WO2007131438A1 - Catalyseur d'hydrogénation principal pour la production d'hydrogène par liquéfaction de charbon en présence d'un solvant et procédé de préparation dudit catalyseur - Google Patents

Catalyseur d'hydrogénation principal pour la production d'hydrogène par liquéfaction de charbon en présence d'un solvant et procédé de préparation dudit catalyseur Download PDF

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WO2007131438A1
WO2007131438A1 PCT/CN2007/001509 CN2007001509W WO2007131438A1 WO 2007131438 A1 WO2007131438 A1 WO 2007131438A1 CN 2007001509 W CN2007001509 W CN 2007001509W WO 2007131438 A1 WO2007131438 A1 WO 2007131438A1
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catalyst
preparation
group
wet
temperature
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PCT/CN2007/001509
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English (en)
French (fr)
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Pai Peng
Ke Wu
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Zhaoqing Shunxin Coal Chemical Industry S.T. Co., Ltd.
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Publication of WO2007131438A1 publication Critical patent/WO2007131438A1/zh

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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • 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
    • 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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution

Definitions

  • the invention relates to a catalyst and a preparation method thereof, in particular to a main hydrogenation catalyst for coal liquefaction hydrogen supply solvent and a preparation method thereof.
  • the direct liquefaction method of coal generally catalyzes the hydrogenation of coal and mineral spirits under high temperature (400 ⁇ 50(TC) high pressure (10.0 ⁇ 30.0MPa) to produce a liquid fuel product with high hydrogen to carbon ratio for supplementation and In place of the increasingly scarce petroleum fuel products.
  • some of the solvents have been hydrotreated to give the solvent a certain hydrogen supply.
  • EDS Exxon's hydrogen supply solvent
  • Japan's NEDOL process uses fixed-bed hydrogenation technology for cyclic solvent hydrogenation, Germany's IGOR+ process and China's direct coal liquefaction process (Chinese patent application CN03102672.9).
  • the solvent hydrogenation is carried out using a conventional petroleum hydrogenation catalyst and reaction conditions.
  • Conventional petroleum hydrogenation catalysts are designed to pursue saturated and or selective hydrogenation.
  • the hydrogenation depth of the solvent can be controlled by changing the conditions, the saturation of the hydrogenation solvent is still similar to that of the hydrogenated petroleum product.
  • the lighter product is essentially a mixture of saturated and unsaturated hydrocarbons and does not provide more free hydrogen (H) to fully satisfy the coal liquefaction reaction.
  • the solvent In order to provide more free hydrogen (H) to the solvent to fully meet the coal liquefaction reaction, the solvent must be uniformly saturated and fully saturated, even if the highly unsaturated substances in the solvent are properly hydrogenated.
  • the saturated substance in the solvent is moderately dehydrogenated.
  • the coal liquefaction cycle solvent contains a large amount of impurity elements which are destructive to the activity of the catalyst and unsaturated polycyclic substances which are easily condensed and coked. It is difficult to carry out a uniform incomplete saturated hydrogenation reaction of the solvent by a single catalyst and reaction conditions. Tests have shown that the use of a pre-hydrogenation catalyst and a main hydrogenation catalyst for the two-stage hydrogenation of the solvent is preferred. Summary of the invention
  • An object of the present invention is to provide a main hydrogenation catalyst for coal liquefaction hydrogen supply solvent for use in a main liquefaction cycle of a coal liquefaction cycle.
  • the present invention employs alumina as a carrier, and VIB or Group VIII metal sulfide as an active component.
  • VIB group metal sulfide VIB group metal sulfide
  • the mass content of the material is 17.5 ⁇ 28.5m% ; the mass content of the metal sulfide of Group VIII is 4.5 ⁇ 13.5m%; the specific surface is 190 ⁇ 280m 2 /g; the pore volume is 0.30 ⁇ 0.60ml/g, and the pore diameter of the catalyst is 5 ⁇
  • the pore volume between 15 nm accounts for more than 85% of the total pore volume, and the pore volume with pore diameter >15 nm accounts for 10 to 15% of the total pore volume.
  • the mass content of the Group VIB metal sulfide is 20.5 to 25.5 m%; the mass content of the Group VIII metal sulfide is 7.5 to 10.5 m%; the specific surface is 220 to 260 m 2 /g; and the pore volume is 0.36 to 0.45 ml/g. .
  • the Group VIB metal is molybdenum and/or tungsten; the Group VIII metal used is cobalt or nickel.
  • the Group VIB metal sulfide may be MoS 2 or WS 2 , and the Group VIII metal sulfide may be Ni 3 S 2 or Co 9 S 8 .
  • the active metal of the catalyst of the present invention is fed in two steps by kneading and dipping, and finally, a finished catalyst containing metal sulfide is prepared as follows:
  • the preparation method of the peptizing solution described in the above (1) is as follows: adding alumina powder to the acid solution, stirring uniformly, forming a peptizing solution with uniform color, and the molar ratio of acid to alumina in the peptizing solution is 0.08 ⁇ 1.2
  • the acid solution is a mixture of sulfuric acid or nitric acid or nitric acid and citric acid in a molar ratio of 5:1.
  • the mol ratio of acid to alumina in the peptizing solution is selected to be 0.15 to 0.35, and the water content is 50 m% to 85 m%, preferably 65 m% to 75 m%.
  • the alumina described in the above (1) is a macroporous alumina having a pore volume of 0.4 to 1.0 ml/g, preferably 0.50 to 0.75 ml/g.
  • the metal salt of Group VIB used is ammonium molybdate or ammonium tungstate, and other water-soluble molybdenum salts and/or tungsten salts may also be used; the metal salt of Group VIII used is cobalt, nickel sulfate and/or nitrate, and other water-soluble materials may also be used. Salt, preferably nitrate.
  • the extruded strip according to the above (2) is generally circular in cross section and has a diameter of 0.6 to 1.2 mm, preferably 0.75 to 0.86 mm.
  • the drying and drying of the wet extruded strip according to the above (3) is firstly heated to a temperature of 105 to 135 ° C at a temperature of 150 to 200 ° C / hr, and dried at a constant temperature of 1.0 to 4.0 hr, and then heated to a temperature of 390 to 500 at the same speed.
  • °C constant temperature baking 1.0 ⁇ 4.0hr; preferably constant temperature drying temperature 110 ⁇ 120 °C, constant temperature baking temperature 410 ⁇ 450 °C, constant temperature time 2.0 ⁇ 3.0hr.
  • the preparation method of the above (4) is prepared by adding a Group VIB metal salt and/or a Group VIII metal salt to NH 3 and H 2 0 2 (0.010 to 0.12 g/ml) having a pH of 7.5 to 12.5. Stir in an aqueous solution.
  • the immersion liquid contains a VIB group metal oxide of 0.01 to 0.60 g/ml, preferably 0.20 to 0.45 g/ml; and a Group VIII metal oxide of 0.001 to 0.25 g/ml, preferably 0.075 to 0.15 g/ml.
  • the impregnation of the dry extruded strip as described in the above (4) may be submerged or impregnated, preferably by spray impregnation.
  • the amount of salt to be impregnated is 55 to 75 m%, preferably 60 to 70 m%, based on the total salt amount required for the above metal sulfide content.
  • the drying temperature is 105 ⁇ 165 ° C, preferably 115 ⁇ 135 ° C ; constant temperature time 1.0 ⁇ 3.5hr, preferably 2. 0 ⁇ 2.5hr.
  • the calcination temperature of the above-mentioned (5) is calcined, the calcination temperature is 420 ⁇ 465 ° C, preferably 430 ⁇ 455 ⁇ ; constant temperature time 1.0 ⁇ 3.5 hr, preferably 2. 0 ⁇ 2.5hr.
  • the semi-finished catalyst described in the above (6) is vulcanized, and can be vulcanized by wet vulcanization or wet vulcanization.
  • a mixed sulfide H 2 S medium wherein, H 2 S concentration of 0. 5 ⁇ 10.0v% ,: preferably 1. 0 ⁇ 3.0v%
  • diesel mixing CS 2 Or a disulfide such as CH 3 —S—S—CH 3 , a mercaptan such as C 4 H 9 SH, etc.
  • the above-mentioned (7) is characterized in that the sulfurized dry catalyst is mixed with a catalyst having a wax content of 10 to 15 m% and a distillation range of 250 to 40 (TC distillate oil and a temperature of 100 to 150 ° C, The direct contact of the sulfurized active component of the catalyst with the air is prevented to prevent the catalyst from generating dust during handling, transportation and filling.
  • the weight of the distillate in the mixing is 5 to 30% by weight of the catalyst, preferably 15 to 20% by weight.
  • the main hydrogenation catalyst of the coal liquefaction hydrogen supply solvent of the invention realizes incomplete saturated hydrogenation of the coal liquefaction solvent under the tempered process strip, even if the unsaturated substance in the solvent is moderately hydrogenated and the saturated substance is made Moderate dehydrogenation. All compounds of the hydrogenation solvent achieve uniform incomplete saturation in molecular structure and are capable of releasing the maximum amount of free hydrogen in the coal liquefaction reaction. Moreover, no dust is generated during the loading, unloading, transportation and filling process, and the hydrogenation reaction can be directly carried out without the vulcanization operation after the filling.
  • the preparation method of the main hydrogenation catalyst has the advantages of simpleness, high efficiency, easy control, and the like. detailed description
  • Example 1 A method of preparing a catalyst.
  • nitric acid concentration: 75 m% was added to 277.3 ml of distilled water to dissolve, and the mixture was uniformly stirred to obtain 293.7 g of a nitric acid solution.
  • the whole nitric acid solution was poured into 82.2 g of alumina powder and stirred uniformly to obtain 377.1 g of a gelatin solution having a water content of 74.7% and a uniform color.
  • the above peptizing solution was uniformly kneaded with 197.2 g of macroporous alumina (pore volume: 0.62 ml/g), 34.2 g of ammonium molybdate, and 29.6 nickel nitrate to obtain 638.1 g of a wet material having a water content of 44.1 m%.
  • the above wet material was placed in an extruder to extrude the strip, and the extruded strip had a diameter of 0.8 mm.
  • the wet extruded strip is placed in a high temperature furnace capable of exhausting, heated to 125 ° C at a rate of 150 ° C / hr, dried at a constant temperature for 2.0 hr, and then heated to 450 ° C at the same speed, heated at a constant temperature for 2.0 hr, then naturally Cool down.
  • the above 130 ml of the impregnation liquid was uniformly sprayed into the dried extruded strip obtained in the step (3) by a spray dipping method to obtain a wet extruded strip containing a sufficient amount of metal.
  • the above-mentioned semi-dry extruded strip containing sufficient metal is placed in a high-temperature furnace capable of exhausting, heated to 125 ° C at a rate of 150 ° C / hr, dried at a constant temperature for 2.0 hr, and then heated to 450 ° C at the same speed, constant temperature It was calcined for 2.0 hr and then naturally cooled to prepare a semi-finished catalyst.
  • a sulfided catalyst is optionally obtained by the following method.
  • Dry-process vulcanization Mixing hydrogen at a flow rate of 5000 ml/hr and H 2 S gas at a flow rate of 250 ml/hr, pressurizing to a pressure of 10 MPa, passing 400 g of catalyst in a tubular reactor, and simultaneously at 15 ° C / hr The catalyst was raised to 16 (TC, after 2 hr constant temperature, the temperature was raised to 230 ° C at 5 ° C / hr, constant temperature 2.5 hr.
  • Example 2 Method for preparing a catalyst.
  • the above peptizing solution was uniformly kneaded with 180 g of macroporous alumina (pore volume: 0.48 ml/g), 16.0 g of molybdenum acid hinge, and 13.0 g of cobalt nitrate, and 12 ml of distilled water was added during kneading to obtain a water content of 35.2 m. % wet material 523.2g.
  • the above wet material was placed in an extruder to extrude the strip, and the extruded strip had a diameter of 0.6 mm.
  • the wet extruded strip is placed in a high-temperature furnace capable of exhausting, heated to 135 ° C at a rate of 200 ° C / hr, dried at a constant temperature for 4.0 hr, and then heated to 500 Torr at the same speed, calcined at a constant temperature of 1.0 hr, and then naturally cooled. .
  • the above 130 ml of the impregnation liquid was uniformly sprayed into the dried extruded strip obtained in the step (3) by a spray dipping method to obtain a wet extruded strip containing a sufficient amount of metal.
  • the above-mentioned semi-dry extruded strip containing sufficient metal is placed in a high-temperature furnace capable of exhausting, and is heated to 135 ° C at a rate of 200 ° C / hr. After drying at a constant temperature for 4.0 hr, the temperature was raised to 500 ° C at the same rate, calcined at a constant temperature for 1.0 hr, and then naturally cooled to prepare a semi-finished catalyst.
  • a sulfided catalyst is optionally obtained by the following method.
  • Dry-process vulcanization After mixing hydrogen gas at a flow rate of 5000 ml/hr and H 2 S gas at a flow rate of 500 ml/hr, it is pressurized to a pressure of 14 MPa, passed through a catalyst of 400 g in a tubular reactor, and simultaneously at 10 ° C / The catalyst was raised to 165 ° C, heated at 1.5 ° C, and heated to 235 ° C at 3 ° C / hr for 1.5 hr.
  • Example 3 Method for preparing a catalyst.
  • the entire mixed acid solution was poured into 45.4 g of alumina powder and stirred well to obtain 384.8 g of a color-stained peptizing solution having a water content of 84.9 m%.
  • the above peptizing solution was uniformly kneaded with 186.8 g of macroporous alumina (pore volume: 0.74 ml/g:), 55.7 g of ammonium tungstate, and 102.5 of nickel nitrate to obtain 729.8 g of a wet material having a water content of 55.1 m%.
  • the above wet material was placed in an extruder to extrude the strip, and the extruded strip had a diameter of 1.2 mm.
  • the wet extruded strip is placed in a high temperature furnace capable of exhausting, heated to 115 ° C at a rate of 175 ° C / hr, dried at a constant temperature for 3.0 hr, and then heated to 390 ° C at the same rate, and baked at a constant temperature for 4.0 hr, then naturally Cool down.
  • a high temperature furnace capable of exhausting, heated to 115 ° C at a rate of 175 ° C / hr, dried at a constant temperature for 3.0 hr, and then heated to 390 ° C at the same rate, and baked at a constant temperature for 4.0 hr, then naturally Cool down.
  • the above 155 ml of the immersion liquid was uniformly sprayed into the dry extruded strip obtained in the step (3) by a spray dipping method to obtain a wet extruded strip containing a sufficient amount of metal.
  • the above-mentioned semi-dry extruded strip containing sufficient metal is placed in a high-temperature furnace capable of exhausting, and is heated to 115 ° C at a temperature of 750 ° C / hr, dried at a constant temperature for 3.0 hr, and then heated to 390 Torr at the same speed, and the constant temperature baking is 4.0. Hr, then naturally cool down to make a semi-finished catalyst.
  • a sulfided catalyst is optionally obtained by the following method.
  • Dry-process vulcanization After mixing hydrogen gas at a flow rate of 5000 ml/hr and H 2 S gas at a flow rate of 500 ml/hr, it is pressurized to a pressure of 14 MPa, passed through a catalyst of 400 g in a tubular reactor, and simultaneously at 10 ° C / The catalyst was raised to 165 ° C, heated at 1.5 ° C, and heated to 235 ° C at 3 ° C hr for 1.5 hr.
  • the catalysts prepared in Examples 1 to 3 have the physicochemical properties as shown in Table 1.
  • the catalysts prepared in Examples 1 to 3 were evaluated for activity in a small fixed bed hydrogenation unit, and an eucalyptus oil was used as a raw material.
  • the reaction conditions were:
  • Example 1 2 3 pore volume ml/g 0.41 0.37 0.55 specific surface m 2 /g 223 275 199 bulk density g/ml 0.88 0.91 0.85 lateral compressive strength N/mm 9.2 9.6 9.0 pore distribution %

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Description

一种煤液化供氢溶剂的主加氢催化剂及其制备方法 技术领域
本发明涉及一种催化剂及其制备方法，特别是一种煤液化供氢溶剂的主加氢催化剂及 其制备方法。 背景技术
煤炭直接液化方法， 一般是在高温 （400〜50(TC ) 高压 （10.0〜30.0MPa) 条件下， 将煤炭和溶剂油进行催化加氢， 生成氢碳比高的液体燃料产物， 用于补充和代替日益短缺 的石油燃料产品。 在现有各种煤炭直接液化工艺中， 有的对溶剂进行了加氢处理， 使溶剂 具有一定的供氢作用。 如 Exxon公司的供氢溶剂 (EDS) 工艺和日本的 NEDOL工艺采用 固定床加氢技术专门对循环溶剂加氢、德国的 IGOR+工艺和中国煤直接液化工艺（中国专 利申请 CN03102672.9) 将液化产物加氢后分离出循环溶剂、 俄罗斯低压液化工艺和日本 褐煤液化工艺 （BCL工艺和 NBCL工艺） 将加氢和不加氢溶剂混合为循环溶剂使用。 尽 管上述工艺不同程度地使溶剂具有供氢作用， 但溶剂中的可转移氢仍然不能满足较高煤炭 转化率的耗氢需要， 均需在液化反应中加入大量气体氢。
溶剂供氢作用相对较好的 EDS工艺， 使用传统的石油加氢催化剂和反应条件进行溶 剂加氢。 传统的石油加氢催化剂旨在追求饱和和或选择性的加氢效果， 虽然通过改变条件 可以控制溶剂的加氢深度， 但加氢溶剂的饱和度仍然与加氢的石油产品相似， 加氢深度较 浅的产物基本是饱和烃和不饱和烃的混合物， 不能提供更多的游离氢 （一 H) 来完全满足 煤液化反应所需。 为了使溶剂提供更多的游离氢 （一 H) 来完全满足煤液化反应所需， 必 须对溶剂进行均匀的不尧全饱和加氢， 既使溶剂中的高度不饱和物质适度加氢， 又使溶剂 中的饱和物质适度脱氢。
煤液化循环溶剂中含有大量对催化剂活性有破坏作用的杂质元素和易于缩合结焦的 不饱和多环物质 采用单一催化剂和反应条件难以持久进行溶剂的均匀不完全饱和加氢反 应。 试验表明， 采用预加氢催化剂和主加氢催化剂进行溶剂两段加氢的效果较佳。 发明内容
本发明的目的是提供一种煤液化供氢溶剂的主加氢催化剂， 用于煤液化循环溶剂主加 氢。
本发明采用氧化铝为载体， VIB或 VIII族金属硫化物为活性组分。 VIB族金属硫化
确认本 物质量含量为 17.5〜28.5m% ; VIII族金属硫化物质量含量为 4.5〜13.5m%；比表面为 190〜 280m2/g; 孔容为 0.30〜0.60ml/g， 该催化剂孔径在 5〜15nm之间的孔容占全部孔容的 85 %以上， 孔径 >15nm的孔容占全部孔容的 10〜15%。
优选地， VIB族金属硫化物质量含量为 20.5〜25.5m% ; VIII族金属硫化物质量含量为 7.5〜10.5m%；比表面为 220〜260m2/g; 孔容为 0.36〜0.45ml/g。
所述 VIB族金属为钼和 /或钨； 所用 VIII族金属为钴或镍。所述 VIB族金属硫化物可 以是 MoS2或 WS2， 所述 VIII族金属硫化物可以是 Ni3S2或 Co9S8。
本发明催化剂的活性金属采取混捏和浸渍两步加入， 按下述步骤， 最终制成含金属硫 化物的成品催化剂：
( 1 )将上述金属硫化物含量所需总盐量的 25〜45m%VIB族和 /或 VIII族金属盐、 胶 溶溶液与氧化铝混捏为均匀的湿料；
(2) 对上述湿料进行挤条， 制成湿挤条；
(3 ) 对上述湿挤条进行干燥和焙烧， 制成干挤条；
(4) 将含有 VIB族和 /或 VIII族金属盐的浸渍液对上述^ ^挤条进行浸渍， 制成 足 上述成品催化剂金属含量的半干 (或全湿） 挤条;
(5) 对上述半干 （或全湿） 挤条进行干燥和焙烧， 制成含有金属氧化物的半成品催 化剂；
(6) 对上述半成品催化剂进行硫化， 制成干品硫化态催化剂；
(7) 对上述硫化态干品催化剂进行混油保护， 制成半干硫化态催化剂。
上述 （1 ) 所述的胶溶溶液的制备方法为： 在酸溶液中加入氧化铝粉， 搅拌均匀， 形 成色泽一致的胶溶溶液， 胶溶溶液中酸与氧化铝的 mol比为 0.08〜1.2， 所述酸溶液为硫 酸或硝酸或硝酸与柠檬酸按 mol比 5:1的混合物。
胶溶溶液中酸与氧化铝的 mol 比选为 0.15〜0.35， 水含量为 50m%〜85m%， 优选 65m%〜75m%。
上述（1 )所述的氧化铝为大孔氧化铝，其孔容为 0.4〜1.0ml/g，最佳为 0.50〜0.75ml/g。 上述 （1 ) 所述的湿料， 其金属盐加入量优选为催化剂金属硫化物含量所需总盐量的 30〜40m%; 湿料含水量为 35m%〜55m%， 优选 40m%〜50m%。 所用 VIB族金属盐为钼 酸铵或钨酸铵， 也可用其它水溶性钼盐和 /或钨盐； 所用 VIII族金属盐为钴、 镍的硫酸盐 和 /或硝酸盐， 也可用其它水溶性盐， 优选硝酸盐。
上述 （2) 所述的挤条， 其截面一般为圆形， 直径 0.6〜1.2mm， 优选 0.75〜0.86mm。 上述 （3) 所述的湿挤条干燥和焙烧， 是先以 150〜200°C/hr速度升温到 105〜135°C， 恒温干燥 1.0〜4.0hr， 再以同样速 井温到 390〜500°C， 恒温焙烧 1.0〜4.0hr; 优选恒温 干燥温度 110〜120°C， 恒温焙烧温度 410〜450°C， 恒温时间 2.0〜3.0hr。
上述 （4) 所述浸渍液的制备方法为： 将 VIB族金属盐和 /或 VIII族金属盐加入到 PH 值为 7.5〜12.5 的 NH3和 H202 (0.010〜0.12g/ml) 的水溶液中搅拌溶解。 该浸渍液含有 VIB 族金属氧化物 0.01〜0.60g/ml， 优选 0.20〜0.45 g/ml; VIII 族金属氧化物 0.001〜 0.25g/ml, 优选 0.075〜0.15g/ml。
上述 （4) 所述的对干挤条浸渍， 可浸没浸渍， 也可喷淋浸渍， 优选喷淋浸渍。 浸渍 上盐量为上述金属硫化物含量所需总盐量的 55〜75m%， 优选 60〜70m%。
上述 （5 ) 所述的对湿挤条进行干燥， 其干燥温度为 105〜165°C， 优选 115〜135°C ; 恒温时间 1.0〜3.5hr， 优选 2. 0〜2.5hr。
上述 （5 ) 所述的对湿挤条进行焙烧， 其焙烧温度为 420〜465°C， 优选 430〜455Ό ; 恒温时间 1.0〜3.5hr， 优选 2. 0〜2.5hr。
上述 （6) 所述的对半成品催化剂进行硫化， 可干法硫化也可湿法硫化。 干法硫化时， 以 混合 H2S为硫化介质， 其中， H2S浓度为 0. 5〜10.0v%，：优选 1. 0~3.0v%; 湿法硫 化时， 以柴油混合 CS2 (或二硫化物如 CH3— S— S— CH3、 硫醇如 C4H9SH等） 为硫化介 质， 临氢硫化， 其中， 液体的硫化物浓度为 1.5〜15.0v%， 优选 3. 5〜7.5v%。 实行程序升 温硫化：先以 3〜5°C/hr升到 230±5°C，在此温度下维持上述气相 H2S浓度并恒温 2〜3hr， 再以 4〜7°C/hr升到 320±5°C， 在此温度下维持上述气相 H2S浓度并恒温 1.5〜2.5hr， 最 后以 5〜10°C/hr升到 370±5°C， 在此温度下维持上述气相 H2S浓度并恒温 1.0〜2hr。
上述 （7) 所述的对硫化态干品催化剂进行混油保护， 是用含蜡量 10〜15m%、 馏程 250〜40(TC的馏份油与温度 100〜150°C的催化剂混合，以阻止催化剂的硫化态活性组分与 空气直接接触， 防止催化剂在装卸、 运输和装填过程产生粉尘。 混合中的馏分油重量为催 化剂重量的 5〜30%， 最佳为 15〜20%。
有益效果
本发明所述煤液化供氢溶剂的主加氢催化剂， 在缓和的工艺条^^下实现煤液化溶剂的 不完全饱和加氢， 既使溶剂中的不饱和物质适度加氢， 又使饱和物质适度脱氢。 加氢溶剂 的所有化合物在分子结构上达到均匀的不完全饱和度， 能够在煤液化反应中释放最大量的 游离氢。 且在装卸、 运输和装填过程不产生粉尘， 装填后无需硫化操作即可直接进行加氢 反应。 该主加氢催化剂的制备方法具有简单、 效率高、 易掌控等优点。 具体实施方式
实施例 1 : 催化剂的制备方法。
( 1 ) 胶溶溶液和湿料制备
将 16.4ml的硝酸（浓度 75m%)加入 277.3ml的蒸馏水中溶解，搅拌均匀，制得 293.7g 硝酸溶液。
将全部硝酸溶液倒入 82.2g氧化铝粉中搅拌均匀， 制得含水量 74.7%的色泽均匀的胶 溶溶液 377.1g。
将上述胶溶溶液与 197.2g的大孔氧化铝 （孔容为 0.62ml/g)、 34.2g钼酸铵、 29.6硝酸 镍进行均匀捏合， 制得含水量 44.1m%的湿料 638.1g。
(2) 湿料挤条
将上述湿料放入挤条机进行挤条， 挤条直径为 0.8mm。
(3 ) 挤条干燥和焙烧
将上述湿挤条放入可排气的高温炉中，以 150°C/hr速度升温到 125°C，恒温干燥 2.0hr， 再以同样速度升温到 450°C， 恒温焙烧 2.0hr， 然后自然降温。
(4) 浸渍液配制和催化剂浸渍
将 63.8g钼酸铰和 30.8g碱式碳酸镍加入 100ml含 NH3 15m%、H202 12m%的水溶液中， 搅拌使金属盐完全溶解后，用含 NH3 45m/O0 12m%的氨水调节溶液的 PH值为 10，制得浸 渍液 130ml。
采用喷淋浸渍法， 将上述 130ml浸渍液全部均匀喷洒到步骤 （3 ) 所得的干燥挤条中， 制得含有足量金属的湿挤条。
(5 ) 含足量金属的湿挤条干燥及焙烧
将上述含足量金属的半干挤条放入可排气的高温炉中，以 150°C/hr速度升温到 125°C， 恒温干燥 2.0hr， 再以同样速度升温到 450°C， 恒温焙烧 2.0hr， 然后自然降温， 制成半成 品催化剂。
(6) 半成品催化剂的硫化： 任选以下一种方法， 制成硫化态催化剂。
①采用干法硫化： 流量 5000ml/hr的氢气和流量 250ml/hr的 H2S气体混合后， 增压到 lOMPa压力，通过装在管式反应器的 400g催化剂， 同时， 以 15°C/hr将催化剂升到 16(TC， 恒温 2hr后，以 5°C/hr升温到 230'C，恒温 2.5hr。 230°C恒温结束后，以 6°C/hr升到 320°C， 恒温 2hr， 最后以 8°C/hr升到 370°C， 恒温 1.5hr。 然后快速降温到 150°C， 停止 H2S气体 进料， 恒温并保持氢气吹扫 2hr， 完成硫化。 ②釆用湿法硫化： 将 480mlCS2 加入 12000ml的柴油中混合均匀， 制成硫化柴油。 在 lOMPa压力下保持氢气流量 5000ml/hr同时， 以 15°C/hr将装在管式反应器的 400g催化剂 升到 160Ό，恒温 2hr后，以 150ml/hr的流速使硫化柴油通过催化剂床层，同时以 5°C/hr升 温到 23(TC， 恒温 2.5hr (在此温度下气相 H2S浓度达到 5.5v%以上）。 230Ό恒温结束后， 以 6°C/hr升到 320°C， 恒温 2hr， 最后以 8°C/hr升到 370°C， 恒温 1.5hr。 然后快速降温到 150°C , 放空硫化柴油， 恒温并保持氢气吹扫 2hr， 完成硫化。
(7) 硫化态催化剂的混油保护
上述硫化完毕的催化剂趁热卸出时，用温度 80°C的含蜡量 12m%、馏程 250〜400°C的 馏份油 70g均匀喷洒在催化剂上， 然后自然冷却至室温。
实施例 2: 催化剂的制备方法。
( 1 ) 胶溶溶液和湿料制备
将 6.8ml的硫酸 （浓度 98m%)加入 155ml的蒸馏水中溶解， 搅拌均匀， 制得 167.2g 硫酸溶液。
将全部硫酸溶液倒入 147g氧化铝粉中搅拌均匀， 制得含水量 50.30 %的色泽均勾的胶 溶溶液 314.2g。
将上述胶溶溶液与 180g的大孔氧化铝 （孔容为 0.48ml/g)、 16.0g钼酸铰、 13.0g硝酸 钴进行均匀捏合， 捏合期间加入蒸熘水 12ml， 制得含水量 35.2m%的湿料 523.2g。
(2) 湿料挤条
将上述湿料放入挤条机进行挤条， 挤条直径为 0.6mm。
(3 ) 挤条干燥和焙烧
将上述湿挤条放入可排气的高温炉中，以 200°C/hr速度升温到 135°C，恒温干燥 4.0hr， 再以同样速度升温到 500Ό， 恒温焙烧 l.Ohr, 然后自然降温。
(4) 浸渍液配制和催化剂浸渍
将 48.0g钼酸铵和 14.0g碱式碳酸钴加入 100ml含 H3 15m%、H202 12m%的水溶液中， 搅拌使金属盐完全溶解后，用含 NH3 45m°/Ofl 12m%的氨水调节溶液的 PH值为 10,制得浸 渍液 130ml。
采用喷淋浸渍法， 将上述 130ml浸渍液全部均匀喷洒到步骤 （3 ) 所得的干燥挤条中， 制得含有足量金属的湿挤条。
(5) 含足量金属的湿挤条干燥及焙烧
将上述含足量金属的半干挤条放入可排气的高温炉中，以 200°C/hr速度升温到 135°C， 恒温干燥 4.0hr, 再以同样速度升温到 500°C， 恒温焙烧 1.0hr， 然后自然降温， 制成半成 品催化剂。
(6) 半成品催化剂的硫化： 任选以下一种方法， 制成硫化态催化剂。
①采用干法硫化：， 流量 5000ml/hr的氢气和流量 500ml/hr的 H2S气体混合后， 增压 到 14MPa压力，通过装在管式反应器的 400g催化剂，同时，以 10°C/hr将催化剂升到 165'C， 恒温 1.5hr后，以 3°C/hr升温到 235°C，恒温 1.5hr。235°C恒温结束后，以 7°C/hr升到 325'C , 恒温 L5hr， 最后以 5°C/hr升到 375 °C， 恒温 lhr。 然后快速降温到 150°C， 停止 H2S气体 进料， 恒温并保持氢气吹扫 lhr， 完成硫化。
②釆用湿法硫化： 将 1800mlCS2加入 12000ml的柴油中混合均匀， 制成硫化柴油。在 14MPa压力下保持氢气流量 5000ml/hr同时， 以 10°C/hr将装在管式反应器的 400g催化剂 升到 165°C ,恒温 2hr后，以 150ml/hr的流速使硫化柴油通过催化剂床层，同时以 3°C/hr升 温到 235°C， 恒温 3hr (在此温度下气相 H2S浓度达到 5.5v%以上）。 235°C恒温结束后， 以 7°C/hr升到 325°C，恒温 1.5hr，最后以 5°C/hr升到 375Ό，恒温 lhr。然后快速降温到 150°C， 放空硫化柴油， 恒温并保持氢气吹扫 lhr， 完成硫化。
(7) 硫化态催化剂的混油保护
上述硫化完毕的催化剂趁热卸出时，用温度 80°C的含蜡量 15m%、馏程 250〜400°C的 馏份油 120g均匀喷洒在催化剂上， 然后自然冷却至室温。
实施例 3: 催化剂的制备方法。
( 1 ) 胶溶溶液和湿料制备
将 26.4ml的硝酸 （浓度 75m%)、 17.1g柠檬酸加入 322.3ml的蒸馏水中溶解， 搅拌均 匀， 制得 367.8g混合酸溶液。
将全部混合酸溶液倒入 45.4g氧化铝粉中搅拌均匀，制得含水量 84.9m%的色泽均匀的 胶溶溶液 384.8g。
将上述胶溶溶液与 186.8g的大孔氧化铝（孔容为 0.74ml/g：)、 55.7g钨酸铵、 102.5硝酸 镍进行均匀捏合， 制得含水量 55.1m%的湿料 729.8g。
(2) 湿料挤条
将上述湿料放入挤条机进行挤条， 挤条直径为 1.2mm。
(3 ) 挤条干燥和焙烧
将上述湿挤条放入可排气的高温炉中，以 175°C/hr速度升温到 115°C，恒温干燥 3.0hr， 再以同样速度升温到 390°C , 恒温焙烧 4.0hr， 然后自然降温。 (4) 浸渍液配制和催化剂浸渍
将 68.1g钨酸铵和 43.9g碱式碳酸镍加入 140ml含 NH3 15m%、¾02 12m%的水溶液中， 搅拌使金属盐完全溶解后，用含 NH3 45m°/ B 12m%的氨水调节溶液的 PH值为 10，制得浸 渍液 155ml。
采用喷淋浸渍法， 将上述 155ml浸渍液全部均匀喷洒到步骤 （3 ) 所得的干燥挤条中， 制得含有足量金属的湿挤条。
(5) 含足量金属的湿挤条干燥及焙烧
将上述含足量金属的半干挤条放入可排气的高温炉中，以 750°C/hr速度升温到 115°C， 恒温干燥 3.0hr， 再以同样速度升温到 390Γ， 恒温焙烧 4.0hr, 然后自然降温， 制成半成 品催化剂。
(6) 半成品催化剂的硫化： 任选以下一种方法， 制成硫化态催化剂。
①采用干法硫化：， 流量 5000ml/hr的氢气和流量 500ml/hr的 H2S气体混合后， 增压 到 14MPa压力，通过装在管式反应器的 400g催化剂，同时，以 10°C/hr将催化剂升到 165°C， 恒温 1.5hr后，以 3°C hr升温到 235°C，恒温 1.5hr。235°C恒温结束后，以 7°C/hr升到 325°C , 恒温 1.5hr， 最后以 5°C/hr升到 375°C， 恒温 lhr。 然后快速降温到 150°C， 停止 H2S气体 进料， 恒温并保持氢气吹扫 lhr， 完成硫化。
②采用湿法硫化： 将 1800mlCS2 加入 12000ml的柴油中混合均匀， 制成硫化柴油。在 14MPa压力下保持氢气流量 5000ml/hr同时， 以 10°C/hr将装在管式反应器的 400g催化剂 升到 165°C，恒温 2hr后，以 150ml/hr的流速使硫化柴油通过催化剂床层，同时以 3°C/hr升 温到 235°C， 恒温 3hr (在此温度下气相 H2S浓度达到 5.5v%以上）。 235°C恒温结束后， 以 7°C/hr升到 325°C，恒温 1.5hr，最后以 5°C/hr升到 375°C，恒温 lhr。然后快速降温到 150°C， 放空硫化柴油， 恒温并保持氢气吹扫 lhr, 完成硫化。
(7) 硫化态催化剂的混油保护
上述硫化完毕的催化剂趁热卸出时，用温度 80°C的含蜡量 15m%、馏程 250〜400°C的 馏份油 120g均匀喷洒在催化剂上， 然后自然冷却至室温。
实施例 4〜6: 催化剂的评价。
实施例 1〜3制备的催化剂， 其物化性质如表 1所示。
实施例 1〜3制备的催化剂在小型固定床加氢装置进行活性评价， 以一种蒽油为原料， 反应条件为：
反应压力： 10MPa， 反应温度： 390°C， 体积空速： 1.5h-'， 氢油比： 100 (v
评价结果如表 2所示。
表 1 催化剂的物化性质
实施例 1 2 3 孔容 ml/g 0.41 0.37 0.55 比表面 m2/g 223 275 199 堆积密度 g/ml 0.88 0.91 0.85 侧压强度 N/mm 9.2 9.6 9.0 孔分布 ％
<5nm 8 13 4
5~15nm 90 87 92
>15nm 12 10 14 红外酸分布 mM/g
160°C 0.193 0.187 0.198
250。C 0.102 0.098 0.105
350。C 0.060 0.056 0.064
450 °C 0.020 0.017 0.022
MoS2 m% 22.19 17.75 ―
WS2 m% ― 28.47
Ni3S2 m% 8.05 13.48
Co9S8 m% ― 4.80 ―
表 2 催化剂的评价结果
评价实施例 4 5 6 催化剂来源 实施例 1 实施例 2 实施例 3 脱 Fe率 m% 34.6 30.3 36.7 脱 Ca率 m% 32.4 29.1 35.0 脱 Ni率 m% 46.6 42.2 50.2 脱 V率 m% 43.3 40.9 47.5 脱残炭率 m% 75.2 73.4 78.4 化学氢耗 m% 6.2 5.6 6.8 生成油密度降低 m% 8.2 7.0 9.3

Claims

权 利 要 求
1.一种煤液化供氢溶剂的主加氢催化剂， 其特征在于， 采用氧化铝为载体， VIB 和 / 或 VIII族金属硫化物为活性组分， VIB族金属硫化物质量含量为 17.5〜28.5m%； VIII族金 属硫化物质量含量为 4.5〜13.5m% ; 比表面为 190〜280m2/g; 孔容为 0.30〜0.60ml/g， 孔 径在 5〜15nm之间的孔容占全部孔容的 85%以上， 孔径 >15nm的孔容占全部孔容的 10〜 15%。
2.根据权利要求 1所述的煤液化供氢溶剂的主加氢催化剂， 其特征在于， VIB族金 属硫化物质量含量为最佳 20.5〜25.5m% ; VIII族金属硫化物质量含量为 7.5〜10.5m% ; 比表面为 220〜260m2/g; 孔容为 0.36〜0.45ml/g。
3. 根据权利要求 1所述的煤液化供氢溶剂的主加氢催化剂， 其特征在于， 所述 VIB 族金属为钼和 /或钨； 所述 VIII族金属为钴或镍。
4.一种制备如权利要求 1所述的煤液化供氢溶剂的专用主加氢催化剂的方法， 其特征 在于， 包括如下步骤：
( 1 )将按上述金属硫化物含量所需总盐量的 25〜45m%的 VIB族和 /或 VIII族金属盐、 胶溶溶液与氧化铝混捏为均匀的湿料； 该胶溶溶液是酸与氧化铝的 mol比为 0.08〜1.2的 混合物， 所述酸为硫酸或硝酸或硝酸与柠檬酸按 mol比 5:1的混合物；
(2) 对上述湿料进行挤条， 制成湿挤条；
(3 ) 对上述湿挤条进行干燥和焙烧， 制成干挤条；
(4) 将含有 VIB族和 /或 VIII族金属盐的浸渍液对上述干挤条进行浸没浸渍或喷淋 浸渍， 制成含有足量金属的半干或全湿挤条；
(5 ) 对步骤 （4) 中的半干或全湿 条进行干燥和焙烧， 制成含有 VIB族和 /或 VIII 族金属氧化物的半成品催化剂；
(6) 对步骤 （4) 中的半成品催化剂进行硫化， 制成干品硫化态催化剂；
(7) 对上述硫化态干品催化剂进行混油保护， 制成半干硫化态催化剂。
5. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤 （1 )所述的胶溶溶液中 酸与氧化铝的 mol比为 0.15〜0.35； 胶溶溶液水含量为 50m%〜85m%。
6. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤 （1 ) 所述的氧化铝为大 孔氧化铝， 其孔容为 0.6〜1.3ml/g。
7. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤 （1 ) 所述的湿料， 其金 属盐加入量为催化剂硫含量所需总盐量的 30~40m%; 湿料含水量为 40m%〜50m%。
8. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤 (3) 所述的湿挤条干燥 和焙烧， 是先以 150〜200°C/hr速度升温到 105〜135°C， 恒温干燥 1.0〜4.0hr， 再以同样 速度升温到 390〜500°C , 恒温焙烧 1.0~4.0hr。
9. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤 （4) 所述的浸渍液含有 VIB族金属氧化物 0.01〜0.60g/ml; VIII族金属氧化物 0.001〜0.25g/ml。
10. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤 （5 ) 所述的对湿挤条 进行干燥， 其干燥温度为 105〜165'C °C ; 对湿挤条进行焙烧， 其焙烧温度为 420〜465'C ; VIB族金属氧化物为钼酸铵， VIII族金属氧化物为碱式碳酸镍。
11. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤（6)所述的对半成品催 化剂进行硫化， 或以 混合 H2S为硫化介质， 其中， H2S浓度为 0. 5〜10.0v%； .或以柴油 混合 CS2、 CH3— S—S—CH3或 C4H9SH为硫化介质， 临氢硫化， 其中 CS2、 CH3— S— S— 。 或。4 811的浓度为 1.5〜15.0v%， 然后分别在 230± 5°C、 320±5°C、 370±5°C恒温 硫化 1.0〜3.0hr。
12. 根据权利要求 4所述的制备方法， 其特征在于， 制备步骤（7)所述的对硫化态干 品催化剂进行混油保护， 是用含蜡量 10〜15m%、 馏程 250〜400°C的熘份油与温度 100〜 150°C的催化剂混合， 镏分油重量为催化剂重量的 15〜20%。
13. 根据权利要求 4所述的制备方法， 其特征在于， 步骤 （1 ) 所述 VIB族金属盐为 钼酸铵或钨酸铵； 所述 VIII族金属盐为钴、 镍的硫酸盐或硝酸盐或碳酸盐。
PCT/CN2007/001509 2006-05-08 2007-05-08 Catalyseur d'hydrogénation principal pour la production d'hydrogène par liquéfaction de charbon en présence d'un solvant et procédé de préparation dudit catalyseur WO2007131438A1 (fr)

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