CN116037198A - Molecular sieve, preparation method, hydroisomerization catalyst and application thereof in pour point depression of tail oil - Google Patents
Molecular sieve, preparation method, hydroisomerization catalyst and application thereof in pour point depression of tail oil Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 108
- 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 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003921 oil Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims description 43
- 238000002425 crystallisation Methods 0.000 claims description 43
- 230000008025 crystallization Effects 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 6
- 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 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000000881 depressing effect Effects 0.000 abstract description 6
- 238000012512 characterization method Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- LDFVINFJZGUOAZ-UHFFFAOYSA-N hexane-1,6-diamine;hydrochloride Chemical compound [Cl-].NCCCCCC[NH3+] LDFVINFJZGUOAZ-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JIAFGCKUXLMTJH-UHFFFAOYSA-N hexane-1,6-diamine;hydrate Chemical compound O.NCCCCCCN JIAFGCKUXLMTJH-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- HZONRRHNQILCNO-UHFFFAOYSA-N 1-methyl-2h-pyridine Chemical compound CN1CC=CC=C1 HZONRRHNQILCNO-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- PDJBCBKQQFANPW-UHFFFAOYSA-L azanide;platinum(2+);dichloride Chemical compound [NH2-].[NH2-].[NH2-].[NH2-].Cl[Pt]Cl PDJBCBKQQFANPW-UHFFFAOYSA-L 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000004474 heteroalkylene group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 tetramethyl amine ion Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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Abstract
The invention discloses a ZSM-48 molecular sieve with specific diffraction characteristics, a preparation method, a hydroisomerization catalyst and application, which are characterized in that the mole ratio of silicon oxide to aluminum oxide in the ZSM-48 molecular sieve is not lower than 45, and the specific surface area is 160-280m 2 And/g, in the X-ray diffraction pattern of the ZSM-48 molecular sieve, two main diffraction peaks exist between 20 and 24 degrees of 2 theta angles, wherein the diffraction peak with larger 2 theta angles has higher peak height. Compared with ZSM-48 molecular sieve obtained by the prior art, the molecular sieve has specific diffraction characteristics andthe molecular sieve of the invention is used as a raw material to prepare a carrier, and when the prepared catalyst is applied to the pour point depressing reaction of tail oil, the product yield and viscosity index are higher, and the pour point is lower.
Description
Technical Field
The invention belongs to the fields of molecular sieves, hydrogenation catalysts and hydroisomerization, and particularly relates to a ZSM-48 molecular sieve with a special morphology, a preparation method, a hydroisomerization catalyst and application of the catalyst in isomerization and pour point depressing of tail oil.
Background
The ZSM-48 molecular sieve is a novel high-silicon molecular sieve developed in the 80 s of the 20 th century, has a one-dimensional ten-membered ring pore path structure, belongs to an orthorhombic system, is connected by 5-membered rings, has the pore diameter of about 0.6nm, and is characterized by higher silicon-aluminum molar ratio and tubular linear pore path, and can accommodate organic molecular reaction with kinetic radius smaller than benzene. Theoretically, ZSM-48 type molecular sieves have smaller pore channel "self-blocking effect", and the pore channel size is suitable for the selective synthesis of hydrocarbons below C5. At present, a plurality of synthesis methods of ZSM-48 molecular sieves are reported at home and abroad.
ZSM-48 was first discovered in the hetero-crystal formed by the extension of ZSM-39 octahedron, and then pure phase ZSM-48 was synthesized in a system of silicon source, aluminum source, tetramethyl amine ion and n-propylamine. In 1983, US4397827 disclosed for the first time the synthesis of ZSM-48 molecular sieves, using a template agent of C2-C12 alkylamine, the ratio of silica to alumina (SiO) of the ZSM-48 molecular sieves obtained 2 /Al 2 O 3 The same applies below) in the range of 25 to infinity. Subsequent research results show that when tetramethyl ammonium ion is used as a template agent and NaOH is used as an alkali source, crystal seeds or other template agents are not added, the synthesized main product is ZSM-39 molecular sieve, and pure-phase ZSM-48 molecular sieve cannot be synthesized. At present, ZSM-48 molecular sieves can be synthesized from a variety of organic templating agents. For example, N-methylpyridine (US 4585747), ethylenediamine (US 5961951), alkylamines and tetramethylammonium (CN 101330975A), N-diethylhexamethyleneimine quaternary ammonium (CN 102040231A), hexamethylenediamine chloride (US 7482300/US 7625478), 1, 6-hexamethylenediamine or 1, 8-octanediamine (US 6923949A), and the like.
In addition to the relatively simple template with simple structure, the template alsoSome structurally complex templating agents are disclosed. EP-A-142317 discloses ZSM-48 molecular sieve synthesis in the presence of specific linear diquaternary ammonium compounds having the general formula: [ (R) 3 N + (Z)m[(R) 3 N + ](X - ) 2 Wherein each R is an alkyl or heteroalkyl group having from 1 to 20 carbon atoms, a cycloalkyl or cycloheteroalkyl group having from 3 to 6 carbon atoms, or an aryl or heteroaryl group, Z is an alkylene or heteroalkylene group having from 1 to 20 carbon atoms, an alkenylene or heteroalkenylene group having from 2 to 20 carbon atoms, or an arylene metal or heteroarylene group, m is 5, 6, 8, 9, or 10, and X-is an anion.
The prior art researches on ZSM-48 mainly focus on screening and optimizing different templates, but pay less attention to the morphology, diffraction peak characteristics and the relation between the diffraction peak characteristics and the performances of the obtained ZSM-48 molecular sieve. In addition, the preparation method for adding seed crystals in liquid phase synthesis is generally to add ZSM-48 seed crystals, and no report of preparing ZSM-48 by adding other seed crystals is seen.
Disclosure of Invention
The invention aims to provide a ZSM-48 molecular sieve with specific diffraction peak characteristics and special morphology, a preparation method thereof, a hydroisomerization catalyst prepared by a carrier containing the molecular sieve, and application of the catalyst in a tail oil pour point depressing reaction, and particularly, the invention mainly comprises the following contents:
the invention provides a ZSM-48 molecular sieve, the mol ratio of silicon oxide to aluminum oxide in the ZSM-48 molecular sieve is not lower than 45, and the specific surface area is 160-280m 2 And/g, in the X-ray diffraction pattern of the ZSM-48 molecular sieve, two main diffraction peaks exist between 20 and 24 degrees of 2 theta angles, wherein the diffraction peak with larger 2 theta angles has higher peak height.
Secondly, the invention also provides a preparation method of the molecular sieve, which comprises the following steps:
(1) Mixing a silicon source, an alkali source, an aluminum source, a template agent and water to form a colloid mixture;
(2) Adding ZSM-12 molecular sieve seed crystal into the colloidal mixture obtained in the step (1);
(3) In the crystallizationCrystallization is performed under conditions including: in turn at t 1 Crystallizing at temperature for 5-24 hr, at t 2 Crystallizing at temperature for 0.5-36 hr, at t 3 Crystallizing for 10-96h at 15 ℃ to less than or equal to t 1 ＜50℃，50℃≤t 2 ＜100℃，100℃≤t 3 ≤200℃
The invention further provides a hydroisomerization catalyst which comprises a carrier and active metals loaded on the carrier, wherein the carrier contains any one of the ZSM-48 molecular sieves or the ZSM-48 molecular sieves prepared by any one of the methods, and the active metals are Pt and/or Pd.
Finally, the invention also provides a tail oil isomerism pour point depressing method, which comprises the steps of contacting tail oil raw oil with a hydroisomerization catalyst under hydroisomerization conditions, wherein the tail oil raw oil is selected from cracked tail oil, biological aviation kerosene production raw material and C 5 C 6 At least one of isomerized raw materials and Fischer-Tropsch wax, wherein the hydroisomerization catalyst is provided by the invention.
Compared with the ZSM-48 molecular sieve obtained by the prior art, the molecular sieve provided by the invention has specific diffraction characteristics and morphology characteristics, and when the catalyst prepared by using the molecular sieve provided by the invention as a raw material to prepare a carrier is applied to hydroisomerization reaction of tail oil, the product yield and viscosity index are higher, the pour point is lower, and the remarkable advantages are achieved.
Drawings
FIG. 1 is an XRD spectrum of a molecular sieve sample synthesized in example 1;
fig. 2 is an SEM picture of a sample of the molecular sieve synthesized in example 1.
FIG. 3 is an XRD spectrum of a molecular sieve sample synthesized in comparative example 1;
Detailed Description
It is first noted that endpoints of the ranges and any values disclosed in the specification are not limited to the precise range or value, and that the range or value is to be understood as encompassing values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention firstly provides a ZSM-48 molecular sieve, the mole ratio of silicon oxide to aluminum oxide in the ZSM-48 molecular sieve is not lower than 45, and the specific surface area is 160-280m 2 And/g, in the X-ray diffraction pattern of the ZSM-48 molecular sieve, two main diffraction peaks exist between 20 and 24 degrees of 2 theta angles, wherein the diffraction peak with larger 2 theta angles has higher peak height.
In the XRD diffraction pattern of the ZSM-48 molecular sieve raw powder synthesized by the prior art method at present, diffraction peaks are generally arranged at positions of 7.5 DEG, 20 DEG to 24 DEG and 31.3 DEG of 2 theta, wherein two diffraction peaks are arranged at the positions of 20 DEG to 24 DEG, and the diffraction peak with a larger 2 theta angle has a lower peak height. The researchers of the invention find that the ZSM-48 molecular sieve can be prepared by adopting a specific synthesis method, and the calcined X-ray diffraction pattern of the ZSM-48 molecular sieve has two diffraction peaks at 20-24 degrees, and the diffraction peak with larger 2 theta angle has higher peak height. Due to the influence of factors such as a sample, an instrument and the like, a specific peak position related to a 2 theta angle can deviate by +/-0.5 degrees. The purpose of the calcination is to remove impurities such as a template agent in the molecular sieve raw powder, and obtain a more accurate XRD characterization result, and the diffraction peaks in the XRD spectrum of the molecular sieve cannot be substantially influenced, so that the calcination conditions are such that the impurities are removed, for example, the calcination can be performed at 400-700 ℃ for 1-8 hours, and the calcination is performed at 600 ℃ for 4 hours before the characterization in the examples and comparative examples in the invention.
The ZSM-48 molecular sieve provided by the invention, wherein the mentioned silicon-aluminum ratio refers to SiO in the molecular sieve 2 And Al 2 O 3 The range of the molar ratio is not particularly limited, and mainly depends on the feeding and preparation methods of the silicon source and the aluminum source in the raw materials. In general, the silicon to aluminum ratio may be not less than 45, and the theoretical upper limit thereof may be infinity, and in actual production, the upper limit may be preferably 2000, 1000, 500, 450, 400, 360, 300, etc., and the lower limit may be preferably 50, 60, 100, 120, etc.
The pair of the inventionThe specific surface area of the molecular sieve is not particularly limited, and preferably the specific surface area is 180 to 270m 2 Preferably 200-260m 2 /g。
The molecular sieve morphology features are obtained through SEM characterization, and the scale in morphology is the average value after the measurement and statistics of crystal grains and clusters in an SEM picture. Wherein the equivalent diameter of the crystal grain refers to the diameter of a sphere having the same volume as the crystal grain, and the crystal grain length refers to the length of the largest dimension of the crystal grain dimension. Under the preferred condition, the ZSM-48 molecular sieve of the invention presents the shape of whisker-shaped cluster compound, the whisker-shaped cluster compound is formed by clustering crystal grains with the equivalent diameter of 10-60nm and the length of 30-100nm, and further preferably, the equivalent diameter of the crystal grains is 20-50nm, and the length of the crystal grains is 50-80nm.
Secondly, the invention provides a preparation method of the molecular sieve, which comprises the steps of contacting a reaction mixture under crystallization conditions, wherein the reaction mixture comprises a silicon source, an alkali source, an aluminum source, a template agent and water, and the specific steps are as follows:
(1) Mixing a silicon source, an alkali source, an aluminum source, a template agent and water to form a colloid mixture;
(2) Adding ZSM-12 molecular sieve seed crystal into the colloidal mixture obtained in the step (1);
(3) Crystallization is performed under crystallization conditions, including: in turn at t 1 Crystallizing at temperature for 5-24 hr, at t 2 Crystallizing at temperature for 0.5-36 hr, at t 3 Crystallizing for 10-96h at 15 ℃ to less than or equal to t 1 ＜50℃，50℃≤t 2 ＜100℃，100℃≤t 3 The temperature is less than or equal to 200 ℃. The crystallization conditions include: in turn at t 1 Crystallizing at temperature for 5-24 hr, at t 2 Crystallizing at temperature for 0.5-36 hr, at t 3 Crystallizing for 10-96h at 15 ℃ to less than or equal to t 1 ＜50℃，50℃≤t 2 ＜100℃，100℃≤t 3 ≤200℃。
Researchers of the invention find that the material proportion, seed crystal selection and specific process in the preparation process of the molecular sieve have obvious influence on the morphology, diffraction characteristic parameters and performance of the molecular sieve product, and particularly, in the invention, the improvement of seed crystal selection and crystallization conditions directly leads to the ZSM-48 molecular sieve with specific diffraction characteristics, and further, the molecular sieve product with more obvious characteristics and more excellent performance can be obtained through the optimization of the proportion of each raw material.
According to the preparation method of the invention, the crystallization conditions mainly comprise three steps of crystallization, and the temperature of each crystallization is higher than the temperature of the previous crystallization. Specifically, the first crystallization temperature t 1 Meets the temperature of 15 ℃ to less than or equal to t 1 Preferably at a temperature of less than 50 ℃, preferably at room temperature, more preferably at a temperature of 20 ℃ less than or equal to t 1 The temperature is less than or equal to 45 ℃, and the crystallization time of the first step is 5-24 hours, preferably 6-15 hours; second step crystallization temperature t 2 Meets the temperature of 50 ℃ to less than or equal to t 2 Less than 100 ℃, preferably 60 ℃ less than or equal to t 2 The temperature is less than or equal to 80 ℃, and the crystallization time of the second step is 0.5-36h, preferably 5-30h; third crystallization temperature t 3 Meets the temperature of 100 ℃ to less than or equal to t 3 200 ℃ or less, preferably 120 ℃ or less t 3 The temperature is less than or equal to 190 ℃, and the crystallization time of the third step is 10-96 hours, preferably 20-80 hours.
The raw materials for forming the reaction mixture are a silicon source, an alkali source, an aluminum source, a template agent, water and seed crystals, and the raw materials are all conventional choices in the field. The raw materials are generally mixed into uniform jelly by adopting corresponding means, and continuous stirring or no stirring can be selected according to actual conditions in the crystallization process. In the present invention, in order to ensure that the ZSM-48 molecular sieve of the present invention is better obtained, it is preferable that stirring is continued in the first crystallization step at such a strength and speed that the reactant forms a uniform gum, and at a stirring speed higher than those of the second and third crystallization steps, for example, the stirring speed of the first crystallization step is 200 to 1000rpm, and the stirring speed of the latter two crystallization steps is independently selected from 0 to 800rpm, and further preferable that the stirring speed is lower than that of the first crystallization step. In order to obtain the molecular sieve raw powder, the reaction system after crystallization can be further filtered, washed, dried and the like. The methods and conditions for filtration, washing and drying are all conventional in the art and will not be described again.
The seed crystal ZSM-12 molecular sieve is not particularly required in the invention, and can be ZSM-12 molecular sieve obtained by any method and synthesis in the prior art, or any commercial ZSM-12 molecular sieve.
With respect to the specific selection of the above reactants, preferably, the template agent is one or more selected from ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexamethylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine, 1, 9-octylenediamine, hexamethylammonium bromide, hexamethylammonium chloride, hexamethylammonium hydroxide; the silicon source is one or more selected from silica sol, white carbon black, fumed silica, water glass and tetraethoxysilane, the aluminum source is a soluble aluminum source and is one or more selected from pseudo-boehmite, aluminum sulfate, aluminum isopropoxide, sodium aluminate and aluminum nitrate; the alkali source is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide; in order to obtain the molecular sieve of the present invention more easily, the water is preferably deionized water, and the crystallization-promoting substances such as mother liquor and seed crystals remaining in the preparation of the molecular sieve are preferably not added to the reaction mixture and during the reaction.
The proportion of each raw material in the reactant has a certain influence on the final performance of the molecular sieve, and on the premise of ensuring that the specific diffraction characteristic is obtained, the invention further optimizes the proportion of each material, and specifically, the calculated composition of the molar quantity of each component in the reaction mixture meets the following relation:
R/SiO 2 =0.01 to 0.50, more preferably 0.01 to 0.3;
H 2 O/SiO 2 =5 to 50, more preferably 5 to 20;
M + /SiO 2 =0.01 to 0.50, more preferably 0.01 to 0.15;
Al 2 O 3 /SiO 2 =0 to 0.02; more preferably 0.01 to 0.017;
wherein R represents a template agent, M + Indicating the source of alkalinity.
The invention further provides a hydroisomerization catalyst which comprises a carrier and active metals loaded on the carrier, wherein the carrier contains any one of the ZSM-48 molecular sieves or the ZSM-48 molecular sieves prepared by any one of the methods, and the active metals are Pt and/or Pd.
According to the catalyst provided by the invention, on the premise that the carrier is ensured to contain the ZSM-48 molecular sieve provided by the invention, the other components of the carrier, the content of the molecular sieve in the carrier, the content of the carrier and active metal in the catalyst and the like are all conventional choices in the field. The hydroisomerization catalyst of the present invention may be prepared by conventional methods of the prior art, while ensuring that the ZSM-48 molecular sieve of the present invention is introduced into the support.
Specifically, the carrier in the catalyst of the invention preferably further contains alumina, and the content of ZSM-48 molecular sieve in the carrier is 20-80 wt%, preferably 30-70 wt%, and more preferably 40-60 wt%; the active metal content in terms of oxide is 0.1-2 wt.%, preferably 0.2-1 wt.%, based on the total catalyst, the remainder being the support.
Finally, the invention also provides a tail oil isomerism pour point depressing method, which comprises the steps of contacting a tail oil raw material with a hydroisomerization catalyst under hydroisomerization conditions, wherein the tail oil raw material is selected from cracked tail oil, biological aviation kerosene production raw material and C 5 C 6 At least one of isomerized raw materials and Fischer-Tropsch wax, wherein the hydroisomerization catalyst is provided by the invention. The hydroisomerization conditions include: the temperature is 200-500 ℃, preferably 250-400 ℃, more preferably 300-350 ℃; the pressure is 1-30MPa, preferably 2-20MPa, more preferably 5-20MPa, and the pressure is absolute pressure; the space velocity is 0.1-5h-1, preferably 0.1-3h-1, more preferably 0.5-2h-1; the hydrogen oil volume ratio is 50-3000, preferably 300-3000, more preferably 400-600.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, XRD characterization of the samples was performed using a Bruker D5005 diffractometer, cu K alpha rays (λ=0.154 nm), tube voltage 40kV, tube current 30mA, scan range 5-35, step 0.013, 1 step per second. The morphology and the size of the sample were characterized by using a Scanning Electron Microscope (SEM) model S-4800 manufactured by Hitachi, inc., and the acceleration voltage was 20kV.
The composition of the sample was measured by using an X-ray fluorescence spectrometer (XRF) of 3271E, japan motor industry Co., ltd., the sample preparation method was a tabletting method, the measurement condition was a terminal window rhodium target, the tube voltage was 50kV, and the tube current was 50mA.
The dry basis of the molecular sieve and pseudo-boehmite in the examples refers to the weight after 2 hours of calcination at 600 ℃.
Pore structure parameters such as specific surface area and pore volume in the product are measured by the BET method.
The measuring method of the element content in the product is DZ/T0279.1-2016.
Example 1
Mixing aluminum sulfate, hexamethylenediamine hydroxide (HMOH), potassium hydroxide and deionized water according to a certain proportion, stirring for 30min, adding silica sol, and mixing with n (Al 2 O 3 ):(HMOH):n(Na + ):n(H 2 O)：n(SiO 2 ) =0.02:0.03:0.3:5:1, with SiO in the starting material 2 Based on the total amount, add SiO 2 ZSM-12 molecular sieve (commercial molecular sieve, siemens Ji Yue Biotechnology Co., ltd.) was used as seed crystals at 5% by mass. Then transferring the mixture into a crystallization kettle, and crystallizing for 12 hours under stirring at room temperature, wherein the stirring speed is 400rpm; crystallizing at 60deg.C for 12 hr, and then heating to 170deg.C for 48 hr. After crystallization, the mixture was filtered and the product was dried at 120℃for 6h. Calcining part of the sample at 600 ℃ for 4 hours, wherein XRD diffraction peaks are shown in figure 1, and determining that the sample is a ZSM-48 molecular sieve, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta angles, and diffraction peaks with larger 2 theta angles have higher peak heights; the morphology of the product is shown in a Scanning Electron Microscope (SEM) picture, namely FIG. 2. FIG. 2 shows that the product is a whisker-like cluster composed of small grains, the equivalent diameter of the grains is 30-50nm, and the length of the grains is 40-80nm; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Example 2
Mixing aluminum sulfate, hexamethylenediamine chloride (HMCl), sodium hydroxide and deionized water according to a certain proportion, stirring for 30min, adding silica sol, and mixing with n (Al 2 O 3 ):(HMCl):n(Na + ):n(H 2 O)：n(SiO 2 ) =0.004:0.03:0.3:30:1, and adding SiO in the raw materials 2 ZSM-12 molecular sieve (commercial molecular sieve, siemens Ji Yue Biotechnology Co., ltd.) was used as seed crystals in an amount of 10% by mass. Then the mixture is transferred into a crystallization kettle, stirred and crystallized for 12 hours at room temperature, crystallized for 12 hours at 60 ℃ and crystallized for 48 hours at 170 ℃. After crystallization, the mixture was filtered and the product was dried at 120℃for 6h. Taking part of samples, roasting for 4 hours at 600 ℃, and determining that the samples are ZSM-48 molecular sieves through XRD characterization, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta angles, and diffraction peaks with larger 2 theta angles have higher peak heights; SEM image shows whisker-shaped cluster compound composed of crystal grains, the equivalent diameter of the crystal grains is 10-50nm, and the length of the crystal grains is 30-80nm; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Example 3
Mixing sodium aluminate, hexamethylenediamine chloride (HMCl), sodium hydroxide and deionized water according to a certain proportion, stirring for 30min, adding silica sol, wherein the mass ratio of each substance is n (Al 2 O 3 ):(HMCl):n(Na + ):n(H 2 O)：n(SiO 2 ) =0.018:0.03:0.3:15:1, and adding SiO in the raw material 2 ZSM-12 molecular sieve (commercial molecular sieve, siemens Ji Yue Biotechnology Co., ltd.) was used as seed crystals in an amount of 10% by mass. Then the mixture is transferred into a crystallization kettle, stirred and crystallized for 24 hours at room temperature, crystallized for 36 hours at 80 ℃ and crystallized for 72 hours at 160 ℃. After crystallization, the mixture was filtered and the product was dried at 120℃for 6h. Taking part of samples, roasting for 4 hours at 600 ℃, and determining that the samples are ZSM-48 molecular sieves through XRD characterization, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta angles, and diffraction peaks with larger 2 theta angles have higher peak heights; SEM image shows whisker-shaped cluster compound composed of crystal grains, the equivalent diameter of the crystal grains is 20-50nm, and the length of the crystal grains is 30-80nm; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Example 4
Mixing sodium aluminate, hexamethylenediamine chloride (HMCl), sodium hydroxide and deionized water according to a certain proportion, stirring for 30min, adding silica sol, wherein the mass ratio of each substance is n (Al 2 O 3 ):(HMCl):n(Na + ):n(H 2 O)：n(SiO 2 ) =0.0125:0.03:0.3:20:1, and adding SiO in the raw materials 2 ZSM-12 molecular sieve (commercial molecular sieve, siemens Ji Yue Biotechnology Co., ltd.) was used as seed crystals at 5% by mass. Then the mixture is transferred into a crystallization kettle, stirred and crystallized for 6 hours at room temperature, crystallized for 24 hours at 80 ℃ and crystallized for 48 hours at 180 ℃. After crystallization, the mixture was filtered and the product was dried at 120℃for 6h. Taking part of samples, roasting for 4 hours at 600 ℃, and determining that the samples are ZSM-48 molecular sieves through XRD characterization, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta angles, and diffraction peaks with larger 2 theta angles have higher peak heights; SEM image shows whisker-shaped cluster compound composed of crystal grains, the equivalent diameter of the crystal grains is 20-50nm, and the length of the crystal grains is 30-70nm; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Example 5
Mixing sodium aluminate, hexamethylenediamine chloride (HMCl), sodium hydroxide and deionized water according to a certain proportion, stirring for 30min, adding silica sol, wherein the mass ratio of each substance is n (Al 2 O 3 ):(HMCl):n(Na + ):n(H 2 O)：n(SiO 2 ) =0.004:0.01:0.3:30:1, and SiO in the raw materials is added 2 ZSM-12 molecular sieve (commercial molecular sieve, siemens Ji Yue Biotechnology Co., ltd.) was used as seed crystals at 7% by mass. Then the mixture is transferred into a crystallization kettle, stirred and crystallized for 6 hours at 40 ℃, crystallized for 24 hours at 70 ℃ and crystallized for 48 hours at 180 ℃. After crystallization, the mixture was filtered and the product was dried at 120℃for 6h. Taking part of samples, roasting for 4 hours at 600 ℃, and determining that the samples are ZSM-48 molecular sieves through XRD characterization, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta angles, and diffraction peaks with larger 2 theta angles have higher peak heights; SEM image shows whisker-shaped cluster compound composed of crystal grains, the equivalent diameter of the crystal grains is 20-60nm, and the length of the crystal grains is 30-60nm; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Example 6
Mixing sodium aluminate, hexamethylenediamine chloride (HMCl), sodium hydroxide and deionized water according to a certain proportion, stirring for 30min, adding white carbon black, and mixing with n (Al 2 O 3 ):(HMCl):n(Na+):n(H 2 O):n(SiO 2 ) =0.01:0.01:0.1:30:1, addSiO in the raw material 2 ZSM-12 molecular sieve (commercial molecular sieve, siemens Ji Yue Biotechnology Co., ltd.) was used as seed crystals at 3% by mass. Then the mixture is transferred into a crystallization kettle, stirred and crystallized for 6 hours at 50 ℃, crystallized for 24 hours at 70 ℃ and crystallized for 72 hours at 160 ℃. After crystallization, the mixture was filtered and the product was dried at 120℃for 6h. Taking part of samples, roasting for 4 hours at 600 ℃, and determining that the samples are ZSM-48 molecular sieves through XRD characterization, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta angles, and diffraction peaks with larger 2 theta angles have higher peak heights; SEM image shows whisker-shaped cluster compound composed of crystal grains, the equivalent diameter of the crystal grains is 10-50nm, and the length of the crystal grains is 30-90nm; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Comparative example 1
Mixing aluminum sulfate, hexamethylenediamine hydroxide (HMOH), sodium hydroxide and deionized water according to a certain proportion, stirring for 30min, adding silica sol, and mixing with n (Al 2 O 3 ):(HMOH):n(Na + ):n(H 2 O):n(SiO 2 ) =0.004:0.03:0.3:5:1, the mixture was transferred into a crystallization kettle and crystallized for 6h under stirring at room temperature, the stirring speed was 400rpm; then crystallizing at 80deg.C for 24 hr, and heating to 180deg.C for 48 hr. After crystallization, the mixture was filtered and the product was dried at 120℃for 6h. Calcining part of the sample at 600 ℃ for 4 hours, wherein XRD diffraction peaks are shown in figure 3, and determining that the sample is a ZSM-48 molecular sieve, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta, and diffraction peaks with larger 2 theta angles have lower peak heights; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Comparative example 2
Molecular sieves were prepared as in example 1, except that the crystallization process was different, specifically:
after the mixture is transferred into a crystallization kettle, the temperature is directly increased to 160 ℃ for crystallization for 96 hours, filtration is carried out after crystallization is finished, and the product is dried for 6 hours at 120 ℃. Calcining part of the sample at 600 ℃ for 4 hours, determining the sample as ZSM-48 molecular sieve through XRD characterization, determining the sample as ZSM-48 molecular sieve, wherein two main diffraction peaks exist between 20 DEG and 24 DEG of 2 theta angles, and the diffraction peak with larger 2 theta angle has lower peak height; SEM pictures show rod-like particles with morphology of about 1-2 microns in length; the silica to alumina ratio results obtained by XRF characterization are shown in table 1.
Catalyst preparation examples and comparative examples
100g of the molecular sieve in the above examples and comparative examples was mixed with 100g of alumina, extruded, and dried to obtain a carrier.
1 g of tetra-ammine platinum dichloride (containing 57.3% Pt by mass) is poured into 100g of deionized water and stirred until uniform. 100g of the support was poured into the above solution and immersed for 4 hours at room temperature. Subsequently, the above catalyst precursor was dried at 120℃for 4 hours. Then, the mixture was baked in an air flow at a baking temperature of 450℃for 4 hours. The semi-finished catalyst was again put into a hydrogen atmosphere and reduced at 400 ℃ for 4 hours to obtain the catalyst. The catalysts prepared from the molecular sieves in examples 1-6 were designated C1-C6 and the catalysts prepared from the molecular sieves in comparative examples 1 and 2 were designated DC1 and DC2.
Evaluation example
The following evaluation methods were used to evaluate C1-C6, DC1-DC 2:
50g of the catalyst was charged into a high pressure hydrogenation reactor. The hydrocracking tail oil raw material was injected into the reactor from top to bottom to react under the reaction conditions shown in table 2 below, and the raw material oil properties shown in table 3. The product was distilled to cut off light components of less than 370 degrees after the reaction was completed, and components of more than 370 degrees were analyzed and yield calculated, and the results are shown in table 4.
From the data and the evaluation results, the ZSM-48 molecular sieve has specific diffraction characteristics and morphological characteristics, and two main diffraction peaks exist between 20 degrees and 24 degrees of 2 theta angles, wherein the diffraction peak with larger 2 theta angles has higher peak height; when the catalyst is applied to the pour point depressing reaction of tail oil, the condensation point of the catalyst is lower than that of a product obtained by the prior art, the yield and the viscosity index are higher, and the catalyst has remarkable effects.
TABLE 1
TABLE 2
| Reaction conditions | Condition 1 |
| Pressure, MPa | 14.0 |
| Airspeed, h-1 | 1.0 |
| Reaction temperature, DEG C | 320 |
| Hydrogen to oil ratio, v/v | 500 |
TABLE 3 Table 3
| Analysis item | Analysis data | Analysis method |
| Density/(kg/m 3) at 20 ℃ | 843.6 | SH/T0604-2000 |
| Kinematic viscosity/(mm 2/s) | ||
| 80℃ | 7.021 | GB/T 265-88 |
| 100℃ | 4.664 | GB/T 265-88 |
| Pour point/. Degree.C | +42 | SH/T 0771-2005 |
| Nitrogen mass fraction/(μg/g) | <1 | NB/SH/T 0704-2010 |
| Sulfur mass fraction/(μg/g) | 3 | SH/T 0842-2010 |
TABLE 4 Table 4
Claims (10)
1. A ZSM-48 molecular sieve, the mole ratio of silicon oxide and aluminum oxide in the ZSM-48 molecular sieve is not less than 45, and the specific surface area is 160-280m 2 In the X-ray diffraction pattern of the ZSM-48 molecular sieve, two main diffraction peaks exist between 20 degrees and 24 degrees of 2 theta anglesWherein the diffraction peak with a larger 2 theta angle has a higher peak height.
2. The ZSM-48 molecular sieve of claim 1, wherein the ZSM-48 molecular sieve exhibits a whisker-like cluster morphology, the whisker-like cluster being clustered from grains having an equivalent diameter of 10-60nm and a length of 30-100 nm.
3. A ZSM-48 molecular sieve according to any of claims 1-3, wherein the molar ratio of silica to alumina is 50-500, preferably 60-300, and the specific surface area is 180-270m 2 /g, preferably 200-260m 2 /g。
4. The method of ZSM-48 molecular sieve of claim 1, comprising the steps of:
(1) Mixing a silicon source, an alkali source, an aluminum source, a template agent and water to form a colloid mixture;
(2) Adding ZSM-12 molecular sieve seed crystal into the colloidal mixture obtained in the step (1);
(3) Crystallization is performed under crystallization conditions, including: in turn at t 1 Crystallizing at temperature for 5-24 hr, at t 2 Crystallizing at temperature for 0.5-36 hr, at t 3 Crystallizing for 10-96h at 15 ℃ to less than or equal to t 1 ＜50℃，50℃≤t 2 ＜100℃，100℃≤t 3 ≤200℃。
5. The method of claim 4, wherein the composition of the components in the reaction mixture calculated on a molar basis satisfies the following relationship:
R/SiO 2 ＝0.01～0.50，
H 2 O/SiO 2 ＝5～50，
M + /SiO 2 ＝0.01～0.50，
Al 2 O 3 /SiO 2 ＝0～0.02；
the ZSM-12 molecular sieve seed crystal is added in a proportion of 0.01 to 30 weight percent, preferably 1 to 15 weight percent, based on the total mass of a silicon source and an aluminum source in the raw material which are calculated as oxides;
wherein R represents a template agent, M + Indicating the source of alkalinity.
6. The method of claim 4, wherein the crystallization conditions comprise: in turn at t 1 Crystallizing at temperature for 6-15 hr, at t 2 Crystallizing at temperature for 5-30 hr, at t 3 Crystallizing for 20-80h at 20 ℃ to less than or equal to t 1 ≤45℃，60℃≤t 2 ≤80℃，120℃≤t 3 ≤190℃。
7. The method according to claim 4, wherein the template agent is one or more selected from ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexamethylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine, 1, 9-octylenediamine, hexamethylammonium bromide, hexamethylammonium chloride, hexamethylammonium hydroxide; the silicon source is one or more selected from silica sol, white carbon black, fumed silica, water glass and tetraethoxysilane, the aluminum source is a soluble aluminum source and is one or more selected from pseudo-boehmite, aluminum sulfate, aluminum isopropoxide, sodium aluminate and aluminum nitrate; the alkali source is one or more of sodium hydroxide, potassium hydroxide and calcium hydroxide.
8. A hydroisomerization catalyst comprising a support and an active metal supported on the support, wherein the support comprises the ZSM-48 molecular sieve of any of claims 1-3 or the ZSM-48 molecular sieve prepared by the process of any of claims 4-7, and the active metal is Pt and/or Pd.
9. Hydroisomerization catalyst according to claim 8, wherein the molecular sieve content in the support is 20-80 wt%, preferably 30-70 wt%, on a dry basis; the active metal content in terms of oxide is 0.1 to 2% by weight, preferably 0.2 to 1% by weight, based on the total amount of catalyst.
10. A method for reducing the isomerization and pour point of tail oil includes such steps as providing tail oil under hydroisomerization conditionContacting oil raw oil with hydroisomerization catalyst, wherein the tail oil raw oil is selected from cracked tail oil, biological aviation kerosene production raw material and C 5 C 6 At least one of isomerized feedstock, fischer-tropsch wax, the hydroisomerization catalyst being the hydroisomerization catalyst of claim 8 or 9, the hydroisomerization conditions comprising: the temperature is 200-500 ℃, preferably 250-400 ℃; the pressure is 1-30MPa, preferably 2-20MPa; space velocity of 0.1-5h -1 Preferably 0.1-3h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume ratio of hydrogen oil is 50-3000, preferably 300-3000.
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| 吴伟;黄娟;吴维果;: "ZSM-12分子筛研究进展", 化工进展, no. 07, 25 July 2007 (2007-07-25) * |
| 唐静思: "低硅铝比ZSM-48分子筛的合成及表征", 中国优秀硕士学位论文全文数据库 工程科技I辑, no. 1, 15 January 2017 (2017-01-15), pages 3 - 1 * |
| 张健;翟绪丽;付凯妹;姜涛;: "短轴纳米ZSM-23的合成及异构化性能", 高等学校化学学报, no. 02, 10 February 2017 (2017-02-10) * |
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