly acid, Wt% | 60 | 60 | 50 | 50 |
| Used carrier, Wt% | 26 | 26 | 36 | 36 |
| Ni，Wt％ | 10 | 10 | 0 | 0 |
| Co，Wt％ | 0 | 0 | 10 | 10 |
Table 2. feedstock property and reaction process condition thereof
| Raw material | N-decane |
| Reaction pressure, MPa | 2.0 |
| WHSV，h -1 | 4.94 |
| Hydrogen to oil volume ratio | 1500 |
| Reaction temperature, ℃ | 300 |
| Curing temperature, ℃ | 300 |
The hydrogenation cracking activity of each routine catalyst of table 3. and selectivity
| Catalyst | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The n-decane conversion ratio, % | 65.7 | 42.7 | 60.3 | 57.9 | 63.7 |
| C 5+ selectivity, % | 73.2 | 79.5 | 77.7 | 76.1 | 72.3 |
| Catalyst | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| The n-decane conversion ratio, % | 52.4 | 50.7 | 47.5 | 58.9 | 66.7 |
| C 5+ selectivity, % | 72.8 | 76.3 | 77.7 | 69.1 | 75.3 |
| Catalyst | Embodiment 11 | Embodiment 12 | Comparative example 1 | ||
| The n-decane conversion ratio, % | 51.4 | 55.4 | 31.7 | ||
| C 5+ selectivity, % | 67.9 | 69.9 | 77.3 |
Claims (1)
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