CN114471675B - Modified ZSM-5 molecular sieve for hydrodewaxing and preparation method thereof - Google Patents
Modified ZSM-5 molecular sieve for hydrodewaxing and preparation method thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 79
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 76
- 238000001035 drying Methods 0.000 claims abstract description 46
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 239000007853 buffer solution Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000005336 cracking Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920013822 aminosilicone Polymers 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 7
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 238000011282 treatment Methods 0.000 claims description 50
- 238000005406 washing Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- 238000010335 hydrothermal treatment Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- HJZJUZPJFRJXLT-UHFFFAOYSA-N diazanium oxalate oxalic acid Chemical compound [NH4+].[NH4+].OC(=O)C(O)=O.[O-]C(=O)C([O-])=O HJZJUZPJFRJXLT-UHFFFAOYSA-N 0.000 claims description 11
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 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 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000005837 radical ions Chemical class 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000012065 filter cake Substances 0.000 description 94
- 238000000967 suction filtration Methods 0.000 description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- OBFQBDOLCADBTP-UHFFFAOYSA-N aminosilicon Chemical compound [Si]N OBFQBDOLCADBTP-UHFFFAOYSA-N 0.000 description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007323 disproportionation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000000329 molecular dynamics simulation Methods 0.000 description 2
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000001502 supplementing effect Effects 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G2400/04—Diesel oil
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a modified ZSM-5 molecular sieve for hydrodewaxing, a preparation method and application thereof. The method comprises the following steps: (1) desilicating a ZSM-5 molecular sieve; (2) dealuminating the material in the step (1); (3) Impregnating the material in the step (2) by adopting an acidic buffer solution; (4) And (3) carrying out drying and roasting on the material loaded amino silicone oil in the step (3) to obtain the modified ZSM-5 molecular sieve finally used for hydrodewaxing. The molecular sieve prepared by the method has large pore volume and low acid quantity, can effectively reduce side reactions such as cyclic hydrocarbon/isoparaffin cracking, linear alkane secondary cracking and the like in the hydrodewaxing process, and promotes the hydrogenation ring opening of polycyclic aromatic hydrocarbon.
Description
Technical Field
The invention relates to a modified ZSM-5 molecular sieve for hydrodewaxing and a preparation method thereof, in particular to a modified ZSM-5 molecular sieve which has large pore volume and low acid content, can effectively reduce side reactions such as cyclic hydrocarbon/isoparaffin cracking, linear alkane secondary cracking and the like in the hydrodewaxing process, and promotes the hydrogenation ring opening of polycyclic aromatic hydrocarbon, and a preparation method thereof.
Background
ZSM-5 is a molecular sieve with a three-dimensional framework structure, and the framework structure comprises two staggered and connected pore channels: (1) A straight pore canal orthogonal to the XY plane, the oval ten-membered ring forms an orifice, and the aperture is 0.58nm multiplied by 0.52nm; (2) The sinusoidal Z-shaped pore canal parallel to the XY plane has pore size of 0.53nm by 0.56nm. This pore structure feature imparts shape selective catalytic properties thereto. Therefore, the ZSM-5 molecular sieve has very wide application in the fields of toluene methanol alkylation, isomerization dewaxing, hydrodewaxing and the like. The toluene methanol alkylation reaction mainly utilizes the fact that the molecular dynamics diameter of the paraxylene is equivalent to that of a ZSM-5 molecular sieve pore canal, and the diffusion rate is faster than that of the ortho-xylene and the meta-xylene, so that the selectivity of the paraxylene is realized. The hydrodewaxing reaction utilizes the fact that the pore canal of most cyclic hydrocarbon and isoparaffin with molecular dynamics size larger than that of ZSM-5 molecular sieve can not enter the ZSM-5 molecular sieve to react, thereby realizing the selective cracking of chain hydrocarbon with poor low-temperature fluidity.
In order to improve the catalytic performance of ZSM-5 molecular sieves, a series of modification methods for ZSM-5 molecular sieves have been developed by the skilled artisan.
CN101259424B discloses a preparation method of a non-binder ZSM-5 zeolite catalyst for toluene shape-selective disproportionation, which is mainly prepared by a series of modification methods of shaping, template-free hydrothermal crystallization, acid pickling dealumination silicon-supplementing silicate chemical liquid deposition treatment and the like by taking ZSM-5 zeolite as a main active component. However, in the method, a large amount of non-framework aluminum is generated in the dealumination and silicon supplementing process to block the pore channels, and the subsequent liquid phase deposition treatment is added to further block the pore channels, so that the diffusion of reactants and products is affected.
CN101380591a discloses a preparation method of an alkali-treated modified ZSM-5 zeolite toluene disproportionation catalyst, which is to remove part of silicon on a framework by alkali, so that part of the framework is partially collapsed to generate part of mesopores. Then washing with organic acid, drying the catalyst, then carrying out chemical liquid phase deposition modification by using cyclohexane solution of tetraethoxysilane, drying and roasting to obtain the catalyst, wherein the obtained catalyst is particularly suitable for preparing benzene and paraxylene by toluene shape-selective disproportionation, and can obviously enhance toluene conversion rate.
The selectivity in toluene methanol disproportionation reaction can be improved through subsequent modification of the ZSM-5 molecular sieve, but when the catalyst is applied to hydrodewaxing reaction, the pore expansion effect can be achieved due to acid, alkali treatment and other modes, the pore expansion can possibly lead the beneficial components isoparaffin and/or monocyclic aromatic hydrocarbon in the diesel fraction to enter the pore passage, even the reaction is carried out, and the non-framework aluminum can block the pore passage to a certain extent, so that the diffusion of cracking products is prevented, the occurrence of secondary cracking reaction is caused, and the yield and quality of target products are reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modified ZSM-5 molecular sieve for hydrodewaxing and a preparation method thereof, wherein the molecular sieve prepared by the method has large pore volume and low acid quantity, can effectively reduce the side reactions such as cyclic hydrocarbon/isoparaffin cracking, linear alkane secondary cracking and the like in the hydrodewaxing process, and promotes the hydrogenation ring opening of polycyclic aromatic hydrocarbon, and the preparation method thereof.
A method for preparing a modified ZSM-5 molecular sieve for hydrodewaxing, comprising the following steps:
(1) Carrying out silicon dissolving treatment on the ZSM-5 molecular sieve;
(2) Dealuminating the material in the step (1);
(3) Impregnating the material in the step (2) by adopting an acidic buffer solution;
(4) And (3) carrying out drying and roasting on the material loaded amino silicone oil in the step (3) to obtain the modified ZSM-5 molecular sieve finally used for hydrodewaxing.
In the process of the present invention, the ZSM-5 molecular sieve in step (1) may be commercially available or may be prepared as follows
Prepared by the prior art. For example, the preparation method comprises the following steps: mixing a certain amount of sodium oxide, deionized water, sodium metaaluminate, silica gel, and template agent (TPA 2 O) mixing, wherein the molar ratio of each material is as follows: (25-300) SiO 2 ：1Al 2 O 3 ：TPA 2 O：（0.01~10）Na 2 O：（100~1100）H 2 O; transferring the mixed materials into a stainless steel crystallization kettle, and crystallizing at a certain temperature; after crystallization, washing the mixture product with deionized water until the pH value is 7-8; the resulting sample was dried at 110 ℃ and ground.
In the method of the invention, the desilication treatment in the step (1) can be one or more of NaOH, quaternary ammonium salt and NaOH under the protection of the quaternary ammonium salt.
In the process of the present invention, the desilication in step (1)The treatment adopts alkali treatment, and the alkali treatment process is as follows: ZSM-5 molecular sieve is placed in OH - Stirring in an alkali solution with the content of 0.1-1.0 mol/L for 0.5-2 h, wherein the liquid-solid volume ratio is (6-10) in terms of ml/g: 1, filtering after treatment, and repeating the process for 2-4 times; and then deionized water is used for washing for 1-5 times until the content of alkali metal ions is lower than 0.1wt%, and the ZSM-5 molecular sieve after alkali modification is obtained after drying. The alkali is one or more of NaOH, KOH and the like. The treatment temperature is 40-70 ℃. The water washing temperature is 40-70 ℃. The liquid-solid ratio of the treatment process is (8-12) 1 in ml/g, and the solid ratio of the water washing process is (Cheng Ye) 1 in ml/g.
In the method of the invention, the dealumination treatment in the step (2) adopts acid treatment, and the acid treatment process is as follows: ZSM-5 molecular sieve in H + Immersing in an acid solution with the content of 0.1-1.0 mol/L for 0.5-2 h, filtering after the treatment, and repeating the process for 2-4 times; and then deionized water is used for washing for 1-5 times until the content of acid radical ions is lower than 0.1wt%, and the ZSM-5 molecular sieve after acid treatment is obtained after drying. The acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and the like. The dipping treatment temperature is 40-70 ℃. The water washing temperature is 40-70 ℃. The liquid-solid ratio in the soaking treatment process is (8-12) in terms of ml/g: 1, the solid ratio of the water washed Cheng Ye is (8-12) in ml/g: 1.
in the method of the invention, the dealumination treatment in the step (2) adopts a hydrothermal treatment, and the hydrothermal treatment process is as follows: and carrying out hydrothermal treatment on the ZSM-5 molecular sieve for 0.5-5 hours under the condition of 400-700 ℃ under the water vapor pressure of 0.05-0.5 MPa, so as to obtain the ZSM-5 molecular sieve after the hydrothermal treatment.
In the embodiment of the invention, the ZSM-5 molecular sieve is subjected to desilication and dealumination by sequentially adopting alkali treatment, acid treatment and hydrothermal treatment, and the acidity and non-framework aluminum of the molecular sieve are modulated while reaming.
In the method of the present invention, the pH of the acidic buffer solution in the step (2) is 5.7 to 6.4, preferably 5.9 to 6.2, and the specific process is as follows: the treated molecular sieve is placed in a buffer solution for soaking treatment for 0.5 to 2 hours, the liquid-solid volume ratio is (8 to 12) in terms of ml/g, 1, the treatment temperature is 40 to 70 ℃, the filtration is carried out after the treatment, and the process is repeated for 2 to 4 times; and then directly drying or washing and drying to obtain the ZSM-5 molecular sieve treated by the acidic buffer solution.
In the method of the invention, the acidic buffer solution in the step (2) is any buffer solution with the pH meeting the requirement, and for the simplification of the subsequent treatment process, oxalic acid-ammonium oxalate buffer solution is adopted in the embodiment, and after the buffer solution containing components which are not easy to bake is selected for treatment, deionized water is used for washing for 2-3 times.
In the method of the present invention, the amino-silicone oil-loaded in the step (3) may be impregnated by an impregnation method, either by isovolumetric impregnation or by overdose impregnation, and preferably by isovolumetric impregnation.
In the method, the ammonia value of the amino silicone oil in the step (3) is 0.6-1.0. In the embodiment of the invention, the material prepared in the step (2) is immersed in the emulsion containing 0.02-0.10wt%, preferably 0.04-0.06 wt%, and the solvent is deionized water, and the immersing time is 5-10 h.
In the method, the drying temperature in the step (3) is 100-150 ℃ and the drying time is 2-4 hours; the roasting temperature is 550 ℃; the roasting time is 3-5 h.
The ZSM-5 molecular sieve prepared by the method has a specific surface area of 350-500 m 2 Preferably 400 to 450m 2 Per gram, pore volume of 0.38-0.50 cm 3 Preferably 0.40 to 0.45cm 3 Per gram, the total acid content is 1.6-2.7 mmol/g, preferably 2.0-2.5 mmol/g, the weak acid content is 0.8-1.4 mmol/g, preferably 1.0-1.2 mmol/g, the non-framework aluminum accounts for 6% -12%, preferably 8% -10%, and the loaded silicon oxide content is 0.02-0.07 wt%, preferably 0.04-0.06 wt%.
The ZSM-5 molecular sieve of the invention has a hydrogen-oil volume ratio of 500:1 and a volume space velocity of 10h under a reaction pressure of 6.0MPa -1 Under the condition of the reaction temperature of 340 ℃, the ring opening rate of the modified ZSM molecular sieve to decalin is as follows: 50% -70% and the secondary cracking rate of the n-hexadecane is 1% -6%.
According to the hydrodewaxing method, diesel raw materials react under the action of a hydrodewaxing catalyst, the hydrodewaxing catalyst contains the ZSM-5 molecular sieve prepared by the method, and the mass content of polycyclic aromatic hydrocarbon in raw oil is higher than 40%, preferably 55% -75%.
In the above hydrodewaxing method, the hydrodewaxing reaction conditions are as follows: the reaction pressure is 5.0-8.0MPa, the hydrogen-oil volume ratio is 400:1-600:1, the volume space velocity is 8-112h < -1 >, and the reaction temperature is 280-400 ℃.
Compared with the prior art, the invention provides the modified ZSM-5 molecular sieve, which generates framework collapse through reaming treatment to form a large number of secondary mesopores, adopts a buffer solution with weaker acidity to remove part of non-framework aluminum in pore channels, enables the molecular sieve to have a more smooth pore channel structure and simultaneously has a certain amount of weak acidic sites in the pore channels, adopts amino silicone oil to partially mask the outer surface and the acidity in the mesopores of the molecular sieve, enables the amino silicone oil to be more preferentially adsorbed in strong acid and medium strong acid centers due to the existence of alkalinity of the amino silicone oil, controls the use amount of the amino silicone oil, can keep the weak acid centers on the outer surface of the molecular sieve, enables polycyclic aromatic hydrocarbon which accounts for more than 40 weight percent of raw materials and is easy to adsorb to be hydrogenated and opened on the weak acidic sites in the mesopores and the outer surface so as to improve the quality of diesel oil, and single-ring hydrocarbon and isomeric chain hydrocarbon with higher condensation point and lower quality are difficult to enter the microporous pore channels of the ZSM-5 molecular sieve due to poorer adsorption capacity in the weak acid centers and are kept in products. Because the adsorption capacity of the normal alkane relative to aromatic hydrocarbon is weaker, the normal alkane does not take advantage of competitive adsorption outside the pore canal, thus entering the micropore canal to perform shape-selective cracking reaction to obtain a primary cracking product with reduced condensation point, the cracked normal alkane can diffuse out of the canal more rapidly, secondary cracking is reduced, and the diesel oil yield is improved.
Detailed Description
The operation and effect of the method of the present invention will be further described with reference to examples and comparative examples, but the following examples are not to be construed as limiting the method of the present invention, and the percentages in the examples and comparative examples are mass percentages unless otherwise specified.
In the embodiment of the invention, the specific surface area and the pore volume are measured by the following methods: pretreatment temperature using ASAP 2420 low temperature liquid nitrogen physical adsorption instrument manufactured by MICROMERITICS, usa: the pretreatment time is 4 hours at 300 ℃; acid contentThe amount and acid distribution were determined as follows: pretreating a sample by adopting a programmed temperature desorption method (NH 3-TPD) under the He gas flow of 500 ℃ for 1h, cooling to below 100 ℃ to adsorb 0.5% NH3/He to saturation, and removing physically adsorbed NH by purging with the He gas 3 Then, the temperature is programmed to 800 ℃ at the heating rate of 10 ℃/min to desorb the NH 3 And detecting by the thermal conductivity cell, and blowing the He gas until the end.
In the embodiment of the invention, the method for measuring the ring opening rate of decalin comprises the following steps: decahydronaphthalene is used as raw material, and the volume ratio of hydrogen to oil is 800:1 and the volume space velocity is 0.5h under the reaction pressure of 6.0MPa -1 The product ratio of ring opening under the condition of the reaction temperature of 350 ℃ is calculated as follows:
(1-molar amount of bicyclic aromatic hydrocarbon in the product/molar amount of decalin in the feedstock) ×100%;
the method for measuring the secondary cracking rate of the n-hexadecane comprises the following steps:
C1-C7 mass/raw material n-hexadecane mass x 100% in the product
The measurement conditions are that the reaction pressure is 6.0MPa, the hydrogen-oil volume ratio is 500:1, and the volume space velocity is 10h -1 The reaction temperature was 340 ℃.
The ZSM-5 of the examples and comparative examples of the present invention is commercially available, and the properties of the ZSM-5 are as follows: specific surface area: 200-250 m 2 /g, pore volume: 0.20-0.30 cm 3 /g。
Example 1
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 50 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.1mol/L and is filtered by suction; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 1000mL of 0.1mol/L and treated for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment for 2 hours at 400 ℃ and 0.1MPa, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 6.4, treating the filter cake for 1 hour at 50 ℃ and repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G1 molecular sieve. ZSM-5G1 was characterized and its properties are shown in Table 2.
Example 2
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 50 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.3mol/L and is filtered by suction; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 0.3mol/L and 1000mL for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment for 2 hours at 450 ℃ and 0.1MPa, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 6.3, treating the filter cake for 1 hour at 50 ℃ and repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.08G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G2 molecular sieve. ZSM-5G2 was characterized and its properties are shown in Table 2.
Example 3
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at the temperature of 60 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.3mol/L and is filtered by suction; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 0.5mol/L and 1000mL for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment for 2 hours at 500 ℃ and 0.1MPa, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 6.2, treating the filter cake for 1.5 hours at 50 ℃ and repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G3 molecular sieve. ZSM-5G3 was characterized and its properties are shown in Table 2.
Example 4
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at the temperature of 60 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.3mol/L and is filtered by suction; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 0.3mol/L and 1000mL for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment for 2 hours at 500 ℃ and 0.1MPa, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 6.1, treating the filter cake for 1.5 hours at 50 ℃ and repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G4 molecular sieve. ZSM-5G4 was characterized and its properties are shown in Table 2.
Example 4
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at the temperature of 60 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.3mol/L and is filtered by suction; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 0.3mol/L and 1000mL for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment for 2 hours at 500 ℃ and 0.1MPa, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 6.1, treating the filter cake for 1.5 hours at 50 ℃ and repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.05G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G4 molecular sieve. ZSM-5G4 was characterized and its properties are shown in Table 2.
Example 5
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at the temperature of 60 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.5mol/L and is filtered by suction; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 0.5mol/L and 1000mL for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 550 ℃ and 0.1MPa for 2 hours, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 6.0, treating the filter cake at 50 ℃ for 2.0 hours, repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.07G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G5 molecular sieve. ZSM-5G5 was characterized and its properties are shown in Table 2.
Example 6
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at the temperature of 60 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.7mol/L and is filtered by suction; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 1000mL of 0.7mol/L and treated for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 550 ℃ and 0.1MPa for 2 hours, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 5.9, treating the filter cake at 50 ℃ for 2.0 hours, repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.07G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G6 molecular sieve. ZSM-5G6 was characterized and its properties are shown in Table 2.
Example 7
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at 70 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 0.9mol/L and is repeated for two times, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 0.9mol/L and 1000mL for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment at 600 ℃ and 0.1MPa for 2 hours, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 5.8, treating the filter cake at 50 ℃ for 3.0 hours, repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.09G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G7 molecular sieve. ZSM-5G7 was characterized and its properties are shown in Table 2.
Example 8
According to the method provided by the invention, 100g of ZSM-5 raw powder is treated for 1h at the temperature of 80 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 1.0mol/L and is repeated for two times, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the filter cake is placed in NaOH solution with the concentration of 1.0mol/L and 1000mL for 1h at 50 ℃ and is repeated twice, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, carrying out hydrothermal treatment for 2 hours at 650 ℃ and 0.1MPa, taking out the filter cake, placing the filter cake in 1000mL of oxalic acid-ammonium oxalate buffer solution with pH value of 5.7, treating the filter cake at 50 ℃ for 5.0 hours, repeating the treatment twice, and carrying out suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; and (3) drying the filter cake at 120 ℃ for 6 hours, measuring 64mL of amino silicon oil-water solution with the concentration of 0.09G/L, soaking for 24 hours in an equal volume, drying at 120 ℃ for 6 hours, taking out, placing in a muffle furnace, programming to be heated to 550 ℃ and roasting for 3 hours to obtain the ZSM-5G8 molecular sieve. ZSM-5G8 was characterized and its properties are shown in Table 2.
Table 1 examples 2-8 molecular sieve treatment conditions
Table 2 results of characterization of molecular sieves of examples 1-8
Preparing a catalyst by using the molecular sieve of the examples 1-8, wherein the preparation process comprises the steps of kneading the molecular sieve with macroporous alumina and a binder, extruding strips, forming, drying and roasting to obtain a carrier; the carrier impregnated with the impregnation liquid of nickel nitrate is dried and roasted to obtain a catalyst; wherein the mass percentage of the molecular sieve is 30wt%, the mass percentage of the macroporous alumina is 50wt%, the mass percentage of NiO is 10wt%, and the rest is the binder. 10g of the catalyst is placed in a fixed bed reactor, and the volume ratio of hydrogen to oil is 500:1 at the reaction pressure of 6.0MPa, and the volume space velocity is 10h -1 The hydrodewaxing reaction is carried out at the reaction temperature of 340 ℃, the raw material properties are shown in table 3, and the product distribution and the product properties are shown in table 4.
TABLE 3 Properties of raw oil
TABLE 4 distribution and Properties of catalyst products prepared with the molecular sieves obtained in this scheme
Comparative example
According to the traditional molecular sieve modification method, 100g of ZSM-5 raw powder is treated for 1h at the temperature of 80 ℃ in a hydrochloric acid solution with the concentration of 1000mL of 1.0mol/L and is repeated for two times, and suction filtration is carried out; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; drying the filter cake at 120 ℃ for 6 hours, placing the filter cake in a hydrothermal treatment kettle, performing hydrothermal treatment at 500 ℃ and 0.1MPa for 2 hours, and performing suction filtration; washing the obtained filter cake in 1000mL of deionized water at 50 ℃ for three times, and carrying out suction filtration; the ZSM-5G molecular sieve is obtained as a cracking component, and is kneaded with macroporous alumina and a binder, extruded, molded, dried and roasted to obtain a carrier; the carrier impregnated with the impregnation liquid of nickel nitrate is dried and roasted to obtain a catalyst; wherein the ZSM-5G mass percent is 30wt%, the macroporous alumina mass percent is 50wt%, the NiO mass percent is 10wt%, and the balance is binder. 10g of the catalyst is placed in a fixed bed reactor, and the volume ratio of hydrogen to oil is 500:1 at the reaction pressure of 6.0MPa, and the volume space velocity is 10h -1 Under the condition of hydrodewaxing at the reaction temperature of 340 ℃. The catalyst performance was examined using a mixture of decalin and 1,3, 5-triisopropylbenzene and n-hexadecane as raw materials, respectively. The physicochemical properties of the molecular sieves and the cracking rates for the different raw materials are shown in Table 5.
TABLE 5 physicochemical and catalytic Properties of HZSM-5
Claims (17)
1. A preparation method of a modified ZSM-5 molecular sieve for hydrodewaxing is characterized by comprising the following steps: the method comprises the following steps:
(1) And (3) desilicating the ZSM-5 molecular sieve, wherein the desilication adopts alkali treatment, and the alkali treatment process is as follows: ZSM-5 molecular sieve is placed in OH - Stirring in an alkali solution with a content of 0.1-1.0 mol/L for 0.5-2 h, wherein the liquid-solid volume ratio is (6-1) in terms of mL/g2): 1, filtering after treatment, and repeating the process for 2-4 times; then deionized water is used for washing for 1-5 times until the content of alkali metal ions is lower than 0.1wt%, and the ZSM-5 molecular sieve after desilication treatment is obtained after drying;
(2) Carrying out dealumination treatment on the material in the step (1), wherein the dealumination treatment adopts acid treatment, and the acid treatment process is as follows: ZSM-5 molecular sieve in H + Immersing in an acid solution with the content of 0.1-1.0 mol/L for 0.5-2 h, filtering after the treatment, and repeating the process for 2-4 times; then deionized water is used for washing for 1-5 times until the content of acid radical ions is lower than 0.1wt%, and the ZSM-5 molecular sieve after dealumination treatment is obtained after drying; the acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and oxalic acid, the soaking treatment temperature is 40-70 ℃, the water washing temperature is 40-70 ℃, and the liquid-solid ratio in the soaking treatment process is (8-12) in terms of mL/g: 1, the solid ratio of the washed water to Cheng Ye is (8-12) in mL/g: 1, a step of; the dealumination treatment adopts hydrothermal treatment, and the hydrothermal treatment process is as follows: performing hydrothermal treatment on the ZSM-5 molecular sieve for 0.5-5 hours under the condition of 400-700 ℃ at the water vapor pressure of 0.05-0.5 MPa to obtain the ZSM-5 molecular sieve after the hydrothermal treatment;
(3) Dipping the material in the step (2) by adopting an acidic buffer solution, wherein the acidic buffer solution is oxalic acid-ammonium oxalate buffer solution; the pH value of the acidic buffer solution is 5.7-6.4, and the specific process is as follows: the treated molecular sieve is placed in a buffer solution for soaking treatment for 0.5 to 2 hours, the liquid-solid volume ratio is (8 to 12) 1 in terms of mL/g, the treatment temperature is 40 to 70 ℃, the filtration is carried out after the treatment, and the process is repeated for 2 to 4 times; then directly drying or washing and drying to obtain ZSM-5 molecular sieve treated by the acidic buffer solution;
(4) And (3) carrying out drying and roasting on the material loaded amino silicone oil in the step (3) to obtain the modified ZSM-5 molecular sieve finally used for hydrodewaxing, wherein the amino silicone oil loaded is subjected to an impregnation method, and the ammonia value of the amino silicone oil is 0.6-1.0.
2. The method according to claim 1, characterized in that: the ZSM-5 molecular sieve in step (1) is commercially available or prepared according to the prior art.
3. The method according to claim 1, characterized in that: the preparation method of the ZSM-5 molecular sieve comprises the following steps: mixing sodium oxide, deionized water, sodium metaaluminate, silica gel and a template agent, wherein the template agent is TPA 2 O, the mole ratio of each material is as follows: (25-300) SiO 2 ：1Al 2 O 3 ：TPA 2 O：（0.01~10）Na 2 O：（100~1100）H 2 O, wherein aluminum is in the form of alumina and silicon is in the form of silica; transferring the mixed materials into a stainless steel crystallization kettle, and crystallizing at a certain temperature; after crystallization, washing the mixture product with deionized water until the pH value is 7-8; the resulting sample was dried at 110 ℃ and ground.
4. The method according to claim 1, characterized in that: and (3) the desilication treatment in the step (1) adopts one or more of NaOH and quaternary ammonium salt as desilication reagent.
5. The method according to claim 1, characterized in that: the alkali is one or more of NaOH and KOH, the treatment temperature is 40-70 ℃, the washing temperature is 40-70 ℃, the liquid-solid ratio of the treatment process is (8-10): 1 in terms of mL/g, and the solid ratio of the washing process is (8-12): 1 in terms of mL/g.
6. The method according to claim 1, characterized in that: the dealumination process in the step (2) sequentially adopts acid treatment and hydrothermal treatment.
7. The method according to claim 1, characterized in that: the amino silicone oil loaded in the step (4) is subjected to isovolumetric impregnation or over volumetric impregnation.
8. The method according to claim 1 or 7, characterized in that: the amino-silicone oil loaded in the step (4) is immersed in an equal volume.
9. The method according to claim 1, characterized in that: in the step (4), the material prepared in the step (3) is immersed in an emulsion containing 0.02-0.10wt% of amino silicone oil in an equal volume, wherein the solvent of the emulsion is deionized water, and the equal volume immersion time is 5-10 h.
10. The method according to claim 1 or 9, characterized in that: and (4) immersing the material prepared in the step (3) in an emulsion containing 0.04-0.06 wt% of amino silicone oil in an equal volume.
11. The method according to claim 1, characterized in that: in the step (4), the drying temperature is 100-150 ℃ and the drying time is 2-4 hours; the roasting temperature is 550 ℃; the roasting time is 3-5 h.
12. A ZSM-5 molecular sieve prepared by the process of any of claims 1-11, characterized in that: the specific surface area of the molecular sieve is 350-500 m 2 Per gram, pore volume of 0.38-0.50 cm 3 Per gram, the total acid content is 1.6-2.7 mmol/g, the weak acid content is 0.8-1.4 mmol/g, the non-framework aluminum accounts for 6-12%, and the content of the loaded silicon oxide is 0.02-0.7wt%.
13. The molecular sieve of claim 12, wherein: the specific surface area of the molecular sieve is 400-450 m 2 Per gram, pore volume of 0.40-0.45 cm 3 Per gram, the total acid content is 2.0-2.5 mmol/g, the weak acid content is 1.0-1.2 mmol/g, the non-framework aluminum accounts for 8% -10%, and the content of the loaded silicon oxide is 0.04-0.06 wt%.
14. The molecular sieve of claim 12, wherein: at a reaction pressure of 6.0MPa, a hydrogen-oil volume ratio of 500:1 and a volume space velocity of 10h -1 Under the condition of the reaction temperature of 340 ℃, the ring opening rate of the ZSM-5 molecular sieve to decalin is as follows: 50% -70% and the secondary cracking rate of the n-hexadecane is 1% -6%.
15. A hydrodewaxing method, wherein a diesel oil raw material reacts under the action of a hydrodewaxing catalyst, the hydrodewaxing catalyst contains the ZSM-5 molecular sieve prepared by the method of any one of claims 1 to 11, and the mass content of polycyclic aromatic hydrocarbon in the diesel oil raw material is higher than 40%.
16. The method according to claim 15, wherein: the mass content of polycyclic aromatic hydrocarbon in the raw oil is 55% -75%.
17. The method according to claim 15, wherein: the hydrodewaxing reaction conditions are as follows: the reaction pressure is 5.0-8.0MPa, the hydrogen-oil volume ratio is 400:1-600:1, and the volume airspeed is 8-12h -1 The reaction temperature is 280-400 ℃.
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