WO2016202076A1 - 用于合成气选择性合成高品质煤油馏分的载体及其催化剂和制备方法 - Google Patents

用于合成气选择性合成高品质煤油馏分的载体及其催化剂和制备方法 Download PDF

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WO2016202076A1
WO2016202076A1 PCT/CN2016/079384 CN2016079384W WO2016202076A1 WO 2016202076 A1 WO2016202076 A1 WO 2016202076A1 CN 2016079384 W CN2016079384 W CN 2016079384W WO 2016202076 A1 WO2016202076 A1 WO 2016202076A1
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parts
carrier
sba
catalyst
hexane
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French (fr)
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许莉
王弯弯
石友良
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Wuhan Kaidi Engineering Technology Research Institute Co Ltd
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Priority to EP16810817.3A priority Critical patent/EP3311917A4/en
Priority to JP2017563351A priority patent/JP6653715B2/ja
Priority to RU2018101199A priority patent/RU2654205C1/ru
Priority to CA2989045A priority patent/CA2989045A1/en
Priority to AU2016278389A priority patent/AU2016278389A1/en
Publication of WO2016202076A1 publication Critical patent/WO2016202076A1/zh
Priority to US15/839,835 priority patent/US10286389B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/60—Synthesis on support
    • B01J2229/62—Synthesis on support in or on other molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/55—Cylinders or rings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • the invention relates to the technical field of catalytic synthesis of oil fractions, in particular to a carrier for synthesizing a high quality kerosene fraction for synthesis gas, a catalyst thereof and a preparation method thereof.
  • the syngas can be converted to a hydrocarbon compound by the reaction of the synthesis reaction in the presence of a catalyst.
  • the hydrocarbon compound is basically composed of a linear hydrocarbon, an olefin, a small amount of an oxygen compound, has the characteristics of sulfur-free, nitrogen-free, and aromatic-free, and is an environmentally friendly fuel oil and chemical.
  • the growth of the Fischer-Tropsch synthesis product chain follows a polymerization mechanism with product selectivity consistent with the ASF (Anderson-Schulz-Flory) distribution.
  • the most notable characteristics of the Fischer-Tropsch synthesis reaction are wide product distribution, low product selectivity, and low isomeric product content. According to this distribution, except for methane and heavy hydrocarbons (C21+), higher selectivity is obtained, and the selectivity of other products is not high.
  • the gasoline fraction (C5-C11) has a selectivity of up to about 45%
  • the selectivity of (C12-C20) is up to about 30%, and most of the product is a linear hydrocarbon with a very low content of isomers.
  • the above characteristics result in a very low octane number of the Fischer-Tropsch gasoline fraction and a high freezing point of the kerosene fraction and the diesel fraction, which limits its use as a fuel oil to some extent. Therefore, in the industry, the Fischer-Tropsch synthesis and the hydrocracking process are usually combined in the industry to selectively increase the content of isoparaffins in the product and improve the Fischer-Tropsch synthesis by selectively breaking and isomerizing the Fischer-Tropsch linear paraffins. Low temperature flow properties of oils. However, in general, the investment cost and operating cost of the hydrogenation unit are high, and these factors also limit the optimization and upgrading of the Fischer-Tropsch synthesis products to some extent.
  • the Chinese Patent Application Publication No. CN1403536A discloses a catalyst for synthesizing high-grade diesel oil using a molecular sieve as a carrier.
  • the catalyst is composed of a molecular sieve and a metal cobalt, and the molecular sieve is Y, Bata, MOR.
  • the diesel product (C10-C20) in the liquid product is about 72% by weight, and the normal hydrocarbon is about 20% by weight, but the selectivity of methane in the product is as high as 28.1% by weight.
  • the Chinese Patent Application Publication No. CN1417291A discloses a synthesis method for selectively preparing a hydrocarbon fraction by a Fischer-Tropsch synthesis gas.
  • the Fischer-Tropsch synthesis catalyst is a metal-containing cobalt/activated carbon supported catalyst, and the obtained diesel fraction product contains at least 95% of an alkane by weight, and the ratio of the isomeric hydrocarbon to the normal hydrocarbon is in the range of 0.03 to 0.3.
  • the Chinese Patent Application Publication No. CN103252238A discloses a catalyst for syngas-selective synthesis of gasoline and diesel comprising the active component cobalt, the promoter nickel, and the support as multi-walled carbon nanotubes.
  • the catalyst can effectively weaken the interaction between the carrier and the active component, improve the utilization ratio of the active component, has the advantages of high catalytic activity and good gasoline and diesel selectivity, but the catalyst has no isomerization function and is obtained.
  • the gasoline-diesel component is essentially a linear normal paraffin.
  • the technical materials disclosed above all involve the catalyst for synthesizing Fischer-Tropsch synthesized gasoline or diesel fuel by synthesizing the synthesis gas, and using ZSM, Y, ⁇ , MOR and other molecular sieves or activated carbon and carbon nanotubes as carriers.
  • these carriers contain strong acid sites, which lead to excessive secondary cracking of long-chain hydrocarbons in the Fischer-Tropsch synthesis products, resulting in more methane; on the other hand, the isomerization ability of these carriers is weak, resulting in products in the product.
  • the content of isomeric hydrocarbons is not high.
  • the catalyst with carbon material as a carrier weakens the interaction between the active component and the carrier to a large extent, and the activity of the catalyst is improved.
  • the carrier since the carrier has substantially no isomerization function, the isomerism in the distillate oil is caused. The proportion of alkanes is very limited.
  • the key to the preparation of high-quality Fischer-Tropsch synthetic distillate from one-step synthesis gas is to develop a catalyst with moderate acidity and isomerization function, which can selectively carry out long-chain hydrocarbons generated during Fischer-Tropsch synthesis. In situ hydrogenation chain scission, and isomerization of linear alkane on the catalyst surface. But so far, the research results of researchers have not yet achieved satisfactory technical results.
  • the object of the present invention is to provide a carrier for synthesizing a high quality kerosene fraction by syngas and its urging Chemical agent and preparation method.
  • the catalyst prepared by using the carrier has the characteristics of low methane selectivity, high middle distillate selectivity and good heterogeneous function.
  • the present invention provides a carrier for synthesizing a high-quality kerosene fraction by syngas, wherein the raw material of the carrier is from 5 to 50 parts by weight of mesoporous zirconia (ZrO 2 ), 10 ⁇ 55 parts of silicoaluminophosphate molecular sieve, 5 to 50 parts of modified Al-SBA-16, 1 to 3 parts of phthalocyanine powder, and 10 to 70 parts of alumina.
  • ZrO 2 mesoporous zirconia
  • the raw material of the carrier is 10 to 30 parts by weight of mesoporous zirconia, 25 to 45 parts of silicoaluminophosphate molecular sieve, 10 to 30 parts of modified Al-SBA-16, 1-3 It is composed of Shitian Jing powder and 30-55 parts of alumina.
  • the raw material of the carrier is 20 parts by weight of mesoporous zirconia, 30 parts of silicoaluminophosphate molecular sieve, 25 parts of modified Al-SBA-16, 1 part of phthalocyanine powder and 30 parts by weight.
  • Alumina composition 20 parts by weight of mesoporous zirconia, 30 parts of silicoaluminophosphate molecular sieve, 25 parts of modified Al-SBA-16, 1 part of phthalocyanine powder and 30 parts by weight.
  • Alumina composition 20 parts by weight of mesoporous zirconia, 30 parts of silicoaluminophosphate molecular sieve, 25 parts of modified Al-SBA-16, 1 part of phthalocyanine powder and 30 parts by weight.
  • the raw material of the modified Al-SBA-16 is composed of SBA-16 and aluminum triethoxide (Al(OC 2 H 7 ) 3 ), and the weight ratio of SBA-16 to aluminum triethanol is 1..3.0-4.5 .
  • the molar ratio n of silicon to aluminum in the modified Al-SBA-16 is 5 to 55, Acid (Chinese name: Bronsted acid, referred to as B acid) content of 39 ⁇ 92 ⁇ mol ⁇ g -1, Lewis acid (Chinese name: Lewis acids, referred to as L acid) content of 71 ⁇ 105 ⁇ mol ⁇ g -1, Na 2 O content ⁇ 0.1 wt%.
  • the modified Al-SBA-16 has a silicon-aluminum molar ratio n of 10 to 25, a specific surface area of 550 to 930 m 2 ⁇ g -1 , an average pore diameter of 4.0 to 7.5 nm, and a total pore volume of 0.45 to 0.70 cm. 3 ⁇ g -1 .
  • the method for preparing the modified Al-SBA-16 comprises the following steps:
  • step 2) Transfer the sample liquid in step 2) to a cloth funnel, wash with n-hexane and suction filtration; repeat 2 to 4 times; obtain a first-stage filter cake;
  • the mesoporous zirconia has a specific surface area of 190 to 350 m 2 ⁇ g -1 , an average pore diameter of 5.0 to 8.5 nm, and a total pore volume of 0.40 to 0.55 cm 3 ⁇ g -1 .
  • the total amount of acid in the silicoaluminophosphate molecular sieve is 0.1-0.35 mmol NH 3 ⁇ g -1 ; the molar ratio of silicon to aluminum is 0-1.0; specific surface area ⁇ 150 m 2 ⁇ g -1 , Na 2 O content ⁇ 0.2 wt%, total pore volume 0.10 to 0.30 cm 3 ⁇ g -1 .
  • the molar ratio of silicon to aluminum in the silicoaluminosilicate molecular sieve is 0.21 to 0.38, the specific surface is ⁇ 180 m 2 ⁇ g -1 , the Na 2 O content is ⁇ 0.2 wt%, and the total pore volume is 0.10 to 0.30 cm. 3 ⁇ g -1 ; alternatively, the ratio of silicon to aluminum in the silicoaluminosilicate molecular sieve is 0 to 1.0, the specific surface is ⁇ 150 m 2 ⁇ g -1 , the content of Na 2 O is ⁇ 0.2 wt%, and the total pore volume is 0.13 ⁇ 0.26 cm 3 ⁇ g -1 .
  • the invention also provides a preparation method of a carrier for synthesizing a high quality kerosene fraction by syngas, comprising the following steps:
  • step 2) Transfer the sample liquid in step 2) to a cloth funnel, wash with n-hexane and suction filtration; repeat 2 to 4 times; obtain a first-stage filter cake;
  • the carrier is in the form of a cylindrical strip, a clover or a four-leaf clover; wherein the cylindrical strip-shaped carrier has a particle diameter of 1.2 to 1.6 mm and a length of 5 to 10 mm; and two of the clover or four-leaf clover carrier The leaf spacing is 1.1 to 1.8 mm and the length is 5 to 10 mm.
  • the present invention also provides a catalyst for the selective synthesis of a high quality kerosene fraction from a synthesis gas comprising a soluble cobalt salt and a support; the soluble cobalt salt supported on the surface of the support.
  • cobalt oxide accounts for 5 to 20% by weight of the catalyst.
  • the soluble cobalt salt is cobalt nitrate, cobalt acetate or cobalt carbonyl.
  • the invention also provides a preparation method of a catalyst, comprising the steps of: impregnating an aqueous solution containing a soluble cobalt salt onto a carrier by an equal volume impregnation method, aging at room temperature for overnight, and then at atmospheric pressure at 90 to 120 ° C; After drying for 4 to 12 hours, it is finally calcined at 500 to 600 ° C for 4 to 10 hours in the air, and then cooled to room temperature to obtain a catalyst.
  • the performance evaluation of the catalyst of the present invention is carried out in a fixed bed reactor under the following operating conditions: the catalyst is first reduced in high purity hydrogen under the conditions of a catalyst bed temperature of 300 to 500 ° C, a reduction pressure of 0.1 to 1.3 mPa, and a hydrogen volume.
  • the space velocity is 500-1200 h -1 and the reduction time is 4-24 h;
  • the reaction conditions are: the volume ratio of syngas to nitrogen is 1.0, the H 2 /CO molar ratio in the syngas is 1.2-2.1, and the syngas gas space velocity is 500 ⁇ . 2000h -1 , the catalyst bed temperature is 180-215 ° C, and the reaction pressure is 1.0-3.5 mpa.
  • the catalyst carrier provided by the invention has moderate acidity and a three-dimensional pore structure, and the mesoporous pores are large and uniform, and the mass transfer and diffusion effect is good, and the formation of methane in the reaction process can be effectively reduced while improving the selectivity of the kerosene distillate.
  • the catalyst carrier provided by the invention has a high isomerization function, and the isomerization of long-chain linear paraffins increases the proportion of isoparaffins in the product, thereby greatly improving the low-temperature flow performance of the kerosene fraction.
  • the present invention provides a mild reaction between the catalyst carrier and the active component, and the active component has a high degree of reduction, and can maintain a high reaction of the catalyst while obtaining a high-quality kerosene fraction. active.
  • the first-stage filter cake was transferred to a Buchner funnel, washed with 50 ml of n-hexane and suction filtered, and repeated three times. Finally, the obtained second-stage filter cake was baked at 650 ° C for 6 h to obtain a modified Al-SBA-16 ( 55), spare.
  • the small pore alumina and the dilute nitric acid solution are kneaded by a weight ratio of 1..0.5 to 1.5, wherein the dilute nitric acid solution has a mass fraction of 5 to 20 wt%.
  • the silicoaluminophosphate molecular sieve was purchased from the market, and the model was SPAO-11 molecular sieve, SPAO-31 molecular sieve, or SPAO-11 and SPAO-31 mixed molecular sieve.
  • SPAO-11 has a specific ratio of silica to alumina of 0.21 to 0.38, specific surface ⁇ 180 m 2 ⁇ g -1 , Na 2 O content ⁇ 0.2 wt%, and total pore volume: 0.10 to 0.30 cm 3 ⁇ g -1
  • SPAO-31 has a silicon to aluminum ratio of 0 to 1.0, a specific surface area of ⁇ 150 m 2 ⁇ g -1 , a Na 2 O content of ⁇ 0.2 wt%, and a total pore volume of 0.13 to 0.26 cm 3 ⁇ g -1 .
  • a carrier for synthesizing a high quality kerosene fraction for synthesis gas is prepared, and the preparation method is as follows:
  • the carrier of the above examples was used to prepare a catalyst, and the preparation method was as follows:
  • the carrier is first transferred into a pear-shaped bottle and placed on a rotary evaporator to keep the carrier in a constantly flipping state.
  • the aqueous solution containing the soluble cobalt salt is impregnated onto the carrier, and the pear-shaped bottle is kept rotated. After 20 to 40 minutes, it is aged at room temperature overnight, then dried at 90 to 120 ° C for 4 to 12 hours under normal pressure, and finally calcined at 500 to 600 ° C for 4 to 10 hours in the air, and then cooled to room temperature to obtain a catalyst.
  • the soluble cobalt salt can be impregnated into the carrier twice to increase the carrier loading efficiency.
  • the carrier prepared by the above-mentioned examples was 40 g, and the soluble cobalt salt was loaded onto the carrier by the above method.
  • the specific optimized reaction conditions are as follows: Table 4:
  • the performance evaluation of the above catalyst was carried out in a fixed bed reactor under the conditions of catalyst activation: 350 ° C, hydrogen pressure of 0.1 mPa, hydrogen space velocity of 500 h -1 , and reduction time of 24 h.
  • Catalyst performance evaluation conditions H 2 /CO molar ratio 2.1, syngas space velocity 2000 h -1 , bed temperature 205 ° C, reaction pressure 3.5 mpa.
  • the results of catalyst performance evaluation are summarized in Table 5.
  • mesoporous zirconia, silicoaluminophosphate molecular sieve, modified SBA-16, and alumina ratio are optimal combinations, and the metal cobalt salt loading is appropriate.
  • the performance of the catalyst is the best. Under the higher conversion rate, the selectivity of the kerosene fraction at 155-265 °C can reach 85.8%, the content of isomers reaches 84.3%, and the freezing point of kerosene fraction is -52 °C.

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Abstract

本发明公开了一种用于合成气选择性合成高品质煤油馏分的载体及其催化剂和制备方法。该载体的原料按重量份数比由5～50份的介孔氧化锆、10～55份的磷酸硅铝分子筛、5～50份的改性Al-SBA-16、1～3份的田菁粉和10～70份的氧化铝组成。该催化剂由可溶性钴盐与载体组成；所述可溶性钴盐负载在载体表面。所述催化剂中，氧化钴占催化剂的重量百分比为5～20％。本发明提供的催化剂载体酸性适中，且具有三维孔道结构，介孔孔道大且均一，传质扩散效果好，在提高煤油馏分油选择性的同时可以有效降低反应过程中甲烷的生成。本发明通过费托合成反应，由合成气经费托合成高选择性地直接获得高品质煤油馏分，有效地解决了传统费托合成后续处理工艺复杂的问题。

Description

用于合成气选择性合成高品质煤油馏分的载体及其催化剂和制备方法 技术领域
本发明涉及催化合成油品馏分的技术领域，具体地指一种用于合成气选择性合成高品质煤油馏分的载体及其催化剂和制备方法。
背景技术
合成气可以在催化剂存在的条件下经费托合成反应转化为烃类化合物。该烃类化合物基本上由直链烃、烯烃、少量含氧化合物组成，具有无硫、无氮、无芳烃的特点，是对环境友好的燃料油和化学品。
费托合成产物链的增长遵循聚合机理，其产物选择性符合ASF(Anderson-Schulz-Flory)分布。费托合成反应最显著的特点是产物分布宽、产物的选择性低、异构产物含量低。根据该分布，除甲烷和重质烃(C21+)可取得较高的选择性外，其他产物的选择性均不高，如汽油馏分(C5-C11)的选择性最高约为45％，柴油馏分(C12-C20)的选择性最高约为30％，且产物绝大部分为直链烃，异构产物含量很低。
上述特性导致了费托合成汽油馏分辛烷值非常低、煤油馏分和柴油馏分凝点偏高，这在一定程度上限制了其作为燃料油的使用。因此，目前工业上通常将费托合成和加氢裂化工艺相结合，通过对费托合成直链烷烃进行选择性地断链和异构化，提高产物中异构烷烃的含量，改善费托合成油品的低温流动性能。但一般情况下，加氢装置投资成本、运行成本都很高，这些因素也在某种程度上限制了费托合成产物在品质上的优化升级。
由此可见，开发一种直接由合成气选择性制备高品质馏分油的催化剂，使得费托合成过程中生成的长链烃在催化剂表面进行原位的加氢断链和异构化，一步法获得液体燃料，已引起愈来愈多的关注。
文献(Y.Li et al.Energy Fuel 2008,22,1897)报道了将SiO2和ZSM-5混合制成复合氧化物，然后负载钴，该催化剂可获得较高的催化性能，CO转化率超过80％，C5-C12选择性达55％，但异构烷烃比例仅为10％左右，并且中间馏分油C12+选择性低于15％。
文献(Kang.J.C et al.Angew.Chem.Int.Ed.2011,50,5200)采用氢氧化钠处理H-ZSM-5沸石，得到中孔的ZSM-5分子筛作为载体负载钌费托催化剂，汽油段产物(C5～C11) 选择性到达79.0％，中间馏分油产物(C12+)的选择性仅为0.5％。
公开号为CN1403536A的中国发明专利申请公开了一种分子筛为载体的合成高品位柴油的催化剂，催化剂由分子筛和金属钴组成，所述的分子筛为Y、Bata、MOR。在一定的试验条件下，液体产物中柴油组分(C10-C20)约为72wt％左右，正构烃为20wt％左右，但产物中甲烷的选择性高达28.1wt％。
公开号为CN1417291A的中国发明专利申请公开了一种通过费托合成气选择性制备主要以柴油馏分烷烃的合成方法。费托合成催化剂为含金属钴/活性炭载体催化剂，得到的柴油馏分产物按重量至少含有95％的烷烃，其异构烃与正构烃的比例在0.03至0.3的范围。
公开号为CN103252238A的中国发明专利申请公开了一种用于合成气选择性合成汽柴油的催化剂，所述催化剂包括活性组分钴、助催化剂镍、载体为多壁碳纳米管。该催化剂虽然可有效地减弱载体和活性组分间的相互作用，提高活性组分的利用率，具有催化活性高、汽柴油选择性好的优点，但由于该催化剂无异构化功能，获得的汽柴油组分基本上为直链正构烷烃。
以上公开的技术资料中，均涉及了由合成气经费托合成高选择性地制备费托合成汽油或柴油的催化剂，以ZSM、Y、β、MOR等分子筛或活性炭、碳纳米管为载体。这些载体一方面含有较强的酸性位，导致费托合成产物中的长链烃过度二次裂解，生成了较多的甲烷；另一方面这些载体的异构化能力很弱，导致产物中的异构烃含量不高。而以碳材料为载体的催化剂，虽然在很大程度上削弱了活性组分与载体的作用力，使催化剂的活性得到了提高，但由于载体基本无异构化功能，导致馏分油中异构烷烃的比例非常有限。
因此，由合成气一步法制备高品质费托合成馏分油的关键是开发一种酸性适中、异构化功能较好的催化剂，既能选择性地对费托合成过程中生成的长链烃进行原位加氢断链，又能在催化剂表面进行直链烷烃的异构化。但迄今为止，科研人员的研究成果尚未取得令人满意的技术效果。
发明内容
本发明的目的就是要提供一种用于合成气选择性合成高品质煤油馏分的载体及其催 化剂和制备方法。采用该载体制得的催化剂具有低甲烷选择性、高中间馏分油选择性、异构功能好的特性，通过对合成气进行费托合成反应，可高选择性地直接获得高品质煤油馏分，有效解决传统费托合成反应后续处理工艺复杂的难题。
为实现上述目的，本发明提供的一种用于合成气选择性合成高品质煤油馏分的载体，该载体的原料按重量份数比由5～50份的介孔氧化锆(ZrO2)、10～55份的磷酸硅铝分子筛、5～50份的改性Al-SBA-16、1～3份田菁粉和10～70份氧化铝组成。
进一步地，所述载体的原料按重量份数比由10～30份的介孔氧化锆、25～45份的磷酸硅铝分子筛、10～30份的改性Al-SBA-16、1～3份田菁粉和30～55份氧化铝组成。
再进一步地，所述载体的原料按重量份数比由20份的介孔氧化锆、30份的磷酸硅铝分子筛、25份的改性Al-SBA-16、1份田菁粉和30份氧化铝组成。
再进一步地，所述改性Al-SBA-16的原料由SBA-16和三乙醇铝(Al(OC2H7)3)组成，SBA-16和三乙醇铝重量比为1︰3.0～4.5。
再进一步地，所述改性Al-SBA-16中的硅铝摩尔比n为5～55，
Figure PCTCN2016079384-appb-000001
酸(中文名为：布朗斯特酸，简称B酸)含量为39～92μmol·g-1，Lewis酸(中文名为：路易斯酸，简称L酸)含量为71～105μmol·g-1，Na2O含量≤0.1wt％。
再进一步地，所述改性Al-SBA-16中硅铝摩尔比n为10～25，比表面积550～930m2·g-1，平均孔径4.0～7.5nm，总孔孔容0.45～0.70cm3·g-1。
再进一步地，所述改性Al-SBA-16的制备方法，包括以下步骤：
1)根据上述重量比称取SBA-16和三乙醇铝，并将三乙醇铝分成两等份备用；
2)将SBA-16加入正己烷中，在室温条件下搅拌均匀，得到混合液；将上述一份的三乙醇铝加入正己烷中，室温下搅拌至溶解；将溶有三乙醇铝的正己烷加入混合液中，室温下搅拌过夜，得到样品液；
3)将步骤2)中的样品液转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到一级滤饼；
4)将滤饼加入正己烷中，在室温下搅拌均匀；再加入另一份的三乙醇铝；室温下搅拌过夜，再转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到二级滤饼；
5)将二级滤饼置于500～650℃下焙烧6～10h；得到改性的Al-SBA-16。
再进一步地，所述介孔氧化锆的比表面积190～350m2·g-1，平均孔径5.0～8.5nm，总 孔孔容0.40～0.55cm3·g-1。
再进一步地，：所述磷酸硅铝分子筛中总酸量为0.1～0.35mmolNH3·g-1；硅铝比摩尔比为0～1.0；比表面积≥150m2·g-1，Na2O含量≤0.2wt％，总孔孔容0.10～0.30cm3·g-1。
再进一步地，所述酸硅铝分子筛中的硅铝比摩尔比为0.21～0.38，比表面≥180m2·g-1，Na2O含量≤0.2wt％，总孔孔容：0.10～0.30cm3·g-1；或者，所述酸硅铝分子筛中的的硅铝比为0～1.0，比表面≥150m2·g-1，Na2O含量≤0.2wt％，总孔孔容0.13～0.26cm3·g-1。
本发明还提供了一种用于合成气选择性合成高品质煤油馏分的载体的制备方法，包括以下步骤：
1)按重量比1︰3.0～4.5称取SBA-16和三乙醇铝；并将三乙醇铝等分为二份；
2)将SBA-16加入正己烷中，在室温条件下搅拌均匀，得到混合液；再将一份的三乙醇铝加入正己烷中，室温下搅拌至溶解；将溶有三乙醇铝的正己烷加入混合液中，室温下搅拌过夜，得到样品液；
3)将步骤2)中的样品液转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到一级滤饼；
4)将滤饼加入正己烷中，在室温下搅拌均匀；再加入另一份的三乙醇铝；室温下搅拌过夜，再转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到二级滤饼；
5)将二级滤饼于500～650℃下焙烧6～10h，得到改性的Al-SBA-16，备用；
6)将小孔氧化铝与稀硝酸溶液按重量比1︰0.5～1.5混捏均匀，制备得到粘稠膏状物，备用；其中，稀硝酸溶液质量分数为5～20wt％；
7)按重量份数比称取5～50份的介孔氧化锆、10～55份的磷酸硅铝分子筛、5～50份的改性Al-SBA-16、1～3份的田菁粉和含有10～70份的氧化铝的粘稠膏状物；并将其混合均匀，碾压、挤条成型，置于90～120℃下干燥6～12h，然后在空气中、500～600℃条件下焙烧4～10h后冷却至室温，得到载体。
作为优先方案，所述载体为圆柱条状、三叶草状或四叶草状；其中，圆柱条状载体的粒径为1.2～1.6mm，长度为5～10mm；三叶草或四叶草状载体的两叶间距为1.1～1.8mm，长度为5～10mm。
本发明还提供了一种用于合成气选择性合成高品质煤油馏分的催化剂，该催化剂由可溶性钴盐与载体组成；所述可溶性钴盐负载在载体表面。
进一步地，所述催化剂中，氧化钴占催化剂的重量百分比为5～20％。
再进一步地，所述可溶性钴盐为硝酸钴、乙酸钴或羰基钴。
本发明还提供了一种催化剂的制备方法，包括以下步骤：采用等体积浸渍法，将含有可溶性钴盐的水溶液浸渍到载体上，置于室温下老化过夜，然后在90～120℃下常压干燥4～12h，最后在空气中500～600℃下焙烧4～10h后冷却至室温，得到催化剂。
本发明所述的催化剂性能评价在固定床反应器中进行，操作条件如下：催化剂首先在高纯氢中进行还原，还原条件为，催化剂床层温度300～500℃，还原压力0.1～1.3mpa，氢气体积空速为500～1200h-1，还原时间4～24h；反应条件为，合成气与氮气体积比为1.0，合成气中H2/CO摩尔比为1.2～2.1，合成气气体空速为500～2000h-1，催化剂床层温度180～215℃，反应压力1.0～3.5mpa。
本发明的有益效果在于：
1)本发明提供的催化剂载体酸性适中，且具有三维孔道结构，介孔孔道大且均一，传质扩散效果好，在提高煤油馏分油选择性的同时可以有效降低反应过程中甲烷的生成。
2)本发明提供的催化剂载体具有较高的异构化功能，通过对长链直链烷烃的异构化增加产物中异构烷烃的比例，大幅提高煤油馏分的低温流动性能。
3)与其他酸性载体相比，本发明提供的催化剂载体与活性组分之间作用力温和，活性组分具有很高的还原度，在获得高品质煤油馏分的同时能够保持催化剂较高的反应活性。
具体实施方式
为了更好地解释本发明，以下结合具体实施例进一步阐明本发明的主要内容，但本发明的内容不仅仅局限于以下实施例。
本发明中载体所需要的原料制备
一.改性Al-SBA-16的制备：
1、改性Al-SBA-16(5)的制备：
1)称取30g的SBA-16于100ml正己烷中，室温下搅拌2h；
2)称取45g的Al(OC2H7)3于100ml正己烷中，室温下搅拌至溶解，然后将溶有Al(OC2H7)3的正己烷溶液加入盛有SBA-16的烧杯中，室温下搅拌过夜；
3)将得到的样品转移到布式漏斗中，用50ml正己烷洗涤并抽滤，重复3次；得到一级滤饼；
4)将一级滤饼转移至烧杯中，加入100ml正己烷，室温下搅拌1h，然后加入45g的Al(OC2H7)3，室温下搅拌过夜，将滤饼转移至布氏漏斗，用50ml正己烷洗涤并抽滤，重复3次；最后将得到的二级滤饼于550℃下焙烧10h，得到改性Al-SBA-16(5)，备用。
2、改性Al-SBA-16(10)的制备：
1)称取30g的SBA-16于100ml正己烷中，室温下搅拌3h；
2)称取41g的Al(OC2H7)3于100ml正己烷中，室温下搅拌至溶解，然后将溶有Al(OC2H7)3的正己烷溶液加入盛有SBA-16的烧杯中，室温下搅拌过夜；
3)将得到的样品转移到布式漏斗中，用50ml正己烷洗涤并抽滤，重复3次，得到一级滤饼；
4)将一级滤饼转移至烧杯中，加入100ml正己烷，室温下搅拌1.5h，然后加入41g的Al(OC2H7)3，室温下搅拌过夜，将滤饼转移至布氏漏斗，用50ml正己烷洗涤并抽滤，重复3次；最后将得到的二级滤饼于550℃下焙烧8h，得到改性Al-SBA-16(10)，备用。
3、改性Al-SBA-16(20)的制备：
1)称取30g的SBA-16于100ml正己烷中，室温下搅拌4h；
2)称取37g的Al(OC2H7)3于100ml正己烷中，室温下搅拌至溶解，然后将溶有Al(OC2H7)3的正己烷溶液加入盛有SBA-16的烧杯中，室温下搅拌过夜；
3)将得到的样品转移到布式漏斗中，用50ml正己烷洗涤并抽滤，重复3次，得到一级滤饼；
4)将一级滤饼转移至烧杯中，加入100ml正己烷，室温下搅拌2h，然后加入37g的Al(OC2H7)3，室温下搅拌过夜，将滤饼转移至布氏漏斗，用50ml正己烷洗涤并抽滤，重复3次；最后将得到的二级滤饼于580℃下焙烧6h，得到改性Al-SBA-16(20)，备用。
4、改性Al-SBA-16(25)的制备：
1)称取30g的SBA-16于100ml正己烷中，室温下搅拌4h；
2)称取35g的Al(OC2H7)3于100ml正己烷中，室温下搅拌至溶解，然后将溶有Al(OC2H7)3的正己烷溶液加入盛有SBA-16的烧杯中，室温下搅拌过夜；
3)将得到的样品转移到布式漏斗中，用50ml正己烷洗涤并抽滤，重复3次，得到一级滤饼；
4)将一级滤饼转移至烧杯中，加入100ml正己烷，室温下搅拌2h，然后加入35g的Al(OC2H7)3，室温下搅拌过夜，将滤饼转移至布氏漏斗，用50ml正己烷洗涤并抽滤，重复3次；最后将得到的二级滤饼于580℃下焙烧6h，得到改性Al-SBA-16(25)，备用。
5、改性Al-SBA-16(40)的制备：
1)称取30g的SBA-16于100ml正己烷中，室温下搅拌4.5h；
2)称取33g的Al(OC2H7)3于100ml正己烷中，室温下搅拌至溶解，然后将溶有Al(OC2H7)3的正己烷溶液加入盛有SBA-16的烧杯中，室温下搅拌过夜；
3)将得到的样品转移到布式漏斗中，用50ml正己烷洗涤并抽滤，重复3次，得到一级滤饼；
4)将一级滤饼转移至烧杯中，加入100ml正己烷，室温下搅拌2.5h，然后加入33g的Al(OC2H7)3，室温下搅拌过夜，将滤饼转移至布氏漏斗，用50ml正己烷洗涤并抽滤，重复3次；。最后将得到的二级滤饼于600℃下焙烧6h，得到改性Al-SBA-16(40)，备用。
6、改性Al-SBA-16(55)的制备：
1)称取30g的SBA-16于100ml正己烷中，室温下搅拌5h；
2)称取30g的Al(OC2H7)3于100ml正己烷中，室温下搅拌至溶解，然后将溶有Al(OC2H7)3的正己烷溶液加入盛有SBA-16的烧杯中，室温下搅拌过夜；
3)将得到的样品转移到布式漏斗中，用50ml正己烷洗涤并抽滤，重复3次。将滤饼转移至烧杯中，加入100ml正己烷，室温下搅拌3h，然后加入30g的Al(OC2H7)3，室温下搅拌过夜得到一级滤饼；
4)将一级滤饼转移至布氏漏斗，用50ml正己烷洗涤并抽滤，重复3次；最后将得到的二级滤饼于650℃下焙烧6h，得到改性Al-SBA-16(55)，备用。
二.氧化铝粘稠膏状物的制备：
将小孔氧化铝与稀硝酸溶液按重量比1︰0.5～1.5混捏而成，其中，稀硝酸溶液质量分数为5～20wt％。
在工业化操作过程中，选取优选方案如下：
称取500g小孔氧化铝干胶粉于捏合机的加料槽中，量取质量分数为8％的稀硝酸750ml缓慢加入加料槽，启动捏合机混捏至均匀粘稠膏状物，备用。
三.磷酸硅铝分子筛的选取
磷酸硅铝分子筛购于市面，选用型号为SPAO-11分子筛、SPAO-31的分子筛、或者SPAO-11和SPAO-31混合的分子筛。其中，SPAO-11的硅铝比摩尔比为0.21～0.38，比表面≥180m2·g-1，Na2O含量≤0.2wt％，总孔孔容：0.10～0.30cm3·g-1；SPAO-31的硅铝比为0～1.0，比表面≥150m2·g-1，Na2O含量≤0.2wt％，总孔孔容0.13～0.26cm3·g-1。
本发明使用的其它原料均购于市面上。
根据上述原料制备用于合成气选择性合成高品质煤油馏分的载体，制备方法如下：
按重量份数比由5～50％的介孔氧化锆、10～55％的磷酸硅铝分子筛、5～50％的改性Al-SBA-16、1～3％的田菁粉和10～70％的粘结剂；并将其混合均匀，碾压、挤条成型，置于90～120℃下干燥6～12h，然后在空气中500～600℃条件下焙烧4～10h后冷却至室温，得到载体。
结合上述方法，工业化生产的其配方如下表1：
Figure PCTCN2016079384-appb-000002
优化的反应条件如下表2
表2
Figure PCTCN2016079384-appb-000003
将上述实施例的载体用于制备催化剂，制备方法如下：
采用等体积浸渍法，首先将载体转入梨形瓶中，并置于旋转蒸发仪上，保持载体处于不断翻动的状态，将含有可溶性钴盐的水溶液浸渍到载体上，并保持梨形瓶旋转20～40min，然后置于室温下老化过夜，然后在90～120℃下常压干燥4～12h，最后在空气中500～600℃下焙烧4～10h后冷却至室温，得到催化剂。
在实际的操作过程中，可以将可溶性钴盐分两次浸渍到载体上，从而提高载体负载效率。
结合上述方法，工业化生产的其催化剂配方中可溶性钴盐使用量如下表3：
表3
Figure PCTCN2016079384-appb-000004
上述称取实施例制备的载体均为40g，利用上述方法将可溶性钴盐负载到载体，具体的优化反应条件如下表4：
表4
Figure PCTCN2016079384-appb-000005
将上述催化剂性能评价在固定床反应器中进行，催化剂活化条件：350℃， 氢气压力0.1mpa，氢气空速500h-1，还原时间24h。催化剂性能评价条件：H2/CO摩尔比2.1，合成气空速2000h-1，床层温度205℃，反应压力3.5mpa。催化剂性能评价结果汇总见表5。
表5
Figure PCTCN2016079384-appb-000006
如表5所示，实施例7制备得到的催化剂载体组成中，介孔氧化锆、磷酸硅铝分子筛、改性的SBA-16、氧化铝配比为最优组合，金属钴盐负载量适宜，催化剂的性能效果最好，在较高的转化率下，155～265℃煤油馏分的选择性可以达到85.8％，异构产物含量达到84.3％，煤油馏分冰点为-52℃。
其它未详细说明的部分均为现有技术。尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。

Claims (16)

  1. 一种用于合成气选择性合成高品质煤油馏分的载体，其特征在于：该载体的原料按重量份数比由5～50份的介孔氧化锆、10～55份的磷酸硅铝分子筛、5～50份的改性Al-SBA-16、1～3份田菁粉和10～70份氧化铝组成。
  2. 根据权利要求1所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述载体的原料按重量份数比由10～30份的介孔氧化锆、25～45份的磷酸硅铝分子筛、10～30份的改性Al-SBA-16、1～3份田菁粉和30～55份氧化铝组成。
  3. 根据权利要求2所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述载体的原料按重量份数比由20份的介孔氧化锆、30份的磷酸硅铝分子筛、25份的改性Al-SBA-16、1份田菁粉和30份氧化铝组成。
  4. 根据权利要求1或2或3所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述改性Al-SBA-16的原料由SBA-16和三乙醇铝组成，SBA-16和三乙醇铝重量比为1︰3.0～4.5。
  5. 根据权利要求1或2或3所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述改性Al-SBA-16中的硅铝摩尔比n为5～55，
    Figure PCTCN2016079384-appb-100001
    酸含量为39～92μmol·g-1，Lewis酸含量为71～105μmol·g-1，Na2O含量≤0.1wt％。
  6. 根据权利要求5所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述改性Al-SBA-16中硅铝摩尔比n为10～25，比表面积550～930m2·g-1，平均孔径4.0～7.5nm，总孔孔容0.45～0.70cm3·g-1。
  7. 根据权利要求1或2或3所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述改性Al-SBA-16的制备方法，包括以下步骤：
    1)根据上述重量比称取SBA-16和三乙醇铝，并将三乙醇铝分成两等份备用；
    2)将SBA-16加入正己烷中，在室温条件下搅拌均匀，得到混合液；将上述一份的三乙醇铝加入正己烷中，室温下搅拌至溶解；将溶有三乙醇铝的正己烷加入混合液中，室温下搅拌过夜，得到样品液；
    3)将步骤2)中的样品液转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到一级滤饼；
    4)将滤饼加入正己烷中，在室温下搅拌均匀；再加入另一份的三乙醇铝；室温下搅拌过夜，再转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到二级滤饼；
    5)将二级滤饼置于500～650℃下焙烧6～10h；得到改性的Al-SBA-16。
  8. 根据权利要求1或2或3所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述介孔氧化锆的比表面积190～350m2·g-1，平均孔径5.0～8.5nm，总孔孔容0.40～0.55cm3·g-1。
  9. 根据权利要求1或2或3所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述磷酸硅铝分子筛中总酸量为0.1～0.35mmolNH3·g-1；硅铝比摩尔比为0～1.0；比表面积≥150m2·g-1，Na2O含量≤0.2wt％，总孔孔容0.10～0.30cm3·g-1。
  10. 根据权利要求9所述用于合成气选择性合成高品质煤油馏分的载体，其特征在于：所述酸硅铝分子筛中的硅铝比摩尔比为0.21～0.38，比表面≥180m2·g-1，Na2O含量≤0.2wt％，总孔孔容：0.10～0.30cm3·g-1；或者，所述酸硅铝分子筛中的的硅铝比为0～1.0，比表面≥150m2·g-1，Na2O含量≤0.2wt％，总孔孔容0.13～0.26cm3·g-1。
  11. 一种用于合成气选择性合成高品质煤油馏分的载体的制备方法，其特征在于：包括以下步骤：
    1)按重量比1︰3.0～4.5称取SBA-16和三乙醇铝；并将三乙醇铝等分为二份；
    2)将SBA-16加入正己烷中，在室温条件下搅拌均匀，得到混合液；再将一份的三乙醇铝加入正己烷中，室温下搅拌至溶解；将溶有三乙醇铝的正己烷加入混合液中，室 温下搅拌过夜，得到样品液；
    3)将步骤2)中的样品液转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到一级滤饼；
    4)将滤饼加入正己烷中，在室温下搅拌均匀；再加入另一份的三乙醇铝；室温下搅拌过夜，再转移到布式漏斗中，并用正己烷洗涤和抽滤；重复2～4次；得到二级滤饼；
    5)将二级滤饼于500～650℃下焙烧6～10h，得到改性的Al-SBA-16，备用；
    6)将小孔氧化铝与稀硝酸溶液按重量比1︰0.5～1.5混捏均匀，制备得到粘稠膏状物，备用；其中，稀硝酸溶液质量分数为5～20wt％；
    7)按重量份数比称取5～50份的介孔氧化锆、10～55份的磷酸硅铝分子筛、5～50份的改性Al-SBA-16、1～3份的田菁粉和含有10～70份的氧化铝的粘稠膏状物；并将其混合均匀，碾压、挤条成型，置于90～120℃下干燥6～12h，然后在空气中、500～600℃条件下焙烧4～10h后冷却至室温，得到载体。
  12. 根据权利要求11所述用于合成气选择性合成高品质煤油馏分的载体的制备方法，其特征在于：所述载体为圆柱条状、三叶草状或四叶草状；其中，圆柱条状载体的粒径为1.2～1.6mm，长度为5～10mm；三叶草或四叶草状载体的两叶间距为1.1～1.8mm，长度为5～10mm。
  13. 一种用于合成气选择性合成高品质煤油馏分的催化剂，其特征在于：该催化剂由可溶性钴盐与权利要求1所述的载体组成；所述可溶性钴盐负载在载体表面。
  14. 根据权利要求13所述用于合成气选择性合成高品质煤油馏分的催化剂，其特征在于：所述催化剂中，氧化钴占催化剂的重量百分比为5～20％。
  15. 根据权利要求13或14所述用于合成气选择性合成高品质煤油馏分的催化剂，其特征在于：所述可溶性钴盐为硝酸钴、乙酸钴或羰基钴。
  16. 一种权利要求13所述催化剂的制备方法，其特征在于：包括以下步骤：采用等 体积浸渍法，将含有可溶性钴盐的水溶液浸渍到载体上，置于室温下老化过夜，然后在90～120℃下常压干燥4～12h，最后在空气中500～600℃下焙烧4～10h后冷却至室温，得到催化剂。
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