CN111659462B - Preparation method of high-activity isomerism pour point depressing catalyst - Google Patents
Preparation method of high-activity isomerism pour point depressing catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 163
- 230000000881 depressing effect Effects 0.000 title claims abstract description 23
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 90
- 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 90
- 239000002253 acid Substances 0.000 claims abstract description 61
- 238000001035 drying Methods 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 12
- 238000004898 kneading Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 16
- 239000002199 base oil Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- 208000010392 Bone Fractures Diseases 0.000 abstract description 2
- 206010017076 Fracture Diseases 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- -1 ZSM-22 Chemical compound 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical group [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a high-activity isomerism pour point depressing catalyst, belonging to the technical field of functional catalyst preparation. The preparation method comprises the steps of carrying out acid washing treatment on a strong acid molecular sieve, carrying out kneading, extruding, drying and roasting on the strong acid molecular sieve, the moderate acid molecular sieve and a binder to prepare a catalyst carrier, and then carrying one or two metals in an eighth main group on the catalyst carrier to prepare the bifunctional high-activity isomerism pour point depressing catalyst. The method improves the overall acidity of the catalyst by acid washing the strong acid molecular sieve, increases the primary fracture and isomerization reaction capacity of macromolecular chain hydrocarbon, improves the reaction activity, and can wash off impurity elements such as non-framework aluminum in the pore canal of the molecular sieve by acid washing and increase the pore volume of the active molecular sieve, so that the isomerization pour point depressing catalyst prepared by the method can obviously improve the reaction activity of the catalyst.
Description
Technical Field
The invention belongs to the technical field of preparation of functional catalyst materials, and particularly relates to a preparation method of a high-activity isomerism pour point depressing catalyst.
Background
The isomerization and pour point depressing catalyst is a double-function catalyst, and the active metal nano particles are dispersed on the carrier in the form of atom clusters to play a role in hydrogenation and dehydrogenation, and the acidity on the molecular sieve promotes the molecular chain of the oil product to have carbon-carbon rearrangement on the acid position of the catalyst, so that cracking and isomerization reactions occur.
US 4859311A, US 5149421a reports a preparation method of SAPO series molecular sieves, and shows better catalytic performance in hydroisomerization pour point depressing because the molecular sieves have proper acidity and one-dimensional decade microporous structure.
CN 100549142C describes the use of a small-grain, low acidity, high silica to alumina ratio, high crystallinity, secondary pore treated beta molecular sieve as a catalyst to produce a lubricant base oil product of good performance without a pour point depressing process.
CN 1762594a describes an alkane hydroisomerization catalyst, which is a composite molecular sieve catalyst formed by a ten-membered silicon-aluminum structure and a ten-membered cyclic silicon-aluminum phosphate structure, and because the adopted composite molecular sieve is mainly composited by molecular sieves such as ZSM-22, ZSM-23, SAPO-11, EU-1 and the like, the silicon-aluminum molecular sieve without medium strong acid breaks long branched chains, so that the highest conversion rate of the catalyst at 325 ℃ is only 84.40%, the base oil selection behavior is 71.13%, and the yield is 60.03%.
CN 108816279A reports an n-alkane isodewaxing catalyst which takes one or more of SAPO-11, ZSM-22, ZSM-23, SSZ-32, SSZ-48, ZSM-48, EU-1, NU-10 and other molecular sieves as a carrier and loads noble metals to prepare the n-alkane isodewaxing catalyst of the city. The selectivity of the catalyst to base oil at 318 ℃ reaches 79.2%, and the yield reaches 67.6%.
The above patents all have the problems of higher reaction temperature, lower selectivity and yield of the lubricating base oil.
Disclosure of Invention
The invention aims to provide a preparation method of a high-activity isomerism pour point depressing catalyst, which is mainly characterized in that a strong acid molecular sieve is subjected to acid washing treatment to enhance the primary chain breaking capacity of macromolecular straight-chain alkane and enhance the internal diffusion of the catalyst, so that the obtained catalyst is suitable for preparing lubricating oil base oil from heavy oil base oil raw materials.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a high-activity isomerism pour point depressing catalyst is prepared by kneading, extruding, drying and roasting a catalyst carrier prepared from a strong acid molecular sieve, a medium-weak acid molecular sieve and a binder, and then loading an eighth main group metal on the catalyst carrier; the preparation method comprises the following steps:
1) Slowly adding the strong acid molecular sieve into an acid solution at 60 ℃ and stirring for 2-4 hours, filtering, washing, drying in a baking oven at 120 ℃ for 12 hours, transferring to a muffle furnace at 500 ℃ and roasting for 2 hours, grinding, and sieving with a 200-mesh sieve to obtain a strong acid molecular sieve A subjected to acid washing treatment;
2) Kneading the acid-washed strong acid molecular sieve A, the acid medium weak molecular sieve B and the binder in a double-screw extruder for 30 minutes, adding nitric acid solution, kneading for 20 minutes, extruding into four-leaf grass with the grain diameter of 1.60-1.64 and mm, airing, drying in a 120 ℃ oven for 24 hours, and transferring to a 500 ℃ muffle furnace for roasting for 4 hours to prepare the catalyst carrier;
3) Drying the obtained catalyst carrier for 2 hours at 120 ℃, then placing the catalyst carrier into a drying dish for cooling to room temperature, then soaking the obtained catalyst carrier in an active metal salt solution for 2 hours by adopting an equal volume soaking method, thereby loading active metal on the catalyst carrier, and then airing the catalyst carrier, and drying the catalyst carrier in a 120 ℃ oven for 12 hours;
4) And (3) placing the dried catalyst into a step-heated muffle furnace, heating to 120 ℃ within 10 minutes at room temperature, roasting for 2 hours, heating to 220 ℃ within 10 minutes, roasting for 2 hours, heating to 500 ℃ within 30 minutes, roasting for 4 hours, and finally cooling to room temperature to obtain the high-activity isomerism pour point depressing catalyst.
The strong acid molecular sieve in the step 1) is a three-dimensional high silicon molecular sieve with a twelve-membered ring, and comprises one or more of a Y molecular sieve, a beta molecular sieve, MCM-41 and ZSM-5, and the specific surface area is 500-800 m 2 Per gram, pore volume is not less than 0.3. 0.3 cm 3 /g。
The acid solution in the step 1) is one or more of nitric acid, hydrochloric acid and acetic acid, and the concentration of the acid solution is 2 wt-10 wt%, preferably 3 wt-5 wt%.
The mass percentage ratio of the strong acid molecular sieve A, the acidic medium weak molecular sieve B and the binder which are subjected to acid washing treatment in the step 2) is (0.5-10) based on dry basis: (60-80): (15-35); the mass of the added nitric acid solution is 48% of the total mass of the acid-washed strong acid molecular sieve A, the acid-medium weak molecular sieve B and the binder dry basis, and the volume concentration of the nitric acid solution is 1-5%.
The molecular sieve B of the moderate acidic weak acid is one or more hydrogen type molecular sieves with one-dimensional ten-membered ring, and comprises SSZ-32, ZSM-22, ZSM-23, SAPO-11 and ZSM-48, and the specific surface area is 150-250 m 2 Per gram, pore volume is not less than 0.2. 0.2 cm 3 /g。
The binder is one or two of pseudo-boehmite, boehmite and amorphous silicon-aluminum.
The active metal in the step 3) is one or two of metals of an eighth main group, including Pt, pd, ru, rh, ir; the loading of the catalyst on the obtained catalyst is 0.2-wt% to 0.4-wt%.
The obtained isomerization pour point depressing catalyst can be used for preparing high-quality lubricating oil base oil through shape selective isomerization.
The invention has the remarkable advantages that:
(1) The acid washing treatment is carried out on the strong acid molecular sieve based on the conventional isomerism pour point depressing catalyst, so that the acidity of the catalyst is enhanced, the capability of once breaking long-chain hydrocarbon in the catalyst is improved, the internal diffusion of macromolecular hydrocarbon in the catalyst is accelerated, the reaction conversion rate is enhanced and the reaction activity of the catalyst is improved on the basis of the same selectivity.
(2) The acid-washed strong acid molecular sieve is utilized to bear the functions of primary fracture and shape selective isomerization of macromolecular chains, so that the macromolecular chains can be broken at a lower temperature, and part of straight-chain hydrocarbons can be shape selective isomerized into a multi-branched-chain hydrocarbon structure; the one-dimensional ten-membered ring molecular sieve with relatively weak acidity can be adopted to isomerize straight-chain alkane into a branched-chain hydrocarbon structure, so that the catalyst can be ensured to carry out isomerization and pour point depressing at a lower temperature, and the conversion rate of the reaction and the yield of the base oil are improved. Experiments prove that the yield of the base oil at 305 ℃ by using the catalyst can reach 85.2%, and the problem of lower yield of the existing catalyst product is remarkably improved.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Hydrothermal synthesis of ZSM-22 molecular sieves: silica, aluminum sulfate, potassium hydroxide, 1, 6-hexamethylenediamine (DAH) and deionized water in a mass ratio of 90:1:15:27:3600, heating and stirring to form sol, loading into a hydrothermal synthesis kettle, crystallizing at 160deg.C for 48 h, filtering, washing, calcining at 600deg.C in a muffle furnace for 6 hr, and removing template to obtain ZSM-22 molecular sieve with silica-alumina ratio of 45 and specific surface of 220cm 2 /g。
Example 1
1. Hydrothermally synthesizing a beta molecular sieve: weighing 190 g tetraethylammonium bromide (TEAOH) and dissolving in 500 ml water, then adding 0.56 g sodium hydroxide solution and 5.9 g sodium metaaluminate solution, and stirring strongly for 30 minutes to mix uniformly; pouring the mixed solution into a high-pressure reaction kettle, slowly adding 150 g silica sol, crystallizing at 140 ℃ for 72 hours, filtering, washing, and using 0.5mol/L NH 4 NO 3 Ammonia exchange (solid-to-liquid ratio is 30:1) is carried out on the solution, constant temperature exchange is carried out at 80 ℃ for 1 to H, after three times of exchange, drying and roasting are carried out at 550 ℃ to obtain the H beta molecular sieve, and the specific surface is 600 g/m 2 ；
2. Acid washing: putting the obtained H beta molecular sieve into 500 ml and 2 wt percent nitric acid solution, stirring for 4 hours, filtering, washing, baking for 12 hours in a baking oven at 120 ℃, transferring to a muffle furnace at 500 ℃ for baking for 2 hours, grinding the baked H beta molecular sieve, and sieving with a 200-mesh sieve to obtain the acid-washed molecular sieve with the specific surface of 617 m 2 /g；
3. Preparation of the catalyst: the H beta molecular sieve after acid washing in the step 2 and the prepared ZSM-22 molecular sieve, pseudo-boehmite are mixed according to the mass percentage ratio of 0.5:69.5:30 Mixing (based on dry basis), adding nitric acid solution (the volume concentration of the nitric acid solution is 2%) accounting for 48% of the total mass of the dry basis of the materials, kneading, extruding to obtain a four-leaf grass-shaped carrier with the particle size of 1.64 and mm, airing, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain the four-leaf grass-shaped catalyst carrier; drying the obtained catalyst carrier at 120 ℃ for 2 hours, cooling to room temperature, soaking the catalyst carrier for 2 hours by adopting 0.3 wt% chloroplatinic acid solution in an equal volume, taking out the catalyst carrier for airing, drying the catalyst carrier in a 120 ℃ oven for 12 hours, then placing the catalyst carrier in a step-heated muffle furnace, heating the catalyst carrier to 120 ℃ in 10 minutes at room temperature, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 220 ℃ in 10 minutes, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 500 ℃ in 30 minutes, roasting the catalyst carrier for 4 hours, and finally cooling the catalyst carrier to the room temperature to obtain the high-activity isomerism pour point catalyst, which is marked as a sample A.
Example 2
1. Hydrothermally synthesizing a beta molecular sieve: 190 g of TEAOH is weighed and dissolved in 500 ml water, then 0.56 g sodium hydroxide solution and 5.9 g sodium metaaluminate solution are added, and the mixture is stirred vigorously for 30 minutes to be mixed uniformly; pouring the mixed solution into a high-pressure reaction kettle, slowly adding 150 g silica sol, crystallizing at 140 ℃ for 72 hours, filtering, washing, and using 0.5mol/L NH 4 NO 3 Ammonia exchange (solid-to-liquid ratio is 30:1) is carried out on the solution, constant temperature exchange is carried out at 80 ℃ for 1 to H, after three times of exchange, drying and roasting are carried out at 550 ℃ to obtain the H beta molecular sieve, and the specific surface is 600 g/m 2 ；
2. Acid washing: putting the obtained H beta molecular sieve into 500 ml and 2 wt percent nitric acid solution, stirring for 4 hours, filtering, washing, baking for 12 hours in a baking oven at 120 ℃, transferring to a muffle furnace at 500 ℃ for baking for 2 hours, grinding the baked H beta molecular sieve, and sieving with a 200-mesh sieve to obtain the acid-washed molecular sieve with the specific surface of 617 m 2 /g。
3. Preparation of the catalyst: the H beta molecular sieve after acid washing in the step 2 and the prepared ZSM-22 molecular sieve, pseudo-boehmite are mixed according to the mass percentage ratio of 1:69:30 Mixing (based on dry basis), adding nitric acid solution (the volume concentration of the nitric acid solution is 2%) accounting for 48% of the total mass of the dry basis of the materials, kneading, extruding to obtain a four-leaf grass-shaped carrier with the particle size of 1.64 and mm, airing, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain the four-leaf grass-shaped catalyst carrier; drying the obtained catalyst carrier at 120 ℃ for 2 hours, cooling to room temperature, soaking the catalyst carrier for 2 hours by adopting 0.3 wt% chloroplatinic acid solution in an equal volume, taking out the catalyst carrier for airing, drying the catalyst carrier in a 120 ℃ oven for 12 hours, then placing the catalyst carrier in a step-heated muffle furnace, heating the catalyst carrier to 120 ℃ in 10 minutes at room temperature, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 220 ℃ in 10 minutes, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 500 ℃ in 30 minutes, roasting the catalyst carrier for 4 hours, and finally cooling the catalyst carrier to the room temperature to obtain the high-activity isomerism pour point catalyst, which is marked as a sample B.
Example 3
1. Hydrothermally synthesizing a beta molecular sieve: 190 g of TEAOH is weighed and dissolved in 500 ml water, then 0.56 g sodium hydroxide solution and 5.9 g sodium metaaluminate solution are added, and the mixture is stirred vigorously for 30 minutes to be mixed uniformly; pouring the mixed solution into a high-pressure reaction kettle, slowly adding 150 g silica sol, crystallizing at 140 ℃ for 72 hours, filtering, washing, and using 0.5mol/L NH 4 NO 3 Ammonia exchange (solid-to-liquid ratio is 30:1) is carried out on the solution, constant temperature exchange is carried out at 80 ℃ for 1 to H, after three times of exchange, drying and roasting are carried out at 550 ℃ to obtain the H beta molecular sieve, and the specific surface is 600 g/m 2 ；
2. Acid washing: putting the obtained H beta molecular sieve into 500 ml and 2 wt percent nitric acid solution, stirring for 4 hours, filtering, washing, baking for 12 hours in a baking oven at 120 ℃, transferring to a muffle furnace at 500 ℃ for baking for 2 hours, grinding the baked H beta molecular sieve, and sieving with a 200-mesh sieve to obtain the acid-washed molecular sieve with the specific surface of 617 m 2 /g。
3. Preparation of the catalyst: the H beta molecular sieve after acid washing in the step 2 and the prepared ZSM-22 molecular sieve are mixed according to the mass percentage ratio of 5:65:30 Mixing (based on dry basis), adding nitric acid solution (the volume concentration of the nitric acid solution is 2%) accounting for 48% of the total mass of the dry basis of the materials, kneading, extruding to obtain a four-leaf grass-shaped carrier with the particle size of 1.64 and mm, airing, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain the four-leaf grass-shaped catalyst carrier; drying the obtained catalyst carrier at 120 ℃ for 2 hours, cooling to room temperature, soaking the catalyst carrier for 2 hours by adopting 0.3 wt% chloroplatinic acid solution in an equal volume, taking out the catalyst carrier for airing, drying the catalyst carrier in a 120 ℃ oven for 12 hours, then placing the catalyst carrier in a step-heated muffle furnace, heating the catalyst carrier to 120 ℃ in 10 minutes at room temperature, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 220 ℃ in 10 minutes, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 500 ℃ in 30 minutes, roasting the catalyst carrier for 4 hours, and finally cooling the catalyst carrier to the room temperature to obtain the high-activity isomerism pour point catalyst, which is marked as a sample C.
Comparative example 1
The prepared ZSM-22 molecular sieve and pseudo-boehmite are mixed according to the mass percentage ratio of 70;30 Mixing (based on dry basis), adding nitric acid solution (the volume concentration of the nitric acid solution is 2%) accounting for 48% of the total mass of the dry basis of the materials, kneading, extruding to obtain a four-leaf grass-shaped carrier with the particle size of 1.64 and mm, airing, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain the four-leaf grass-shaped catalyst carrier; drying the obtained catalyst carrier at 120 ℃ for 2 hours, cooling to room temperature, soaking the catalyst carrier for 2 hours by adopting 0.3 wt% chloroplatinic acid solution in an equal volume, taking out the catalyst carrier for airing, drying the catalyst carrier in a 120 ℃ oven for 12 hours, then placing the catalyst carrier in a step-heated muffle furnace, heating the catalyst carrier to 120 ℃ in 10 minutes at room temperature, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 220 ℃ in 10 minutes, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 500 ℃ in 30 minutes, roasting the catalyst carrier for 4 hours, and finally cooling the catalyst carrier to the room temperature to obtain the isomerism pour point reducing catalyst, which is marked as a sample D.
Comparative example 2
1. Hydrothermally synthesizing a beta molecular sieve: weighing 190 g tetraethylammonium bromide (TEAOH) and dissolving in 500 ml water, then adding 0.56 g sodium hydroxide solution and 5.9 g sodium metaaluminate solution, and stirring strongly for 30 minutes to mix uniformly; pouring the mixed solution into a high-pressure reaction kettle, slowly adding 150 g silica sol, crystallizing at 140 ℃ for 72 hours, filtering, washing, and using 0.5mol/L NH 4 NO 3 Ammonia exchange (solid-to-liquid ratio is 30:1) is carried out on the solution, constant temperature exchange is carried out at 80 ℃ for 1 to H, after three times of exchange, drying and roasting are carried out at 550 ℃ to obtain the H beta molecular sieve, and the specific surface is 600 g/m 2 ；
2. Acid washing: putting the prepared ZSM-22 molecular sieve into 500 ml and 2 wt percent nitric acid solution, stirring for 4 hours, filtering, washing, baking for 12 hours in a baking oven at 120 ℃, transferring to a muffle furnace at 500 ℃ for baking for 2 hours, grinding the baked ZSM-22 molecular sieve, and sieving with a 200-mesh sieve to obtain the molecular sieve with the specific surface of 210 m after acid washing 2 /g；
3. Preparation of the catalyst: the H beta molecular sieve prepared in the step 1 and the ZSM-22 molecular sieve after pickling in the step 2 are mixed according to the mass percentage ratio of 1:69:30 Mixing (based on dry basis), adding nitric acid solution (the volume concentration of the nitric acid solution is 2%) accounting for 48% of the total mass of the dry basis of the materials, kneading, extruding to obtain a four-leaf grass-shaped carrier with the particle size of 1.60 multiplied by 1.64 mm, airing, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain the four-leaf grass-shaped catalyst carrier; drying the obtained catalyst carrier at 120 ℃ for 2 hours, cooling to room temperature, soaking the catalyst carrier for 2 hours by adopting 0.3 wt% chloroplatinic acid solution in an equal volume, taking out the catalyst carrier for airing, drying the catalyst carrier in a 120 ℃ oven for 12 hours, then placing the catalyst carrier in a step-heated muffle furnace, heating the catalyst carrier to 120 ℃ in 10 minutes at room temperature, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 220 ℃ in 10 minutes, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 500 ℃ in 30 minutes, roasting the catalyst carrier for 4 hours, and finally cooling the catalyst carrier to the room temperature to obtain the isomerism pour point reducing catalyst, which is marked as a sample E.
Comparative example 3
1. Hydrothermally synthesizing a beta molecular sieve: weighing 190 g tetraethylammonium bromide (TEAOH) and dissolving in 500 ml water, then adding 0.56 g sodium hydroxide solution and 5.9 g sodium metaaluminate solution, and stirring strongly for 30 minutes to mix uniformly; pouring the mixed solution into a high-pressure reaction kettle, slowly adding 150 g silica sol, crystallizing at 140 ℃ for 72 hours, filtering, washing, and using 0.5mol/L NH 4 NO 3 Ammonia exchange (solid-to-liquid ratio is 30:1) is carried out on the solution, constant temperature exchange is carried out at 80 ℃ for 1 to H, after three times of exchange, drying and roasting are carried out at 550 ℃ to obtain the H beta molecular sieve, and the specific surface is 600 g/m 2 ；
2. Acid washing: the prepared H beta molecular sieve and ZSM-22 molecular sieve are mixed according to the mass ratio of 1:69 are put into 500 ml and 2 wt percent nitric acid solution together, stirred for 4 hours, filtered, washed and baked in a baking oven at 120 ℃ for 12 hours, then are transferred into a muffle furnace at 500 ℃ for baking for 2 hours, and are ground and pass through a 200-mesh screen to obtain the H beta molecular sieve and ZSM-22 molecular sieve mixed molecular sieve, wherein the average value of the specific surface is 320 m 2 /g；
3. Preparation of the catalyst: and (2) mixing the mixed molecular sieve subjected to acid washing in the step (2) with pseudo-boehmite according to the mass percentage ratio of 70:30 Mixing (based on dry basis), adding nitric acid solution (the volume concentration of the nitric acid solution is 2%) accounting for 48% of the total mass of the dry basis of the materials, kneading, extruding to obtain a four-leaf grass-shaped carrier with the particle size of 1.60 multiplied by 1.64 mm, airing, drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain the four-leaf grass-shaped catalyst carrier; drying the obtained catalyst carrier at 120 ℃ for 2 hours, cooling to room temperature, soaking the catalyst carrier for 2 hours by adopting 0.3 wt% chloroplatinic acid solution in an equal volume, taking out the catalyst carrier for airing, drying the catalyst carrier in a 120 ℃ oven for 12 hours, then placing the catalyst carrier in a step-heated muffle furnace, heating the catalyst carrier to 120 ℃ in 10 minutes at room temperature, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 220 ℃ in 10 minutes, roasting the catalyst carrier for 2 hours, heating the catalyst carrier to 500 ℃ in 30 minutes, roasting the catalyst carrier for 4 hours, and finally cooling the catalyst carrier to the room temperature to obtain the isomerism pour point reducing catalyst, which is marked as a sample F.
Samples A-F of the catalysts prepared above were ground to 14-20 mesh for performance testing of the catalysts. The test method is that the hydrocracking tail oil is used as a raw material, and the catalyst filling mass is 25 ml on a fixed bed reactor. The catalyst is reduced in a reactor at 350 deg.c and 1.0-3.0 MPa for 3-12 hr; reaction conditions: the reaction temperature is 200-350 ℃, the pressure is 8-15 Mpa, and the volume space velocity is 0.5-2 h -1 The hydrogen oil molar ratio was 500-800, and the results are shown in tables 1 and 2.
The base oil yield is calculated as follows:
。
table 1 results of raw oil simulated distillation data
Table 2 catalyst evaluation results
As can be seen from tables 1 and 2, the catalyst (A-C) prepared by using the H beta molecular sieve after acid washing has higher activity and base oil yield because the catalyst acidity is more suitable for long linear alkane and can cause isomerization reaction at an active site. The catalyst (E) prepared by the H beta molecular sieve which is not pickled has higher components before 350 ℃, increases cracking reaction and reduces the yield of base oil. The catalyst (F) prepared by mixing and pickling the H beta molecular sieve and the ZSM-22 changes the acidity of the ZSM-22, and the yield of the base oil is reduced because the acid pickling reduces the isomerization reaction proportion of linear alkane although the reaction temperature is reduced and the activity is improved.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. The preparation method of the high-activity isomerism pour point depressing catalyst is characterized by comprising the following steps:
1) Slowly adding the strong acid molecular sieve into an acid solution at 60 ℃ and stirring for 2-4 hours, filtering, washing, drying at 120 ℃ for 12 hours, transferring to a muffle furnace at 500 ℃ for roasting for 2 hours, grinding, and sieving with a 200-mesh sieve to obtain a strong acid molecular sieve A subjected to acid washing treatment;
2) Kneading the acid-washed strong acid molecular sieve A, the acid medium weak molecular sieve B and the binder in a double-screw extruder for 30 minutes, adding nitric acid solution, kneading for 20 minutes, extruding into four-leaf grass with the grain diameter of 1.60-1.64 and mm, airing, drying at 120 ℃ for 24 hours, and then transferring to a muffle furnace at 500 ℃ for roasting for 4 hours to obtain a catalyst carrier;
3) Drying the obtained catalyst carrier at 120 ℃ for 2 hours, then placing the catalyst carrier into a drying dish for cooling to room temperature, loading active metal on the catalyst carrier by adopting an equal volume impregnation method, and then airing the catalyst carrier and drying the catalyst carrier at 120 ℃ for 12 hours;
4) Placing the dried catalyst into a step-heated muffle furnace, heating to 120 ℃ in 10 minutes at room temperature, roasting for 2 hours, heating to 220 ℃ in 10 minutes, roasting for 2 hours, heating to 500 ℃ in 30 minutes, roasting for 4 hours, and finally cooling to room temperature to obtain the high-activity isomerism pour point depressing catalyst;
the strong acid molecular sieve in the step 1) is a three-dimensional twelve-membered ring high silicon molecular sieve, and comprises a Y molecular sieveOne or more of beta molecular sieve, MCM-41, its specific surface area is 500-800 m 2 Per gram, pore volume is not less than 0.3. 0.3 cm 3 /g；
Step 2) the molecular sieve B of the acidic medium weak acid is one or more hydrogen type molecular sieves with one-dimensional ten-membered ring and comprises SSZ-32, ZSM-22, ZSM-23, SAPO-11 and ZSM-48, and the specific surface area is 150-250 m 2 Per gram, pore volume is not less than 0.2. 0.2 cm 3 /g；
The mass percentage ratio of the strong acid molecular sieve A, the acidic medium weak molecular sieve B and the binder which are subjected to acid washing treatment in the step 2) is (0.5-10) based on dry basis: (60-80): (15-35);
the active metal in the step 3) is one of metals in the eighth main group, including Pt, pd, ru, rh, ir; the loading of the catalyst on the obtained catalyst is 0.2-wt% to 0.4-wt%.
2. The method for preparing the high-activity isomerism pour point depressing catalyst according to claim 1, wherein the method is characterized in that: the acid solution in the step 1) is one or more of nitric acid, hydrochloric acid and acetic acid, and the concentration of the acid solution is 2 wt% -10 wt%.
3. The method for preparing the high-activity isomerism pour point depressing catalyst according to claim 1, wherein the method is characterized in that: the mass of the nitric acid solution added in the step 2) is 48% of the total mass of the acid-washed strong acid molecular sieve A, the acid medium weak molecular sieve B and the binder dry basis, and the volume concentration of the nitric acid solution is 1-5%.
4. The method for preparing the high-activity isomerism pour point depressing catalyst according to claim 1, wherein the method is characterized in that: the binder in the step 2) is one or two of pseudo-boehmite, boehmite and amorphous silicon-aluminum.
5. The method for preparing the high-activity isomerism pour point depressing catalyst according to claim 1, wherein the method is characterized in that: the impregnation time in step 3) was 2 hours.
6. A high activity heterogeneous pour point depressing catalyst made by the method of claim 1.
7. The use of the isomerisation pour point depressing catalyst according to claim 6 for the preparation of high quality lube base oils by shape selective isomerisation.
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