CN109395772A - A kind of isomerization catalyst and its preparation method and application - Google Patents
A kind of isomerization catalyst and its preparation method and application Download PDFInfo
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- CN109395772A CN109395772A CN201710710401.XA CN201710710401A CN109395772A CN 109395772 A CN109395772 A CN 109395772A CN 201710710401 A CN201710710401 A CN 201710710401A CN 109395772 A CN109395772 A CN 109395772A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002808 molecular sieve Substances 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000320 mechanical mixture Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 229910001593 boehmite Inorganic materials 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 nitrogenous compound Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of isomerization catalysts and its preparation method and application, wherein, the method for preparing the isomerization catalyst includes: that (1) mixes the active metal presoma of the raw material for being used to prepare SAPO-11 molecular sieve and isomerization catalyst, obtains mixture A；(2) spawn is made by mechanical mixture in the mixture A；(3) Crystallizing treatment is carried out to the spawn, the isomerization catalyst is made after the washing of crystallization product crystalline substance, dry, roasting.Solution process provided by the invention is simply time saving, without external adding water as blending agent, saves water resource and reduces sewage discharge, protect environment；Metal precursor is introduced into carrier synthetic system, realizes the one-step synthesis of catalyst, saves the drying during Metal Supported and roasting process, reduces energy consumption；Catalyst shows higher hexane conversion rate and isomer selective simultaneously.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of isomerization catalyst and its preparation method and application.
Background technique
Isomerization process is one of the ideal technology for producing high-knock rating gasoline, which is improving the same of octane number
When, any sulfur-bearing, nitrogenous compound are not introduced, and the content of gained gasoline olefin is lower, and stability is preferable, and develops isomery chemical industry
The key of skill is the research and development of high performance catalyst.Catalyst used by isomerization process is bifunctional catalyst,
It is made of the acid carrier of metal component and heterogeneous activity with hydrogenation/dehydrogenation function.Currently, the metal group of catalyst
The shortcomings that dividing is mostly noble metal, but it is expensive and easy poisoning and deactivation greatly limits its development, carries on the back herein
Under scape, base metal (such as nickel, tungsten, cobalt etc.) base isomerization catalyst causes the research interest of people.Carrier is as catalysis
Another important component of agent, property equally have an important influence the performance of catalyst.In numerous acidic molecular sieves
In material, SAPO-11 molecular sieve due to being used extensively with unique one-dimensional ten-ring cellular structure and mild Acidity
Make the carrier of isomerization catalyst.Up to now, the main conventional hydrothermal method of the preparation method of molecular sieve, dry gel method, microwave close
Cheng Fa, solvent-thermal method, ionic liquid synthetic method.Conventional hydrothermal method is due to having the characteristics that relative cost is low and easy amplification and wide
It is general to be applied to industrial circle.However this method generates largely containing the industrial wastewater of organic amine, brings greatly for waste water downstream processing
Burden.Although discharge of wastewater can be effectively reduced in xerogel synthetic method, this method is still needed to through aqueous solvent mixed raw material, and
It not only will increase energy consumption when heating solvent evaporated preparation dry glue, to water resources shortage area, the popularization of this method nevertheless suffers from pole
Big limitation.In addition, after obtaining acid carrier, how metal component is carried on carrier, the method being widely used at present has leaching
Stain method, ion-exchange and coprecipitation etc..Wherein, infusion process is used extensively because having the characteristics that process is simple and manageable
In industrial production, but when the non-precious metal catalyst of this method preparation, metal dispersity is lower, this can reduce isomerization catalyst
Hydrogenation/dehydrogenation performance, to influence its isomerization activity.Meanwhile in metallic solution impregnate after carrier also need through drying,
Roasting and etc., energy consumption is larger.Therefore, how high-performance, low cost be prepared by simple and easy, energy-saving and environment-friendly technique
Isomerization catalyst, be the key that push isomerization process development.
Summary of the invention
To solve the above problems, the purpose of the present invention is to provide a kind of preparation methods of isomerization catalyst.
It is a further object of the present invention to provide a kind of isomerization catalysts as made from the above method.
It is a further object of the present invention to provide a kind of application of above-mentioned isomerization catalyst in Isomerization of Hexane technique.
In order to achieve the above objectives, the present invention provides a kind of preparation method of isomerization catalyst, this method includes following
Step:
(1) the active metal presoma of the raw material for being used to prepare SAPO-11 molecular sieve and isomerization catalyst is mixed
It closes, obtains mixture A；The raw material includes boehmite, phosphoric acid, silica solution and organic amine；In the mixture A, intend thin
The dosage of diaspore is with Al2O3Meter, water and Al2O3Molar ratio be 2.9-8.7:1；
(2) by the mixture A by mechanical mixture at spawn is made；
(3) Crystallizing treatment is carried out to the spawn, is made described different after the washing of crystallization product crystalline substance, dry, roasting
Structure catalyst.
The method of the present invention is will directly to prepare raw material and the work of SAPO-11 molecular sieve under conditions of without aqueous solvent is added outside
Property metal precursor is mixed, and mixes by stirring (such as mechanical stirring) and spawn is made, and then carries out crystallization
Reaction, so that a kind of isomerization catalyst haveing excellent performance be made.Compared with conventional method, the isomery of the method for the present invention preparation
Change catalyst have it is higher activity and isomery hydrocarbon-selective, this may with formd under specific preparation condition high activity crystal phase with
And to improve active metal dispersion degree related.What the method for the present invention utilized is that (such as phosphoric acid, silica solution intend thin water to Molecular sieve raw material
Aluminium stone) included water and metal salt presoma the crystallization water, therefore, water and Al2O3Molar ratio (2.9-8.7:1) be much smaller than
The water content of customary preparation methods, after spawn is made, then it is same with AEL structure through crystallization, washing, calcination process preparation
When load the isomerization catalyst of active metal.
Method provided by the invention prepares gelatinous mass under conditions of additionally not adding aqueous medium, and synchronization will be before metal
Body is driven to be introduced into the synthetic system of molecular sieve；Moreover, with this condition, AEL structure molecular sieve has still successfully been made.This method is not
Only preparation process is simple, energy conservation and environmental protection, and prepared catalyst has isomerization performance outstanding.
In the preparation method of above-mentioned isomerization catalyst, it is preferable that in above-mentioned steps (1), in the mixture A,
Water and Al2O3Molar ratio be 3.5-7.5:1, preferably 4.8-5.2:1.
In the preparation method of above-mentioned isomerization catalyst, it is preferable that in above-mentioned steps (1), the use of boehmite
Amount is with Al2O3Meter, the dosage of phosphoric acid is with P2O5Meter, the dosage of active metal presoma is in terms of atomic state metal Re, the use of silica solution
Amount is with SiO2Meter, the molar ratio of each raw material are as follows:
Boehmite: phosphoric acid: silica solution: organic amine: Re=(0.8-1.0): 1.0:(0.2-0.8): (1.5-2.0):
(0.06-0.25)。
In the preparation method of above-mentioned isomerization catalyst, it is preferable that in above-mentioned steps (1), before the active metal
Drive the soluble compound and/or hydrolyzable compound that body is nickel element, preferably Nickelous nitrate hexahydrate.
In the preparation method of above-mentioned isomerization catalyst, it is preferable that in above-mentioned steps (1), the organic amine includes
Di-n-propylamine and/or di-n-butylamine；Preferably di-n-propylamine.
In the preparation method of above-mentioned isomerization catalyst, it is preferable that the item in above-mentioned steps (3), when Crystallizing treatment
Part are as follows: crystallization 18-36 hours at 180-200 DEG C.
In the preparation method of above-mentioned isomerization catalyst, it is preferable that in above-mentioned steps (3), washed to crystallization product
When, by weight, the dosage of deionized water is 5-15 times of crystallization product.
In the preparation method of above-mentioned isomerization catalyst, it is preferable that in above-mentioned steps (3), the condition of the drying
Are as follows: it is 4-12 hours dry at 80-120 DEG C.
In the preparation method of above-mentioned isomerization catalyst, it is preferable that in above-mentioned steps (3), the condition of the roasting
Are as follows: it is roasted 4-6 hours at 500-600 DEG C.
The present invention also provides a kind of isomerization catalysts prepared by the above method.
The present invention also provides a kind of application of above-mentioned isomerization catalyst in Isomerization of Hexane technique.
Raw material is mixed gelled crystallization predecessor using the method for mechanical mixture by scheme provided by the invention, using one
Isomerization catalyst is prepared in footwork, and the simple process is time saving, without external adding water as blending agent, saves water resource and subtracts
Few sewage discharge, protects environment；Metal precursor is introduced into carrier synthetic system, the one-step synthesis of catalyst is realized, saves gold
Belong to the drying in loading process and roasting process, reduces energy consumption, alleviating energy crisis；The catalyst of this method preparation simultaneously has
Excellent isomerization performance shows higher hexane conversion rate and isomer selective.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Raw material used in embodiment:
Boehmite, the production of Yantai Heng Hui Chemical Co., Ltd., Al2O3Content 70wt%；
Phosphoric acid, Xilong Chemical Co., Ltd's production, 85%, it analyzes pure；
Acidic silicasol, Qingdao northeast part of China Chemical Co., Ltd., SiO2Content 30%, H2O content about 70%；
Di-n-propylamine, Sinopharm Chemical Reagent Co., Ltd.'s production, is analyzed pure；
Nickelous nitrate hexahydrate, Sinopharm Chemical Reagent Co., Ltd.'s production, is analyzed pure.
Embodiment 1
A kind of isomerization catalyst is present embodiments provided, the preparation process of the catalyst is as follows:
(1) by boehmite, phosphoric acid, silica solution, organic amine (di-n-propylamine) and active metal presoma (six hydration nitre
Sour nickel) it is mixed by following molar ratio:
Boehmite is (with Al2O3Meter): phosphoric acid is (with P2O5Meter): silica solution is (with SiO2Meter): organic amine: before active metal
Drive body (Re, with metal atoms): water=0.8:1.0:0.4:1.9:0.125:4.8 obtains mixture A；
(2) said mixture A is formed into spawn (crystallization predecessor) by mechanical stirring；
(3) above-mentioned spawn is placed in high pressure crystallizing kettle, 200 DEG C obtain crystallization product in thermostatic crystallization 24 hours；
It is then 10 hours dry in 100 DEG C using the deionized water filtration washing crystallization product of 10 times of crystallization product quality, finally
The SAPO-11 isomerization catalyst that load has metal can be obtained for 6 hours in 500 DEG C of roastings.
After tested, which is 360 DEG C of temperature in reaction condition, pressure 2.0MPa, air speed 1h-1, hydrogen oil
Hexane conversion rate when than being 4.0 is up to 78.9%, isohexane selectively up to 84.5%, and isohexane yield is up to 66.7%.
Embodiment 2
A kind of isomerization catalyst is present embodiments provided, the preparation process of the catalyst is as follows:
(1) by boehmite, phosphoric acid, silica solution, organic amine (di-n-propylamine) and active metal presoma (six hydration nitre
Sour nickel) it is mixed by following molar ratio:
Boehmite is (with Al2O3Meter): phosphoric acid is (with P2O5Meter): silica solution is (with SiO2Meter): organic amine: before active metal
Drive body (Re, with metal atoms): water=0.9:1.0:0.4:1.8:0.25:5.6 obtains mixture A；
(2) said mixture A is formed into spawn (crystallization predecessor) by mechanical stirring；
(3) above-mentioned spawn is placed in high pressure crystallizing kettle, 200 DEG C obtain crystallization product in thermostatic crystallization 24 hours；
It is then 8 hours dry in 110 DEG C using the deionized water filtration washing crystallization product of 15 times of crystallization product quality, last 500
The SAPO-11 isomerization catalyst that load has metal can be obtained for 5 hours in DEG C roasting.
After tested, which is 340 DEG C of temperature in reaction condition, pressure 2.0MPa, air speed 1h-1, hydrogen oil
Hexane conversion rate when than being 4.0 is up to 71.2%, isohexane selectively up to 91.5%, and isohexane yield is up to 65.2%.
Embodiment 3
A kind of isomerization catalyst is present embodiments provided, the preparation process of the catalyst is as follows:
(1) by boehmite, phosphoric acid, silica solution, organic amine (di-n-propylamine) and active metal presoma (six hydration nitre
Sour nickel) it is mixed by following molar ratio:
Boehmite is (with Al2O3Meter): phosphoric acid is (with P2O5Meter): silica solution is (with SiO2Meter): organic amine: metal precursor
(Re, with metal atoms)=1.0:1.0:0.4:1.9:0.19:5.2, obtains mixture A；
(2) said mixture A is formed into spawn (crystallization predecessor) by mechanical stirring；
(3) above-mentioned spawn is placed in high pressure crystallizing kettle, 200 DEG C obtain crystallization product in thermostatic crystallization 24 hours；
It is then 6 hours dry in 120 DEG C using the deionized water filtration washing crystallization product of 15 times of crystallization product quality, last 500
The SAPO-11 isomerization catalyst that load has metal can be obtained for 6 hours in DEG C roasting.
After tested, which is 340 DEG C of temperature in reaction condition, pressure 2.0MPa, air speed 1h-1, hydrogen oil
Hexane conversion rate when than being 4.0 is up to 68.5%, isohexane selectively up to 93.6%, and isohexane yield is up to 64.1%.
Comparative example 1
This comparative example provides a kind of isomerization catalyst of conventional impregnation method preparation.Raw material used in this comparative example with
Embodiment 3 is identical, on the one hand difference be to have used external adding water (before crystallization in material, water and Al2O3Molar ratio be 80:1)；
On the other hand difference is first to prepare SAPO-11 catalyst, then infusion process nickel-loaded.
Using test condition same as Example 3, test result are as follows: hexane conversion rate is 59.2%, isohexane choosing
Selecting property is 67.4%, and isohexane yield is 39.9%.
By the above comparative experiments it is found that the catalyst of the method for the present invention preparation has a clear superiority.
Claims (10)
1. a kind of preparation method of isomerization catalyst, which is characterized in that method includes the following steps:
(1) the active metal presoma of the raw material for being used to prepare SAPO-11 molecular sieve and isomerization catalyst is mixed, is obtained
To mixture A；The raw material includes boehmite, phosphoric acid, silica solution and organic amine；In the mixture A, boehmite
Dosage with Al2O3Meter, water and Al2O3Molar ratio be 2.9-8.7:1；
(2) spawn is made by mechanical mixture in the mixture A；
(3) Crystallizing treatment is carried out to the spawn, the isomerization is made after the washing of crystallization product crystalline substance, dry, roasting
Catalyst.
2. the preparation method of isomerization catalyst according to claim 1, which is characterized in that in the mixture A, water with
Al2O3Molar ratio be 3.5-7.5:1, preferably 4.8-5.2:1.
3. the preparation method of isomerization catalyst according to claim 1, which is characterized in that in above-mentioned steps (1), intend
The dosage of boehmite is with Al2O3Meter, the dosage of phosphoric acid is with P2O5Meter, the dosage of active metal presoma is with atomic state metal Re
Meter, the dosage of silica solution is with SiO2Meter, the molar ratio of each raw material are as follows:
Boehmite: phosphoric acid: silica solution: organic amine: Re=(0.8-1.0): 1.0:(0.2-0.8): (1.5-2.0):
(0.06-0.25)。
4. the preparation method of isomerization catalyst according to claim 1, which is characterized in that in above-mentioned steps (1), institute
State the soluble compound and/or hydrolyzable compound that active metal presoma is nickel element, preferably Nickelous nitrate hexahydrate.
5. the preparation method of isomerization catalyst according to claim 1, which is characterized in that in above-mentioned steps (1), institute
Stating organic amine includes di-n-propylamine and/or di-n-butylamine；Preferably di-n-propylamine.
6. the preparation method of isomerization catalyst according to claim 1, which is characterized in that brilliant in above-mentioned steps (3)
Change condition when processing are as follows: crystallization 18-36 hours at 180-200 DEG C.
7. the preparation method of isomerization catalyst according to claim 1, which is characterized in that right in above-mentioned steps (3)
When crystallization product washs, by weight, the dosage of deionized water is 5-15 times of crystallization product；
Preferably, the condition of the drying are as follows: 4-12 hours dry at 80-120 DEG C.
8. the preparation method of isomerization catalyst according to claim 1, which is characterized in that in above-mentioned steps (3), institute
State the condition of roasting are as follows: roast 4-6 hours at 500-600 DEG C.
9. a kind of isomerization catalyst as made from claim 1-8 described in any item methods.
10. application of the isomerization catalyst as claimed in claim 9 in Isomerization of Hexane technique.
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| CN114939434A (en) * | 2022-06-01 | 2022-08-26 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexane |
| CN114956942A (en) * | 2022-06-01 | 2022-08-30 | 南京工业大学 | Process for catalyzing hydroisomerization of n-hexadecane |
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