WO2019080922A1 - 具有介孔的分子筛及其制备方法和应用 - Google Patents

具有介孔的分子筛及其制备方法和应用

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Publication number
WO2019080922A1
WO2019080922A1 PCT/CN2018/112072 CN2018112072W WO2019080922A1 WO 2019080922 A1 WO2019080922 A1 WO 2019080922A1 CN 2018112072 W CN2018112072 W CN 2018112072W WO 2019080922 A1 WO2019080922 A1 WO 2019080922A1
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WIPO (PCT)
Prior art keywords
molecular sieve
weight
still
hours
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2018/112072
Other languages
English (en)
French (fr)
Inventor
毕云飞
夏国富
李明丰
杨清河
黄卫国
郭庆洲
方文秀
王鲁强
李洪宝
李洪辉
高杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201711016179.XA external-priority patent/CN109704357B/zh
Priority claimed from CN201711016098.XA external-priority patent/CN109701589B/zh
Application filed by Sinopec Research Institute of Petroleum Processing , China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to MYPI2020001998A priority Critical patent/MY201287A/en
Priority to KR1020207014343A priority patent/KR102621017B1/ko
Priority to US16/759,225 priority patent/US11572283B2/en
Publication of WO2019080922A1 publication Critical patent/WO2019080922A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Definitions

  • the invention relates to a molecular sieve having mesopores, a preparation method thereof and an application thereof. More particularly, the present invention relates to a high silica-alumina ratio molecular sieve having mesopores, a process for preparing the molecular sieve, and a catalyst comprising the molecular sieve and use thereof.
  • molecular sieve materials usually have high acidity and high specific surface area. At the same time, molecular sieve materials have strong chemical stability and hydrothermal stability, and are difficult to be destroyed by corrosion and dissolution of reactants, so they are an excellent solid acid catalyst. Compared to the homogeneous catalysts typically used, molecular sieve material catalysts can be directly reused without separation without contaminating the environment and products. In addition, the specific surface area, pore structure and other parameters of the molecular sieve material have an important influence on the characteristics of the molecular sieve, such as catalytic performance. Therefore, preparing a molecular sieve having a specific specific surface area or a special pore is an important research direction in the chemical industry.
  • U.S. Patent No. 5,282,958 discloses a catalyst for isomerization dewaxing which contains a mesoporous molecular sieve such as ZSM-5, ZSM-22, ZSM-23, ZSM-11 and the like.
  • An isomerization catalyst containing ZSM-48 is disclosed in U.S. Patent Nos. 7,482,300 and 5,075,269.
  • U.S. Patent No. 8,513,150 discloses a Y-type molecular sieve having a mesoporous. In this patent application, the Y-type molecular sieve is first calcined at a low temperature and then calcined at a high temperature (1250 ° F to 1450 ° F) in a gas containing water vapor.
  • U.S. Patent No. 5,397,454 discloses the use of a molecular sieve (e.g., SSZ-32) having a small grain size and a post-fired hydrogen type with a Constraint Index of 13 or greater, wherein the catalyst is silica and alumina. The molar ratio is greater than 20 and less than 40.
  • U.S. Patent Application No. 5,300,210 also relates to a process for the conversion of hydrocarbons using SSZ-32. SSZ-32 disclosed in U.S. Patent Application No.
  • U.S. Patent No. 7,141,529 discloses the use of different metals (metals selected from the group consisting of Ca, Cr, Mg, La, Ba, Pr, Sr, K and Nd and Group VIII metals) for metal modification of molecular sieves to provide for use.
  • Beta molecular sieve is the only zeolite with a three-dimensional 12-membered ring channel system. Its unique pore structure and acidity make Beta zeolite have high hydrocracking, hydroisomerization catalytic activity and adsorption of linear paraffins. Ability and good resistance to sulfur and nitrogen poisoning. Generally, it is used in the petrochemical industry for the preparation of catalysts in various conversion reactions for the production of cumene by benzene and propylene alkylation. In addition, the combination of Beta molecular sieve and USY can increase the octane number of gasoline. Moreover, in the field of fine chemicals, Beta molecular sieves also have good activity and selectivity in dehydration and deamination.
  • CN1350981A discloses a preparation method of high-silicon Beta zeolite, which mainly comprises the following steps: firstly, the crystallized Beta zeolite slurry is subjected to ammonium exchange, filtered and dried, and then calcined and then treated with an organic acid or a mineral acid, and finally. Further, a pressurized hydrothermal treatment is carried out to finally obtain a Beta zeolite having a silica-alumina ratio of 60 to 80.
  • CN1769169A discloses a synthesis method of a stepped channel Beta zeolite, wherein the obtained Beta zeolite has a silica-alumina ratio of 80-120 and has three pore size distributions of 0.1-1.7 nm, 1.7-6 nm and 10-90 nm, thereby greatly
  • the surface utilization of Beta zeolite was improved, but the micropore volume of the obtained sample was not large enough, and the pore volume contribution mainly came from mesopores and macropores (the total volume of mesopores and macropores accounted for more than 67% of the total pore volume).
  • CN104353484A discloses a preparation method of a cheap and strong acid multi-stage pore Beta zeolite, which solves the problem of weakening of acidity of the multi-stage pore Beta zeolite molecular sieve after the prior desiliconization treatment.
  • CN103964458A discloses a high-silica-aluminum ratio multi-stage channel Beta zeolite and a preparation method thereof.
  • the preparation method of the patent application is simple and efficient to operate, and the prepared high silica-alumina has strong acid stability compared with the multi-stage channel Beta zeolite. , thermal stability and hydrothermal stability as well as good diffusion properties.
  • the existing zeolite molecular sieve still has a low ratio of mesoporous surface area, and the ratio of silicon to aluminum is not sufficiently satisfactory, so that when the molecular sieve is used as a catalyst or a catalyst carrier, the catalytic performance of the obtained catalyst remains. There is a lot of room for improvement.
  • the inventors of the present invention conducted intensive studies and surprisingly found that in the synthesis step of the molecular sieve, after preparing the crystallized mother liquor, a suitable mesopore ratio can be prepared, and a mesoporous surface area can be prepared with a large mesoporous surface area.
  • Molecular sieves Thus, a molecular sieve having a high mesopore volume and a high mesoporous surface area was prepared, and the present invention was completed.
  • the catalytic activity of the catalyst prepared by using the molecular sieve is greatly improved.
  • the inventors of the present invention have found that by preparing a catalyst by a specific step, the catalytically active component can be well dispersed in a highly dispersed state on the carrier, thereby further improving the catalyst while maintaining the long life of the catalyst. active.
  • the present invention provides a molecular sieve having mesopores (hereinafter also referred to as a molecular sieve of the present invention) whose chemical composition formula is represented by an oxide form: Al 2 O 3 ⁇ SiO 2 ⁇ M 2 O ⁇ Z x O y , wherein the M is at least one selected from the group consisting of alkali metals, and Z is at least one selected from the group consisting of Mg, Ca, Zn, Ti, Fe, Ga, Ge, B, P, and rare earth metals, x The number of atoms representing Z is an integer of 1 to 6, and y represents the number required to satisfy the Z oxidation state. In terms of molar ratio, Al 2 O 3 : SiO 2 : M 2 O: Z x O y is 1: (100) ⁇ 300): (0 to 100): (0 to 100).
  • the silica/alumina molar ratio is from 100 to 300.
  • the mesopore surface area in the molecular sieve is from 30 m 2 /g to 280 m 2 /g, preferably from 50 m 2 /g to 250 m 2 /g, more preferably It is 80 m 2 /g to 200 m 2 /g, more preferably 100 m 2 /g to 180 m 2 /g, still more preferably 120 m 2 /g to 150 m 2 /g.
  • a specific surface area of the molecular sieve may be 150m 2 / g ⁇ 400m 2 / g, preferably from 180m 2 / g ⁇ 350m 2 / g, more preferably 200m 2 / g ⁇ 320m 2 / g, still more preferably 240m 2 / g ⁇ 300m 2 / g, still more preferably 260m 2 / g ⁇ 280m 2 / g.
  • the molecular sieve of the present invention has a mesoporous surface area ratio of 20% to 70%, preferably 25% to 65%, more preferably 28% to 60%, still more preferably 30% to 55%, more preferably 35% to 50%.
  • the molecular sieve of the present invention may be a ten-membered ring-aluminum silica molecular sieve having mesopores or a twelve-membered cycloaluminum molecular sieve having mesopores.
  • the molecular sieve of the present invention may be selected from the group consisting of ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, Nu-10, Nu-13, Nu-87, EU-1, EU-13. At least one of ITQ-13, ZSM-12 and Beta molecular sieves, preferably ZSM-22 or Beta molecular sieves.
  • the invention also provides an aqueous molecular sieve precursor whose chemical composition formula is represented by: Al 2 O 3 ⁇ SiO 2 ⁇ M 2 O ⁇ Z x O y ⁇ templating agent ⁇ water, wherein the M, Z, x
  • the molar ratio of Al 2 O 3 to SiO 2 is 1: (20-100)
  • the molar ratio of Al 2 O 3 to M 2 O is 1: (0-100)
  • the molar ratio of 3 to Z x O y is 1: (0 to 100)
  • the molar ratio of Al 2 O 3 to the templating agent is 1: (0.001 to 10)
  • the dry molecular content of the aqueous molecular sieve precursor is 5 weight. From 3% to 30% by weight, preferably from 6% to 15% by weight.
  • the invention also provides a method for producing a molecular sieve having mesopores, the method comprising the steps of:
  • a mother liquor preparation step wherein a mixture comprising an alumina source, a silica source, a templating agent, an optional alkali metal oxide source, an optional third oxide source, and water (hereinafter simply referred to as a mixture) is subjected to crystallization conditions Decrystallization to obtain a crystallized mother liquor;
  • the filter cake is directly calcined to obtain a molecular sieve precursor
  • the hydrothermally treated product is filtered, optionally washed, dried, and calcined.
  • the invention also provides a preparation method of an aqueous molecular sieve precursor, which comprises the following steps:
  • a mother liquor preparation step wherein a mixture comprising an alumina source, a silica source, a templating agent, an optional alkali metal oxide source, an optional third oxide source, and water (hereinafter simply referred to as a mixture) is subjected to crystallization conditions Decrystallization to obtain a crystallized mother liquor;
  • the step of preparing the aqueous molecular sieve precursor the step of filtering the crystallized mother liquor to obtain an aqueous molecular sieve precursor, wherein the aqueous molecular sieve precursor has a dry basis content of 5 wt% to 30 wt%, preferably 6 wt% % to 15% by weight.
  • the invention also provides a catalyst comprising a support and an active metal component supported on the support.
  • the active metal component is highly dispersed on the molecular sieve.
  • the individual particles of the active metal component have a size of less than 3 nm, for example 0.1 to 2.8 nm.
  • the invention also provides a preparation method of a catalyst, comprising the following steps:
  • the present invention provides a hydroisomerization catalyst in which at least one active metal component selected from the group VIII noble metals is supported on the molecular sieve of the present invention.
  • the present invention provides a hydroisomerization process in which the hydroisomerization catalyst of the present invention is used.
  • the ratio of the pore volume to the surface area in the molecular sieve is decreased, and the ratio of the mesopore volume to the surface area is increased, whereby the reactant easily enters the mesopores of the molecular sieve during the reaction, and The mesoporous surface area is increased, whereby the molecular sieve can provide more reactive sites in the pores.
  • the catalytic efficiency of the catalyst can be greatly improved, and the physical properties of the obtained product can be improved.
  • hydroisomerization catalyst of the present invention after the raw material oil is treated, an excellent heterogeneous pour point depressing effect can be achieved.
  • the service life of the catalyst can be greatly improved, and the active metal as a catalytic site is highly dispersed in the carrier, thereby further enhancing the activity of the catalyst.
  • Example 1 is a 27 Al NMR spectrum of the molecular sieve precursor C-1-1 prepared in Example 1-1.
  • Figure 3 is an XRD pattern of the molecular sieve finished product H-1-1 prepared in Example 1-1.
  • Example 4 is a nitrogen adsorption-desorption curve of the molecular sieve finished product H-1-1 prepared in Example 1-1.
  • Figure 5 is a 27 Al NMR spectrum of the molecular sieve precursor DC-1-2 prepared in Comparative Example 1-2.
  • Figure 6 is a nitrogen adsorption-desorption curve of the molecular sieve finished product DH-1-2 prepared in Comparative Example 1-2.
  • Figure 7 is a 27 Al NMR spectrum of the molecular sieve precursor C-2-1 prepared in Example 2-1.
  • Figure 8 is a 27 Al NMR spectrum of the molecular sieve finished product H-2-1 prepared in Example 2-1.
  • Figure 9 is an XRD pattern of the molecular sieve finished product H-2-1 prepared in Example 2-1.
  • Figure 10 is a nitrogen adsorption-desorption curve of the molecular sieve finished product H-2-1 prepared in Example 2-1.
  • Figure 11 is a 27 Al NMR spectrum of the molecular sieve precursor DC-2-2 prepared in Comparative Example 2-2.
  • Figure 12 is a nitrogen adsorption-desorption curve of the molecular sieve finished product DH-2-2 prepared in Comparative Example 2-2.
  • hydrocarbons or hydrocarbon derivative groups of more than 3 carbon atoms such as propyl, propoxy, butyl, unless otherwise explicitly defined, or the meaning is beyond the understanding of those skilled in the art
  • butane, butene, butenyl, hexane, etc. have the same meaning as when the prefix is "positive" when the prefix is "positive”.
  • propyl is generally understood to be n-propyl
  • butyl is generally understood to be n-butyl.
  • the number followed by a carbon atom means the number of carbon atoms, for example, C2-C7 means a number of carbon atoms of 2-7, and when used for a compound, it means the number of carbon atoms contained in the compound, for example, C2-
  • the C7 carboxylic acid means a carboxylic acid having 2 to 7 carbon atoms.
  • aqueous molecular sieve precursor the intermediate after calcination of the filter cake obtained from the crystallization mother liquor.
  • the structure of the molecular sieve is determined by X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • the X-ray diffraction spectrum (XRD) was measured by an X-ray powder diffractometer using a Cu-K ⁇ ray source and a nickel filter.
  • SEM scanning electron microscope
  • the term "specific surface area” refers to the total area of a unit mass sample, including internal surface area and external surface area.
  • Non-porous samples have only external surface areas, such as Portland cement, some clay mineral particles, etc.; porous and porous samples have external surface area and internal surface area, such as asbestos fibers, diatomaceous earth and molecular sieves.
  • the comparative area in the present invention is measured using a BET method well known in the art.
  • mesopore refers to a pore in the molecular sieve having a pore diameter of from 2 to 50 nm
  • mesoporous surface area refers to the surface area of a pore having a pore diameter of from 2 to 50 nm.
  • the mesoporous surface area of the present invention can be calculated by the BET method using the BET equation and the t-plot equation.
  • dry basis is defined as the percentage of the mass of the material after calcination at 600 ° C for 4 hours in an air atmosphere relative to the mass of the substance before calcination.
  • the physical property values (such as boiling points) of the substance are measured at normal temperature (25 ° C) and atmospheric pressure (101325 Pa) unless otherwise specified.
  • the present invention relates to a molecular sieve having mesopores.
  • the molecular sieve of the present invention has mesopores which are not possessed by molecular sieves synthesized in the prior art.
  • the present invention provides a molecular sieve having mesopores, the chemical composition formula of which is represented by an oxide form: Al 2 O 3 ⁇ SiO 2 ⁇ M 2 O ⁇ Z x O y , wherein the M is selected From at least one of the alkali metals, Z is at least one selected from the group consisting of Mg, Ca, Zn, Ti, Fe, Ga, Ge, B, P, and a rare earth metal, and x represents the atomic number of Z, which is 1 to 6
  • the integer, y represents the number required to satisfy the Z oxidation state, and in terms of molar ratio, Al 2 O 3 : SiO 2 : M 2 O: Z x O y is 1: (100 to 300): (0 to 100): (0 to 100).
  • molecular sieves sometimes contain a certain amount of water (especially just after preparation is completed), but it is considered that it is not necessary to specify the amount of water because the water is usually channel water, and its presence and No does not substantially affect the composition of the molecular sieve and its XRD spectrum.
  • the chemical composition of the present invention actually represents the anhydrous chemical composition of the molecular sieve.
  • the molecular sieve has a silica/alumina (SiO 2 /Al 2 O 3 ) molar ratio (silicon to aluminum ratio) of usually less than 100.
  • the silica/alumina (SiO 2 /Al 2 O 3 ) molar ratio of the mesoporous molecular sieve according to the present invention is from 100 to 300.
  • the silica/alumina molar ratio may be, for example, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280. 290, 300 and any value of the range formed by any two of these point values.
  • the silica/alumina molar ratio of the mesoporous molecular sieve is preferably from 120 to 260, more preferably from 150 to 200.
  • the mesoporous molecular sieve of the present invention represented by an oxide composition, in addition to aluminum oxide and silicon oxide, optionally containing at least one alkali metal oxide (M 2 O), such as lithium oxide, oxidation Sodium, potassium oxide, cerium oxide, cerium oxide.
  • M 2 O alkali metal oxide
  • the molar ratio of the alkali metal oxide to the Al 2 O 3 is 0 to 100, and may be 0.01 to 80, 0.05 to 60, 0.1 to 40, or 1 to 20 .
  • the molar ratio of the alkali metal oxide may be 0.005, 0.01, 0.03, 0.05, 0.08, 0.1, 0.3, 0.5, 0.8, 1, 5, 10, 15, 25, 30 with respect to Al 2 O 3 .
  • the molecular sieve has a molar ratio of the alkali metal oxide of 0 (ie, does not contain an alkali metal oxide). In one embodiment of the invention, the molecular sieve has a molar ratio of the alkali metal oxide of from 1 to 50. When the molecular sieve of the present invention contains two or more alkali metal oxides, the molar ratio is the total of all alkali metal oxides.
  • the molecular sieve of the present invention may be represented by an oxide composition, and may further optionally contain an oxide of at least one selected from the group consisting of Mg, Ca, Zn, Ti, Fe, Ga, Ge, B, P, and a rare earth metal (Z).
  • Z a rare earth metal
  • x O y hereinafter also referred to as the third oxide).
  • x represents the number of atoms of Z and is an integer of 1 to 6
  • y represents the number required to satisfy the Z oxidation state.
  • x is preferably 1, 2, 3 or 4.
  • the molar ratio of the oxide selected from at least one of Mg, Ca, Zn, Ti, Fe, Ga, Ge, B, P, and rare earth metals is from 0 to 100 with respect to Al 2 O 3 , which may be 0.01 to 80, which may be 0.05 to 60, may be 0.1 to 40, and may be 1 to 20.
  • the molar ratio of the third oxide may be 0.005, 0.01, 0.03, 0.05, 0.08, 0.1, 0.3, 0.5, 0.8, 1, 5, 10, 15, 25, 30 with respect to Al 2 O 3 . 35, 45, 50, 55, 65, 70, 75, 80 and any value of the range formed by any two of these point values.
  • the third oxide in the molecular sieve, has a molar ratio of 0 (ie, does not contain the third oxide). In one embodiment of the invention, the molar ratio of the third oxide in the molecular sieve is from 3 to 50. When the molecular sieve of the present invention contains two or more third oxides, the molar ratio is the total of all the third oxides.
  • the mesoporous molecular sieve is characterized by a nitrogen adsorption BET (Brunner Emmet Teller) method, and the mesopore surface area in the molecular sieve is from 30 m 2 /g to 280 m 2 /g, preferably 50 m 2 /g to 250 m 2 /g, more preferably 80 m 2 /g to 200 m 2 /g, still more preferably 100 m 2 /g to 180 m 2 /g, still more preferably 120 m 2 /g to 150 m 2 /g.
  • BET Brunauer-E Teller
  • the molecular sieve having mesoporous nitrogen adsorption BET (Brunner Emmet Teller) method of characterizing a specific surface area of the molecular sieve may be 150m 2 / g ⁇ 400m 2 / g, preferably from 180m 2 / g ⁇ 350m 2 / g, more preferably 200m 2 / g ⁇ 320m 2 / g, still more preferably 240m 2 / g ⁇ 300m 2 / g, still more preferably 260m 2 / g ⁇ 280m 2 / g.
  • the ratio of the mesopore surface area to the molecular sieve specific surface area may be 20% to 70%, preferably 25% to 65%, and more preferably 28% to 60%. % is more preferably 30% to 55%, still more preferably 35% to 50%.
  • the mesoporous molecular sieve of the present invention contains a mesoporous structure.
  • the standard for mesopores is defined as pores of 2 to 50 nm.
  • the pore diameter of the mesopores is in the range of the numerical value, but it is not intended that the lower limit of the mesopores of the present invention must be 2 nm, and the upper limit of the mesopores must be 50 nm.
  • the mesoporous of the molecular sieve of the present invention means that, as described above, the ratio of the mesoporous surface area to the surface area of the molecular sieve may be from 20% to 70%, preferably from 25% to 65%, more preferably from 28% to 60%, more preferably. It is 30% to 55%, more preferably 35% to 50%.
  • molecular sieves prepared by the prior art do not have this feature, i.e., there is no hysteresis loop or the starting position of the hysteresis loop in this interval occurs at a higher partial pressure (usually at P/P0 > 0.7).
  • the precursor of the mesoporous molecular sieve of the present invention is enriched in pentacoordinated aluminum, while the content of pentacoordinated aluminum in the finished molecular sieve is small.
  • the content of the pentacoordinate aluminum in the precursor of the molecular sieve having mesopores is 4% to 35%, preferably 10% to 30%, more preferably 15 % ⁇ 25%.
  • the content of the pentacoordinate aluminum in the finished product of the molecular sieve is 5% or less, preferably 3% or less, more preferably 2% or less, still more preferably 1% or less.
  • the molecular sieve finished product is substantially free of pentacoordinated aluminum.
  • the mesoporous molecular sieve of the present invention is a ten-membered ring-aluminum silica molecular sieve having mesopores or a twelve-membered cycloaluminum molecular sieve having mesopores. More specifically, as the ten-membered ring molecular sieve, it may be ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, Nu-10, Nu-13, Nu-87, EU At least one of -1, EU-13 and ITQ-13, preferably ZSM-22. As the twelve-membered ring molecular sieve, it may be a Beta molecular sieve or ZSM-12.
  • the present invention also provides an aqueous molecular sieve precursor having a chemical composition formula of: Al 2 O 3 ⁇ SiO 2 ⁇ M 2 O ⁇ Z x O y ⁇ templating agent ⁇ water, wherein the M, Z, x, The meaning of y is the same as above, and the molar ratio of Al 2 O 3 to SiO 2 is 1: (20 to 100), preferably 1: (25 to 90), and more preferably 1: (30 to 80).
  • the molar ratio of Al 2 O 3 to M 2 O is 1: (0 to 100), preferably 1: (0.001 to 90), more preferably 1: (0.05 to 80), still more preferably 1: (0.1 to 70) Further, it is more preferably 1: (0.5 to 60), still more preferably 1: (1 to 50).
  • the molar ratio of Al 2 O 3 to Z x O y is 1: (0 to 100), preferably 1: (0.001 to 90), more preferably 1: (0.05 to 80), still more preferably 1: (0.1) 70) is more preferably 1: (0.5 to 60), still more preferably 1: (1 to 50).
  • the molar ratio of Al 2 O 3 to the templating agent is 1: (0.001 to 10), preferably 1: (0.005 to 5), more preferably 1: (0.01 to 4), still more preferably 1: (0.05 to 3) Further, it is preferably 1: (0.1 to 2), more preferably 1: (0.5 to 1.5), still more preferably 1: (0.8 to 1).
  • the aqueous molecular sieve precursor has a dry basis content of from 5% by weight to 30% by weight.
  • the dry molecular content of the aqueous molecular sieve precursor may be 6 wt%, 7 wt%, 8 wt%, 10 wt%, 11 wt%, 12 wt%, 14 wt%, 15 wt%, 17 wt%, 18 wt%. Any value of the range of %, 20% by weight, 22% by weight, 25% by weight, 27% by weight, and any two of these point values.
  • the dry molecular content of the aqueous molecular sieve precursor is preferably from 6% by weight to 15% by weight.
  • the templating agent of the present invention can be used as the templating agent.
  • the mesoporous molecular sieve of the present invention can be produced by the following production method.
  • the present invention also provides a method for producing a molecular sieve having mesopores, the method comprising the steps of: comprising an alumina source, a silica source, a templating agent, an optional alkali metal oxide source, optionally a mixture of a third oxide source and water (hereinafter simply referred to as a mixture) is crystallized under crystallization conditions to obtain the crystallization mother liquid (hereinafter also referred to as a mother liquid preparation step); the mother liquid after crystallization is filtered, a step of forming a filter cake having a dry content of 5 to 30% by weight (hereinafter also referred to as a filtration step); a step of directly calcining the filter cake to obtain a molecular sieve precursor (hereinafter also referred to as a precursor preparation step) a step of hydrothermally treating the molecular sieve precursor (hereinafter
  • the mother liquor preparation step can be carried out in accordance with a conventional method for preparing a mother liquid after crystallization in the art.
  • the mother liquor preparation step may vary depending on the type of molecular sieve prepared.
  • the method of preparing the mother liquor after crystallization can be referred to the method of U.S. Patent Application No. 5,200,168.
  • the preparation of the mother liquor after crystallization can be referred to the method of O. Muraza et al., Microporous and Mesoporous Materials 206 (2015) 136-143.
  • the preparation of the mother liquor after crystallization can be referred to the method of P. Me'riaudeau et al/Journal of Catalysis, 1999 (185), 435-444, or by reference to US Patent Application US5961951.
  • the method for preparing the crystallization mother liquid comprises: preparing a silicon-containing source solution, an aluminum-containing source solution, an optional alkaline solution (alkali metal source solution), and optionally a third oxide.
  • a mixture of source solutions is prepared by mixing the above liquids, followed by crystallization.
  • the method for preparing the crystallization mother liquid comprises: adding a silicon source, an aluminum source, an optional alkali metal source, and an optional third oxide source to a solvent, and performing the obtained solution. Gelation treatment followed by crystallization.
  • the crystallization of the mother liquor preparation step is as follows: dissolving an alumina source, a templating agent, and an optional alkali metal oxide source in water to prepare a raw solution;
  • the above raw solution is optionally activated at 50 to 160 ° C (preferably 60 to 150 ° C, more preferably 90 to 140 ° C, further preferably 95 to 130 ° C) for 2 to 24 hours (preferably 4 to 22 hours, more preferably 6 to). 20 hours, further preferably 8 to 18 hours, a mixed solution is obtained.
  • the mixed solution may be prepared without performing the above heat activation treatment.
  • a silica source, an optional third oxide source, and the above-mentioned mixed solution are mixed and stirred; the obtained slurry is at 120 to 180 ° C (preferably 130 to 170 ° C, more preferably 140 to 160 ° C, further preferably 145). ⁇ 155° C.) maintaining a constant temperature for 24 to 150 hours (preferably 30 to 130 hours, more preferably 35 to 120 hours, still more preferably 40 to 100 hours, still more preferably 50 to 80 hours), and performing a crystallization treatment to prepare a mother liquid after crystallization .
  • the conditions for preparing the mother liquid after crystallization are not particularly limited as long as the mother liquid after crystallization for preparing the molecular sieve of the present invention can be prepared.
  • examples of the silica source include silicic acid, silica gel, silica sol, tetraalkyl silicate or water glass. These silica sources may be used singly or in combination of a plurality of them in a desired ratio.
  • examples of the alumina source include aluminum hydroxide, sodium aluminate, aluminum salt, aluminum alkoxide, kaolin or montmorillonite, aluminum sulfate, aluminum nitrate, and carbonic acid.
  • any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the corresponding one of the third oxides.
  • the magnesium source include magnesium sulfate, magnesium chloride, magnesium nitrate, and magnesium gluconate.
  • the calcium source include calcium hydroxide, calcium sulfate, calcium chloride, and calcium nitrate.
  • the zinc source include zinc sulfate, zinc chloride, and zinc nitrate.
  • Examples of the titanium source include titanium tetraalkoxide, titanium oxide, and titanium nitrate.
  • iron source iron chloride, iron nitrate, and iron sulfate can be used.
  • Examples of the gallium source include gallium nitrate, gallium sulfate, and gallium oxide.
  • Examples of the cerium source include a tetraalkoxy cerium, cerium oxide, cerium nitrate, and the like.
  • Examples of the boron source include boric acid, borate, borax, and boron trioxide.
  • Examples of the phosphorus source include phosphoric acid, phosphate, and phosphorus pentoxide.
  • Examples of the rare earth metal source include cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium nitrate, cerium nitrate, cerium nitrate, ammonium cerium sulfate, and the like.
  • an alkali metal acid salt, an acetate, an oxalate, an ammonium salt, a sulfate, a nitrate or the like can be used as the alkali metal oxide source.
  • an alkali metal hydroxide which functions as an alkaline solution can be used as the alkali metal source.
  • a templating agent for synthesizing molecular sieves well known to those skilled in the art can be used.
  • it can be used to prepare ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, Nu-10, Nu-13, Nu-87, EU-1, EU-13.
  • a commonly used template for ITQ-13, ZSM-12 and Beta molecular sieves can be used.
  • a templating agent which can be used includes an amine compound, a quaternary phosphorus compound, and a quaternary ammonium compound.
  • the latter two can usually be represented by the formula (R 4 X + ⁇ counterion), wherein X is nitrogen or phosphorus, and each R independently represents a C1-C12 linear or branched alkyl group, a C5-C10 cycloalkane.
  • a C6-C12 aryl group, a C1-C12 alkyl C6-C12 aryl group, and the coordination number of R 4 X + varies depending on the valence of the counter ion, and may be 1 or 2, and the counter ion represents a valence and R 4 X +
  • a group of equivalent negative ions may be selected from the group consisting of chloride, fluoride, bromide, nitrate, sulfate, and hydroxide.
  • a monoamine, a diamine, and a triamine, including a mixed amine as a templating agent may be used as a templating agent, or a templating agent obtained by mixing a plurality of templating agents.
  • representative templating agents include: tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tetraamylammonium salt di-n-polyamine, trimerization Amine, triethylamine, triethanolamine, cycloethylamine, lutidine, diethylpyridine, N,N-dimethylbenzene, N,N-diethanol, dicycloethyl, N,N-di Methylethanolamine, 1,4-diazabicyclo(2,2,2)octane ion, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t -butylamine, pyrrolidine and 2-imidazolidone, cetyltrimethylammonium bromide, tetramethylammonium hydro
  • the crystallized mother liquor is filtered to form a filter cake having a dry content of from 5% by weight to 30% by weight.
  • the purpose of filtering the mother liquor after crystallization is to remove the excess mother liquor.
  • the filtration conditions are controlled such that the dry basis content in the formed filter cake is within a specific range. Specifically, in the present invention, the filter cake has a dry basis content of from 5% by weight to 30% by weight.
  • the dry content of the filter cake may be 6 wt%, 7 wt%, 8 wt%, 10 wt%, 11 wt%, 12 wt%, 14 wt%, 15 wt%, 17 wt%, 18 wt%, 20% by weight, 22% by weight, 25% by weight, 27% by weight, and any value in the range of any two of these point values.
  • the filter cake preferably has a dry basis content of from 6% by weight to 15% by weight.
  • the filter cake is directly calcined, thereby obtaining a molecular sieve precursor.
  • the filter cake obtained in the filtration step is directly calcined at a high temperature without being subjected to a drying treatment.
  • the calcination temperature is from 300 ° C to 900 ° C, preferably from 350 ° C to 800 ° C, more preferably from 400 ° C to 700 ° C, still more preferably from 450 ° C to 600 ° C, further It is preferably 450 ° C to 550 ° C.
  • the heating rate during calcination may be from 5 ° C / min to 100 ° C / min, preferably from 10 ° C / min to 50 ° C / min, more preferably from 20 ° C / min to 40 ° C / min, It is still more preferably 30 ° C / min to 40 ° C / min.
  • the calcination time may be from 1 hour to 20 hours, preferably from 2 hours to 16 hours, more preferably from 5 hours to 15 hours, still more preferably from 6 hours to 12 hours.
  • the calcination environment may be a natural environment, that is, it is not required to specifically introduce an oxygen-containing gas during calcination, or may be calcined by introducing oxygen as needed.
  • the inventors of the present invention presume that by calcination, the residual water in the filter cake can oxidize and remove the templating agent, and at the same time, by the calcination under such conditions, the water and the aluminum in the molecular sieve can also be carried out. Act to form non-framework aluminum.
  • the product obtained by the precursor preparation step contains a large amount of pentacoordinated non-framework aluminum (i.e., pentacoordinated aluminum).
  • the molecular sieve precursor has a pentacoordinated aluminum content of from 4% to 35%, preferably from 10% to 30%, more preferably from 15% to 25%.
  • the five-coordinate non-skeletal aluminum is defined as a peak having a chemical shift ⁇ of 10 to 40 ppm in a 27 Al NMR spectrum.
  • the 27 Al NMR spectrum measurement conditions can be found in the published literature, such as Guoliang Zhao et al, Applied Catalysis A: General 299 (2006) 167-174.
  • the molecular sieve precursor obtained after the calcination treatment can be cooled by natural cooling. It is preferred to cool down to room temperature.
  • the molecular sieve precursor is subjected to a hydrothermal treatment.
  • the hydrothermally treated medium is an acidic aqueous solution.
  • the acidic aqueous solution means an aqueous solution containing H + .
  • the water can be tap water, purified water, deionized water, and the like.
  • H + is an ion released by dissociation of an organic acid and/or an inorganic acid.
  • hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexane may be added to the water.
  • At least one of amine tetraacetic acid, tartaric acid and malic acid is preferably hydrochloric acid and/or citric acid.
  • the content of the inorganic acid and/or the organic acid in the acidic aqueous solution may be from 0.01 M to 5 M, preferably from 0.05 M to 2 M, more preferably from 0.2 M to 1.5 M, further preferably 0.5. It is -1.2 M, and more preferably 0.8 to 1.1 M.
  • the liquid-solid content ratio in the hydrothermal treatment step, may be 5 to 200, preferably 20 to 100, more preferably 40 to 80, still more preferably 50 to 70.
  • the hydrothermal treatment in the hydrothermal treatment step, may have a temperature of 80 ° C to 300 ° C, preferably 100 ° C to 200 ° C, more preferably 120 ° C to 180 ° C, and still more preferably 140 ° C ⁇ 160 ° C.
  • the hydrothermal treatment in the hydrothermal treatment step, may be carried out for a period of from 0.1 to 24 hours, preferably from 0.5 to 18 hours, more preferably from 1 to 12 hours, still more preferably 2 hours. ⁇ 10 hours.
  • the hydrothermal treatment in the hydrothermal treatment step, may be carried out in an open vessel or in a closed vessel. It is preferably carried out in a closed container.
  • the hydrothermal treatment pressure is a self-pressure formed by a closed vessel under hydrothermal conditions.
  • the hydrothermally treated product is filtered and optionally subjected to washing and drying.
  • the filtration method is not particularly limited and may be a method known to those skilled in the art, such as filtration, suction filtration using a Buchner funnel, or the like.
  • the washing method is not particularly limited, and water washing can be carried out using deionized water.
  • the water is washed until the filtrate has a pH of 4 to 8, preferably a pH of 6 to 7.
  • the pH measurement of the solution can be measured by a pH test paper or a pH meter, and the measurement method is not particularly limited and can be a method known to those skilled in the art.
  • the molecular sieve obtained by filtration is optionally dried.
  • the drying method is not particularly limited and may be a method known to those skilled in the art, and for example, it may be dried at 120 ° C for 6 hours in accordance with a conventional method.
  • calcination is further carried out, which is a condition commonly used in the preparation of molecular sieves in the art, and may be a calcination condition in the above-mentioned precursor preparation step. For example, it can be calcined at 400 ° C to 600 ° C for 2 to 8 hours.
  • the mesoporous molecular sieve of the present invention can be obtained.
  • the molecular sieves prepared in the prior art do not have a hysteresis loop or a starting position of the hysteresis loop at the higher partial pressure (usually at P/P0 > 0.7).
  • the invention also provides a preparation method of an aqueous molecular sieve precursor, which comprises the following steps:
  • a mother liquor preparation step wherein a mixture comprising an alumina source, a silica source, a templating agent, an optional alkali metal oxide source, an optional third oxide source, and water (hereinafter simply referred to as a mixture) is subjected to crystallization conditions Decrystallization to obtain a crystallized mother liquor;
  • a step of preparing a water-containing molecular sieve precursor wherein the crystallization of the mother liquor is carried out to obtain an aqueous molecular sieve precursor, wherein the aqueous molecular sieve precursor has a dry basis content of 5 wt% to 30 wt%, preferably 6 wt% to 15 wt%.
  • the ratios and conditions of the respective components in the mother liquid preparation step are the same as those in the mother liquor preparation step in the above-described molecular sieve preparation method of the present invention.
  • the aqueous molecular sieve precursor can be prepared by the method for preparing the aqueous molecular sieve precursor of the present invention.
  • the dry basis content of the aqueous molecular sieve precursor may be the dry basis content of the filter cake obtained in the above filtration step of the present invention.
  • the aqueous molecular sieve precursor can be directly used in the precursor preparation step in the method for producing the above molecular sieve of the present invention.
  • the mesoporous molecular sieve of the present invention can be directly used as a solid acid catalyst. Further, in one embodiment of the present invention, an active component may be carried on the molecular sieve having mesopores according to the present invention to prepare a catalyst.
  • the catalyst of the present invention thus obtained not only has good hydroisomerization activity, but also has a high yield of the target product in the obtained product and a low pour point of the product.
  • the invention also provides a catalyst comprising a support and an active metal component supported on the support.
  • the active metal component is at least one selected from the group VIII noble metals.
  • the Group VIII noble metal is preferably at least one selected from the group consisting of ruthenium, rhodium, palladium, platinum, rhodium, and iridium.
  • the active metal component is a combination of a platinum component and a palladium component.
  • the molar ratio of the Pt component to the Pd component is from 1:2 to 10, preferably from 1:2 to 8, more preferably from 1:2 to 6, more preferably 1:2. 4.
  • the active metal component in the catalyst of the invention, is in a highly dispersed state on the support.
  • the individual particles of the active metal component have a size of less than 3 nm, and may be, for example, 0.1 to 2.8 nm.
  • the active metal component may be provided by an active metal component precursor.
  • the active metal component precursor is preferably a compound selected from the group consisting of Group VIII noble metal elements.
  • the compound containing a Group VIII noble metal element it may be selected from the group consisting of nitrates, chlorides, sulfates, formates, acetates, phosphates, citrates, oxalates, carbons containing a noble metal element of Group VIII.
  • the content of the active metal component based on the elemental weight may be appropriately selected as required based on the total weight of the catalyst, and may be usually 0.001% by weight to 5% by weight, preferably 0.005% by weight to 4.5% by weight.
  • the weight % is preferably 0.01% by weight to 4% by weight, more preferably 0.1% by weight to 3% by weight, still more preferably 0.2% by weight to 1% by weight, still more preferably 0.4% by weight to 0.8% by weight.
  • porous carrier those organic or inorganic porous solids conventionally used as a carrier in the production of a supported catalyst in the art can be cited.
  • examples of the organic porous solid include an olefin homopolymer or copolymer, polyvinyl alcohol or a copolymer thereof, a cyclodextrin, a (co)polyester, a (co)polyamide, and a vinyl chloride.
  • a polymer or copolymer an acrylate homopolymer or copolymer, a methacrylate homopolymer or copolymer, a styrene homopolymer or copolymer, and the like, and a partially crosslinked form of these homopolymers or copolymers, Among them, a styrene polymer which is partially crosslinked (for example, a degree of crosslinking of at least 2% but less than 100%) is preferred.
  • the organic porous solid is subjected to a heat activation treatment and/or a chemical activation treatment prior to use.
  • the organic porous solid may be subjected to only heat activation treatment before use, or may be subjected to only chemical activation treatment before use, or the heat activation treatment and the treatment may be sequentially performed in any combination order before use.
  • the chemical activation treatment is not particularly limited.
  • the organic porous solid is heat treated, for example, under reduced pressure or under an inert atmosphere.
  • the inert atmosphere as used herein means that the gas contains only a very small amount or no component which can react with the organic porous solid.
  • the inert atmosphere for example, nitrogen gas or a rare gas atmosphere may be mentioned, and a nitrogen atmosphere is preferable. Since the heat resistance of the organic porous solid is poor, the heat activation process is premised on not destroying the structure and basic composition of the organic porous solid itself.
  • the heat activation temperature is from 50 to 400 ° C, preferably from 100 to 250 ° C
  • the heat activation time is from 1 to 24 h, preferably from 2 to 12 h.
  • the organic porous solid needs to be stored under positive pressure under an inert atmosphere for use.
  • a refractory oxide of a metal of Group IIA, IIIA, IVA or IVB of the periodic table such as silica (also called silica or silica gel), alumina, magnesia, oxidation
  • a metal of Group IIA, IIIA, IVA or IVB of the periodic table such as silica (also called silica or silica gel), alumina, magnesia, oxidation
  • titaniumium, zirconia or yttrium oxide, etc., or any refractory composite oxide of these metals such as silica alumina, magnesia alumina, titania, titanium oxide, titanium oxide, etc.
  • clays such as ZSM-5 and MCM-41
  • mica montmorillonite
  • bentonite and diatomaceous earth
  • Examples of the inorganic porous solid include oxides formed by hydrolysis of a gaseous metal halide or a gaseous silicon compound by high temperature, such as silica gel obtained by high temperature hydrolysis of silicon tetrachloride, or high temperature hydrolysis of aluminum trichloride. Alumina, etc.
  • silica, alumina, magnesia, silica alumina, magnesia alumina, titania, titania, molecular sieve, montmorillonite or the like is preferable, and silica and montmorillonite are particularly preferable.
  • suitable silica can be produced by a conventional method, or can be any commercially available product, such as Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace, Grace. SP9-10046, Davsion Syloid 245 and Aerosil 812, ES70, ES70X, ES70Y, ES70W, ES757, EP10X and EP11 from Ineos, and CS-2133 and MS-3040 from PQ.
  • the inorganic porous solid is subjected to a heat activation treatment and/or a chemical activation treatment prior to use.
  • the inorganic porous solid may be subjected to only heat activation treatment before use, or may be subjected to only chemical activation treatment before use, or the heat activation treatment and the treatment may be sequentially performed in any combination order before use.
  • the chemical activation treatment is not particularly limited.
  • the heat activation treatment can be carried out in a usual manner, such as heat treatment of the inorganic porous solid under reduced pressure or under an inert atmosphere.
  • the inert atmosphere as used herein means that the gas contains only a very small amount or does not contain a component which can react with the inorganic porous solid.
  • nitrogen gas or a rare gas atmosphere may be mentioned, and a nitrogen atmosphere is preferable.
  • the heat activation temperature is 200 to 800 ° C, preferably 400 to 700 ° C, most preferably 400 to 650 ° C
  • the heating time is, for example, 0.5 to 24 h, preferably 2 to 12 h, and most preferably 4 to 8 h.
  • the inorganic porous solid needs to be stored under positive pressure under an inert atmosphere for use.
  • the carrier is the above-described mesoporous molecular sieve of the invention.
  • the mesoporous molecular sieve is a ten-membered ring-aluminum silica molecular sieve having mesopores or a twelve-membered cycloaluminum molecular sieve having mesopores.
  • the ten-membered ring molecular sieve it may be ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, Nu-10, Nu-13, Nu-87, EU-1, EU- At least one of 13 and ITQ-13, preferably ZSM-22.
  • the twelve-membered ring molecular sieve it may be ZSM-12 or Beta molecular sieve.
  • the carrier is a combination of the above-described mesoporous molecular sieve of the invention and a carrier other than the molecular sieve of the invention.
  • the metal carrier of the present invention may further support a group selected from at least one of Mg, Ca, Zn, Ti, Fe, Ga, Ge, B, P, and a rare earth metal. Parts (hereinafter also referred to as auxiliary ingredients).
  • the content of the auxiliary component based on the elemental weight may be appropriately selected as needed, and may be usually 0.001% by weight to 5 parts by weight based on the total weight of the catalyst.
  • % is preferably 0.005 wt% to 4.5 wt%, preferably 0.01 wt% to 4 wt%, more preferably 0.1 wt% to 3% wt%, still more preferably 0.2 wt% to 1 wt%, still more preferably 0.4 wt%. ⁇ 0.8% by weight.
  • the invention also provides a preparation method of a catalyst, comprising the following steps:
  • the catalyst is prepared by a two-step impregnation method, and the first impregnation and the second impregnation are respectively used to introduce the active metal component and the organic complexing agent.
  • the first impregnation process an organic complexing agent is added and converted into char by roasting, thereby not only improving the activity of the catalyst, but also effectively maintaining the high activity of the catalyst for a long time, thereby greatly increasing the service life of the catalyst.
  • the inventors of the present invention speculate that the reason may be due to the organic complexing agent added during the first impregnation process, and the presence of the organic complexing agent hinders the aggregation of the active metal on the carrier during the calcination process.
  • the dispersion is more uniform on the carrier; at the same time, the first step of post-impregnation calcination can convert the metal compound into a metal oxide, and the organic complexing agent is converted into carbon, thereby making the bond between the active metal and the carrier stronger and improving.
  • the activity and stability of the catalyst; the organic complexing agent added during the second impregnation process covers the surface of the catalyst, can effectively prevent the aggregation between the active metals during the reduction process, and ensures high metal dispersion, thereby further improving Catalyst activity. Therefore, by the preparation method of the catalyst of the present invention, the problem of uneven distribution of the active metal component on the catalyst can be effectively solved. Thereby, the active metal component is highly dispersed on the support, thereby greatly increasing the catalytic activity of the catalyst while prolonging the service life of the catalyst.
  • the organic complexing agent used in the step (I) may be at least one selected from the group consisting of an oxygen-containing organic compound, an organic acid, and a nitrogen-containing organic compound.
  • the oxygen-containing organic substance may be a dihydric or higher polyhydric alcohol, preferably a polyhydric alcohol having 2 to 6 carbon atoms or an oligomer or a polymer thereof, and for example, ethylene At least one of an alcohol, glycerin, polyethylene glycol, diethylene glycol, and butylene glycol.
  • the polyethylene glycol preferably has a molecular weight of 200 to 1,500.
  • the organic acid may be a C2-C15 compound having one or more carboxyl groups, and specific examples thereof include acetic acid, maleic acid, oxalic acid, aminotriacetic acid, and 1,2-cyclohexane. At least one of diaminetetraacetic acid, citric acid, tartaric acid, and malic acid.
  • the nitrogen-containing organic substance may be at least one of an organic amine and an organic ammonium salt.
  • the organic amine is preferably a C2-C10 compound containing one or more amino groups, and may be a primary amine, a secondary amine or a tertiary amine, and particularly preferably ethylenediamine.
  • the organic complexing agent in the step (I) is at least one selected from the group consisting of organic acids, and more preferably, the organic complexing agent of the step (I) is at least one selected from the group consisting of C2 to C15 fatty acids.
  • the organic complexing agent of the step (I) is at least one selected from the group consisting of C2 to C15 fatty acids.
  • the molar ratio of the organic complexing agent to the active metal component precursor may be from 2 to 100:1, preferably from 4 to 80:1, more preferably from 6 to 70:1, More preferably, it is 10-50:1.
  • the impregnation can be carried out by a dipping method well known in the art.
  • the temperature of the immersion liquid at the time of immersion is not particularly limited, and may be various temperatures achievable by the immersion liquid.
  • the time of the immersion is not particularly limited as long as it can load the desired amount of the desired component.
  • the temperature of the immersion is not particularly limited and may be 15 to 60 °C.
  • the immersion time is not particularly limited and may be 0.5 to 5 hours.
  • the mass ratio of the organic compound liquid to the carrier during the immersion is not particularly limited, and may be from 0.6:1 to 2:1, preferably from 0.8:1 to 1.4:1.
  • the drying conditions are not particularly limited and may be various drying conditions known in the art.
  • the drying temperature in the step (1) is 100 to 250 ° C for 1 to 12 hours.
  • the calcination conditions are such that the carbon content in the semi-finished catalyst may be from 0.05% by weight to 0.5% by weight, preferably from 0.1% by weight to 0.4% by weight based on the total amount of the semi-finished catalyst.
  • the above carbon content can be obtained by controlling the calcination temperature in the calcination condition and the permeation amount of the combustion-supporting gas, and the combustion-supporting gas can be a gas having various oxygen contents of not less than 20% by volume, for example, It is at least one of air, oxygen, and a mixed gas thereof.
  • the combustion-supporting gas is supplied in an amount of not less than 0.2 liter/g ⁇ hr.
  • the passage of the combustion-supporting gas satisfies the conditions of combustion, so that the precursor of the active metal component is converted into an active metal oxide, and the organic complexing agent is converted into carbon; on the other hand, the carbon dioxide formed by combustion and Water and other components are emitted to avoid deposition on the catalyst causing steric hindrance to the active phase.
  • the amount of the combustion-supporting gas to be introduced is 0.2 to 20 liters / gram per hour, preferably 0.3 to 10 liters / gram per hour. "G" herein means the weight of the carrier treated.
  • the calcination temperature may be from 350 to 500 ° C, preferably from 360 to 450 ° C.
  • the calcination time may be from 0.5 to 8 hours, preferably from 1 to 6 hours. Controlling the calcination temperature within the above range ensures that the organic complexing agent can form carbon on the support in the above content range to obtain a semi-finished catalyst.
  • the amount of the active metal component precursor in terms of elemental substance may be appropriately selected as needed, and may be usually 0.001% by weight to 5% by weight, preferably 0.005 by weight, based on the weight of the carrier to be impregnated. From 5% to 4.5% by weight, preferably from 0.01% by weight to 4% by weight, more preferably from 0.1% by weight to 3% by weight, still more preferably from 0.2% by weight to 1% by weight, still more preferably from 0.4% by weight to 0.8% by weight.
  • the active metal component precursor used may be the active metal component precursor in the above-described catalyst of the present invention.
  • the carrier to be used may be the carrier used in the above catalyst of the present invention.
  • the carrier in step (I) is preferably a molecular sieve having mesopores of the invention described above. More specifically, the mesoporous molecular sieve is a ten-membered ring-aluminum silica molecular sieve having mesopores or a twelve-membered cycloaluminum molecular sieve having mesopores.
  • the carrier in step (I) is a combination of the above-described mesoporous molecular sieve of the invention and a carrier other than the molecular sieve of the invention.
  • the selection range of the organic complexing agent used is the same as in the step (I).
  • the organic complexing agent used in the step (II) may be the same as or different from the organic complexing agent used in the step (I).
  • the molar ratio of the organic complexing agent to the active metal used in the step (II) may be from 2 to 100:1, preferably from 4 to 80:1, more preferably from 6 to 70:1, still more preferably from 10 to 50:1. Specifically, the molar ratio may be the same as in the step (I) or may be different from the step (I).
  • immersion conditions and drying conditions used in the step (II) immersion conditions well known in the art and known drying conditions can be used.
  • the impregnation conditions and drying conditions used in the step (II) may be the same as in the step (I).
  • the catalyst obtained after the drying of the step (II) does not need to be calcined.
  • the calcination may be further carried out as needed, and the calcination temperature is not particularly limited, and may be 350 to 500 ° C, preferably 360 to 450 ° C.
  • the baking time is not particularly limited and may be 0.5 to 8 hours, preferably 1 to 6 hours.
  • the method for preparing the catalyst may further comprise the step of subjecting the catalyst obtained in the step (II) to a reduction treatment.
  • the reducing conditions can be reducing conditions well known in the art.
  • the reducing atmosphere is hydrogen
  • the reduction temperature may be 300 to 500 ° C
  • the reduction time may be 2 to 6 hours.
  • the method for preparing the catalyst may further include impregnating at least one selected from the group consisting of Mg, Ca, Zn, Ti, Fe, Ga, Ge, B, P, and rare earth metals by impregnation.
  • the step of a solution of metal ions This impregnation can be carried out in the step (I) to obtain a semi-finished catalyst carrying the active metal component and the auxiliary component.
  • This impregnation can also be carried out in the step (II) to obtain a catalyst supporting the active metal component and the auxiliary component.
  • the impregnation step may be carried out before step (I), between step (I) and step (II), and after step (II).
  • the impregnation step is carried out before step (I), or in step (I), or between step (I) and step (II).
  • the conditions of the impregnation are not particularly limited, and the above-described impregnation conditions of the present invention can be used.
  • the amount of the auxiliary component in terms of the elemental substance can be appropriately selected as required, and may be usually 0.001% by weight to 5% by weight, preferably 0.005% by weight to 4.5% by weight, preferably 0.01, based on the weight of the carrier to be impregnated.
  • the weight% to 4% by weight more preferably 0.1% by weight to 3% by weight, still more preferably 0.2% by weight to 1% by weight, still more preferably 0.4% by weight to 0.8% by weight.
  • the catalyst of the invention may be a hydroisomerization catalyst.
  • one of the Group VIII noble metals is supported on the mesoporous molecular sieve of the present invention as a carrier.
  • two or more kinds of Group VIII noble metals are supported on the mesoporous molecular sieve of the present invention as a carrier.
  • the hydroisomerization catalyst is the above catalyst of the invention.
  • the present invention also provides a hydroisomerization treatment process in which the hydroisomerization catalyst of the present invention is used.
  • the hydroisomerization of the present invention may include a treatment step well known in the art as long as the catalyst of the present invention is used therein.
  • Hydroisomerization is one of the important reactions in the petroleum refining process, mainly used in the production of high quality fuel oils and high-grade lubricants. Among them, the isomerization reaction of a normal paraffin having a relatively high freezing point in a feedstock oil and a long-side paraffin on an aromatic hydrocarbon can produce a high-octane gasoline blending component. For long-chain alkanes, It can improve the low temperature flow properties of middle distillates (jet fuel and diesel) as well as lubricating oils.
  • the feedstock for hydroisomerization is a hydrocracked tail oil.
  • the hydrocracking tail oil is contacted with the hydroisomerization catalyst of the present invention under hydroisomerization conditions for hydroisomerization.
  • the distillation range of the hydrocracking tail oil may generally be 350 to 500 ° C (measured by a normal distillation method under normal pressure).
  • the hydroisomerization reaction conditions are not particularly limited as long as it is sufficient to cause a hydroisomerization reaction of the feedstock oil.
  • the hydroisomerization reaction conditions may include a temperature of 200 to 500 ° C, preferably 250 to 400 ° C, more preferably 300 to 350 ° C; a pressure of 1 to 30 MPa, preferably 2 to 20 MPa, more It is preferably 5 to 20 MPa.
  • the pressure referred to in the present invention means absolute pressure.
  • the space velocity is 0.1 to 5 h -1 , preferably 0.1 to 3 h -1 , more preferably 0.5 to 2 h -1 ; and the hydrogen oil volume ratio is 50 to 3,000, preferably 300 to 3,000, more It is preferably 400 to 600.
  • the hydrocracking tail oil is brought into contact with the hydroisomerization catalyst of the present invention to carry out a hydroisomerization reaction, whereby a high isomerization product yield can be obtained.
  • the resulting isomerized product has a lower viscosity index while having a lower pour point, which is suitable as a lubricating base oil.
  • a 3271E X-ray fluorescence spectrometer (XRF) commercially available from Nippon Rigaku Electric Co., Ltd. was used.
  • the sample preparation method was a tableting method, and the measurement condition was an end window target, and the tube voltage was 50 kV.
  • the current was 50 mA), and the content of each element in the measurement sample was analyzed and determined, and the molar ratio of each oxide in each sample (molecular sieve precursor, molecular sieve) was measured.
  • the X-ray diffraction spectrum (XRD) of the molecular sieve was measured by an X-ray powder diffractometer using a standard method (such as the German Bruker D8 Advance powder diffractometer, the light source was CuK ⁇ ray, nickel filter, The tube voltage was 40 kV, the tube current was 40 mA, the lambda value was 0.15418 nm, the step was 0.02°, and the 2 ⁇ scan range was 5° to 55°. Before the sample test, the crystallographic condition of the molecular sieve sample was observed by scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the sample contained only one crystal, that is, the molecular sieve sample was pure phase, and then XRD test was performed to ensure diffraction in the XRD spectrum. There are no interference peaks of other crystals in the peak.
  • the samples were fired at 600 ° C for 3 hours before testing.
  • the measurement of the 27 Al NMR spectrum can be carried out by a method known in the art, for example, the measurement methods and conditions used in Guoliang Zhao et al, Applied Catalysis A: General 299 (2006) 167-174. It is well known in the art that in the 27 Al NMR spectrum, a peak having a chemical shift ⁇ of 10 to 40 ppm is a characteristic peak attributed to pentacoordinate aluminum, and a peak having a chemical shift ⁇ of -10 to 10 ppm is attributed to a six-coordinate position.
  • the specific surface area and external surface area of the sample were measured by a Micromeritics company DIGISORB 2500 automatic adsorption apparatus.
  • the sample was calcined at 600 ° C for 3 hours before the test, and the measurement methods were all carried out in accordance with the ASTM D4222-98 standard method.
  • Mesoporous area measurement methods and conditions can be carried out by methods well known in the art, such as the assay methods and conditions used in the publication Danny Verboekend et al, Cryst Eng Comm 2011, 13, 3408 - 3416.
  • the content of water and organic templating agent in the molecular sieve is determined by thermogravimetric analysis (for example, using a US TA company SDT Q600 synchronous thermal analyzer, starting from 25 ° C at 10 ° C under an oxygen atmosphere / The heating rate of the minute was increased to 800 ° C. The weight loss curve of the test sample was measured.
  • the carbon content of the catalyst semi-finished product in the following examples and comparative examples was analyzed using an EMIA-320V carbon sulfur analyzer manufactured by Japan HORIBA Co., Ltd.
  • the mother liquid after crystallization prepared in the step (1) is filtered, and the filter cake F-1-1 is obtained by continuously filtering for 5 minutes without the filtrate on the filter cake, and the filter cake F-1-1 is
  • the aqueous molecular sieve precursor had a dry basis content of 11.2% by weight.
  • the silica/alumina molar ratio in the filter cake was 30.2 and the molar ratio of templating agent to alumina was 1:5.
  • the filter cake F-1-1 was raised from room temperature to 450 ° C at a temperature increase rate of 25 ° C / min, and was kept at a constant temperature for 4 hours.
  • the molecular sieve precursor C-1-1 was obtained, and its 27 Al NMR spectrum is shown in Fig. 1.
  • the molecular sieve precursor C-1-1 was placed in a 1 M HCl solution for a closed hydrothermal treatment. Among them, the liquid-solid ratio is 50, the hydrothermal treatment temperature is 180 ° C, and the hydrothermal treatment time is 3 hours. After completion of the hydrothermal treatment, the product was filtered and washed with water until the pH of the filtrate was 7, and after drying at 120 ° C for 4 hours, it was calcined at 550 ° C for 4 hours to obtain a finished molecular sieve of H-1.
  • the Beta molecular sieve had a silica/alumina molar ratio of 159.2.
  • the mesoporous surface area, specific surface area, and ratio of mesoporous surface area to comparative area are shown in Table 1.
  • the Beta molecular sieve was prepared according to the method of Example 1-1, except that in the step (2), there was no filtrate timing on the filter cake, and filtration filtration was continued for 50 minutes to obtain a filter cake DF-1-1.
  • the dry content of the cake DF-1-1 was 46.5 wt%.
  • a final molecular sieve DH-1-1 having a silica/alumina molar ratio of 122.7 was prepared, and the mesoporous surface area, specific surface area, and mesoporous surface area to comparative area ratio are shown in Table 1.
  • the Beta molecular sieve was prepared according to the method of Example 1-1, except that in the step (3), the filter cake F-1-1 was raised from room temperature to 350 ° C at a heating rate of 5 ° C / minute, and the temperature was 14 hour.
  • the baking furnace is a baking furnace, and the molecular sieve precursor C-1-2 is obtained.
  • the Beta molecular sieve finished product H-1-2 having a silica/alumina molar ratio of 121.3 was prepared, and the mesoporous surface area, specific surface area, and ratio of mesoporous surface area to comparative area are shown in Table 1.
  • the Beta molecular sieve was prepared according to the method of Example 1-1, except that in the step (3), the filter cake F-1-1 was raised from room temperature to 850 ° C at a heating rate of 15 ° C / minute, and the temperature was constant 4 hour. Air was introduced during the heating, and the air flow rate was 1.0 liter/min to obtain the molecular sieve precursor C-1-3.
  • the Beta molecular sieve finished product H-1-3 was prepared.
  • the silica molecular sieve had a silica/alumina molar ratio of 183.6.
  • the mesoporous surface area, specific surface area, and mesoporous surface area to comparative area ratio are shown in Table 1.
  • a Beta molecular sieve was prepared according to the method of Example 1-1, except that in the step (4), the molecular sieve precursor C-1-1 was placed in a citric acid solution having a concentration of 1.0 M to carry out a closed hydrothermal treatment.
  • the liquid-solid ratio is 100
  • the temperature of the hydrothermal treatment is 180 ° C
  • the time of the hydrothermal treatment is 2 hours.
  • the product is filtered and washed with water until the pH of the filtrate is 7, after drying at 120 ° C for 4 hours, After calcination at 550 ° C for 4 hours, the obtained molecular sieve finished product H-1-4, the silica/alumina molar ratio of the Beta molecular sieve is 168.2, the ratio of mesoporous surface area, specific surface area and mesoporous surface area to comparative area is shown in the table. 1.
  • a Beta molecular sieve was prepared according to the method of Example 1-1, except that in the step (4), the molecular sieve precursor C-1-1 was placed in a citric acid solution having a concentration of 0.05 M to carry out a closed hydrothermal treatment.
  • the liquid-solid ratio is 10
  • the temperature of the hydrothermal treatment is 90 ° C
  • the time of the hydrothermal treatment is 0.1 hour.
  • the product is filtered and washed with water until the pH of the filtrate is 7, after drying at 120 ° C for 4 hours, After calcination at 550 ° C for 4 hours, the obtained molecular sieve finished product H-1-5 having a silica/alumina molar ratio of 159.3, the mesoporous surface area, specific surface area and the ratio of mesoporous surface area to comparative area are shown in the table. 1.
  • a Beta molecular sieve was prepared according to the method of Example 1-1, except that in the step (4), the molecular sieve precursor C-1-1 was placed in a hydrochloric acid solution having a concentration of 1 M to carry out a closed hydrothermal treatment.
  • the liquid-solid ratio is 50
  • the temperature of the hydrothermal treatment is 180 ° C
  • the time of the hydrothermal treatment is 3 hours.
  • the product is filtered and washed with water until the pH of the filtrate is 4, and after drying at 120 ° C for 4 hours, After calcination at 550 ° C for 4 hours, the finished molecular sieve of H-1-6 was obtained.
  • the silica/alumina molar ratio of the Beta sieve was 158.5.
  • the mesoporous surface area, specific surface area and the ratio of mesoporous surface area to comparative area are shown in the table. 1.
  • the mother liquid after crystallization prepared in the step (1) is filtered, and the filtrate is not filtered for 10 minutes, and the filter cake F-1-7 is obtained, and the filter cake F-1-7 is
  • the aqueous molecular sieve precursor had a dry basis content of 11.2% by weight.
  • the filter cake had a silica/alumina molar ratio of 45.8 and a templating agent to alumina molar ratio of 1:6.
  • the filter cake F-1-7 was raised from room temperature to 450 ° C at a heating rate of 25 ° C / min in a roasting oven at a constant temperature for 4 hours.
  • the molecular sieve precursor C-1-7 was obtained.
  • the molecular sieve precursor C-1-7 was placed in a 1 M HCl solution for a closed hydrothermal treatment.
  • the liquid-solid ratio is 50
  • the hydrothermal treatment temperature is 180 ° C
  • the hydrothermal treatment time is 3 hours.
  • the product was filtered and washed with water until the pH of the filtrate was 7, and after drying at 120 ° C for 4 hours, it was calcined at 550 ° C for 4 hours to obtain a finished molecular sieve of H-7.
  • the silica molecular sieve has a silica/alumina molar ratio of 164.5.
  • the mesoporous surface area, specific surface area, and mesoporous surface area to comparative area ratio are shown in Table 1.
  • the mother liquid after crystallization prepared in the step (1) is filtered, and the filtrate is not filtered for 10 minutes, and the filter cake F-1-8 is obtained, and the filter cake F-1-8 is
  • the aqueous molecular sieve precursor had a dry basis content of 11.2% by weight.
  • the silica/alumina molar ratio in the filter cake was 22.6 and the molar ratio of templating agent to alumina was 1:4.
  • the filter cake F-1-8 was raised from room temperature to 450 ° C at a temperature increase rate of 25 ° C / min, and the temperature was maintained for 4 hours.
  • the molecular sieve precursor C-1-8 was obtained.
  • the molecular sieve precursor C-1-8 was placed in a 1 M HCl solution for a closed hydrothermal treatment. Among them, the liquid-solid ratio is 50, the hydrothermal treatment temperature is 180 ° C, and the hydrothermal treatment time is 3 hours. After completion of the hydrothermal treatment, the product was filtered and washed with water until the pH of the filtrate was 7, and after drying at 120 ° C for 4 hours, it was calcined at 550 ° C for 4 hours to obtain a finished molecular sieve of H-8.
  • the silica molecular sieve has a silica/alumina molar ratio of 145.6.
  • the mesoporous surface area, specific surface area, and mesoporous surface area to comparative area ratio are shown in Table 1.
  • the mother liquid after crystallization was prepared according to the step (1) in Example 1-1, followed by filtration, and the filter cake obtained after the filtration was dried at 120 ° C for 4 hours to sufficiently dry the filter cake. It was then calcined at 550 ° C for 4 hours to obtain a molecular sieve precursor DC-1-2.
  • the molecular sieve precursor DC-1-2 was subjected to ammonium exchange treatment with 10 times volume of 0.5M hydrochloric acid solution at 90 ° C for 4 hours, and finally filtered, dried and calcined at 550 ° C for 4 hours to obtain the finished molecular sieve DH-1- 2.
  • the silica/alumina molar ratio of the Beta molecular sieve was 32.3, and the ratio of mesoporous surface area, specific surface area, and mesoporous surface area to comparative area is shown in Table 1.
  • the 27 Al NMR spectrum is shown in Fig. 5, and the nitrogen adsorption-desorption curve is shown in Fig. 6.
  • the semi-finished catalyst was again placed in a 100 g deionized water solution containing 3.2 g of citric acid, and after immersion for 4 hours, it was dried at 120 ° C for 4 hours to obtain catalysts Cat-1-1 to Cat-1-8, respectively, and compared. Catalysts D-Cat-1-1 to D-Cat-1-2.
  • Beta molecular sieve of the present invention when used as a catalyst for solid acid formation as a hydroisomerization catalyst, not only a good isomeric depressing ability but also a product obtained is obtained.
  • the viscosity index is high, the yield is high, and the pour point is low.
  • silica sol containing 40% by weight of SiO 2 1.77 g of analytically pure Al 2 (SO 4 ) 3 ⁇ 18H 2 O, 3.94 g of analytically pure KOH and 8.44 g of hexamethylene diamine were used.
  • the hexamethylenediamine is mixed with the silica sol.
  • KOH and Al 2 (SO 4 ) 3 ⁇ 18H 2 O and 89.4 g of deionized water were mixed, and then the two solutions were mixed, stirred for 1 h, transferred to a reaction vessel, and crystallized at 160 ° C for 72 hours.
  • the mother liquid after crystallization prepared in the step (1) is filtered, and the filtrate is filtered for 5 minutes without the filtrate on the filter cake, and the obtained filter cake F-2-1 is an aqueous molecular sieve precursor, and the dry content thereof is
  • the ratio of silica to alumina was 30.2, the molar ratio of potassium oxide to alumina was 2:1, and the molar ratio of templating agent to alumina was 1:8.
  • the filter cake F-2-1 was raised from room temperature to 450 ° C at a heating rate of 25 ° C / min in a roasting oven at a constant temperature for 4 hours.
  • the molecular sieve precursor C-2-1 was obtained, and its 27 Al NMR spectrum is shown in Fig. 7.
  • the molecular sieve precursor C-2-1 was placed in a 1 M HCl solution for a closed hydrothermal treatment.
  • the liquid-solid ratio is 50
  • the hydrothermal treatment temperature is 180 ° C
  • the hydrothermal treatment time is 3 hours.
  • the product is filtered and washed with water until the filtrate pH is 7, after drying at 120 ° C for 4 hours, at 550
  • the obtained ZSM-22 molecular sieve finished product H-2-1 was obtained.
  • the ZSM-22 molecular sieve had a silica/alumina molar ratio of 165.2.
  • the mesoporous surface area, specific surface area, and ratio of mesoporous surface area to comparative area are shown in Table 4.
  • the ZSM-22 molecular sieve was prepared according to the method of Example 2-1 except that in step (2), there was no filtrate on the filter cake, and filtration filtration was continued for 50 minutes to obtain a filter cake DF-2-1.
  • the filter cake DF-2-1 had a dry basis content of 46.5 wt%.
  • the ZSM-22 molecular sieve finished product DH-2-1 was obtained.
  • the ZSM-22 molecular sieve had a silica/alumina molar ratio of 142.7.
  • the mesoporous surface area, specific surface area, and the ratio of mesoporous surface area to comparative area are shown in Table 4. .
  • the ZSM-22 molecular sieve was prepared according to the method of Example 2-1, except that in the step (3), the filter cake F-2-1 was raised from room temperature to 350 ° C at a heating rate of 5 ° C / minute. Constant temperature for 14 hours. In the heating process, the baking furnace is a calcining furnace, and the molecular sieve precursor C-2-2 is obtained. The ZSM-22 molecular sieve finished product H-2-2 was prepared. The ZSM-22 molecular sieve had a silica/alumina molar ratio of 141.3. The mesoporous surface area, specific surface area, and mesoporous surface area to comparative area ratio are shown in Table 4.
  • the ZSM-22 molecular sieve was prepared according to the method of Example 2-1, except that in the step (3), the filter cake F-2-1 was raised from room temperature to 850 ° C at a heating rate of 15 ° C / minute. Constant temperature for 4 hours. Air was introduced during the heating, and the air flow rate was 1.0 liter/min to obtain the molecular sieve precursor C-1-3.
  • the ZSM-22 molecular sieve finished product H-1-3 was prepared.
  • the ZSM-22 molecular sieve had a silica/alumina molar ratio of 182.6.
  • the mesoporous surface area, specific surface area, and mesoporous surface area to comparative area ratio are shown in Table 4.
  • the ZSM-22 molecular sieve was prepared according to the method of Example 2-1 except that in the step (4), the molecular sieve precursor C-2-1 was placed in a citric acid solution having a concentration of 1.0 M to carry out a closed hydrothermal treatment.
  • the liquid-solid ratio is 100
  • the temperature of the hydrothermal treatment is 180 ° C
  • the time of the hydrothermal treatment is 2 hours.
  • the product is filtered and washed with water until the pH of the filtrate is 7, after drying at 120 ° C for 4 hours, After calcination at 550 ° C for 4 hours, the obtained ZSM-22 molecular sieve finished product H-2-4, the ZSM-22 molecular sieve has a silica/alumina molar ratio of 172.2, mesoporous surface area, specific surface area, mesoporous surface area and comparative area. The ratio is shown in Table 4.
  • the ZSM-22 molecular sieve was prepared according to the method of Example 2-1, except that in the step (4), the molecular sieve precursor C-2-1 was placed in a citric acid solution having a concentration of 0.05 M for a closed hydrothermal treatment.
  • the liquid-solid ratio is 10
  • the temperature of the hydrothermal treatment is 90 ° C
  • the time of the hydrothermal treatment is 0.1 hour.
  • the product is filtered and washed with water until the pH of the filtrate is 7, after drying at 120 ° C for 4 hours, After calcination at 550 ° C for 4 hours, the obtained ZSM-22 molecular sieve finished product H-2-5, the ZSM-22 molecular sieve has a silica/alumina molar ratio of 162.3, mesoporous surface area, specific surface area, mesoporous surface area and comparative area. The ratio is shown in Table 4.
  • the ZSM-22 molecular sieve was prepared according to the method of Example 2-1, except that in the step (4), the molecular sieve precursor C-2-1 was placed in a hydrochloric acid solution having a concentration of 1 M to carry out a closed hydrothermal treatment.
  • the liquid-solid ratio is 50
  • the temperature of the hydrothermal treatment is 180 ° C
  • the time of the hydrothermal treatment is 3 hours.
  • the product is filtered and washed with water until the pH of the filtrate is 4, and after drying at 120 ° C for 4 hours, After calcination at 550 ° C for 4 hours, the obtained ZSM-22 molecular sieve finished product H-2-6, the ZSM-22 molecular sieve has a silica/alumina molar ratio of 161.5, mesoporous surface area, specific surface area, mesoporous surface area and comparative area. The ratio is shown in Table 4.
  • silica sol containing 40% by weight of SiO 2 1.18 g of analytically pure Al 2 (SO 4 ) 3 ⁇ 18H 2 O, 3.94 g of analytically pure KOH and 8.44 g of hexamethylene diamine were used.
  • the hexamethylenediamine is mixed with the silica sol.
  • KOH and Al 2 (SO 4 ) 3 ⁇ 18H 2 O and 89.4 g of deionized water were mixed, and then the two solutions were mixed, stirred for 1 h, transferred to a reaction vessel, and crystallized at 160 ° C for 72 hours.
  • the mother liquid after crystallization prepared in the step (1) is filtered, and the filtrate is not counted on the filter cake, and filtration is continued for 5 minutes, and the obtained filter cake F-2-7 is an aqueous molecular sieve precursor, and the dry content thereof is It was 11.2% by weight, the silica/alumina molar ratio was 45.6, the molar ratio of potassium oxide to aluminum oxide was 2:1, and the molar ratio of templating agent to alumina was 1:10.
  • the filter cake F-2-7 was raised from room temperature to 450 ° C at a temperature increase rate of 25 ° C / min, and the temperature was maintained for 4 hours.
  • the molecular sieve precursor C-2-7 was obtained.
  • the molecular sieve precursor C-2-7 was placed in a 1 M HCl solution for a closed hydrothermal treatment.
  • the liquid-solid ratio is 40
  • the temperature of the hydrothermal treatment is 180 ° C
  • the time of the hydrothermal treatment is 3 hours.
  • the product is filtered and washed with water until the pH of the filtrate is 7, after drying at 120 ° C for 4 hours, at 550 After calcination at ° C for 4 hours, the obtained ZSM-22 molecular sieve finished product H-2-7.
  • the ZSM-22 molecular sieve had a silica/alumina molar ratio of 174.8, and the mesoporous surface area, specific surface area, and ratio of mesoporous surface area to comparative area are shown in Table 4.
  • silica sol containing 40% by weight of SiO 2 2.36 g of analytically pure Al 2 (SO 4 ) 3 ⁇ 18H 2 O, 3.94 g of analytically pure KOH and 8.44 g of hexamethylene diamine were used.
  • the hexamethylenediamine is mixed with the silica sol.
  • KOH and Al 2 (SO 4 ) 3 ⁇ 18H 2 O and 89.4 g of deionized water were mixed, and then the two solutions were mixed, stirred for 1 h, transferred to a reaction vessel, and crystallized at 160 ° C for 72 hours.
  • the mother liquid after crystallization prepared in the step (1) is filtered, and the filtrate is not counted on the filter cake, and filtration is continued for 5 minutes, and the obtained filter cake F-2-8 is an aqueous molecular sieve precursor, and the dry content thereof is It was 11.2% by weight, the silica/alumina molar ratio was 22.8, the molar ratio of potassium oxide to aluminum oxide was 2:1, and the molar ratio of templating agent to alumina was 1:7.
  • the filter cake F-2-8 was raised from room temperature to 450 ° C at a temperature increase rate of 25 ° C / min, and was kept at a constant temperature for 4 hours.
  • the molecular sieve precursor C-2-8 was obtained.
  • the molecular sieve precursor C-2-8 was placed in a 1 M HCl solution for a closed hydrothermal treatment.
  • the liquid-solid ratio is 40
  • the temperature of the hydrothermal treatment is 180 ° C
  • the time of the hydrothermal treatment is 3 hours.
  • the product is filtered and washed with water until the pH of the filtrate is 7, after drying at 120 ° C for 4 hours, at 550 After calcination at ° C for 4 hours, the obtained ZSM-22 molecular sieve finished product H-2-8.
  • the ZSM-22 molecular sieve had a silica/alumina molar ratio of 159.3, and the ratio of mesoporous surface area, specific surface area, and mesoporous surface area to comparative area is shown in Table 4.
  • the mother liquid after crystallization was prepared according to the step (1) in Example 2-1, followed by filtration, and the filter cake obtained after the filtration was dried at 120 ° C for 4 hours to sufficiently dry the filter cake. It was then calcined at 550 ° C for 4 hours to obtain a molecular sieve precursor DC-2-2.
  • the molecular sieve precursor DC-2-2 was subjected to ammonium exchange treatment with 10 times volume of 0.5 M hydrochloric acid solution at 90 ° C for 4 hours, and finally filtered, dried and calcined at 550 ° C for 4 hours to obtain ZSM-22 molecular sieve finished product DH- 2-2, the ZSM-22 molecular sieve had a silica/alumina molar ratio of 32.3, and the ratio of mesoporous surface area, specific surface area, and mesoporous surface area to comparative area is shown in Table 4.
  • the 27 Al NMR spectrum is shown in Fig. 11, and the nitrogen adsorption-desorption curve is shown in Fig. 12.
  • Example 2-1 40 g of molecular sieve H-2-1 prepared in Example 2-1 was mixed with 40 g of alumina, extruded, and dried to obtain a carrier E-2-1.
  • the catalyst was prepared according to the method of Application Example 2-1 except that the molecular sieves H-2-2 to H-2-8 prepared in Examples 2-2 to 2-8 and Comparative Examples 2-1 to 2, respectively.
  • -2 prepared molecular sieves DH-2-1 to DH-2-2 were used instead of the molecular sieve H-1-1 used in Example 2-1 to prepare catalysts IC-2 to IC-8 and comparative catalyst DIC-1.
  • DIC-2 To DIC-2.
  • Carrier E-2-1 was prepared according to the method of Application Example 2-1.
  • Carrier E-2-1 was prepared according to the method of Application Example 2-1.
  • Carrier E-2-1 was prepared according to the method of Application Example 2-1.
  • Carrier E-2-1 was prepared according to the method of Application Example 2-1.
  • Carrier E-2-1 was prepared according to the method of Application Example 2-1.
  • the semi-finished catalyst was again placed in a 100 g deionized water solution containing 1.0 g of citric acid. After immersion for 4 hours, it was dried at 120 ° C for 4 hours to obtain a catalyst IC-13 having a zinc content of 0.42% by weight in terms of zinc oxide.
  • the molecular sieve of the present invention has a high mesoporous area, whereby the activity of the molecular sieve as a solid acid catalyst can be greatly enhanced. Further, when the molecular sieve of the present invention is used as a support for preparing a catalyst, the catalytic activity of the catalyst can be improved, and the physical properties of the obtained product can be improved. Further, the method for producing a catalyst of the present invention can prepare a catalyst having a high degree of dispersion of an active ingredient, thereby not only prolonging the life of the catalyst, but further improving the catalytic activity of the catalyst.

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Abstract

一种具有介孔的分子筛及其制备方法和应用。该分子筛的氧化硅/氧化铝摩尔比为100～300；含有介孔结构且在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处出现一个闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.7处。将分子筛作为固体酸形成的催化剂，其不仅具有较好的异构降凝能力，而且产物中目标产物的收率高、倾点低。还提供一种催化剂的制备方法，利用该催化剂的制备方法，可以制备活性成分分散度高的催化剂，由此不仅延长了催化剂的寿命，而且进一步提高了催化剂的催化活性。

Description

[根据细则37.2由ISA制定的发明名称]　具有介孔的分子筛及其制备方法和应用 技术领域
本发明涉及一种具有介孔的分子筛及其制备方法和其应用。更具体而言，本发明涉及一种具有介孔的高硅铝比分子筛，制备该分子筛的方法，以及包含该分子筛的催化剂及其应用。
背景技术
分子筛材料通常具有高酸性与高比表面积，同时，分子筛材料具有很强的化学稳定性及水热稳定性，很难被反应物腐蚀溶解而破坏，因而是一种优秀的固体酸催化剂。相对于通常所使用的均相催化剂，分子筛材料催化剂可以直接重复利用而无需进行分离，同时不会对环境和产品造成污染。另外，分子筛材料的比表面积、孔道结构等参数对分子筛的特性、例如催化性能具有重要的影响，因而制备具有特定比表面积或特殊孔道的分子筛是化工领域一个重要研究方向。
例如，在美国专利申请US4518485、US5990371、US5135638、US4419420、US5110445等中都报道了异构脱蜡技术生产润滑油基础油的方法，其中使用的作为酸性组分的分子筛主要有MOR、ZSM-22、ZSM-23、ZSM-48、SAPO-11、SAPO-31、SAPO-41、Nu-10和KZ-2等，这些分子筛材料都能够在一定程度上使石蜡烃发生异构化反应。但是，对于这些分子筛而言，由于自身的性质，通常只能使反应物中的一部分发生异构化反应，而其余反应物发生裂解反应，而异构化程度越大，相应地发生裂解反应的比例就越高，最终导致产物的收率下降。
美国专利申请US5282958公开了一种用于异构脱蜡的催化剂，该催化剂中含有中孔分子筛，如ZSM-5、ZSM-22、ZSM-23、ZSM-11等。美国专利申请US7482300、US5075269公开了一种含有ZSM-48的异构化催化剂。美国专利申请US8513150公开了一种具有介孔的Y型分子筛，在该专利申请中，Y型分子筛先在低温下焙烧随后在含有水蒸汽的气体里高温(1250°F～1450°F)下焙烧，经焙烧后分子筛内形成介孔结构，且大介孔相对于小介孔的比例为5以上。美国专利申请US5397454公开了使用具有小晶粒尺寸和焙烧后氢型的约束指数为13或更大的分 子筛(例如SSZ-32)进行加氢转化的方法，其中，催化剂的氧化硅与氧化铝的摩尔比大于20且小于40。美国专利申请US5300210也涉及使用SSZ-32进行烃转化的方法。美国专利申请US5300210中公开的SSZ-32不限定于小晶粒尺寸。美国专利申请US7141529公开了用不同的金属(选自Ca、Cr、Mg、La、Ba、Pr、Sr、K和Nd的金属以及第VIII族金属)对分子筛进行金属改性的方法，以提供使用nC-16进料时具有改进的异构化选择性的催化剂，该专利申请所用的方法为，在载体成型之后用含有金属离子的液体进行浸渍从而使分子筛负载改性金属。
另外，Beta分子筛是唯一具有三维十二元环直通道体系的沸石，其独特的孔道结构以及酸性使得Beta分子筛具备很高的加氢裂化、加氢异构化催化活性和对直链烷烃的吸附能力，并有良好的抗硫、氮中毒能力。通常，其在石化工业中，可用于由苯与丙烯烃化制备异丙苯等的各种转化反应中的催化剂的制备。另外，Beta分子筛同USY的联合使用情况下，可以提高汽油的辛烷值。并且，在精细化工领域，Beta分子筛在脱水脱胺方面也具有良好的活性和选择性。
CN1350981A公开了一种高硅Beta沸石的制备方法，其主要包括以下步骤：首先将晶化后的Beta沸石浆液进行铵交换，过滤干燥并焙烧脱模后再使用有机酸或无机酸进行处理，最后再进行加压水热处理，最终得到硅铝比在60-80之间的Beta沸石。CN1769169A公开了一种具有梯级孔道Beta沸石的合成方法，其中所得的Beta沸石硅铝比达80-120，并具有0.1-1.7nm、1.7-6nm及10-90nm三种孔径分布，由此极大地提高了Beta沸石的表面利用率，但是所得样品的微孔体积不够大，孔体积的贡献主要来自于介孔和大孔(介孔和大孔总体积占总孔体积的67％以上)。
CN104353484A公开了一种廉价强酸性多级孔Beta沸石的制备方法，其要解决现有脱硅处理后多级孔Beta沸石分子筛的酸性减弱的问题。CN103964458A公开了一种高硅铝比多级孔道的Beta沸石及其制备方法，该专利申请的制备方法操作简单高效，制备得到的高硅铝比多级孔道的Beta沸石具有很强的酸稳定性、热稳定性和水热稳定性以及良好的扩散性能。
另外在CN102602958A、CN103073020A、CN104891526A、 CN1683245C、CN102050459A和CN1565969A的专利文献中，都公开了具有一定孔道的沸石分子筛的制备方法。
但是，现有的沸石分子筛的依然存在介孔表面积比例偏低、硅铝比偏低等的不能充分令人满意之处，这使得将分子筛用作催化剂或催化剂载体时，所得催化剂的催化性能依然有很大提升空间。
发明内容
本发明的发明人进行了深入地研究，令人惊奇地发现，在分子筛的合成步骤中，在制备出晶化母液后，通过适当的后处理步骤，可以制备介孔比例高、介孔表面积大的分子筛。从而，制备出具有高介孔容积、高介孔表面积的分子筛，完成了本发明。并且，本发明的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4～0.99处出现一个闭合滞后环、且所述闭合滞后环的起始位置在P/P0＝0.4～0.6处。利用该分子筛制备的催化剂的催化活性得到极大改善。另外，本发明的发明人还发现，通过特定的步骤来制备催化剂，可以使催化活性成分在载体上以高度分散的状态良好地分散，从而在保持催化剂的长寿命的前提下，进一步提高催化剂的活性。
具体而言，本发明提供一种具有介孔的分子筛(以下也称为本发明的分子筛)，其化学组成式以氧化物形式表示为：Al 2O 3·SiO 2·M 2O·Z xO y，其中，所述M为选自碱金属中的至少一种，Z为选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种，x表示Z的原子数，是1～6的整数，y表示满足Z氧化态所需的数，以摩尔比计，Al 2O 3:SiO 2:M 2O:Z xO y为1:(100～300):(0～100):(0～100)。
本发明的分子筛中，氧化硅/氧化铝摩尔比为100～300。
本发明的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4～0.99处出现一个闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4～0.6处，更优选起始位置在P/P0＝0.4～0.55处。
本发明的分子筛经氮气吸附BET(Brunner Emmet Teller)方法表征时，所述分子筛中的介孔表面积为30m 2/g～280m 2/g，优选为50m 2/g～250m 2/g，更优选为80m 2/g～200m 2/g，进一步优选为100m 2/g～180m 2/g，进一步优选为120m 2/g～150m 2/g。
本发明的分子筛经氮气吸附BET(Brunner Emmet Teller)方法表征 时，所述分子筛的比表面积可以为150m 2/g～400m 2/g，优选为180m 2/g～350m 2/g，更优选为200m 2/g～320m 2/g，更进一步优选为240m 2/g～300m 2/g，更进一步优选为260m 2/g～280m 2/g。
本发明的分子筛的介孔表面积占比分子筛表面积的比例为20％～70％，优选为25％～65％，更优选为28％～60％，更优选为30％～55％，更优选为35％～50％。
本发明的分子筛可以是具有介孔的十元环硅铝分子筛或具有介孔的十二元环硅铝分子筛。
本发明的分子筛可以选自ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、Nu-10、Nu-13、Nu-87、EU-1、EU-13、ITQ-13、ZSM-12和Beta分子筛中的至少一种，优选为ZSM-22或Beta分子筛。
本发明发明还提供一种含水分子筛前体，其化学组成式表示为：Al 2O 3·SiO 2·M 2O·Z xO y·模板剂·水，其中，所述M、Z、x、y的含义与上述相同，Al 2O 3与SiO 2的摩尔比为1:(20～100)，Al 2O 3与M 2O的摩尔比为1:(0～100)，Al 2O 3与Z xO y的摩尔比为1:(0～100)，Al 2O 3与模板剂的摩尔比为1:(0.001～10)，所述含水分子筛前体的干基含量为5重量％～30重量％，优选为6重量％～15重量％。
本发明还提供一种具有介孔的分子筛的制造方法，所述方法包括以下步骤：
母液制备步骤，其中，使包含氧化铝源、氧化硅源、模板剂、任选的碱金属氧化物源、任选的第三氧化物源和水的混合物(以下简称为混合物)在晶化条件下晶化以获得晶化母液；
过滤步骤，将晶化后的母液进行过滤，以形成干基含量为5重量％～30重量％的滤饼；
前体制备步骤，将所述滤饼直接进行焙烧，得到分子筛前体；
水热处理步骤，将所述分子筛前体进行水热处理；和
成品制备步骤，将水热处理产物进行过滤，并任选地进行洗涤、干燥处理，并进行焙烧。
本发明还提供一种含水分子筛前体的制备方法，其包括以下步骤：
母液制备步骤，其中，使包含氧化铝源、氧化硅源、模板剂、任选的碱金属氧化物源、任选的第三氧化物源和水的混合物(以下简称为混合物)在晶化条件下晶化以获得晶化母液；
含水分子筛前体的制备步骤，将晶化后的母液进行过滤，得到含水分子筛前体的步骤，其中，所述含水分子筛前体的干基含量为5重量％～30重量％，优选为6重量％～15重量％。
本发明还提供一种催化剂，其包含载体和负载在所述载体上的活性金属组分。在本发明的催化剂中，所述活性金属组分在分子筛上呈高度分散状态。具体而言，所述活性金属组分的单个颗粒的尺寸小于3nm，例如可以为0.1～2.8nm。
本发明还提供一种催化剂的制备方法，其包括以下步骤：
(I)采用浸渍法将活性金属组分前驱体和有机络合剂负载在载体上，然后进行任选的干燥、然后进行焙烧，得到半成品催化剂；和
(II)以含有有机络合剂的溶液作为浸渍液，对步骤(I)所得半成品催化剂进行浸渍，然后进行干燥。
本发明提供一种加氢异构化催化剂，其中在本发明的分子筛上负载选自VIII族贵金属中的至少一种活性金属组份。
本发明提供一种加氢异构化方法，其中，使用本发明的加氢异构化催化剂。
技术效果
通过本发明的具有介孔的分子筛，分子筛中的微孔容积和表面积的比例减小，介孔容积和表面积的比例增加，由此在反应过程中，反应物易进入分子筛的介孔，并且由于介孔表面积增大，由此分子筛可以在孔道中提供更多的反应活性位点。这样，通过将本发明的分子筛作为载体制备催化剂，可以极大地提高催化剂的催化效率，改善所得产物的物性。
通过本发明的加氢异构化催化剂，对于原料油进行处理后，可以实现优异的异构降凝效果。
另外，通过本发明的催化剂的制备方法，可以极大地提高催化剂的使用寿命，并且作为催化位点的活性金属高分散地分布于载体，由此进一步提高了催化剂的活性。
附图说明
图1是实施例1-1中制备的分子筛前体C-1-1的 27Al NMR图谱。
图2是实施例1-1中制备的分子筛成品H-1-1的 27Al NMR图谱。
图3是实施例1-1中制备的分子筛成品H-1-1的XRD图谱。
图4是实施例1-1中制备的分子筛成品H-1-1的氮气吸附-脱附曲线图。
图5是对比例1-2中制备的分子筛前体DC-1-2的 27Al NMR图谱。
图6是对比例1-2中制备的分子筛成品DH-1-2的氮气吸附-脱附曲线图。
图7是实施例2-1中制备的分子筛前体C-2-1的 27Al NMR图谱。
图8是实施例2-1中制备的分子筛成品H-2-1的 27Al NMR图谱。
图9是实施例2-1中制备的分子筛成品H-2-1的XRD图谱。
图10是实施例2-1中制备的分子筛成品H-2-1的氮气吸附-脱附曲线图。
图11是对比例2-2中制备的分子筛前体DC-2-2的 27Al NMR图谱。
图12是对比例2-2中制备的分子筛成品DH-2-2的氮气吸附-脱附曲线图。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此而形成的技术方案或技术思想均视为本发明原 始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合是明显不合理的。
在本发明的上下文中，除非另有明确定义，或者该含义超出了本领域技术人员的理解范围，3个碳原子以上的烃或烃衍生物基团(比如丙基、丙氧基、丁基、丁烷、丁烯、丁烯基、己烷等)在未冠以词头“正”时均具有与冠以词头“正”时相同的含义。比如，丙基一般理解为正丙基，而丁基一般理解为正丁基。另外，本发明中，碳原子后所跟数字表示碳原子的数目，例如C2-C7即表示碳原子数2-7，用于化合物时即表示化合物中所包含的碳原子的数目，例如C2-C7羧酸表示具有2-7个碳原子的羧酸。
在本说明书的上下文中，对于分子筛，在其孔道中的除水及金属离子以外的其他合成该分子筛时填充在孔道中的物质(比如模板剂分子、水分子等)未被脱除之前，称为“含水分子筛前体”。在本发明中，对于由晶化母液得到的滤饼进行焙烧后的中间体，称为“(分子筛)前体”
在本说明书的上下文中，分子筛的结构是由X-射线衍射谱图(XRD)确定的。X-射线衍射谱图(XRD)由X-射线粉末衍射仪测定，使用Cu-Kα射线源、镍滤光片。样品测试前，采用扫描电子显微镜(SEM)观察分子筛样品的结晶情况，确认样品中只含有一种晶体，即分子筛样品为纯相，在此基础上再进行XRD测试，确保XRD谱图中的衍射峰中没有其他晶体的干扰峰。
在本说明书的上下文中，所谓比表面积，是指单位质量样品所具有的总面积，包括内表面积和外表面积。非孔性样品只具有外表面积，如硅酸盐水泥、一些粘土矿物粉粒等；有孔和多孔样品具有外表面积和内表面积，如石棉纤维、硅藻土和分子筛等。本发明中的比较面积使用本领域公知的BET法进行测定。
在本说明书的上下文中，所谓介孔，是指分子筛中，孔径在2-50nm的孔道，介孔表面积是指孔径在2-50nm的孔道的表面积。本发明的介孔表面积可以通过BET法，利用BET方程式和t-plot方程式进行计算。
在本发明中，“干基”定义为：物料在空气气氛中在600℃下焙烧4小时后的物质质量相对于焙烧前的物质质量的百分比。
在本发明的上下文中，除非另有特别说明，物质的物性值(比如沸点)都是常温(25℃)和常压(101325Pa)下的测量值。
本发明涉及一种具有介孔的分子筛。本发明的分子筛具有现有技术中合成的分子筛所不具有的介孔。并且，本发明的分子筛满足以下条件：在低温氮气吸附-脱附曲线上，吸附支和脱附支在P/P0＝0.4-0.99处出现一个闭合滞后环，且闭合滞后环的起始位置在P/P0＝0.4-0.7处。
具体而言，本发明提供一种具有介孔的分子筛，其化学组成式以氧化物形式表示为：Al 2O 3·SiO 2·M 2O·Z xO y，其中，所述M为选自碱金属中的至少一种，Z为选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种，x表示Z的原子数，是1～6的整数，y表示满足Z氧化态所需的数，以摩尔比计，Al 2O 3:SiO 2:M 2O:Z xO y为1:(100～300):(0～100):(0～100)。
已知的是，分子筛中有时会(尤其是在刚制备完成之后)含有一定量的水分，但本发明认为并没有必要对该水分的量进行特定，因为该水分通常为通道水，其存在与否并不会实质上影响该分子筛组成及其XRD谱图。鉴于此，本发明的化学组成实际上代表的是该分子筛的无水化学组成。
在现有技术中，分子筛的氧化硅/氧化铝(SiO 2/Al 2O 3)摩尔比(硅铝比)通常小于100。但是，根据本发明的具有介孔的分子筛的氧化硅/氧化铝(SiO 2/Al 2O 3)摩尔比为100～300。具体地，所述氧化硅/氧化铝摩尔比例如可以为110、120、130、140、150、160、170、180、190、200、210、220、230、240、250、260、270、280、290、300以及这些点值中的任意两个所构成的范围的任意值。在本发明的优选实施方案中，所述具有介孔的分子筛的氧化硅/氧化铝摩尔比优选为120～260，更优选为150～200。
在本发明的具有介孔的分子筛中，以氧化物组成表示，除氧化铝、氧化硅之外，还可以任选地含有至少一种碱金属氧化物(M 2O)，例如氧化锂、氧化钠、氧化钾、氧化铷、氧化铯。本发明的分子筛中，相对于Al 2O 3，所述碱金属氧化物的摩尔比为0～100，可以为0.01～80，可以为0.05～60，可以为0.1～40，可以为1～20。另外，相对于Al 2O 3，所述碱金属氧化物的摩尔比可以为0.005、0.01、0.03、0.05、0.08、0.1、0.3、0.5、0.8、1、5、10、15、25、30、35、45、50、55、65、70、75、80以及这些点值中的任意两个所构成的范围的任意值。在本发明的一个实施方式中，分子筛中，所述碱金属氧化物的摩尔比为0(即，不含 有碱金属氧化物)。在本发明的一个实施方式中，分子筛中，所述碱金属氧化物的摩尔比为1～50。在本发明的分子筛包含两种以上的碱金属氧化物时，所述摩尔比是所有碱金属氧化物的总计。
本发明的分子筛中，以氧化物组成表示，还可以任选地含有选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种的氧化物(Z xO y，以下也称为第三氧化物)。其中，x表示Z的原子数，是1～6的整数，y表示满足Z氧化态所需的数。x优选为1、2、3或4。分子筛中，相对于Al 2O 3，选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种的氧化物的摩尔比为0～100，可以为0.01～80，可以为0.05～60，可以为0.1～40，可以为1～20。另外，相对于Al 2O 3，所述第三氧化物的摩尔比可以为0.005、0.01、0.03、0.05、0.08、0.1、0.3、0.5、0.8、1、5、10、15、25、30、35、45、50、55、65、70、75、80以及这些点值中的任意两个所构成的范围的任意值。在本发明的一个实施方式中，分子筛中，所述第三氧化物的摩尔比为0(即，不含有第三氧化物)。在本发明的一个实施方式中，分子筛中，所述第三氧化物的摩尔比为3～50。在本发明的分子筛包含两种以上的第三氧化物时，所述摩尔比是所有第三氧化物的总计。
在本发明的一个实施方式中，具有介孔的分子筛经氮气吸附BET(Brunner Emmet Teller)方法表征时，所述分子筛中的介孔表面积为30m 2/g～280m 2/g，优选为50m 2/g～250m 2/g，更优选为80m 2/g～200m 2/g，进一步优选为100m 2/g～180m 2/g，进一步优选为120m 2/g～150m 2/g。
在本发明的一个实施方式中，具有介孔的分子筛经氮气吸附BET(Brunner Emmet Teller)方法表征时，所述分子筛的比表面积可以为150m 2/g～400m 2/g，优选为180m 2/g～350m 2/g，更优选为200m 2/g～320m 2/g，更进一步优选为240m 2/g～300m 2/g，更进一步优选为260m 2/g～280m 2/g。
在本发明的一个实施方式中，具有介孔的分子筛中，所述介孔表面积占分子筛比表面积的比例可以为20％～70％，优选为25％～65％，更优选为28％～60％，更优选为30％～55％，更优选为35％～50％。
本发明的具有介孔的分子筛含有介孔结构。根据国际纯粹与应用化学联合会(IUPAC)的规定，介孔的标准定义为2～50nm的孔。本发明的分子筛中，介孔的孔径范围在该数值范围内，但是并不是说本发明 的介孔的下限必须达到2nm，介孔的上限必须达到50nm。本发明的分子筛具有介孔是指，如上所述，介孔表面积占比分子筛表面积的比例可以为20％～70％，优选为25％～65％，更优选为28％～60％，更优选为30％～55％，更优选为35％～50％。
本发明所述的具有介孔的分子筛满足以下条件：在低温氮气吸附-脱附曲线上，吸附支和脱附支在P/P0＝0.4-0.99处出现一个闭合滞后环，且闭合滞后环的起始位置在P/P0＝0.4-0.7处。与此相对地，现有技术制备的分子筛不具有该特征，即在该区间内没有滞后环或滞后环的起始位置出现在较高分压处(通常在P/P0>0.7处)。在本发明的一个实施方式中，所述闭合滞后环的起始位置优选在P/P0＝0.4-0.6处，更优选起始位置在P/P0＝0.4-0.55处。
在本发明的具有介孔的分子筛的前体中富含五配位铝，而分子筛成品中五配位铝的含量很少。具体地，在本发明的一个实施方式中，在所述具有介孔的分子筛的前体中，五配位铝的含量为4％～35％，优选为10％～30％，更优选为15％～25％。在本发明的一个实施方式中，分子筛的成品中五配位铝的含量为5％以下，优选3％以下，更优选为2％以下，进一步优选为1％以下。在本发明的一个实施方式中，所述分子筛成品中基本上不含五配位铝。
在本发明的一个实施方式中，本发明的具有介孔的分子筛是具有介孔的十元环硅铝分子筛或具有介孔的十二元环硅铝分子筛。更具体而言，作为十元环分子筛，可以是ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、Nu-10、Nu-13、Nu-87、EU-1、EU-13和ITQ-13中的至少一种，优选为ZSM-22。作为十二元环分子筛，可以是Beta分子筛、ZSM-12。
本发明还提供一种含水分子筛前体，其化学组成式表示为：Al 2O 3·SiO 2·M 2O·Z xO y·模板剂·水，其中，所述M、Z、x、y的含义与上述相同，Al 2O 3与SiO 2的摩尔比为1:(20～100)，优选为1:(25～90)，更优选为1:(30～80)。Al 2O 3与M 2O的摩尔比为1:(0～100)，优选为1:(0.001～90)，更优选为1:(0.05～80)，更优选为1:(0.1～70)，进一步优选为1:(0.5～60)，更进一步优选为1:(1～50)。Al 2O 3与Z xO y的摩尔比为1:(0～100)，优选为1:(0.001～90)，更优选为1:(0.05～80)，进一步优选为1:(0.1～70)，进一步优选为1:(0.5～60)，更进一步优选为1:(1～50)。Al 2O 3与模板剂的摩 尔比为1:(0.001～10)，优选为1:(0.005～5)，更优选为1:(0.01～4)，更优选为1:(0.05～3)，进一步优选为1:(0.1～2)，进一步优选为1:(0.5～1.5)，更进一步优选为1:(0.8～1)。
所述含水分子筛前体的干基含量为5重量％～30重量％。所述含水分子筛前体的干基含量可以为6重量％、7重量％、8重量％、10重量％、11重量％、12重量％、14重量％、15重量％、17重量％、18重量％、20重量％、22重量％、25重量％、27重量％以及这些点值中的任意两个所构成的范围的任意值。所述含水分子筛前体的干基含量优选为6重量％～15重量％。
本发明的含水分子筛前体中，模板剂可以采用本发明下述的模板剂。
本发明的具有介孔的分子筛可以通过如下的制造方法进行制造。鉴于此，本发明还提供一种具有介孔的分子筛的制造方法，所述方法包括以下步骤：使包含氧化铝源、氧化硅源、模板剂、任选的碱金属氧化物源、任选的第三氧化物源和水的混合物(以下简称为混合物)在晶化条件下晶化以获得所述晶化母液的步骤(以下也称为母液制备步骤)；将晶化后的母液进行过滤，形成干基含量为5重量％～30重量％的滤饼的步骤(以下也称为过滤步骤)；将所述滤饼直接进行焙烧，得到分子筛前体的步骤(以下也称为前体制备步骤)；将所述分子筛前体进行水热处理的步骤(以下也称为水热处理步骤)和将水热处理产物进行过滤，并任选地进行洗涤、干燥处理，并进行焙烧的步骤(以下也称为成品制备步骤)。
本发明中，母液制备步骤可以按照本领域常规的制备晶化后的母液的方法进行制备。母液制备步骤可以根据所制备的分子筛的种类而异。例如，在Beta分子筛的情况下，晶化后的母液的制备方法可以参照美国专利申请US5200168中的方法。在ZSM-22分子筛的情况下，晶化后的母液的制备方法可以参照文献O.Muraza et al.，Microporous and Mesoporous Materials 206(2015)136–143中的方法。在ZSM-48分子筛的情况下，晶化后的母液的制备方法可以参照文献P.Me′riaudeau et al/Journal of Catalysis,1999(185),435–444中的方法，或者参照美国专利申请US5961951中的方法。
在本发明的一个实施方式中，所述晶化母液的制备方法包括：制 备含硅源溶液、含铝源溶液、任选的碱性溶液(碱金属源溶液)、任选的第三氧化物源溶液的混合物，将上述液体混合进行成胶，随后进行晶化。在本发明的一个实施方式中，所述晶化母液的制备方法包括：在溶剂中添加硅源、铝源、任选的碱金属源、任选的第三氧化物源，将得到的溶液进行成胶处理，随后进行晶化。
在本发明的一个示例性的实施方式中，所述晶化后的母液制备步骤的过程如下：将氧化铝源、模板剂和任选的碱金属氧化物源溶于水中，配成原始溶液；将上述原始溶液任选地于50～160℃(优选60～150℃、更优选90～140℃、进一步优选95～130℃)活化处理2～24小时(优选4～22小时、更优选6～20小时、进一步优选8～18小时)，得到混合溶液。在氧化铝源、模板剂和任选的碱金属氧化物源易溶于水的情况下，可以不进行上述热活化处理，制备混合溶液。随后，将氧化硅源、任选的第三氧化物源与上述所得混合溶液混合并搅拌；将所得浆料在120～180℃(优选130～170℃、更优选140～160℃、进一步优选145～155℃)恒温保持24～150小时(优选30～130小时、更优选35～120小时、进一步优选40～100小时、进一步优选50～80小时)，进行晶化处理，制备晶化后的母液。
在母液制备步骤中，各原料成分以氧化物换算以摩尔比记的比例为：SiO 2/Al 2O 3＝5～600，优选为10～550，更优选为20～500，更优选为50～450，进一步优选60～400，更进一步优选80～300；碱金属氧化物/Al 2O 3＝0～100，优选为0.01～90，更优选为0.1～80，进一步优选为0.5～70，进一步优选为1～60，更进一步优选为2～50；第三氧化物/Al 2O 3＝0～100，优选为0.01～90，更优选为0.1～80，进一步优选为0.5～70，进一步优选为1～60，更进一步优选为2～50；模板剂/Al 2O 3＝0.001～8，优选为0.01～6，更优选为0.02～5，更优选为0.1～4，进一步优选为0.2～3，进一步优选为0.5～2，更进一步优选为0.8～1.5；H 2O/Al 2O 3＝4～5000，优选为10～4000，更优选为70～3000，进一步优选为100～2500，进一步优选为150～2000，更进一步优选为200～1500。制备晶化后的母液的条件没有特别限定，只要能够制备出用于制备本发明的分子筛的晶化后的母液即可。
根据本发明，在晶化后的母液的制造中，作为二氧化硅源，比如可以举出硅酸、硅胶、硅溶胶、硅酸四烷基酯或者水玻璃等。这些氧化硅源可以单独使用一种，或者以需要的比例组合使用多种。
根据本发明，在晶化后的母液的制造中，作为氧化铝源，比如可以举出氢氧化铝、铝酸钠、铝盐、醇铝、高岭土或蒙脱土、硫酸铝、硝酸铝、碳酸铝、磷酸铝、氯化铝、明矾、异丙醇铝、乙醇铝、丁醇铝等。
根据本发明，在晶化后的母液的制造中，作为第三氧化物源，可以使用本领域为此目的而常规使用的任何相应氧化物源，包括但不限于所述第三氧化物中相应金属的氧化物、烷醇盐、金属含氧酸盐、乙酸盐、草酸盐、铵盐、硫酸盐和硝酸盐等。例如镁源，可以列举硫酸镁、氯化镁、硝酸镁、葡萄糖镁等。例如钙源，可以列举氢氧化钙、硫酸钙、氯化钙、硝酸钙等。作为锌源，可以列举硫酸锌、氯化锌、硝酸锌等。作为钛源，可以列举四烷氧基钛、二氧化钛、硝酸钛等。作为铁源，可以使用氯化铁、硝酸铁、硫酸铁。作为镓源，比如可以举出硝酸镓、硫酸镓、氧化镓等。作为锗源，比如可以举出四烷氧基锗、氧化锗、硝酸锗等。作为硼源，可以列举硼酸、硼酸盐、硼砂、三氧化二硼等。作为磷源，可以列举磷酸、磷酸盐、五氧化二磷。作为稀土金属源，可以列举氧化镧、氧化钕、氧化钇、氧化铈、硝酸镧、硝酸钕、硝酸钇、硫酸铈铵等。
根据本发明，在晶化后的母液的制造中，作为碱金属氧化物源，可以使用碱金属的酸盐、乙酸盐、草酸盐、铵盐、硫酸盐和硝酸盐等。另外，作为碱金属源，可以使用碱金属氢氧化物，其兼具碱性溶液的作用。
根据本发明，在晶化后的母液的制造中，作为模板剂，可以使用本领域技术人员公知的用于合成分子筛的模板剂。例如，可以是用于制备ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、Nu-10、Nu-13、Nu-87、EU-1、EU-13、ITQ-13、ZSM-12和Beta分子筛的常用的模板剂。
本发明中，可以使用的模板剂包括胺化合物、四元磷化合物和四元铵化合物。后两者通常可以用式(R 4X +·抗衡离子)表示，其中X是氮或磷，每个R各自独立地表示C1-C12的直链或支链烷基、C5-C10的环烷基、C6-C12芳基、C1-C12烷基C6-C12芳基，R 4X +的配位数根据抗衡离子的化合价而异，可以为1或2，抗衡离子表示化合价与R 4X +基团相当的负离子，可以选自氯离子、氟离子、溴离子、硝酸根、硫 酸根、氢氧根。作为模板剂，也可以采用单胺、双胺和三胺，包括混合胺作模板剂，既可是单一模板剂也可是多种模板剂混合而得的模板剂。
在本发明中，代表性的模板剂包括：四甲基铵盐、四乙基铵盐、四丙基铵盐、四丁基铵盐、四戊基铵盐二-n-聚胺、三聚胺、三乙胺、三乙醇胺、环乙基胺、二甲基吡啶、二乙基吡啶、N,N-二甲基苯、N,N-二乙醇，二环乙基、N,N-二甲基乙醇胺、1,4-二氮杂双环(2,2,2)辛烷离子、二-n-丁基胺、新戊基胺、二-n-戊基胺，异丙基胺、t-丁基胺、吡啶咯烷和2-咪唑酮、十六烷基三甲基溴化铵、四甲基氢氧化(氯化、溴化、碘化)铵、四乙基氢氧化(氯化、溴化、碘化)铵、四丙基氢氧化(氯化、溴化、碘化)铵、四丁基氢氧化(氯化、溴化、碘化)铵、四戊基氢氧化(氯化、溴化、碘化)铵。但不限于此。
在所述过滤步骤中，将晶化后的母液进行过滤，以形成干基含量为5重量％～30重量％的滤饼。对晶化后的母液进行过滤的目的是去除合成多余的母液。本发明中，通过对过滤条件进行控制，以使得形成的滤饼中的干基含量为特定范围。具体而言，本发明中，所述滤饼的干基含量为5重量％～30重量％。另外，滤饼的干基含量可以为6重量％、7重量％、8重量％、10重量％、11重量％、12重量％、14重量％、15重量％、17重量％、18重量％、20重量％、22重量％、25重量％、27重量％以及这些点值中的任意两个所构成的范围的任意值。所述滤饼的干基含量优选为6重量％～15重量％。当所述滤饼中干基含量不在上述范围内时，最终制备的分子筛不满足本发明的具有介孔的分子筛的要求，其物化性质无法实现本发明的目的。
在所述前体制备步骤中，将所述滤饼直接进行焙烧，由此得到分子筛前体。在此步骤中，将过滤步骤中得到的滤饼直接在高温下进行焙烧而不进行烘干处理。在本发明的一个实施方式中，所述焙烧的温度为300℃～900℃，优选为350℃～800℃，更优选为400℃～700℃，更进一步优选为450℃～600℃，更进一步优选为450℃～550℃。在本发明的一个实施方式中，焙烧时升温速率可以为5℃/分钟～100℃/分钟，优选为10℃/分钟～50℃/分钟，更优选为20℃/分钟～40℃/分钟，更进一步优选为30℃/分钟～40℃/分钟。在本发明的一个实施方式中，所述焙烧的时间可以为1小时～20小时，优选为2小时～16小时，更优选为5小 时～15小时，更进一步优选为6小时～12小时。所述焙烧的环境可以为自然环境，即焙烧时不需特意通入含氧气体，也可以根据需要在通入氧气的情况下进行焙烧。不受任何理论限定地，本发明的发明人推测，通过焙烧，滤饼中的残留的水能够把模板剂氧化去除，同时通过这种条件下的焙烧，也可以使水与分子筛中的铝进行作用从而形成非骨架铝。
这样，本发明中通过前体制备步骤得到的产物(即分子筛前体)含有大量的五配位非骨架铝(即五配位铝)。在本发明的一个实施方式中，分子筛前体的五配位铝的含量为4％～35％，优选为10％～30％，更优选为15％～25％。其中，五配位非骨架铝的定义为在 27Al NMR图谱中化学位移б为10～40ppm的峰。 27Al NMR图谱测量条件可以参见公开文献，如Guoliang Zhao et al,Applied Catalysis A:General 299(2006)167–174。
在本发明的一个实施方式中，焙烧处理后得到的分子筛前体可以自然冷却降温。优选降温至室温。
在所述水热处理步骤中，将所述分子筛前体进行水热处理。在本发明的一个实施方式中，所述水热处理的介质为酸性水溶液。在本发明中，所述酸性水溶液是指含H +的水溶液。其中，水可以为自来水、纯净水、去离子水等。H +为有机酸和/或无机酸解离释放的离子。本发明的一个实施方式中，为了获得所述酸性水溶液，可以在水中添加盐酸、硫酸、磷酸、硝酸、柠檬酸、乙酸、马来酸、草酸、氨基三乙酸、1,2-环己烷二胺四乙酸、酒石酸和苹果酸中的至少一种，优选为盐酸和/或柠檬酸。在本发明的一个实施方式中，所述酸性水溶液中无机酸和/或有机酸的含量可以为0.01M～5M，优选为0.05M～2M，更优选为0.2M～1.5M，进一步优选为0.5～1.2M，更进一步优选为0.8～1.1M。
在本发明的一个实施方式中，所述水热处理步骤中，液固体积比可以为5～200，优选为20～100，更优选为40～80，进一步优选为50～70。
在本发明的一个实施方式中，所述水热处理步骤中，所述水热处理的温度可以为80℃～300℃，优选为100℃～200℃，更优选为120℃～180℃，进一步优选为140℃～160℃。
在本发明的一个实施方式中，所述水热处理步骤中，水热处理的时间可以为0.1小时～24小时，优选为0.5小时～18小时，更优选为1小时～12小时，更优选为2小时～10小时。
在本发明的一个实施方式中，所述水热处理步骤中，所述水热处理可以在开放容器中实施，也可以在密闭容器中实施。优选在密闭容器中实施。在本发明的一个实施方式中，所述水热处理的压力为密闭容器在水热条件下形成的自压。
在成品制备步骤中，将水热处理产物进行过滤，并任选地进行洗涤、干燥处理。过滤方法没有特别限定，可以为本领域技术人员所公知的方法，例如过滤、利用布氏漏斗的抽滤等。洗涤方法没有特别限定，可以使用去离子水进行水洗。在本发明的一个实施方式中，进行水洗直到滤液pH值为4～8，优选pH为6～7。溶液的pH值测量可以用pH试纸或pH计进行测量，测量方法没有特别限定，可以为本领域技术人员所公知的方法。
在成品制备步骤中，任选地将过滤得到的分子筛的进行干燥处理。干燥方法没有特别的限定，可以为本领域技术人员所公知的方法，例如可以按照常规方法在120℃下干燥6小时。然后，进一步进行焙烧，所述焙烧条件为本领域中制备分子筛常用的条件，可以为上述前体制备步骤中的焙烧条件。例如，可以在400℃～600℃下焙烧2～8小时。
由此，可以得到本发明的具有介孔的分子筛。
在本发明所述的具有介孔的分子筛的低温氮气吸附-脱附曲线上，吸附支和脱附支在P/P0＝0.4-0.99处出现一个闭合滞后环，且闭合滞后环的起始位置在P/P0＝0.4-0.7处。与此相对地，现有技术制备的分子筛在该区间内没有滞后环或滞后环的起始位置出现在较高分压处(通常在P/P0>0.7处)。在本发明的一个实施方式中，所述闭合滞后环的起始位置在P/P0＝0.4-0.6处，更优选起始位置在P/P0＝0.4-0.55处。
本发明还提供一种含水分子筛前体的制备方法，其包括以下步骤：
母液制备步骤，其中，使包含氧化铝源、氧化硅源、模板剂、任选的碱金属氧化物源、任选的第三氧化物源和水的混合物(以下简称为混合物)在晶化条件下晶化以获得晶化母液；
含水分子筛前体的制备步骤，将所述晶化后的母液进行过滤，得到含水分子筛前体的步骤，其中，所述含水分子筛前体的干基含量为5重量％～30重量％，优选为6重量％～15重量％。
本发明的含水分子筛前体的制备方法中，母液制备步骤中的各成分比例和条件与上述本发明的分子筛的制备方法中母液制备步骤中的 各成分比例和条件相同。
通过本发明的含水分子筛前体的制备方法，可以制备出含水分子筛前体。所述含水分子筛前体的干基含量可以是本发明上述过滤步骤中所得到的滤饼的干基含量。该含水分子筛前体可以直接用于本发明上述分子筛的制备方法中的前体制备步骤。
本发明的具有介孔的分子筛可以作为固体酸催化剂直接使用。另外，在本发明的一个实施方式中，可以在本发明所述的具有介孔的分子筛上担载活性成分来制成催化剂而使用。由此得到的本发明的催化剂不仅具有较好的加氢异构化活性，而且所得产物中的目标产物的收率高、产物的倾点低。
本发明还提供一种催化剂，其包含载体和负载在所述载体上的活性金属组分。
在本发明的一个实施方式中，所述活性金属组分为选自VIII族贵金属中的至少一种。在本发明的一个实施方式中，VIII族贵金属优选为选自钌、锇、钯、铂、铑和铱中的至少一种。在本发明的一个实施方式中，所述活性金属组分为铂组分和钯组分的组合。在本发明的一个实施方式中，Pt组分与Pd组分的摩尔比为1:2～10，优选为1:2～8，进一步优选为1:2～6，更优选为1:2～4。
在本发明的一个实施方式中，在本发明的催化剂中，所述活性金属组分在载体上呈高度分散状态。具体地，所述活性金属组分的单个颗粒的尺寸小于3nm，例如可以为0.1～2.8nm。
在本发明中，所述活性金属组分可以由活性金属组分前驱体来提供。所述活性金属组分前驱体优选为选自含VIII族贵金属元素的化合物。作为所述含VIII族贵金属元素的化合物，可以是选自含VIII族贵金属元素的硝酸盐、氯化物、硫酸盐、甲酸盐、乙酸盐、磷酸盐、柠檬酸盐、草酸盐、碳酸盐、碱式碳酸盐、氢氧化物、磷酸盐、磷化物、硫化物、铝酸盐、钼酸盐、钨酸盐这些盐的络合物和水溶性氧化物中的至少一种。
在本发明的催化剂中，以催化剂的总重量为基准，以元素单质计的活性金属组分的含量可以根据需要适当选择，通常可以为0.001重量％～5重量％，优选为0.005重量％～4.5重量％，优选为0.01重量％～4重量％，更优选为0.1重量％～3重量％，更加优选为0.2重量％～1重量％， 更进一步优选0.4重量％～0.8重量％。
在本发明的催化剂中，作为所述多孔载体，可以列举本领域在制造负载型催化剂时作为载体而常规使用的那些有机或无机多孔固体。
具体而言，作为所述有机多孔固体，比如可以举出烯烃均聚物或共聚物、聚乙烯醇或其共聚物、环糊精、(共)聚酯、(共)聚酰胺、氯乙烯均聚物或共聚物、丙烯酸酯均聚物或共聚物、甲基丙烯酸酯均聚物或共聚物、苯乙烯均聚物或共聚物等，以及这些均聚物或共聚物的部分交联形式，其中优选部分交联(比如交联度至少为2％但小于100％)的苯乙烯聚合物。
根据本发明一个实施方案，在使用前对所述有机多孔固体进行热活化处理和/或化学活化处理。根据本发明，所述有机多孔固体在使用前可以仅进行热活化处理，或者在使用前也可以仅进行化学活化处理，或者可以在使用前按照任意的组合顺序先后进行所述热活化处理和所述化学活化处理，并没有特别的限定。
该热活化处理可以按照通常的方式进行。比如在减压条件下或惰性气氛下对所述有机多孔固体进行加热处理。这里所说的惰性气氛是指气体中仅含有极其微量或者不含有可与所述有机多孔固体反应的组分。作为所述惰性气氛，比如可以举出氮气或稀有气体气氛，优选氮气气氛。由于有机多孔固体的耐热性差，因此该热活化过程以不破坏所述有机多孔固体本身的结构和基本组成为前提。一般地，该热活化的温度为50～400℃，优选100～250℃，而热活化时间为1～24h，优选2～12h。
热活化/化学活化处理后，所述有机多孔固体需要在惰性气氛下正压保存备用。
作为所述无机多孔固体，比如可以举出元素周期表ⅡA、ⅢA、IVA或IVB族金属的难熔氧化物(比如二氧化硅(又称为氧化硅或硅胶)、氧化铝、氧化镁、氧化钛、氧化锆或氧化钍等)，或者这些金属的任意难熔复合氧化物(比如氧化硅铝、氧化镁铝、氧化钛硅、氧化钛镁和氧化钛铝等)，以及粘土、分子筛(比如ZSM-5和MCM-41)、云母、蒙脱土、膨润土和硅藻土等。作为所述无机多孔固体，还可以举出由气态金属卤化物或气态硅化合物通过高温水解而生成的氧化物，比如由四氯化硅高温水解得到的硅胶，或者由三氯化铝高温水解得到的氧化铝等。
作为所述无机多孔固体，优选二氧化硅、氧化铝、氧化镁、氧化硅铝、氧化镁铝、氧化钛硅、二氧化钛、分子筛和蒙脱土等，特别优选二氧化硅和蒙脱土。
根据本发明，适宜的二氧化硅可以通过常规方法制造，或者可以是任意的可购买的商业产品，比如可以举出Grace公司的Grace 955、Grace 948、Grace SP9-351、Grace SP9-485、Grace SP9-10046、Davsion Syloid 245和Aerosil812，Ineos公司的ES70、ES70X、ES70Y、ES70W、ES757、EP10X和EP11，以及PQ公司的CS-2133和MS-3040。
根据本发明，在一个实施方案中，在使用前对所述无机多孔固体进行热活化处理和/或化学活化处理。
根据本发明，所述无机多孔固体在使用前可以仅进行热活化处理，或者在使用前也可以仅进行化学活化处理，或者可以在使用前按照任意的组合顺序先后进行所述热活化处理和所述化学活化处理，并没有特别的限定。
该热活化处理可以按照通常的方式进行，比如在减压条件下或惰性气氛下对所述无机多孔固体进行加热处理。这里所说的惰性气氛是指气体中仅含有极其微量或者不含有可与所述无机多孔固体反应的组分。作为所述惰性气氛，比如可以举出氮气或稀有气体气氛，优选氮气气氛。一般地，该热活化的温度为200～800℃，优选400～700℃，最优选400～650℃，加热时间比如为0.5～24h，优选2～12h，最优选4～8h。
热活化/化学活化处理后，所述无机多孔固体需要在惰性气氛下正压保存备用。
在本发明的一个实施方式中，所述载体为本发明的上述的具有介孔的分子筛。更具体而言，该具有介孔的分子筛是具有介孔的十元环硅铝分子筛或具有介孔的十二元环硅铝分子筛。作为十元环分子筛，可以是ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、Nu-10、Nu-13、Nu-87、EU-1、EU-13和ITQ-13中的至少一种，优选为ZSM-22。作为十二元环分子筛，可以是ZSM-12、Beta分子筛。在本发明的一个实施方式中，所述载体为本发明的上述的具有介孔的分子筛和除本发明的分子筛之外的载体的组合。
在本发明的一个实施方式中，上述本发明的金属载体上，可以进一步担载选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的 至少一种的组份(以下也称为助剂组份)。在本发明的一个实施方式中，在本发明的催化剂中，以催化剂的总重量为基准，以元素单质计的助剂组份的含量可以根据需要适当选择，通常可以为0.001重量％～5重量％，优选为0.005重量％～4.5重量％，优选为0.01重量％～4重量％，更优选为0.1重量％～3重量％，更加优选为0.2重量％～1重量％，更进一步优选0.4重量％～0.8重量％。
本发明还提供一种催化剂的制备方法，其包括以下步骤：
(I)采用浸渍法将活性金属组分前驱体和有机络合剂负载在载体上，然后进行任选的干燥、进行焙烧，得到半成品催化剂；和
(II)以含有有机络合剂的溶液作为浸渍液，对步骤(I)所得半成品催化剂进行浸渍，然后进行干燥。
在本发明中，通过两步浸渍法制备催化剂，第一步浸渍和第二步浸渍分别用于引入活性金属组分和有机络合剂。在第一步浸渍过程中加入有机络合剂并使之通过焙烧转化为炭，由此，不仅能够提高催化剂的活性，而且能够有效地长时间保持催化剂的高活性，从而大大提高催化剂的使用寿命。不受任何理论限定地，本发明的发明人推测其原因可能是因为第一步浸渍过程中加入的有机络合剂，有机络合剂的存在阻碍了焙烧过程中活性金属在载体上的聚集，使其在载体上分散更加均匀；同时，第一步浸渍后焙烧能够使金属化合物转化为金属氧化物，使有机络合剂转化为炭，从而使活性金属与载体之间的结合更加牢固，提高了催化剂的活性和稳定性；在第二步浸渍过程中加入的有机络合剂覆盖在催化剂表面，能够有效防止活性金属之间在还原过程中的聚集，保证高金属分散度，从而进一步提高了催化剂的活性。因此，通过本发明的催化剂的制备方法，可以有效解决活性金属组分在催化剂上分布不均匀的问题。由此，使得活性金属组分在载体上呈高度分散状态，由此在延长催化剂的使用寿命的同时，极大地提高了催化剂的催化活性。
在本发明的催化剂的制备方法中，步骤(I)所用的有机络合剂可以选自含氧有机物、有机酸和含氮有机物中的至少一种。在本发明的一个实施方式中，所述含氧有机物可以为二元以上的多元醇，优选为碳原子数为2～6的多元醇或其低聚体或多聚体，例如可以列举乙二醇、丙三醇、聚乙二醇、二乙二醇、丁二醇中的至少一种。所述聚乙二醇 的分子量优选为200～1500。在本发明的一个实施方式中，所述有机酸可以为C2～C15的含一个或多个羧基的化合物，具体可以列举乙酸、马来酸、草酸、氨基三乙酸、1,2-环己烷二胺四乙酸、柠檬酸、酒石酸和苹果酸中的至少一种。在本发明的一个实施方式中，所述含氮有机物可以为有机胺和有机铵盐中的至少一种。作为所述有机胺，优选为C2～C10的含一个或多个氨基的化合物，可以是伯胺、仲胺或叔胺，特别优选为乙二胺。作为所述有机铵盐，优选为EDTA。优选地是，步骤(I)中的有机络合剂为选自有机酸中的至少一种，更优选地是，步骤(I)的有机络合剂为选自C2～C15的脂肪酸中的至少一种。通过使用有机酸作为步骤(I)的有机络合剂，可以获得具有更高活性的催化剂。
在步骤(I)中，所述有机络合剂与所述活性金属组分前驱体的摩尔比可以为2～100：1，优选为4～80:1，更优选为6～70:1，进一步优选为10～50：1。
在步骤(I)中，浸渍可以通过本领域公知的浸渍方法来进行。浸渍时对所述浸渍液的温度没有特别限定，可以是浸渍液所能达到的各种温度。对浸渍的时间没有特别限定，只要能负载上所需量的所需组分即可。例如：浸渍的温度没有特别限定，可以为15～60℃。浸渍时间没有特别限定，可以为0.5～5小时。浸渍时含有机络合剂液体与载体的质量比没有特别限定，可以为0.6:1～2:1，优选为0.8:1～1.4:1。
在步骤(I)中，所述干燥的条件没有特别的限定，可以是本领域公知的各种干燥条件。优选地，步骤(1)所述干燥的温度为100～250℃，时间为1～12小时。
在步骤(I)中，优选地是，所述焙烧的条件使得以半成品催化剂的总量为基准，半成品催化剂中炭含量可以为0.05重量％～0.5重量％，优选为0.1重量％～0.4重量％。在本发明中，可以通过控制焙烧条件中的焙烧温度和助燃性气体的通入量来获得上述炭含量，所述助燃性气体可以为各种氧气含量不低于20体积％的气体，例如可以是空气、氧气以及它们的混合气体中的至少一种。
在本发明的一个实施方式中，所述助燃性气体的通入量不低于0.2升/克·小时。所述助燃性气体的通入，一方面满足燃烧的条件，使得活性金属组分前驱体转化为活性金属氧化物，使有机络合剂转化为炭；另一方面也能将燃烧形成的二氧化碳和水以及其他成分排放出去，以 避免沉积在催化剂上造成对活性相的空位阻碍。在本发明的一个实施方式中，助燃性气体的通入量为0.2～20升/(克·小时)，优选为0.3～10升/(克·小时)。此处的“克”表示所处理的载体的重量。
在步骤(I)中，所述焙烧的温度可以为350～500℃，优选为360～450℃。焙烧的时间可以为0.5～8小时，优选为1～6小时。控制焙烧温度在上述范围内即可保证有机络合剂能以上述含量范围将炭形成于载体上，得到半成品催化剂。
在步骤(I)中，相对于所要浸渍的载体的重量，以元素单质计的活性金属组分前驱体的量可以根据需要适当选择，通常可以为0.001重量％～5重量％，优选为0.005重量％～4.5重量％，优选为0.01重量％～4重量％，更优选为0.1重量％～3重量％，更加优选为0.2重量％～1重量％，更进一步优选0.4重量％～0.8重量％。
在步骤(I)中，所使用的活性金属组分前驱体可以是上述本发明的催化剂中的活性金属组分前驱体。
在步骤(I)中，所使用的载体可以是上述本发明的催化剂中所使用的载体。在本发明的一个实施方式中，步骤(I)中的载体优选为上述本发明的具有介孔的分子筛。更具体而言，该具有介孔的分子筛是具有介孔的十元环硅铝分子筛或具有介孔的十二元环硅铝分子筛。作为十元环分子筛，可以是ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、Nu-10、Nu-13、Nu-87、EU-1、EU-13和ITQ-13中的至少一种，优选为ZSM-22。作为十二元环分子筛，可以是ZSM-12、Beta分子筛。在本发明的一个实施方式中，步骤(I)中的载体为本发明的上述的具有介孔的分子筛和除本发明的分子筛之外的载体的组合。
在步骤(II)中，所用有机络合剂的选择范围与步骤(I)中相同。步骤(II)中所用有机络合剂可以与步骤(I)所用有机络合剂相同，也可以不同。
步骤(II)中所用有机络合剂与活性金属的摩尔比可以为2～100：1，优选为4～80:1，更优选为6～70:1，进一步优选为10～50：1。具体而言，该摩尔比可以与步骤(I)中相同，也可以与步骤(I)中不同。
步骤(II)中所用浸渍条件、干燥条件可以使用本领域中公知的浸渍条件、公知的干燥条件。具体而言，步骤(II)中所用浸渍条件、干燥条件可以与步骤(I)中相同。
在本发明所述的方法中，步骤(II)干燥后得到的催化剂不需要再进 行焙烧。也可以根据需要进一步进行焙烧，所述焙烧的温度没有特别限定，可以为350～500℃，优选为360～450℃。焙烧的时间没有特别限定，可以为0.5～8小时，优选为1～6小时。
在本发明的一个实施方式中，所述催化剂的制备方法还可以进一步包括对步骤(II)所得催化剂进行还原处理的步骤。还原条件可以是本领域公知的还原条件。通常，还原气氛为氢气，还原温度可以为300～500℃，还原时间可以为2～6小时。
在本发明的一个实施方式中，所述催化剂的制备方法还可以包括通过浸渗法浸渍选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种金属离子的溶液的步骤。该浸渗可以在步骤(I)中进行，得到担载有活性金属组分和助剂组份的半成品催化剂。该浸渍也可以在步骤(II)中进行，得到得到担载有活性金属组分和助剂组份的催化剂。另外，也可以在步骤(I)之前、步骤(I)和步骤(II)之间、步骤(II)之后，进行该浸渍步骤。在本发明的一个实施方式中，优选的是，在步骤(I)之前、或者步骤(I)之中、或者步骤(I)和步骤(II)之间进行该浸渗步骤。浸渍的条件没有特别限定，可以使用本发明上述的浸渍条件。相对于所要浸渍的载体的重量，以元素单质计的助剂组份的量可以根据需要适当选择，通常可以为0.001重量％～5重量％，优选为0.005重量％～4.5重量％，优选为0.01重量％～4重量％，更优选为0.1重量％～3重量％，更加优选为0.2重量％～1重量％，更进一步优选0.4重量％～0.8重量％。
在本发明的一个实施方式中，本发明的催化剂可以为加氢异构化催化剂。在本发明的一个实施方式中，加氢异构化催化剂中，在作为载体的本发明的具有介孔的分子筛上担载VIII族贵金属中的一种。在本发明的一个实施方式中，加氢异构化催化剂中，在作为载体的本发明的具有介孔的分子筛上担载VIII族贵金属中的两种以上。本发明的一个实施方式中，所述加氢异构化催化剂为本发明上述催化剂。
本发明还提供一种加氢异构化处理方法，其中使用本发明的加氢异构化催化剂。本发明的加氢异构化可以包括本领域中公知的处理步骤，只要其中使用本发明的催化剂即可。加氢异构化是石油炼制过程的重要反应之一，主要应用于生产优质燃料油和高档润滑油。其中，通过原料油中凝点相对高的正构烷烃和芳烃上的长侧链烷烃进行异构化反应，轻质烷烃可生产出高辛烷值的汽油调合组分，对于长链烷烃， 可以改善中间馏分油(喷气燃料和柴油)以及润滑油的低温流动性能。
在本发明的一个实施方式中，用于加氢异构化的原料是加氢裂化尾油。在本发明的一个实施方式中，在加氢异构化反应条件下，将加氢裂化尾油与本发明的加氢异构化催化剂接触进行加氢异构化反应。所述加氢裂化尾油的馏程一般可以为350～500℃(采用模拟蒸馏方法在常压下测定)。
在本发明中，所述加氢异构化反应条件没有特别的限定，只要足以使原料油发生加氢异构化反应即可。一般地，所述加氢异构化反应条件可以包括：温度为200～500℃，优选为250～400℃，更优选为300～350℃；压力为1～30MPa，优选为2～20MPa，更优选为5～20MPa。本发明中所述的压力是指绝对压力。加氢异构化方法中，空速为0.1～5h -1，优选为0.1～3h -1，更优选为0.5～2h -1；氢油体积比为50～3000，优选为300～3000，更优选为400～600。
通过本发明的加氢异构化方法，使加氢裂化尾油与本发明的加氢异构化催化剂接触，进行加氢异构化反应，能够获得较高的异构化产物收率。并且，所得异构化产物在具有较高的粘度指数的同时，还具有较低的倾点，其适于作为润滑油基础油。
实施例
以下结合实施例详细说明本发明，但并不因此限制本发明的范围。
以下实施例和对比例中，采用商购自日本理学电机工业株式会社的3271E型X射线荧光光谱仪(XRF，样品制备方式为压片法，测量条件为端窗铑靶，管电压为50kV，管电流为50mA)，对测定样品中各元素的含量进行分析测定，测定各样品(分子筛前体、分子筛)中各氧化物的摩尔比。
以下实施例和对比例中，分子筛的X-射线衍射谱图(XRD)采用标准方法由X-射线粉末衍射仪(比如德国Bruker公司D8 Advance粉末衍射仪，光源为CuKα射线,镍滤光片，管电压为40kV，管电流为40mA，λ值为0.15418nm，步进为0.02°，2θ扫描范围5°～55°)测定。样品测试前，采用扫描电子显微镜(SEM)观察分子筛样品的结晶情况，确认样品中只含有一种晶体，即分子筛样品为纯相，在此基础上再进行XRD测试，确保XRD谱图中的衍射峰中没有其他晶体的干扰峰。样 品测试前在600℃下焙烧3小时。
27Al NMR图谱的测定可以采用本领域中公知的方法来进行，例如在Guoliang Zhao et al,Applied Catalysis A:General 299(2006)167-174中使用的测定方法和条件。本领域中公知的是，在 27Al NMR图谱中，化学位移б为10～40ppm的峰为归属于五配位铝的特征峰，化学位移б为-10～10ppm的峰为归属于六配位铝的特征峰，化学位移б为50～70ppm的峰为归属于四配位铝的特征峰。因此，五配位铝的含量(％)＝五配位铝峰积分面积/铝峰总积分面积×100％。
以下实施例和对比例中采用美国Micromeritics公司DIGISORB 2500型自动吸附仪测定样品的比表面积、外表面积，样品测试前在600℃下焙烧3小时，测量方法均可以按照ASTM D4222-98标准方法进行。
介孔面积测量方法和条件可以采用本领域中公知的方法来进行，例如在公开文献Danny Verboekend et al,CrystEngComm 2011,13,3408–3416中使用的测定方法和条件。
在以下的实施例和比较例中，分子筛中水和有机模板剂的含量是通过热重分析法(比如使用美国TA公司SDT Q600同步热分析仪，在氧气氛下从25℃开始以10℃/分钟的升温速度升高至800℃测试样品的失重曲线)测量。
以下实施例和对比例中，干基是指一定量的物料在空气气氛中于马弗炉中在600℃焙烧4小时后得到的产物的重量与焙烧前物料的重量之比的百分数。即干基＝(焙烧后得到的产物的重量/焙烧前物料的重量)×100％。
以下实施例和对比例中催化剂半成品中炭含量使用日本HORIBA公司生产的EMIA-320V碳硫分析仪进行分析测定。
以下实施例和对比例中粘度指数是按照GB/T 1995-1998方法测量，倾点是按照GB/T 3535方法测量。
实施例1-1
(1)制备晶化后的母液
取6.05克白炭黑，0.51克分析纯的仲丁醇铝，以及18.4mL四乙基氢氧化铵的水溶液(40重量％)待用。将15克去离子水、四乙基氢氧化铵和仲丁醇铝的37克去离子水溶液混合，随后将白炭黑加入，搅拌1h后移入反应釜中，在140℃下晶化120小时。
(2)制备滤饼
将工序(1)中制备的晶化后的母液进行过滤，以滤饼上没有滤液计，继续抽滤5分钟，获得的滤饼F-1-1，该滤饼F-1-1即为含水分子筛前体，其干基含量为11.2重量％。该滤饼中的氧化硅/氧化铝摩尔比为30.2，模板剂与氧化铝的摩尔比为1:5。
(3)制备分子筛前体
在大气环境中，于焙烧炉中，将滤饼F-1-1以25℃/分钟的升温速率从室温升到450℃，恒温4小时。获得分子筛前体C-1-1，其 27Al NMR图谱见图1。
(4)水热处理并制备分子筛成品
将分子筛前体C-1-1放入浓度为1M的HCl溶液中进行密闭水热处理。其中，液固比为50，水热处理的温度为180℃，水热处理的时间为3小时。水热处理结束后将产物过滤、水洗，直至滤液pH为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的Beta分子筛成品H-1。该Beta分子筛的氧化硅/氧化铝摩尔比为159.2。介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。
该分子筛的XRD图谱、 27Al NMR图谱以及氮气吸附-脱附曲线分别见图2、图3和图4。
由图4可以看出，所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处出现一个闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
对比例1-1
根据实施例1-1的方法制备Beta分子筛，所不同的是，在步骤(2)中，以滤饼上没有滤液计时，继续抽滤50分钟，获得的滤饼DF-1-1，该滤饼DF-1-1的干基含量为46.5重量％。最终，制得Beta分子筛成品DH-1-1，该Beta分子筛的氧化硅/氧化铝摩尔比为122.7，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.7-0.99处出现一个闭合滞后环。
实施例1-2
根据实施例1-1的方法制备Beta分子筛，所不同的是，在步骤(3) 中，将滤饼F-1-1以5℃/分钟的升温速率从室温升到350℃，恒温14小时。升温过程中焙烧炉为焙烧炉，获得分子筛前体C-1-2。制得Beta分子筛成品H-1-2，该Beta分子筛的氧化硅/氧化铝摩尔比为121.3，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例1-3
根据实施例1-1的方法制备Beta分子筛，所不同的是，在步骤(3)中，将滤饼F-1-1以15℃/分钟的升温速率从室温升到850℃，恒温4小时。升温过程中通入空气，空气流速为1.0升/分钟，获得分子筛前体C-1-3。制得Beta分子筛成品H-1-3，该Beta分子筛的氧化硅/氧化铝摩尔比为183.6，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例1-4
根据实施例1-1的方法制备Beta分子筛，所不同的是，在步骤(4)中，将分子筛前体C-1-1放入浓度为1.0M的柠檬酸溶液中进行密闭水热处理。其中，液固比为100，水热处理的温度为180℃，水热处理的时间为2小时，水热处理结束后将产物过滤、水洗，直至滤液pH值为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的Beta分子筛成品H-1-4，该Beta分子筛的氧化硅/氧化铝摩尔比为168.2，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例1-5
根据实施例1-1的方法制备Beta分子筛，所不同的是，在步骤(4)中，将分子筛前体C-1-1放入浓度为0.05M的柠檬酸溶液中进行密闭水热处理。其中，液固比为10，水热处理的温度为90℃，水热处理的时间为0.1小时，水热处理结束后将产物过滤、水洗，直至滤液pH值 为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的Beta分子筛成品H-1-5，该Beta分子筛的氧化硅/氧化铝摩尔比为159.3，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例1-6
根据实施例1-1的方法制备Beta分子筛，所不同的是，在步骤(4)中，将分子筛前体C-1-1放入浓度为1M的盐酸溶液中进行密闭水热处理。其中，液固比为50，水热处理的温度为180℃，水热处理的时间为3小时，水热处理结束后将产物过滤、水洗，直至滤液pH值为4，经120℃干燥4小时后，在550℃下焙烧4小时，获得的Beta分子筛成品H-1-6，该Beta分子筛的氧化硅/氧化铝摩尔比为158.5，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例1-7
(1)制备晶化后的母液
取6.05克白炭黑，0.34克分析纯的仲丁醇铝，以及18.4mL四乙基氢氧化铵的水溶液(40重量％)待用。将15克去离子水、四乙基氢氧化铵和仲丁醇铝的37克去离子水溶液混合，随后将白炭黑加入，搅拌1h后移入反应釜中，在140℃下晶化120小时。
(2)制备滤饼
将工序(1)中制备的晶化后的母液进行过滤，以滤饼上没有滤液计时，继续抽滤5分钟，获得的滤饼F-1-7，该滤饼F-1-7即为含水分子筛前体，其干基含量为11.2重量％。该滤饼中的氧化硅/氧化铝摩尔比为45.8，模板剂与氧化铝的摩尔比为1:6。
(3)制备分子筛前体
在大气环境中，于焙烧炉中，将滤饼F-1-7以25℃/分钟的升温速率从室温升到450℃，恒温4小时。获得分子筛前体C-1-7。
(4)水热处理并制备分子筛成品
将分子筛前体C-1-7放入浓度为1M的HCl溶液中进行密闭水热处理。其中，液固比为50，水热处理的温度为180℃，水热处理的时间为3小时。水热处理结束后将产物过滤、水洗，直至滤液pH为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的Beta分子筛成品H-7。该Beta分子筛的氧化硅/氧化铝摩尔比为164.5，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例1-8
(1)制备晶化后的母液
取6.05克白炭黑，0.68克分析纯的仲丁醇铝，以及18.4mL四乙基氢氧化铵的水溶液(40重量％)待用。将15克去离子水、四乙基氢氧化铵和仲丁醇铝的37克去离子水混合，随后将白炭黑加入，搅拌1h后移入反应釜中，在140℃下晶化120小时。
(2)制备滤饼
将工序(1)中制备的晶化后的母液进行过滤，以滤饼上没有滤液计时，继续抽滤5分钟，获得的滤饼F-1-8，该滤饼F-1-8即为含水分子筛前体，其干基含量为11.2重量％。该滤饼中的氧化硅/氧化铝摩尔比为22.6，模板剂与氧化铝的摩尔比为1:4。
(3)制备分子筛前体
在大气环境中，于焙烧炉中，将滤饼F-1-8以25℃/分钟的升温速率从室温升到450℃，恒温4小时。获得分子筛前体C-1-8。
(4)水热处理并制备分子筛成品
将分子筛前体C-1-8放入浓度为1M的HCl溶液中进行密闭水热处理。其中，液固比为50，水热处理的温度为180℃，水热处理的时间为3小时。水热处理结束后将产物过滤、水洗，直至滤液pH为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的Beta分子筛成品H-8。该Beta分子筛的氧化硅/氧化铝摩尔比为145.6，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
对比例1-2
根据实施例1-1中工序(1)制备晶化后的母液，接着过滤，并将过滤后的得到的滤饼在120℃下干燥4小时，使滤饼充分干燥。然后在550℃下焙烧4小时，获得分子筛前体DC-1-2。将分子筛前体DC-1-2与10倍体积的0.5M盐酸溶液在90℃下进行铵交换处理4小时，最后经过滤、干燥和550℃下焙烧4小时后获得Beta分子筛成品DH-1-2，该Beta分子筛的氧化硅/氧化铝摩尔比为32.3，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表1。其 27Al NMR图谱如图5所示，氮气吸附-脱附曲线如图6所示。从图中可见，分子筛在低温氮气吸附-脱附曲线P/P0＝0.7-0.99处出现一个闭合滞后环。
测试例1-1
(1)采用美国Micromeritics公司DIGISORB 2500型自动吸附仪测定上述实施例1-1～1-8和对比例1-1～1-2制备的分子筛成品的介孔面积、比表面积，并计算介孔表面积占比表面积的比例(介孔表面积占比＝介孔表面积/比表面积×100％)，结果如下表1所示。
(2)采用商购自日本理学电机工业株式会社的3271E型X射线荧光光谱仪，对上述实施例1-1～1-8和对比例1-1～1-2制备的分子筛前体和分子筛成品中各元素的含量进行分析测定，确定硅铝比，结果如下表1所示。
表1
Figure PCTCN2018112072-appb-000001
应用实施例1-1～1-9和应用对比例1-1～1-2
将上述实施例1-1～1-8和对比例1-1～1-2中制备的分子筛成品分别与40克氧化铝进行混合、挤条、干燥，分别获得载体条E-1-1至E-1-8以及DE-1-1至DE-1-2。
将1克二氯四氨合铂以及3.2克柠檬酸倒入100克去离子水中，搅拌至均匀，制备浸渗溶液。将80克上述载体条分别倒入上述溶液中， 在室温下浸渍4小时，得到催化剂前体。随后将催化剂前体在120℃下干燥4小时。接着将其在通入空气流的状态下进行焙烧，焙烧温度为450℃，时间为4小时，气剂比为2.0升/(克·小时)，得到半成品催化剂。将该半成品催化剂再次放入含有3.2克柠檬酸的100克去离子水溶液中，浸渍4小时后，在120℃下干燥4小时，分别获得的催化剂Cat-1-1至Cat-1-8以及对比催化剂D-Cat-1-1至D-Cat-1-2。
另外，在1克硝酸镁和1克二氯四氨合铂以及3.2克柠檬酸倒入100克去离子水中，搅拌均匀。用该溶液代替上述浸渍溶液，以E-1-1为载体，由此制备催化剂Cat-1-9，催化剂中以氧化镁计的镁含量为0.33重量％。
测试例1-2
分别将100g、20-30目上述催化剂Cat-1-1至Cat-1-9以及D-Cat-1-1至D-Cat-1-3放入反应管中，在氢气气氛下还原4小时，还原温度为400℃，还原时氢气压力为常压。还原结束后降温到120℃，进料加氢裂化尾油，反应温度为310℃，油料的体积空速为1.0h -1，调整氢气压力为10.0MPa，调整氢气流量使氢油体积比为500，进料195g，反应120小时。加氢裂化尾油性质如下表2所示。各催化剂评价结果如下表3所示。
表2
分析项目 分析数据 分析方法
20℃密度/(kg/m 3) 843.6 SH/T0604-2000
运动粘度/(mm 2/s)    
80℃ 7.021 GB/T 265-88
100℃ 4.664 GB/T 265-88
倾点/℃ +42 GB/T 3535
氮质量分数/(μg/g) <1  
硫质量分数/(μg/g) 3 SH/T 0842-2010
表3
催化剂 倾点 收率/％ 粘度指数
Cat-1-1 -31 61.1 131
Cat-1-2 -25 55.3 130
Cat-1-3 -28 50.4 124
Cat-1-4 -32 61.2 133
Cat-1-5 -22 53.5 130
Cat-1-6 -23 60.3 132
Cat-1-7 -24 58.6 128
Cat-1-8 -26 60.3 130
Cat-1-9 -32 64.5 132
D-Cat-1 -17 39.2 114
D-Cat-2 -19 40.2 116
由上表3的数据可以看出，采用本发明所述的Beta分子筛作为固体酸形成的催化剂用作加氢异构化催化剂时，不仅表现出较好的异构降凝能力，而且所得产物的粘度指数较高、收率高、倾点低。
实施例2-1
(1)制备晶化后的母液
取36.3克含40重量％的SiO 2的硅溶胶，1.77克分析纯的Al 2(SO 4) 3·18H 2O，3.94克分析纯的KOH以及8.44克己二胺待用。将己二胺与硅溶胶混合。另外，将KOH和Al 2(SO 4) 3·18H 2O以及89.4克去离子水混合，随后将两种溶液混合，搅拌1h后移入反应釜中，在160℃下晶化72小时。
(2)制备滤饼
将工序(1)中制备的晶化后的母液进行过滤，以滤饼上没有滤液计，继续抽滤5分钟，获得的滤饼F-2-1即为含水分子筛前体，其干基含量为11.2重量％，氧化硅/氧化铝摩尔比为30.2，氧化钾与氧化铝的摩尔比为2:1，模板剂与氧化铝的摩尔比为1:8。
(3)制备分子筛前体
在大气环境中，于焙烧炉中，将滤饼F-2-1以25℃/分钟的升温速率从室温升到450℃，恒温4小时。获得分子筛前体C-2-1，其 27Al NMR图谱见图7。
(4)制备分子筛成品
将分子筛前体C-2-1放入浓度为1M的HCl溶液中进行密闭水热处理。其中，液固比为50，水热处理的温度为180℃，水热处理的时间为3小时，水热处理结束后将产物过滤、水洗，直至滤液pH为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的ZSM-22分子筛成品H-2-1。该ZSM-22分子筛的氧化硅/氧化铝摩尔比为165.2。介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。
该分子筛的XRD图谱、 27Al NMR图谱以及氮气吸附-脱附曲线分别见图8、图9和图10。
由图10可以看出，所制备的ZSM-22分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处出现一个闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
对比例2-1
根据实施例2-1的方法制备ZSM-22分子筛，所不同的是，在步骤(2)中，以滤饼上没有滤液计时，继续抽滤50分钟，获得的滤饼DF-2-1，该滤饼DF-2-1的干基含量为46.5重量％。最终，制得ZSM-22分子筛成品DH-2-1，该ZSM-22分子筛的氧化硅/氧化铝摩尔比为142.7，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.7-0.99处出现一个闭合滞后环。
实施例2-2
根据实施例2-1的方法制备ZSM-22分子筛，所不同的是，在步骤(3)中，将滤饼F-2-1以5℃/分钟的升温速率从室温升到350℃，恒温14小时。升温过程中焙烧炉为焙烧炉，获得分子筛前体C-2-2。制得ZSM-22分子筛成品H-2-2，该ZSM-22分子筛的氧化硅/氧化铝摩尔比为141.3，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在 闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例2-3
根据实施例2-1的方法制备ZSM-22分子筛，所不同的是，在步骤(3)中，将滤饼F-2-1以15℃/分钟的升温速率从室温升到850℃，恒温4小时。升温过程中通入空气，空气流速为1.0升/分钟，获得分子筛前体C-1-3。制得ZSM-22分子筛成品H-1-3该ZSM-22分子筛的氧化硅/氧化铝摩尔比为182.6，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例2-4
根据实施例2-1的方法制备ZSM-22分子筛，所不同的是，在步骤(4)中，将分子筛前体C-2-1放入浓度为1.0M的柠檬酸溶液中进行密闭水热处理。其中，液固比为100，水热处理的温度为180℃，水热处理的时间为2小时，水热处理结束后将产物过滤、水洗，直至滤液pH值为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的ZSM-22分子筛成品H-2-4，该ZSM-22分子筛的氧化硅/氧化铝摩尔比为172.2，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例2-5
根据实施例2-1的方法制备ZSM-22分子筛，所不同的是，在步骤(4)中，将分子筛前体C-2-1放入浓度为0.05M的柠檬酸溶液中进行密闭水热处理。其中，液固比为10，水热处理的温度为90℃，水热处理的时间为0.1小时，水热处理结束后将产物过滤、水洗，直至滤液pH值为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的ZSM-22分子筛成品H-2-5，该ZSM-22分子筛的氧化硅/氧化铝摩尔比为162.3，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环， 且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例2-6
根据实施例2-1的方法制备ZSM-22分子筛，所不同的是，在步骤(4)中，将分子筛前体C-2-1放入浓度为1M的盐酸溶液中进行密闭水热处理。其中，液固比为50，水热处理的温度为180℃，水热处理的时间为3小时，水热处理结束后将产物过滤、水洗，直至滤液pH值为4，经120℃干燥4小时后，在550℃下焙烧4小时，获得的ZSM-22分子筛成品H-2-6，该ZSM-22分子筛的氧化硅/氧化铝摩尔比为161.5，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例2-7
(1)制备晶化后的母液
取36.3克含40重量％的SiO 2的硅溶胶，1.18克分析纯的Al 2(SO 4) 3·18H 2O，3.94克分析纯的KOH以及8.44克己二胺待用。将己二胺与硅溶胶混合。另外，将KOH和Al 2(SO 4) 3·18H 2O以及89.4克去离子水混合，随后将两种溶液混合，搅拌1h后移入反应釜中，在160℃下晶化72小时。
(2)制备滤饼
将工序(1)中制备的晶化后的母液进行过滤，以滤饼上没有滤液计时，继续抽滤5分钟，获得的滤饼F-2-7即为含水分子筛前体，其干基含量为11.2重量％，氧化硅/氧化铝摩尔比为45.6，氧化钾与氧化铝的摩尔比为2:1，模板剂与氧化铝的摩尔比为1:10。
(3)制备分子筛前体
在大气环境中，于焙烧炉中，将滤饼F-2-7以25℃/分钟的升温速率从室温升到450℃，恒温4小时。获得分子筛前体C-2-7。
(4)制备分子筛成品
将分子筛前体C-2-7放入浓度为1M的HCl溶液中进行密闭水热处理。其中，液固比为40，水热处理的温度为180℃，水热处理的时间为3小时，水热处理结束后将产物过滤、水洗，直至滤液pH为7，经 120℃干燥4小时后，在550℃下焙烧4小时，获得的ZSM-22分子筛成品H-2-7。该ZSM-22分子筛的氧化硅/氧化铝摩尔比为174.8，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
实施例2-8
(1)制备晶化后的母液
取36.3克含40重量％的SiO 2的硅溶胶，2.36克分析纯的Al 2(SO 4) 3·18H 2O，3.94克分析纯的KOH以及8.44克己二胺待用。将己二胺与硅溶胶混合。另外，将KOH和Al 2(SO 4) 3·18H 2O以及89.4克去离子水混合，随后将两种溶液混合，搅拌1h后移入反应釜中，在160℃下晶化72小时。
(2)制备滤饼
将工序(1)中制备的晶化后的母液进行过滤，以滤饼上没有滤液计时，继续抽滤5分钟，获得的滤饼F-2-8即为含水分子筛前体，其干基含量为11.2重量％，氧化硅/氧化铝摩尔比为22.8，氧化钾与氧化铝的摩尔比为2:1，模板剂与氧化铝的摩尔比为1:7。
(3)制备分子筛前体
在大气环境中，于焙烧炉中，将滤饼F-2-8以25℃/分钟的升温速率从室温升到450℃，恒温4小时。获得分子筛前体C-2-8。
(4)制备分子筛成品
将分子筛前体C-2-8放入浓度为1M的HCl溶液中进行密闭水热处理。其中，液固比为40，水热处理的温度为180℃，水热处理的时间为3小时，水热处理结束后将产物过滤、水洗，直至滤液pH为7，经120℃干燥4小时后，在550℃下焙烧4小时，获得的ZSM-22分子筛成品H-2-8。该ZSM-22分子筛的氧化硅/氧化铝摩尔比为159.3，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。所制备的分子筛在低温氮气吸附-脱附曲线P/P0＝0.4-0.99处存在闭合滞后环，且所述闭合滞后环的起始位置在P/P0＝0.4-0.5处。
对比例2-2
根据实施例2-1中工序(1)制备晶化后的母液，接着过滤，并将过滤后的得到的滤饼在120℃下干燥4小时，使滤饼充分干燥。然后在550℃下焙烧4小时，获得分子筛前体DC-2-2。将分子筛前体DC-2-2与10倍体积的0.5M盐酸溶液在90℃下进行铵交换处理4小时，最后经过滤、干燥和550℃下焙烧4小时后获得ZSM-22分子筛成品DH-2-2，该ZSM-22分子筛的氧化硅/氧化铝摩尔比为32.3，介孔表面积、比表面积以及介孔表面积与比较面积之比示于表4。其 27Al NMR图谱如图11所示，氮气吸附-脱附曲线如图12所示。从图中可见，分子筛在低温氮气吸附-脱附曲线P/P0＝0.7-0.99处出现一个闭合滞后环。
测试例2-1
(1)采用美国Micromeritics公司DIGISORB 2500型自动吸附仪测定上述实施例2-1～2-8和对比例2-1～2-2的分子筛成品的介孔面积、比表面积，并计算介孔面积占比表面积的比例，结果如下表4所示。
(2)采用商购自日本理学电机工业株式会社的3271E型X射线荧光光谱仪，对上述制备例和制备对比例制备的分子筛前体和分子筛成品中各元素的含量进行分析测定，确定硅铝比，结果如下表4所示。
表4
Figure PCTCN2018112072-appb-000002
应用实施例2-1
将实施例2-1制备的40g分子筛H-2-1与40g氧化铝进行混合、挤条、干燥，得到载体E-2-1。
将0.4克二氯四氨合铂、0.6克二氯四氨钯以及3.2克柠檬酸倒入100克去离子水中，搅拌至均匀。将80克载体E-2-1倒入上述溶液中，在室温下浸渍4小时，得到催化剂前体。随后，将上述催化剂前体在120℃下干燥4小时。接着将其在通入空气流的状态下进行焙烧，焙烧温度为450℃，时间为4小时，气剂比为2.0升/(克·小时)，得到半成品催化剂。将该半成品催化剂再次放入含有3.2克柠檬酸的100克去离子水溶液。浸渍4小时后，在120℃下干燥4小时，获得的催化剂IC-1。
应用实施例2-2～2-8和应用对比例2-1～2-2
根据应用实施例2-1的方法制备催化剂，所不同的是，分别用实施例2-2～2-8制备的分子筛H-2-2至H-2-8以及对比例2-1～2-2制备的分子筛DH-2-1至DH-2-2代替应用实施例2-1中使用的分子筛H-1-1，从而制得催化剂IC-2至IC-8以及对比催化剂DIC-1至DIC-2。
应用实施例2-9
根据应用实施例2-1的方法制备载体E-2-1。
将0.4克二氯四氨合铂、0.6克二氯四氨钯以及16克柠檬酸倒入100克去离子水中，搅拌至均匀。将80克载体E-2-1倒入上述溶液中，在室温下浸渍4小时，得到催化剂前体。随后，将上述催化剂前体在120℃下干燥4小时。接着将其在通入空气流的状态下进行焙烧，焙烧温度为450℃，时间为4小时，气剂比为2.0升/(克·小时)，得到半成品催化剂。将该半成品催化剂再次放入含有16克柠檬酸的100克去离子水溶液。浸渍4小时后，在120℃下干燥4小时，获得的催化剂IC-9。
应用实施例2-10
根据应用实施例2-1的方法制备载体E-2-1。
将0.4克二氯四氨合铂、0.6克二氯四氨钯以及18克EDTA倒入100克去离子水中，搅拌至均匀。将80克载体E-2-1倒入上述溶液中， 在室温下浸渍4小时，得到催化剂前体。随后，将上述催化剂前体在120℃下干燥4小时。接着将其在通入空气流的状态下进行焙烧，焙烧温度为450℃，时间为4小时，气剂比为2.0升/(克·小时)，得到半成品催化剂。将该半成品催化剂再次放入含有6.4克二甘醇的100克去离子水溶液。浸渍4小时后，在120℃下干燥4小时，获得的催化剂IC-10。
应用实施例2-11
根据应用实施例2-1的方法制备载体E-2-1。
将0.4克二氯四氨合铂、0.6克二氯四氨钯以及20克丁二醇倒入100克去离子水中，搅拌至均匀。将80克载体E-2-1倒入上述溶液中，在室温下浸渍4小时，得到催化剂前体。随后，将上述催化剂前体在120℃下干燥4小时。接着将其在通入空气流的状态下进行焙烧，焙烧温度为350℃，时间为4小时，气剂比为1.0升/(克·小时)，得到半成品催化剂。将该半成品催化剂再次放入含有3.2克柠檬酸的100克去离子水溶液。浸渍4小时后，在120℃下干燥4小时，获得的催化剂IC-11。
应用实施例2-12
根据应用实施例2-1的方法制备载体E-2-1。
将0.4克二氯四氨合铂、0.6克二氯四氨钯以及19克乙二胺倒入100克去离子水中，搅拌至均匀。将80克载体E-2-1倒入上述溶液中，在室温下浸渍4小时，得到催化剂前体。随后，将上述催化剂前体在120℃下干燥4小时。接着将其在通入空气流的状态下进行焙烧，焙烧温度为350℃，时间为4小时，气剂比为1.0升/(克·小时)，得到半成品催化剂。将该半成品催化剂再次放入含有1.0克柠檬酸的100克去离子水溶液。浸渍4小时后，在120℃下干燥4小时，获得的催化剂IC-12。
应用实施例2-13
根据应用实施例2-1的方法制备载体E-2-1。
将1克硝酸锌、0.4克二氯四氨合铂、0.6克二氯四氨钯以及19克乙二胺倒入100克去离子水中，搅拌至均匀。将80克载体E-2-1倒入上述溶液中，在室温下浸渍4小时。随后，将上述催化剂前体在120℃下干燥4小时，得到催化剂前体。接着将其在通入空气流的状态下 进行焙烧，焙烧温度为350℃，时间为4小时，气剂比为1.0升/(克·小时)，得到半成品催化剂。将该半成品催化剂再次放入含有1.0克柠檬酸的100克去离子水溶液。浸渍4小时后，在120℃下干燥4小时，获得的催化剂IC-13，催化剂中以氧化锌计的锌含量为0.42重量％。
测试例2-2
(1)应用实施例和应用对比例中催化剂半成品中炭含量使用日本HORIBA公司生产的EMIA-320V碳硫分析仪进行分析测定，结果如下表6所示。
(2)分别将100g、20-30目上述应用实施例和应用对比例制备的催化剂放入反应管中，在氢气气氛下还原4小时，还原温度为400℃，还原时氢气压力为常压。还原结束后降温到120℃，进料加氢裂化尾油，反应温度为310℃，油料的体积空速为1.0h -1，调整氢气压力为10.0MPa，调整氢气流量使氢油体积比为500，进料195g，反应120小时。加氢裂化尾油性质如下表5所示，催化剂评价结果如下表6所示。
表5
分析项目 分析数据 分析方法
20℃密度/(kg/m 3) 843.6 SH/T0604-2000
运动粘度/(mm 2/s)    
80℃ 7.021 GB/T 265-88
100℃ 4.664 GB/T 265-88
倾点/℃ +42 GB/T 3535
氮质量分数/(μg/g) <1  
硫质量分数/(μg/g) 3 SH/T 0842-2010
表6
Figure PCTCN2018112072-appb-000003
由上表6的数据可以看出，采用本发明所述的加氢异构化催化剂对加氢裂化尾油进行加氢处理，所获得的目标产物的粘度指数较高、倾点较低且收率较高。
产业实用性
本发明的分子筛具有高介孔面积，由此可以极大地提高分子筛作为固体酸催化剂时的活性。并且，本发明的分子筛作为载体制备催化剂时，也可以提高催化剂的催化活性，改善所得产物的物性。进而，本发明的催化剂的制备方法可以制备活性成分分散度高的催化剂，由此不仅延长了催化剂的寿命，而且进一步提高了催化剂的催化活性。

Claims (18)

  1. 具有介孔的分子筛，其化学组成式以氧化物形式表示为：Al 2O 3·SiO 2·M 2O·Z xO y，其中，所述M为选自碱金属中的至少一种，Z为选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种，x表示Z的原子数，是1～6的整数，优选为1、2、3或4，y表示满足Z氧化态所需的数，以摩尔比计，Al 2O 3:SiO 2:M 2O:Z xO y为1:(100～300):(0～100):(0～100)，Al 2O 3:SiO 2摩尔比优选为120～260，更优选为150～200，Al 2O 3:M 2O的摩尔比还可以为0.01～80，或者0.05～60，或者0.1～40，或者1～20，Al 2O 3:Z xO y的摩尔比还可以为0.01～80，或者0.05～60，或者0.1～40，或者1～20。
  2. 根据权利要求1所述的分子筛，其中，其中，所述分子筛的介孔表面积为30m 2/g～280m 2/g，优选为50m 2/g～250m 2/g，更优选为80m 2/g～200m 2/g，进一步优选为100m 2/g～180m 2/g，进一步优选为120m 2/g～150m 2/g。
  3. 根据权利要求1或2所述的分子筛，其中，所述分子筛的比表面积可以为150m 2/g～400m 2/g，优选为180m 2/g～350m 2/g，更优选为200m 2/g～320m 2/g，更进一步优选为240m 2/g～300m 2/g，更进一步优选为260m 2/g～280m 2/g。
  4. 根据权利要求1～3任一项所述的的分子筛，其中，介孔表面积占比分子筛表面积的比例可以为20％～70％，优选为25％～65％，更优选为28％～60％，更优选为30％～55％，更优选为35％～50％。
  5. 根据权利要求1～4任一项所述的分子筛，其中，在所述分子筛的低温氮气吸附-脱附曲线上，吸附支和脱附支在P/P0＝0.4-0.99处出现一个闭合滞后环，且闭合滞后环的起始位置在P/P0＝0.4-0.7处，优选起始位置在P/P0＝0.4-0.6处，更优选起始位置在P/P0＝0.4-0.55处。
  6. 根据权利要求1～5任一项所述的分子筛，其中，所述分子筛的五配位铝的含量为5％以下，优选为3％以下，更优选为2％以下，进一步优选为1％以下，特别优选基本不含五配位铝。
  7. 根据权利要求1～5任一项所述的分子筛，其中，所述分子筛为选自十元环硅铝分子筛和十二元环硅铝分子筛中的至少一种，更优选为选自ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、ZSM-57、Nu-10、 Nu-13、Nu-87、EU-1、EU-13、ITQ-13、ZSM-12和Beta分子筛中的至少一种。
  8. 含水分子筛前体，其化学组成式表示为：Al 2O 3·SiO 2·M 2O·Z xO y·模板剂·水，其中，所述M、Z、x、y的含义权利要求1中相同，Al 2O 3与SiO 2的摩尔比为1:(20～100)，优选为1:(25～90)，更优选为1:(30～80)，Al 2O 3与M 2O的摩尔比为1:(0～100)，优选为1:(0.001～90)，更优选为1:(0.05～80)，更优选为1:(0.1～70)，进一步优选为1:(0.5～60)，更进一步优选为1:(1～50)，Al 2O 3与Z xO y的摩尔比为1:(0～100)，优选为1:(0.001～90)，更优选为1:(0.05～80)，进一步优选为1:(0.1～70)，进一步优选为1:(0.5～60)，更进一步优选为1:(1～50)，Al 2O 3与模板剂的摩尔比为1:(0.001～10)，优选为1:(0.005～5)，更优选为1:(0.01～4)，更优选为1:(0.05～3)，进一步优选为1:(0.1～2)，进一步优选为1:(0.5～1.5)，更进一步优选为1:(0.8～1)，所述含水分子筛前体的干基含量为5重量％～30重量％，优选为6重量％～15重量％。
  9. 具有介孔的分子筛的制造方法，所述方法包括以下步骤：
    母液制备步骤，其中，使包含氧化铝源、氧化硅源、模板剂、任选的碱金属氧化物源、任选的第三氧化物(Z xO y，其中，Z为选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种)源和水的混合物在晶化条件下晶化以获得晶化母液；所述母液制备步骤优选包括将氧化铝源、模板剂和任选的碱金属氧化物源的混合物进行热活化的步骤和将热活化后的混合物与氧化硅源、任选的第三氧化物源一起进行晶化处理的步骤；所述热活化条件为：在50～160℃、优选60～150℃、更优选90～140℃、进一步优选95～130℃下进行2～24小时、优选4～22小时、更优选6～20小时、进一步优选8～18小时；所述晶化处理条件为：在120～180℃、优选130～170℃、更优选140～160℃、进一步优选145～155℃下进行24～150小时、优选30～130小时、更优选35～120小时、进一步优选40～100小时、进一步优选50～80小时；
    过滤步骤，将晶化后的母液进行过滤，以形成干基含量为5重量％～30重量％、优选为6重量％～15重量％的滤饼；
    前体制备步骤，将所述滤饼直接进行焙烧，得到分子筛前体；所述焙烧条件为：焙烧的温度为400～600℃，优选为450～550℃；焙烧时升温速率为5℃/分钟～100℃/分钟，优选为10℃/分钟～50℃/分钟，更优 选为20℃/分钟～40℃/分钟，更进一步优选为30℃/分钟～40℃/分钟；焙烧的时间可以为1小时～20小时，优选为2小时～16小时，更优选为5小时～15小时，更进一步优选为6小时～12小时；
    水热处理步骤，将所述分子筛前体进行水热处理；所述水热处理条件为：在无机酸和/或有机酸的含量为0.01M～5M、优选为0.05M～2M、更优选为0.2M～1.5M、进一步优选为0.5～1.2M、更进一步优选为0.8～1.1M的酸性水溶液中，以液固体积比为5～200、优选为20～100、更优选为40～80、进一步优选为50～70，在温度为80℃～300℃、优选为100℃～200℃更优选为120℃～180℃、进一步优选为140℃～160℃的条件下，处理0.1小时～24小时，优选为0.5小时～18小时，更优选为1小时～12小时，更优选为2小时～10小时；和
    成品制备步骤，将水热处理产物进行过滤，并任选地进行洗涤、干燥处理，并进行焙烧，焙烧条件优选为：在400℃～600℃下焙烧2～8小时。
  10. 根据权利要求9所述的制造方法，其中，在母液制备步骤中，各原料成分以氧化物换算以摩尔比记的比例为：SiO 2/Al 2O 3＝5～600，优选为10～550，更优选为20～500，更优选为50～450，进一步优选60～400，更进一步优选80～300；碱金属氧化物/Al 2O 3＝0～100，优选为0.01～90，更优选为0.1～80，进一步优选为0.5～70，进一步优选为1～60，更进一步优选为2～50；第三氧化物/Al 2O 3＝0～100，优选为0.01～90，更优选为0.1～80，进一步优选为0.5～70，进一步优选为1～60，更进一步优选为2～50；模板剂/Al 2O 3＝0.001～8，优选为0.01～6，更优选为0.02～5，更优选为0.1～4，进一步优选为0.2～3，进一步优选为0.5～2，更进一步优选为0.8～1.5；H 2O/Al 2O 3＝4～5000，优选为10～4000，更优选为70～3000，进一步优选为100～2500，进一步优选为150～2000，更进一步优选为200～1500，所述模板剂为选自胺化合物、R 4X +·抗衡离子(X是氮或磷，每个R各自独立地表示C1-C12的直链或支链烷基、C5-C10的环烷基、C6-C12芳基、C1-C12烷基C6-C12芳基，R 4X +的配位数根据抗衡离子的化合价而异，优选为1或2，抗衡离子表示化合价与R 4X +基团相当的负离子，其可以选自氯离子、氟离子、溴离子、硝酸根、硫酸根、氢氧根)中的至少一种，优选为选自四甲基铵盐、四乙基铵盐、四丙基铵盐、四丁基铵盐、四戊基铵盐二-n-聚胺、三聚胺、三乙胺、三乙醇 胺、环乙基胺、二甲基吡啶、二乙基吡啶、N,N-二甲基苯、N,N-二乙醇，二环乙基、N,N-二甲基乙醇胺、1,4-二氮杂双环(2,2,2)辛烷离子、二-n-丁基胺、新戊基胺、二-n-戊基胺，异丙基胺、t-丁基胺、吡啶咯烷、2-咪唑酮、十六烷基三甲基溴化铵、四甲基氢氧化(氯化、溴化、碘化)铵、四乙基氢氧化(氯化、溴化、碘化)铵、四丙基氢氧化(氯化、溴化、碘化)铵、四丁基氢氧化(氯化、溴化、碘化)铵、四戊基氢氧化(氯化、溴化、碘化)铵中的至少一种。
  11. 根据权利要求9或10所述的制造方法，其中，所制备的分子筛前体的五配位铝的含量为4％～35％，优选为10％～30％，更优选为15％～25％。
  12. 催化剂，其包含载体和负载在所述载体上的活性金属组分，以催化剂的总重量为基准，优选以元素单质计的活性金属组分的含量为0.001重量％～5重量％，优选为0.005重量％～4.5重量％，优选为0.01重量％～4重量％，更优选为0.1重量％～3重量％，更加优选为0.2重量％～1重量％，更进一步优选0.4重量％～0.8重量％，所述载体优选包含权利要求1～8任一项所的具有介孔的分子筛，更优选包含权利要求1～8任一项所的具有介孔的分子筛和除该分子筛之外的载体的组合。
  13. 根据权利要求12所述的催化剂，其中，所述活性金属组分为选自VIII族贵金属中的至少一种，优选为选自钌、锇、钯、铂、铑和铱中的至少一种，更进一步优选所述活性金属组分为铂组分和钯组分的组合，Pt组分与Pd组分的摩尔比为1:2～10，优选为1:2～8，进一步优选为1:2～6，更优选为1:2～4。
  14. 根据权利要求12或13所述的催化剂，其中，活性金属组分在载体上呈高度分散状态，优选所述活性金属组分的单个颗粒的尺寸小于3nm，优选为0.1-2.8nm。
  15. 根据权利要求12～14任一项所述的催化剂，其中，金属载体上，可以进一步担载选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种的组份，以催化剂的总重量为基准，优选以元素单质计的助剂组份的含量为0.001重量％～5重量％，优选为0.005重量％～4.5重量％，优选为0.01重量％～4重量％，更优选为0.1重量％～3重量％，更加优选为0.2重量％～1重量％，更进一步优选0.4重量％～0.8重量％。
  16. 催化剂的制备方法，其包括以下步骤：
    (I)采用浸渍法将活性金属组分前驱体和有机络合剂负载在载体上，然后进行任选的干燥、进行焙烧，得到半成品催化剂；和
    (II)以含有有机络合剂的溶液作为浸渍液，对步骤(I)所得半成品催化剂进行浸渍，然后进行干燥，
    其中，步骤(I)的优选条件为：所述活性金属组分为选自VIII族贵金属中的至少一种，优选为选自钌、锇、钯、铂、铑和铱中的至少一种；所述有机络合剂为选自含氧有机物、有机酸和含氮有机物中的至少一种，更优选为选自乙二醇、丙三醇、聚乙二醇、二乙二醇、丁二醇、乙酸、马来酸、草酸、氨基三乙酸、1,2-环己烷二胺四乙酸、柠檬酸、酒石酸、苹果酸、乙二胺、EDTA中的至少一种；所述有机络合剂与所述活性金属组分前驱体的摩尔比优选2～100：1，优选为4～80:1，更优选为6～70:1，进一步优选为10～50：1；所述焙烧的温度可以为350～500℃，优选为360～450℃；焙烧的时间可以为0.5～8小时，优选为1～6小时；相对于所要浸渍的载体的重量，以元素单质计的活性金属组分前驱体的量为0.001重量％～5重量％，优选为0.005重量％～4.5重量％，优选为0.01重量％～4重量％，更优选为0.1重量％～3重量％，更加优选为0.2重量％～1重量％，更进一步优选0.4重量％～0.8重量％；所述载体包含权利要求1～8任一项所的具有介孔的分子筛，优选包含权利要求1～8任一项所的具有介孔的分子筛和除该分子筛之外的载体的组合；
    步骤(II)的优选条件为：有机络合剂独立地选自步骤(I)的有机络合剂，机络合剂与活性金属的摩尔比可以为2～100：1，优选为4～80:1，更优选为6～70:1，进一步优选为10～50：1。
  17. 根据权利要求16的催化剂的制备方法，其中进一步包括通过浸渗法浸渍选自Mg、Ca、Zn、Ti、Fe、Ga、Ge、B、P、稀土金属中的至少一种金属离子的溶液的步骤，优选在步骤(I)之前、步骤(I)之中、步骤(I)和步骤(II)之间进行该浸渗步骤。
  18. 加氢异构化处理方法，其使用权利要求12～15任一项所述的催化剂。
PCT/CN2018/112072 2017-10-26 2018-10-26 具有介孔的分子筛及其制备方法和应用 Ceased WO2019080922A1 (zh)

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