WO2014026353A1 - 提高ft合成制高碳醇选择性的催化剂和其制备方法及应用 - Google Patents

提高ft合成制高碳醇选择性的催化剂和其制备方法及应用 Download PDF

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WO2014026353A1
WO2014026353A1 PCT/CN2012/080222 CN2012080222W WO2014026353A1 WO 2014026353 A1 WO2014026353 A1 WO 2014026353A1 CN 2012080222 W CN2012080222 W CN 2012080222W WO 2014026353 A1 WO2014026353 A1 WO 2014026353A1
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catalyst
activated carbon
carbon
hours
gas
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French (fr)
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丁云杰
裴彦鹏
朱何俊
王涛
吕元
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • B01J23/825—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 gallium, indium or thallium
    • 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
    • B01J21/18—Carbon
    • 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
    • B01J23/75—Cobalt
    • 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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01J35/61—Surface area
    • B01J35/617—500-1000 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
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 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
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof

Definitions

  • the present invention relates to a catalyst, a preparation method and an application thereof for improving the selectivity of CO hydrogenation to a high-carbon primary alcohol (C 6 or higher) in a mixed primary alcohol.
  • the present invention relates to a Co-based catalyst supported on activated carbon as a carrier, wherein an additive such as Al, B or Ga is added to improve the selectivity of high carbon primary alcohol (C 6 or higher) in the hydrogenation of CO mixed synthetic primary alcohol.
  • c 6 ⁇ c 18 high carbon primary alcohol has unique and excellent properties, and has wide application in many fields of national economy, among which c 6 ⁇ c u higher alcohol can be used as plasticizer, and c 12 ⁇ c 18 high Carbon alcohols can be used as a raw material for surfactants.
  • synthetic high-carbon primary alcohol has a large unit weight output value and high added value, and the market price of high-carbon linear primary alcohol with even carbon is 15000 ⁇ 20,000 yuan/ton, and the high carbon straight chain of odd carbon The market price of alcohol is between 30,000 and 40,000 yuan.
  • the main methods for industrial chemical synthesis of higher alcohols are the Ziegler process and the high carbon olefin hydroformylation process.
  • the Ziegler method uses ethylene as a raw material, uses triethylaluminum as a catalyst to achieve carbon chain growth, and then performs oxidation, hydrolysis and separation processes to obtain c 6 -c 12 linear even primary alcohol.
  • the method has a long process flow, complicated technology, and difficulty in development, and the catalyst triethylene aluminum has large consumption and poor safety.
  • the high carbon olefin hydroformylation process is a production process represented by the South African Sasol process. Hydrocarbon products (alkanes and olefins) are prepared by Fischer-Tropsch (FT) synthesis, and then the olefins are separated and then cobalt carbonyl is used.
  • the catalyst is hydroformylated with a mixture of CO and H 2 under high temperature and high pressure conditions to produce a high carbon aldehyde, and finally hydrogenated to produce a higher alcohol.
  • the process is long and the reaction conditions are harsh.
  • the homogeneous catalyst carbonyl cobalt and the reaction product are separated and the production cost is high.
  • the CO hydrogenation one-step method can directly synthesize mixed alcohols (d Cs), which has the advantages of simple process.
  • the US 4,775,696 patent discloses a process for synthesizing a low carbon mixed alcohol using synthesis gas, the catalyst of which is a Mo, W or Re based catalyst.
  • U.S. Patent No. 4,752,622 and U.S. Patent No. 4,826, 630 each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each of each. each.
  • US6753353 discloses nano-sized MoS 2 or W 2 C as a catalyst for the catalytic hydrogenation of CO to a low-carbon mixed alcohol.
  • U.S. Patent No. 8,089,933 discloses a process for the production of low-carbon mixed alcohols from syngas.
  • the catalyst used is Mo 2 C and M and/or Na are added as auxiliaries to improve the performance of the catalyst for the synthesis of alcohol.
  • CN 01130481 discloses a Mn-Ni-K-MoS 2 catalyst, which introduces Mn element in the preparation of a MoS 2 -based catalyst, so that the activity of catalytically synthesized alcohol is significantly improved, and the selectivity of C 2 + alcohol is improved.
  • CN 200610097869 provides a catalyst for syngas synthesis of lower alcohols and a preparation method thereof, the main components of the catalyst are CuO, ZnO, Cr 2 O 3 , A1 2 0 3 and an appropriate amount of other auxiliary agents (V, Mo, Mn) , Mg, Ce), with higher CO conversion and higher selectivity of alcohol above C 2 .
  • the carbon number of the above-mentioned mixed alcohol produced by Fischer-Tropsch synthesis is relatively low, generally d Cs, and substantially no high-carbon alcohol having a high added value of C 6 or more is obtained, and the specific value of the methanol having a low added value is large, reaching 40%.
  • the carbon chain of the hydrocarbon and the alcohol thereby improving the selectivity of the c 6 -c 18 high carbon mixed primary alcohol, and further improving the economics of the CO hydrogenation synthesis high carbon mixed primary alcohol technology.
  • the inventors of the present invention have conducted intensive research to carry a Co-based on activated carbon (the main active phase of the synthetic alcohol is a metallic Co and a noble metal-like Co 2 C, and the active center of the metal Co has a catalytic effect of dissociating CO and increasing the carbon chain, Co 2 C active site has strong CO non-dissociative adsorption activation and CO linear insertion performance)
  • the performance of the catalyst was modified by adding additives such as Al, B or Ga, thereby improving the selectivity of the long carbon chain (C 6 -C 18 ) high carbon primary alcohol, and further improving the hydrogenation of CO to high carbon.
  • additives such as Al, B or Ga
  • the present invention provides the following.
  • a catalyst for increasing the selectivity of CO hydrogenation to a high primary alcohol in a mixed primary alcohol comprising an active component, an adjuvant, and a carrier, wherein the active component is a mixed phase of metal Co and Co 2 C, the auxiliary agent is one or more of Al, B or Ga, and the carrier is activated carbon, wherein the high carbon primary alcohol means a carbon number of 6 or more Primary alcohol.
  • the carrier is apricot shell activated carbon or coconut shell activated carbon.
  • the activated carbon has a specific surface area of 200 2000 m 2 /g, an average pore diameter of 1 to 10 nm, and a pore volume of 0.1 2 mL/g.
  • the active component is present in an amount of from 1 to 30% by weight based on the weight of the catalyst.
  • the auxiliary agent has a weight content of catalyst weight
  • the catalyst consists of the active component, the adjuvant and the carrier.
  • a process for the preparation of a catalyst as described above comprising the steps of: (1) activating the activated carbon by a deionized water; (2) using a wet impregnation method to activate the main active group An aqueous solution of a soluble salt or an acid of the auxiliary agent and the auxiliary agent is impregnated on the activated carbon support, and dried at room temperature; dried at 323 353 K in an air atmosphere for 8 to 24 hours to prepare a catalyst soluble salt precursor; (3) The precursor is dried at 373 393 K for 2 to 10 hours under an inert atmosphere of nitrogen or argon, and calcined at 473 773 K for 4 to 20 hours under an inert atmosphere of nitrogen or argon to prepare a catalyst oxide precursor; and (4) The catalyst oxide precursor is reductively activated to form a catalytic precursor in which the main active component is in a metallic state.
  • the carrier is apricot shell activated carbon or coconut shell activated carbon; the activated carbon has a specific surface area of 200 2000 m 2 /g, an average pore diameter of 1 to 10 nm, and a pore
  • the content of the active component is 1 to 30% by weight of the catalyst, or the weight of the auxiliary agent is 0.01 to 5% by weight of the catalyst.
  • the method further comprises the following steps: (5) pre-treating a catalyst precursor having a main active component in a metallic state via a H 2 /CO mixture gas to prepare the catalyst , wherein the H 2 /CO molar ratio is 0.5 to 4.0: 1.
  • the catalyst is used in a fixed bed reaction or in a slurry bed reaction.
  • the catalyst for the fixed bed reaction is carried out in situ reduction.
  • the catalyst for the slurry bed reaction is carried out using fluidized bed reduction, and after reduction, it is transferred to the slurry bed reactor by gas purge.
  • the reducing gas used for the reduction is a hydrogen-containing mixed gas having a hydrogen content of 10 100%, and the gas other than hydrogen in the hydrogen-containing mixed gas is nitrogen or argon, and is used for reduction.
  • the temperature is 473 873 K
  • the pressure is 0.1 to 1.0 MPa
  • the space velocity is 300 2000 h" 1
  • the time is 2 to 48 hours.
  • the pretreatment is in situ pretreatment. The treatment is carried out for 1 to 24 hours under a condition of a H 2 /CO mixture gas space velocity of 100 10000 h" 1 and a pressure of 0.1 to 10.0 MPa, wherein the H 2 /CO molar ratio is 0.5 to 4.0: 1.
  • a method for increasing the selectivity of CO hydrogenation to a high primary alcohol in a mixed primary alcohol comprising hydrogenating CO from H 2 in the presence of a catalyst as described above Dd ⁇ is a primary alcohol, wherein the high carbon primary alcohol refers to a primary alcohol having a carbon number of 6 or more.
  • the method is carried out under the following conditions: a reaction temperature of 473-500 K, a reaction pressure of 0.5 to 8.0 MPa, a space velocity of 500 to 3000 h -1 , and a H 2 /CO molar ratio of 0.5. ⁇ 4.0: 1.
  • the H 2 /CO mixture is continuously fed to provide a reaction tail gas, a gas phase product and a liquid phase product wherein the H 2 /CO molar ratio is 0.5 4.0:1.
  • the process is carried out using a fixed bed wherein the reaction off-gas and gas phase products are continuously discharged and the liquid phase product is collected using a cold trap.
  • the method is carried out using a slurry bed in which the reaction tail gas and the gas phase product are continuously discharged, the liquid phase product is collected by a cold trap, and the liquid phase product is continuously filtered through the filter after filtering the catalyst. material.
  • the methanol distribution in the alcohol produced by CO hydrogenation is 2
  • the -4%, C 6 -C 18 linear mixed primary alcohol distribution is 56% or more.
  • the catalyst can be used for CO hydrogenation to directly synthesize C 2 -C 18 linear mixed primary alcohols to produce naphtha and diesel oil. It has high CO conversion rate and the choice of synthetic c 2 -c 18 linear mixed primary alcohol. Sex, especially the selectivity of c 6 -c 18 linear mixed primary alcohols.
  • the present invention can provide a catalyst and a preparation method for improving the selectivity of hydrogenation of CO to a high-carbon primary alcohol (C 6 and above) in a mixed primary alcohol
  • the catalyst can be composed of a main active component, an auxiliary agent and a carrier.
  • the main active component may be a metallic Co and a noble metal-like Co 2 C.
  • the metal Co active center has a dissociation of CO and a growth of a carbon chain.
  • the Co 2 C active site has strong CO non-dissociation adsorption activation and CO linear insertion performance, and the auxiliary agent may be one or several auxiliary agents of Al, B or Ga.
  • the activated carbon support may have a specific surface area of 200 2000 m 2 /g, an average pore diameter of 1 to 10 nm, and a pore volume of 0.1 2 mL/g.
  • the active component may be present in an amount of from 1 to 30% by weight based on the weight of the catalyst (based on Co;); the additive may be present in an amount of from 0.01 to 5% by weight.
  • the high carbon primary alcohol herein refers to a primary alcohol having 6 or more carbon atoms, preferably a primary alcohol having 6 to 18 carbon atoms.
  • the catalyst component can be supported onto the activated carbon support by impregnation.
  • the carrier may be apricot shell activated carbon or coconut shell activated carbon.
  • After the catalyst may be by drying, calcination, the reducing atmosphere containing H 2 activation and pretreatment by H 2 / CO.'S gas, wherein the molar ratio H 2 CO.'S / 0.5 to 4.0: 1.
  • the activated carbon can be subjected to boiling washing treatment with deionized water, followed by impregnation of the supported catalyst component to prepare a catalyst soluble acid salt precursor.
  • the catalyst precursor can be first dried in an air atmosphere of 323 353 K for 8 to 24 hours, followed by drying in an inert gas atmosphere of 373 393 K for 2 to 10 hours.
  • the catalyst can be calcined in a 473 773 K argon or nitrogen atmosphere for 4 to 20 hours to prepare a catalyst oxide precursor.
  • the catalyst oxide precursor can be reductively activated such that at least a portion of the cobalt element is reduced to metallic cobalt, preferably at least 10% by weight, more preferably at least 50% by weight, still more preferably at least 80% by weight, and most preferably at least 95% by weight.
  • the cobalt element is reduced to metallic cobalt. In one embodiment, substantially all of the cobalt element is reduced to metallic cobalt.
  • the reducing condition may be: the reducing gas is a hydrogen-containing mixed gas, the hydrogen content is 10 to 100% by mole, and the gas other than hydrogen in the hydrogen-containing mixed gas is nitrogen, argon or helium, and the temperature may be 473 873 K,
  • the pressure can be 0.1 1 MPa, the airspeed can be 300 2000 h- 1 , and the time can be 2 to 48 hours.
  • a catalyst in which the main active component is in a metallic state is prepared.
  • the catalyst can be subjected to H 2 /CO pretreatment before use, wherein the H 2 /CO molar ratio is 0.5 4.0:1.
  • the catalyst reacted in the fixed bed and the slurry bed can be pretreated in situ, and the pretreatment temperature can be
  • the 453-553 K, H 2 /CO mixture gas space velocity can be 100 10000 ⁇ 1 , and the pressure can be pretreated for 0.1 to 24 hours under the condition of 0.1 10.0 MPa, thereby preparing a high-carbon alcohol synthesis catalyst.
  • the selectivity of the C 6 -C 18 linear mixed primary alcohol in the CO hydrogenation product can be higher.
  • the active component is a metal Co, a Co soluble salt impregnating the aqueous solution It may be one or more of cobalt nitrate, cobalt oxalate and cobalt citrate, preferably cobalt nitrate, wherein the weight of the catalyst is based on The amount of the active component in terms of cobalt may be from 1 to 30% by weight, preferably from 5 to 25% by weight of the cobalt element.
  • the auxiliary component may be one or more of Al, B or Ga.
  • the weight of the auxiliary component may be 0.015% by weight based on the weight of the catalyst, and when A1 is used as the auxiliary, the raw material may be aluminum nitrate ( ⁇ 1( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0). When hydrazine is used as an auxiliary, the raw material may be boric acid. When Ga is used as an auxiliary agent, the raw material may be gallium nitrate (Ga(N0 3 ) 3 ).
  • the catalyst carrier may be activated carbon, wherein the activated carbon may be apricot or carbon shell carbon, and the activated carbon carrier may have a specific surface area of 200 2000 m 2 /g, an average pore diameter of 1 to 10 nm, and a pore volume of 0.1 to 2 mL. /g.
  • the preferred activated carbon may have a specific surface area of 500 1500 m 2 /g, an average pore diameter of 3 to 8 nm, and a pore volume of 0.5 1 mL/g.
  • the catalyst component may be supported on the carrier by a wet impregnation method, wherein an excessive impregnation method may be employed, or an equal volume impregnation method may be employed, and the preferred method is an equal volume impregnation method; a conventional impregnation method may be employed, or a vacuum impregnation method may be employed.
  • the preferred method is a conventional impregnation method.
  • the components contained in the impregnation liquid may include a catalyst active component and an auxiliary component, wherein co-impregnation or partial leaching may be employed, and a preferred method is a co-impregnation method.
  • the catalyst can be applied to CO hydrogenation to increase the C 6 -C 18 linear mixed primary alcohol selectivity in the product.
  • An example of a specific method of preparing a catalyst is as follows:
  • Activated carbon is used as the carrier, activated carbon is boiled and washed by deionized water, and Co and all the soluble salts of the auxiliary or the aqueous solution of the acid are impregnated on the activated carbon support.
  • the impregnated catalyst can be immersed in the active component of the catalyst.
  • the component, or the first immersion catalyst auxiliary component may be immersed in the active component of the catalyst, and may also be co-impregnated. After immersion, the sample was dried at room temperature, and baked at 323 353 K in an air atmosphere for 8 to 24 hours to prepare a catalyst soluble salt precursor.
  • the precursor was dried in 337 393 K argon or nitrogen for 2 to 10 hours, and then calcined in a 473 773 K argon or nitrogen atmosphere for 4 to 20 hours to obtain a catalyst oxide precursor.
  • hydrogen-containing mixture gas hydrogen content is 10 ⁇ 100%, other gases other than hydrogen in the hydrogen-containing mixture gas are nitrogen or argon
  • 473 873 K reduction activation for 2 ⁇ 48 hours reduction pressure is 0.1 1 MPa, empty
  • the rate is 300 2000 h, and the precursor of the main catalytic component of the catalyst is obtained.
  • the catalyst was subjected to H 2 /CO pretreatment before use, wherein the H 2 /CO molar ratio was 0.5 4.0 :1.
  • the catalysts reacted in the fixed bed and the slurry bed are pretreated in situ.
  • the pretreatment temperature is 453-553 K
  • the H 2 /CO mixture gas space velocity is 100-10000 h" 1
  • the pressure is 0.1-10.0 MPa.
  • Preparation of a high-carbon alcohol synthesis catalyst the catalyst comprising an active component, an auxiliary agent and a carrier, wherein the active component is a mixed phase of metal Co and Co 2 C,
  • the auxiliary agent is one or more of Al, B or Ga, and the carrier is activated carbon.
  • the metal cobalt during the pretreatment process Some of it is carbonized to Co 2 C.
  • the degree of carbonization depends on the conditions of carbonization, such as temperature, pressure, time, activated carbon carrier and H 2 /CO mixture ratio. Wait. In the mixed phase of metal Co and Co 2 C, the ratio of Co to Co 2 C varies, and thus need not be limited.
  • the carrier is activated carbon, elemental analysis cannot be used to determine the content of cobalt carbide.
  • the Co/Co 2 C molar ratio is Approximately 0.5-99.5: 1, more preferably from about 1 to 99: 1, and most preferably from about 5 to 95:1.
  • the metal Co active center has the catalysis of dissociating CO and increasing the carbon chain, and the Co 2 C active site has strong CO non-dissociative adsorption activation and CO linear insertion performance.
  • reaction of the present invention may be carried out in a slurry bed reactor or in a fixed bed reactor, and a slurry bed reactor is preferably employed.
  • Reaction temperature 473 500 K
  • reaction pressure 0.5 8.0 MPa
  • airspeed 500 3000! ⁇ 1 ⁇ 1 .
  • Ga(N0 3 ) 3 China Pharmaceutical (Group) Shanghai Chemical Test Qi Wei Division, Analytical Pure
  • H 2 /CO mixture (containing 66.6 vol% H 2 , 33.4 vol% CO): Dalian Dante Gas Co., Ltd., purity ⁇ 99.999 vol%
  • Example 1 The specific surface area and pore size distribution of the coconut shell activated carbon were measured on a QUANTHROME AS-1 type adsorber. The sample was degassed for 3 h at 573 K, and subjected to nitrogen adsorption test at liquid nitrogen temperature. The cross-sectional area of the N 2 molecule was 0.162 nm 2 . The specific surface area of the sample was calculated by the BET method, and the pore distribution was calculated by the BJH method. The measured coconut shell activated carbon had a specific surface area of 1012 m 2 /g, an average pore diameter of 3.5 nm, and a pore volume of 0.42 mL/g.
  • the composition of Catalyst A was 15Co0.1Al/ACl.
  • the activated carbon treated with 20-40 mesh was used as a carrier, and the catalyst was prepared according to the following procedure. Weigh 10 grams of treated activated carbon. 0.163 g of ⁇ 1 ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 and 8.7 g of Co(N0 3 ) 2 -6H 2 0 were weighed out and dissolved in 10 mL of deionized water to prepare a solution. The obtained solution is supported on activated carbon by a conventional impregnation method, that is, the activated carbon is immersed in the obtained solution at room temperature, and stirred for 1 to 2 minutes to uniformly impregnate the solution on the activated carbon support.
  • the time is based on the time taken for the catalyst to reach a dry state, then dried at 333 K in an air atmosphere for 24 hours, then dried at 393 K for 4 hours in an argon atmosphere; finally 623 K in an argon atmosphere.
  • the mixture was calcined at a temperature for 8 hours to obtain a catalyst A oxide precursor having a Co content of 15% by weight and an A1 content of 0.1% by weight.
  • the catalyst A oxide precursor had the same BET as above, and had a specific surface area of 778 m 2 /g, an average pore diameter of 3.8 nm, and a pore volume of 0.35 mL/g.
  • the active component and the auxiliary content of the catalyst A oxide precursor were measured by a Magix type X-ray fluorescence (XRF) instrument of PHILIPS, and the Co content was actually measured to be 14.83% by weight and the A1 content was 0.12% by weight.
  • XRF X-ray fluorescence
  • the composition of the catalyst B was 15Co0.5Al/ACl.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in the following manner. Weigh 10 grams of treated activated carbon and place it in a suction filter bottle. Weigh 0.822 g of ⁇ 1 ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 and 8.7 g ⁇ ) ( ⁇ 0 3 ;) 2 ⁇ 6 ⁇ 2 0, dissolve them in 10 mL of deionized water to make a solution, and place in a separatory funnel. The separatory funnel was sealingly connected to the tapered suction bottle with a rubber stopper in the middle opening.
  • the prepared solution was immersed on the activated carbon by vacuum impregnation, that is, the separator funnel piston was closed at room temperature, and the activated carbon was first treated under vacuum (O.OlMPa) for 20 minutes, and then the piston was opened to separate the separator.
  • the solution flows into the activated carbon in the filter flask and is immersed in the solution.
  • the prepared sample was dried at room temperature, and the dry time was taken as the time required for the catalyst to reach a dry state, followed by drying in an air atmosphere at a temperature of 353 K for 24 hours, followed by argon gas.
  • the atmosphere was dried at 383 K for 8 hours; finally, it was calcined at 603 Torr for 8 hours in an argon atmosphere to obtain a catalyst B oxide precursor having a Co content of 15% by weight and an A1 weight of 0.5%.
  • the catalyst B oxide precursor had the same BET as above, and had a specific surface area of 810 m 2 /g, an average pore diameter of 3.8 nm, and a pore volume of 0.345 mL/g.
  • the active component and the auxiliary content of the catalyst B oxide precursor were measured as above, and the Co content was actually measured to be 14.75% by weight and the A1 content was 0.54% by weight.
  • the crystal phase of Co in the catalyst after the reaction was detected by XRD, and the XRD test was carried out on a PANalytical X'Pert PRO type X-ray diffractometer.
  • the composition of the catalyst C was 15 ColAl/ACl.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in the following manner. Weigh 10 g of treated activated carbon, weigh 1.65 g of ⁇ 1 ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 and 5.53 g of CoC 2 (V2H 2 0 in 13 mL of deionized water to make a solution, which is prepared by the above conventional impregnation method. The solution is immersed in activated carbon.
  • the catalyst C oxide precursor was obtained by calcining at a temperature of 623 K for 4 hours in an argon atmosphere to obtain a catalyst C oxide precursor having a Co content of 15% by weight and an A1 content of 1% by weight.
  • the BET of the catalyst C oxide precursor was the same as above, and its specific surface area was 804 m 2 /g, the average pore diameter is 3.9 nm, and the pore volume is 0.33 mL/g.
  • the active component and the additive content of the catalyst C oxide precursor are measured as above, and the actual measured Co content is 14.62% by weight, and the A1 content is 1.13% by weight.
  • the composition of the catalyst D was 15Co2Al/ACl.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in the following manner. Weigh 10 g of treated activated carbon, weigh 3.34 g of ⁇ 1 ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 and 5.67 g of cobalt citrate dihydrate in 10 mL of deionized water to make a solution.
  • the prepared solution is prepared by the above conventional impregnation method. Immerse on activated carbon.
  • the dry time is based on the time taken for the catalyst to reach a dry state, then dried at 333 K in an air atmosphere for 24 hours, then dried at 393 K for 2 hours in an argon atmosphere; finally in an argon atmosphere 623 Calcination at K temperature for 6 hours gave a catalyst D oxide precursor having a Co content of 15% by weight and an A1 by weight of 2%.
  • the BET measurement method of the catalyst was the same as above, and its specific surface area was 804 m 2 /g, the average pore diameter was 3.9 nm, and the pore volume was 0.32 mL/g.
  • the active component and the additive content of the catalyst D oxide precursor were measured in the same manner as above, and the Co content was actually measured to be 14.55 wt%, and the A1 content was 2.31 wt%.
  • the composition of the catalyst E was 30Co4Al/AC2.
  • the catalyst was prepared as follows.
  • the specific surface area and pore size distribution of the apricot shell activated carbon were measured on a QUANTHROME AS-1 type adsorber.
  • the sample was degassed for 3 h at 573 K, and subjected to nitrogen adsorption test at liquid nitrogen temperature.
  • the cross-sectional area of the N 2 molecule was 0.162 nm 2 .
  • the specific surface area of the sample was calculated by the BET method, the pore distribution was calculated by the BJH method, and the specific surface area of the sample was calculated by the BET method, and the pore distribution was calculated by the BJH method.
  • the apricot shell activated carbon has a specific surface area of 646 m 2 /g, an average pore diameter of 3.7 nm, and a pore volume of 0.60 mL/g.
  • apricot shell activated carbon carrier 1000 g was treated by deionized water boiling method for 3 times.
  • the specific method was as follows: Take 1000 g of apricot shell activated carbon, add 5000 g of deionized water, boil for 0.5 hour, then separate the activated carbon from boiling water, and then add again. Deionized water is used for the next boiled wash. The washed activated carbon was dried at 393 K for 8 hours and at 393 K for 8 hours, and was set aside as AC2.
  • the specific surface area and pore distribution of AC2 activated carbon were determined by the above method.
  • the specific surface area of AC2 apricot shell activated carbon was 673 m 2 /g, the average pore diameter was 3.8 nm, and the pore volume was 0.64 mL/g.
  • the catalyst preparation steps are as follows. Weigh 10 g of AC2 activated carbon, weigh 8.41 g of ⁇ 1 ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0 and 22.41 g of Co (N0 3 ;> 6H 2 0 in 20 mL of deionized water to make a solution, which is prepared by the above conventional impregnation method.
  • the solution is impregnated on the activated carbon, that is, the activated carbon is immersed in the prepared solution at room temperature, and stirred for 1 to 2 minutes, so that the solution is uniformly impregnated on the activated carbon carrier.
  • the drying is carried out at room temperature, and the time takes the catalyst to reach a dry state.
  • Catalyst E oxide precursor with A1 weight content of 4%.
  • Catalyst E oxide precursor has the same BET as above, with a specific surface area of 561 m 2 /g, an average pore diameter of 3.8 nm and a pore volume of 0.51 mL/g.
  • the active component and the additive content of the catalyst E oxide precursor were measured as above, and the Co content was actually measured to be 29.21% by weight and the A1 content was 4.2% by weight.
  • the composition of the catalyst F was 15Co0.5B/ACl.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in the following manner. Weigh 10 grams of treated activated carbon, weigh 0.328 grams of H 3 B0 3 and 8.7 grams of Co(N0 3 ) 2 -6H 2 0 in 10 mL of deionized water, heat to 333 K to make a solution, using the above conventional dipping method The resulting solution was impregnated on activated carbon. Dry at room temperature, the dry time is based on the time taken for the catalyst to reach a dry state, then dried at 333 K in an air atmosphere for 24 hours, then at 393 K in an argon atmosphere.
  • Example 7 It was dried for 6 hours; finally, it was calcined at 623 K for 4 hours in an argon atmosphere to obtain a catalyst F oxide precursor having a Co content of 15% by weight and a B content of 0.5% by weight.
  • the BET determination method of the catalyst F oxide precursor was the same as above, and its specific surface area was 812 m 2 /g, the average pore diameter was 3.8 nm, and the pore volume was 0.34 mL/g.
  • the active component and the additive content of the catalyst F oxide precursor were measured in the same manner as in Example 1, and the Co content was actually measured to be 14.8% by weight and the B content was 0.42% by weight.
  • the active component and the additive content of the catalyst F oxide precursor were measured in the same manner as above, and the Co content was actually measured to be 14.86% by weight and the B content was 0.46% by weight.
  • Example 7 Example 7
  • the composition of the catalyst G was 1CO0.01B/AC1.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in the following manner. Weigh 10 grams of treated activated carbon, weigh 0.007 grams of H 3 B0 3 and 0.498 grams of ⁇ ) ( ⁇ 0 3 ) 2 ⁇ 6 ⁇ 2 0 in 10mL of deionized water, heated to 333 K to make a solution, using the above conventional dipping method The resulting solution was impregnated on activated carbon.
  • the dry time is based on the time taken for the catalyst to reach a dry state, then dried at 333 K in an air atmosphere for 24 hours, then dried at 393 K for 4 hours in an argon atmosphere; finally in an argon atmosphere 623 Calcination at K temperature for 6 hours gave a catalyst G oxide precursor having a Co content of 1% by weight and a B content of 0.01% by weight.
  • the BET measurement method of the catalyst G oxide precursor was the same as above, and its specific surface area was 853 m 2 /g, the average pore diameter was 3.8 nm, and the pore volume was 0.37 mL/g.
  • the active component and the additive content of the catalyst G oxide precursor were measured in the same manner as above, and the Co content was actually measured to be 0.87% by weight and the B content was 0.01% by weight.
  • the composition of the catalyst H was 15Co0.5Ga/ACl.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in the following manner. Weigh 10 g of treated activated carbon, weigh 0.216 g of Ga(N0 3 ) 3 and 8.7 g of ⁇ )( ⁇ 0 3 ) 2 ⁇ 6 ⁇ 20 in a solution of 10 mL of deionized water, and prepare it by the above conventional impregnation method. The solution was impregnated on activated carbon.
  • the dry time is based on the time taken for the catalyst to reach a dry state, and the dry time is based on the actual time when the catalyst reaches a dry state, followed by drying at an air atmosphere of 333 K for 24 hours, followed by an 393 K temperature in an argon atmosphere.
  • the mixture was dried for 4 hours; finally, it was calcined at 623 K for 6 hours in an argon atmosphere to obtain a catalyst H oxide precursor having a Co content of 15% by weight and a Ga content of 0.5% by weight.
  • the BET measurement method of the catalyst H oxide precursor was the same as above, and its specific surface area was 785 m 2 /g, the average pore diameter was 3.8 nm, and the pore volume was 0.35 mL/g.
  • the active component and the additive content of the catalyst H oxide precursor were measured in the same manner as above, and the Co content was actually measured to be 14.83% by weight and the Ga content was 0.51% by weight.
  • the composition of the catalyst I was 15ColA10.5B/ACl.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in accordance with the following procedure.
  • the dry time is based on the time taken for the catalyst to reach a dry state, then dried at an air atmosphere of 343 K for 24 hours, then dried at 393 K for 2 hours in an argon atmosphere; finally in an argon atmosphere 673
  • the calcination was carried out at K temperature for 2 hours to obtain a catalyst I oxide precursor having a Co content of 15% by weight, an A1 content of 1% by weight, and a B content of 0.5% by weight.
  • the BET determination method of the catalyst I oxide precursor was the same as above, and its specific surface area was 812 m 2 /g, the average pore diameter was 3.8 nm, and the pore volume was 0.34 mL/g.
  • the active component and the additive content of the catalyst I oxide precursor were measured in the same manner as above, and the Co content was actually measured to be 14.76% by weight and the A1 content was 1.07% by weight.
  • the B content was 0.47% by weight.
  • the crystal phase of Co in the catalyst after the reaction was measured by XRD, and the XRD test was performed on a PANalytical X'Pert PRO type X-ray diffractometer.
  • the composition of the catalyst J was 15Co2Zr/ACl.
  • the coconut shell activated carbon treated in Example 1 was used as a carrier, and the catalyst was prepared in accordance with the following procedure.
  • the BET determination method of the catalyst J oxide precursor was the same as above, and its specific surface area was 802 m 2 /g, the average pore diameter was 3.7 nm, and the pore volume was 0.35 mL/g.
  • the active component and the additive content of the catalyst J oxide precursor were measured in the same manner as above, and the Co content was actually measured to be 14.73% by weight and the Zr content was 1.95 wt%.
  • the crystal phase of Co in the catalyst after the reaction was determined by XRD.
  • the XRD test was performed on a PANalytical X'Pert PRO X-ray diffractometer. get on.
  • the Cukoa radiation source has a tube pressure of 40 kV and a tube flow of 40 mA.
  • the composition of the catalyst K was 15Co/ACl. Using the coconut shell activated carbon treated in Example 1 as a carrier, the catalyst was prepared as follows.
  • the BET determination method of the catalyst K oxide precursor was the same as above, and its specific surface area was 810 m 2 /g, the average pore diameter was 3.8 nm, and the pore volume was 0.37 mL/g.
  • the active component and the additive content of the catalyst K oxide precursor were measured in the same manner as above, and the actual measured Co content was 14.82% by weight.
  • the crystal phase of Co in the catalyst after the reaction was measured by XRD, and the XRD test was carried out on a PANalytical X'Pert PRO type X-ray diffractometer.
  • the composition of the catalyst L was 15Co/Si0 2 .
  • the catalyst was prepared as follows.
  • Si0 2 100 g was treated by deionized water boiling method for 3 times. The specific method: 100 g of Si0 2 was added, 500 g of deionized water was added, and boiled for 0.5 hour, then the activated carbon was separated from boiling water, and deionized water was added again. For the next treatment, the washed Si0 2 was dried at 393 K for 8 hours and set aside. The specific surface area and pore distribution of Si0 2 were measured on an AS-1 type adsorption apparatus of QUANTACHROME. The sample was degassed for 3 h at 573 K, and subjected to nitrogen adsorption test at liquid nitrogen temperature. The cross-sectional area of the N 2 molecule was 0.162 nm 2 .
  • the specific surface area of the sample was calculated by the BET method, and the pore distribution was calculated by the BJH method.
  • the treated Si0 2 had a specific surface area of 276 m 2 /g, an average pore diameter of 10.8 nm, and a pore volume of 0.85 mL/g.
  • the BET determination method of the catalyst L oxide precursor was the same as above, and its specific surface area was 247 m 2 /g, the average pore diameter was 10.1 nm, and the pore volume was 0.78 mL/g.
  • the active component and the additive content of the catalyst L oxide precursor were measured in the same manner as above, and the Co content was actually measured to be 14.86% by weight.
  • Catalyst AL reaction evaluation was carried out in a fixed bed reactor. 4 mL of each catalyst was packed in a fixed bed reactor having a diameter of 9 mm and a length of 40 mm. The catalyst needs to be reduced and activated before the reaction.
  • the conditions of reduction and activation are pure hydrogen atmosphere, the pressure is normal pressure, the space velocity is 500 h- 1 , the temperature is 703 K, and the time is 6 hours. That is, the main active component is a metal precursor.
  • the catalyst bed temperature dropped below 373 , switching syngas (containing 66.6 vol% ⁇ 2 , 33.4 vol% CO, wherein the syngas component used in Catalyst D was: 60.0 vol% H 2 , 40.0 vol% CO, And wherein the synthesis gas component used in the catalyst G is: 75.0 vol% 3 ⁇ 4, 25.0 vol% CO), under the condition of a temperature of 493 K, a reaction pressure of 3.0 MPa, and a space velocity of 500 h -1 continuous feed.
  • Pretreatment was carried out for 24 hours to obtain a high carbon mixed alcohol catalyst.
  • the reaction was continued under the conditions of a temperature of 493 K, a reaction pressure of 3.0 MPa, and a space velocity of 500 h -1 .
  • the reaction tail gas and the gas phase product were continuously discharged, and the liquid phase product was collected by a cold trap, and the temperature of the cold trap was maintained.
  • the reaction tail gas was analyzed online using HP-6890 gas chromatograph (Porapark QS packed column, TCD detector).
  • the liquid products included oil phase and water phase products, and were taken offline by HP-6890 gas chromatograph (HP-5 capillary, FID detector).
  • HP-6890 gas chromatograph HP-5 capillary, FID detector
  • the oil phase and the aqueous phase product were analyzed, and the aqueous phase product was analyzed with sec-butanol as an internal standard.
  • the conversion of CO and the selectivity of the product were calculated based on the analysis results.
  • the composition and evaluation results of the catalyst AL are shown in Table 1.
  • the purge gas is H 2 , the volumetric space velocity is 3000 h" 1 , and the purge time is 2 hours.
  • the H 2 and CO mixture gas (containing 66.6 vol% 13 ⁇ 4, 33.4 vol% CO) is introduced into the autoclave.
  • the pretreatment was carried out at a pretreatment temperature of 493 K, a pressure of 3.0 MPa, and a space velocity of 500 h" 1 .
  • the synthesis gas was continuously fed for 24 hours.
  • the CO hydrogenation reaction has the same reaction conditions as the pretreatment conditions.
  • the reaction tail gas and the product were continuously discharged, and the liquid phase product was collected by a cold trap.
  • the temperature of the cold trap was maintained at 273 293 K, and the liquid phase product was continuously filtered by filtering the catalyst through a filter. After 24 hours of pretreatment gas and stationary phase, the reaction samples were taken every 48 hours for analysis.
  • the reaction tail gas was analyzed online using a ⁇ -6890 gas chromatograph (Porapark QS packed column, TCD detector).
  • the liquid product consisted of oil phase and aqueous phase product, and was taken offline by HP-6890 gas chromatograph (HP-5 capillary, FID detector).
  • HP-6890 gas chromatograph HP-5 capillary, FID detector
  • the oil phase and the aqueous phase product were analyzed, and the aqueous phase product was analyzed with sec-butanol as an internal standard.
  • the conversion of CO and the selectivity of the product were calculated based on the analysis results, and the evaluation results are shown in Table 1.
  • the catalyst modified by one or more of the additives of Al, B or Ga in the examples has higher activity and synthesis of C 2 -C 18 higher alcohol selectivity, and the resulting alcohol
  • the distribution of C 6 ⁇ C 18 high carbon alcohol is higher than 50%, and the highest is 56.4%.
  • Patent US 7670985 discloses a Zr CN101310856 and other additives modulated supported on activated carbon catalyst synthesis activity and selectivity c 2 ⁇ c 18 alcohols, the distribution is not given to 8 ⁇ higher alcohols.
  • Comparative Example 1 The catalyst ZCo2Zr/ACl was developed by a representative Zr promoter in the patents US Pat. No. 7,670,985 and CN101310856.
  • Table 1 shows the synthesis product in the alcohol. 6-8 alcohol distribution of 47.3%, lower than the present application distribution in Catalyst Synthesis Example product alcohol in C 6 ⁇ C 18 higher alcohols embodiment.
  • Comparative Example 2 an activated carbon-supported 15Co/ACl was prepared without using an auxiliary agent. It can be seen from the table that the selectivity of C 6 -C 18 alcohol in the synthetic product alcohol is low.
  • Table 1 shows that the selectivity of synthesizing C 2 -C 18 alcohol using the SiO 2 supported 15Co/SiO 2 catalyst in Comparative Example 3 is extremely low, and the synthesized product alcohol is d ⁇ C 5 lower alcohol, and no C 6 ⁇ C 18 is formed. High alcohol.

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Description

提高 FT合成制高碳醇选择性的催化剂和其制备方法及应用 技术领域
本发明涉及提高 CO加氢生成混合伯醇中高碳伯醇 (C6以上)选择性的催化剂和制 备方法及其应用。 具体地， 本发明涉及一种以活性炭为载体负载的 Co基催化剂， 其 中添加 Al、 B或 Ga等助剂提高 CO加氢合成混合伯醇中高碳伯醇 (C6以上)选择性。 技术背景
c6~c18高碳伯醇具有独特的优良性能，在国民经济的多个领域中有着广泛的应用， 其中 c6~cu高碳醇可作为增塑剂， 并且 c12~c18高碳醇可作为表面活性剂的原料。 与合 成油相比， 合成高碳伯醇的单位重量产值大和附加值高， 其中偶数碳的高碳直链伯醇 的市场售价在 15000~20000元 /吨，奇数碳的高碳直链伯醇的市场售价在 30000~40000元
/吨。 近年来全球高碳醇的需求量很大， 年均增长率为约 3.1%。 我国是一个高碳醇的消 费大国， 高碳醇市场前景广阔， 对高碳醇的需求也在逐年增加。
目前， 工业上化学合成生产高碳醇的主要方法是齐格勒法和高碳烯烃氢甲酰化 法。
齐格勒法以乙烯为原料， 以三乙基铝为催化剂实现碳链增长， 再进行氧化、 水解 和分离工艺， 制得 c6-c12直链偶数伯醇。 但是， 该方法工艺流程长， 技术复杂， 开发 难度大， 催化剂三乙基铝消耗量大且安全性差。
高碳烯烃氢甲酰化法是以南非 Sasol工艺为代表的生产方法， 通过费托 (FT)合成 制取烃类产品 (烷烃和烯烃)， 随后将其中的烯烃分离出来， 再以羰基钴为催化剂在高 温高压条件下烯烃与 CO和 H2的混合气进行氢甲酰化生产高碳醛，最后再加氢生产高 碳醇。但是， 该工艺流程长， 反应条件苛刻， 均相催化剂羰基钴与反应产物分离复杂， 生产成本较高。
因此， 迫切需求工艺简单、 反应条件温和、 原料易得， 来源广泛的高碳醇生产新 技术。
CO加氢一步法可以直接合成混合醇 (d Cs), 具有工艺简单的优点。 US 4775696 专利公开了一种利用合成气合成低碳混合醇的方法，其催化剂为 Mo、 W或 Re基催化 剂。 US 4752622 和 US 4882630 专利提供了以合成气为原料气合成低碳混合醇的方 法， 采用 Fe、 Co和 Ni助剂调变的 Mo、 W基催化剂， 并添加碱金属或碱土金属。
US6753353公开了纳米的 MoS2或 W2C作为催化剂催化 CO加氢合成低碳混合醇。
US 8048933专利公开了一种以合成气为原料生产低碳混合醇的方法， 采用的催化 剂为 Mo2C， 并添加 M和 /或 Na作为助剂， 改善了催化剂合成醇的性能。
CN 01130481公开了 Mn-Ni-K-MoS2催化剂， 在 MoS2基催化剂的制备中引入 Mn 元素， 使得催化剂催化合成醇活性显著提高， 同时， C2 +醇的选择性有所提高。
CN 200610097869提供一种用于合成气合成低碳醇的催化剂及其制备方法， 催化 剂主要组分为 CuO、 ZnO、 Cr203、 A1203和适量的其它助剂 (V、 Mo、 Mn、 Mg、 Ce), 具有较高的 CO转化率和较高的 C2以上醇的选择性。
但是， 以上通过费托合成生产混合醇的碳数比较低， 一般为 d Cs, 基本上得不 到高附加值 C6以上的高碳醇， 且附加值低的甲醇比重较大， 达到 40%以上， 制约了该 技术的经济性。
中国科学院大连化学物理研究所研发了用于通过费托合成制取含有 C6以上的高 碳醇的 C2~C18混合醇产物的催化剂， 其中 US 7670985和 CN101310856公开了其催化 剂体系为活性炭负载的 Co基催化剂， 在其催化作用下 CO加氢直接合成高碳混合伯 醇， 液体产品中 C2~C18醇的选择性可以高达约 60%， 其中甲醇在醇中的分布只占约 2~4%。
但是， 在本领域中仍然需要提供一种进一步提高 FT合成制高碳醇选择性的催化 剂和其制备方法及应用。 发明内容
因此，本发明的一个目的在于提供一种提高 CO加氢生成混合伯醇中高碳伯醇 (C6 以上)选择性的催化剂和制备方法及其应用， 所述的催化剂可以调控 CO加氢产物中烃 和醇的碳链， 从而提高 c6-c18高碳混合伯醇的选择性， 进一步提高 CO加氢合成高碳 混合伯醇技术的经济性。
本发明的发明人经过深入细致的研究， 在活性炭负载 Co基 (合成醇的主要活性相 为金属态 Co和类贵金属 Co2C， 金属 Co活性中心具有解离 CO以及增长碳链的催化 作用， Co2C活性位具有较强的 CO非解离吸附活化以及 CO线性插入的性能)催化剂的 研究基础上，通过添加 Al、 B或 Ga等助剂调变催化剂性能，从而提高了长碳链 (C6-C18) 高碳伯醇的选择性， 进一步提高了 CO加氢合成高碳伯醇技术的经济性。
为实现上述目的， 本发明提供以下内容。
在本发明的一个方面， 提供一种用于提高 CO加氢生成混合伯醇中高碳伯醇选择 性的催化剂， 所述催化剂包括活性组分、 助剂和载体， 其中， 所述活性组分为金属 Co 及 Co2C的混合相，所述助剂为 Al、 B或 Ga中的一种或多种，并且所述载体为活性炭， 其中所述高碳伯醇是指碳数为 6以上的伯醇。
在本发明的一个优选的实施方案中， 所述载体为杏壳活性炭或椰壳活性炭。
在本发明的另一个优选的实施方案中， 所述活性炭的比表面积为 200 2000 m2/g， 平均孔径为 1~10 nm， 并且孔容为 0.1 2 mL/g。
在本发明的另一个优选的实施方案中，所述活性组分重量含量以 Co计为催化剂重 量的 1~30%。
在本发明的另一个优选的实施方案中， 所述助剂重量含量为催化剂重量的
0.01~5%。
在本发明的另一个更优选的实施方案中， 所述催化剂由活性组分、 助剂和载体组 成。
在本发明的另一个方面， 提供一种制备如上所述的催化剂的方法， 所述方法包括 以下步骤： （1) 活性炭经过去离子水煮沸洗涤处理； （2) 采用湿式浸渍方法将主活性组 分和助剂的可溶性盐或酸的水溶液浸渍在活性炭载体上，在室温下阴干；在 323 353 K 温度下空气气氛中烘干 8~24小时， 制得催化剂可溶性盐前驱物； （3) 所述前驱物在氮 气或氩气惰性气氛下 373 393 K干燥 2~10小时，在氮气或氩气惰性气氛下 473 773 K 焙烧 4~20小时， 制备得到催化剂氧化物前驱物； 以及 (4) 上述催化剂氧化物前驱物还 原活化成主活性组分为金属态的催化剂前驱体。
在根据本发明的一个优选的实施方案的方法中， 所述载体为杏壳活性炭或椰壳活 性炭；所述活性炭的比表面积为 200 2000 m2/g，平均孔径为 1~10 nm，并且孔容为 0.1~2 mL/g; 所述活性组分重量含量以 Co计为催化剂重量的 1~30%； 或者所述助剂重量含 量为催化剂重量的 0.01~5%。
在本发明的一个更优选的实施方案中，所述方法还包括以下步骤： (5) 主活性组分 为金属态的催化剂前驱体经 H2/CO混合气进行预处理， 制备得到所述催化剂， 其中 H2/CO摩尔比为 0.5~4.0： 1。 在本发明的另一个优选的实施方案中， 所述催化剂用于固定床反应或用于浆态床 反应。 在本发明的另一个更优选的实施方案中， 用于固定床反应的催化剂采用原位还 原方式进行。 在本发明的另一个更优选的实施方案中， 用于浆态床反应的催化剂采用 流化床还原进行， 还原后通过气体吹扫转移至浆态床反应器。
在本发明的另一个优选的实施方案中， 还原所用的还原气体为含氢混合气， 氢含 量为 10 100 %， 含氢混合气中氢气以外的其他气体为氮气或氩气， 并且还原所用的温 度为 473 873 K, 压力为 0.1~1.0 MPa, 空速为 300 2000 h"1, 时间为 2~48小时。 在本 发明的另一个更优选的实施方案中， 所述预处理为原位预处理， 并且所述预处理在 H2/CO混合气空速为 100 10000 h"1, 压力为 0.1~10.0 MPa的条件下进行 1~24小时， 其中 H2/CO摩尔比为 0.5-4.0： 1。
在本发明的再一个方面， 提供一种用于提高 CO加氢生成混合伯醇中高碳伯醇选 择性的方法， 所述方法包括在如上所述的催化剂存在下， CO由 H2加氢生成 d-d^ 合伯醇， 其中所述高碳伯醇是指碳数为 6以上的伯醇。
在本发明的一个优选的实施方案中， 所述方法在如下条件下进行： 反应温度 473-500 K 反应压力 0.5~8.0 MPa、 空速 500~3000 h-1， H2/CO摩尔比为 0.5~4.0： 1。
在本发明的另一个优选的实施方案中， H2/CO 混合气连续进料， 得到反应尾气、 气相产物和液相产物， 其中 H2/CO摩尔比为 0.5 4.0： 1。
在本发明的另一个优选的实施方案中， 所述方法采用固定床进行， 其中反应尾气 和气相产物持续出料， 并且用冷阱收集液相产物。
在本发明的另一个优选的实施方案中， 所述方法采用浆态床进行， 其中反应尾气 和气相产物持续出料， 用冷阱收集液相产物， 并且液相产物经过滤器过滤催化剂后连 续出料。
采用本发明的催化剂或本发明的制备方法所制备的催化剂或采用本发明的用于提 高 CO加氢生成混合伯醇中高碳伯醇选择性的方法， CO加氢生成的醇中甲醇分布为 2-4%, C6-C18直链混合伯醇分布为 56%以上。 该催化剂可以用于 CO加氢直接合成 C2-C18直链混合伯醇联产石脑油和柴油， 具有较高的 CO转化率和合成的 c2-c18直链 混合伯醇的选择性， 尤其是 c6-c18直链混合伯醇的选择性。
本发明可以提供一种提高 CO加氢生成混合伯醇中高碳伯醇 (C6及其以上)选择性 的催化剂和制备方法， 其催化剂可以由主活性组分， 助剂和载体组成。 主活性组分可 以为金属态 Co和类贵金属 Co2C， 金属 Co活性中心具有解离 CO以及增长碳链的催 化作用， Co2C活性位具有较强的 CO非解离吸附活化以及 CO线性插入的性能， 助剂 可以为 Al、 B或 Ga中的一种或几种助剂。 活性炭载体的比表面积可以为 200 2000 m2/g， 平均孔径可以为 l~10 nm， 孔容可以为 0.1 2 mL/g。
基于催化剂的重量， 活性组分重量含量可以为 1~30 % (以 Co计；)； 助剂重量含量 可以为 0.01-5 %。
本文中的高碳伯醇是指碳原子数为 6以上的伯醇， 优选碳原子数为 6至 18的伯 醇。
可以采用浸渍法将催化剂组分负载到活性炭载体上。所述载体可以为杏壳活性炭 或椰壳活性炭。 催化剂可以经烘干、 焙烧后， 含 H2气氛中还原活化以及经 H2/CO气 进行预处理， 其中 H2/CO摩尔比为 0.5-4.0： 1。
活性炭可以经过去离子水煮沸洗涤处理， 然后进行浸渍负载催化剂组分， 制备得 到催化剂可溶性酸盐前驱物。
催化剂前驱物可以首先在 323 353 K空气气氛中干燥 8~24小时， 随后在 373 393 K惰性气体气氛中干燥 2~10小时。 催化剂可以在 473 773 K氩气或氮气气氛中焙烧 4~20小时， 制备得到催化剂氧化物前驱物。
催化剂氧化物前驱物可以进行还原活化， 使至少一部分钴元素被还原为金属钴， 优选至少 10重量％， 更优选至少 50重量％， 还更优选至少 80重量％， 并且最优选至 少 95重量％的钴元素被还原为金属钴。在一个实施方案中， 基本上所有的钴元素被还 原为金属钴。还原条件可以为： 还原气体为含氢混合气，氢含量按摩尔计为 10~100%， 含氢混合气中氢气以外的其他气体为氮气、 氩气或氦气， 温度可以为 473 873 K， 压 力可以为 0.1 1 MPa， 空速可以为 300 2000 h—1 , 时间可以为 2~48小时。 制备得到主 活性组分为金属态的催化剂。
催化剂可以在使用前， 进行 H2/CO预处理， 其中 H2/CO摩尔比为 0.5 4.0： 1。 在 固定床和浆态床中反应的催化剂可以采用原位预处理方式， 预处理温度可以为
453-553 K, H2/CO混合气空速可以为 100 10000 Ιι·1, 压力可以为 0.1 10.0 MPa的条 件下预处理 1~24小时， 由此可以制备得到高碳醇合成催化剂。
在该催化剂的作用下， CO加氢产物中 C6-C18直链混合伯醇的选择性可以较高。 根据本发明， 提供所述用于提高 CO加氢生成混合伯醇中高碳伯醇 (C6及其以上) 选择性的催化剂的制备方法， 其中活性组分为金属 Co， 浸渍水溶液的 Co可溶性盐可 以为硝酸钴、 草酸钴和柠檬酸钴中的一种以上， 优选为硝酸钴， 其中基于催化剂的重 量，活性组分以钴计的重量含量可以为 1~30重量％，优选钴元素的重量含量为 5~25 %。 助剂组分可以是 Al、 B或 Ga中的一种或几种。 基于催化剂的重量， 助剂组分重 量含量可以为 0.01 5重量％，其中以 A1为助剂时，原料可以为硝酸铝 (Α1(Ν03)3·9Η20)。 以 Β为助剂时， 原料可以为硼酸。 以 Ga为助剂时， 原料可以为硝酸镓 (Ga(N03)3)。
催化剂载体可以为活性炭， 其中活性炭可以是杏核炭或椰壳炭， 活性炭载体的比 表面积可以为 200 2000 m2/g，平均孔径可以为 1~10 nm，并且孔容可以为 0.1~2 mL/g。 优选的活性炭比表面积可以为 500 1500 m2/g， 平均孔径可以为 3~8 nm， 并且孔容可 以为 0.5 1 mL/g。 可以采用湿式浸渍方法将催化剂组分负载到载体上， 其中可以采用 过量浸渍法， 也可采用等体积浸渍法， 优选的方法为等体积浸渍法； 可以采用常规浸 渍方法， 也可以采用真空浸渍方法， 优选的方法为常规浸渍方法。 用于浸渍液中所含 有的组分可以包括催化剂活性组分和助剂组分， 其中可以采用共浸或分浸， 优选的方 法为共浸法。
该催化剂可以应用于 CO加氢可提高产物中的 C6-C18直链混合伯醇选择性。 制备 催化剂的具体方法的实例如下：
以活性炭为载体， 活性炭经过去离子水煮沸洗涤处理，将 Co以及所有助剂的可溶 性盐或酸的水溶液等体积浸渍在活性炭载体上， 浸渍时可以先浸催化剂的活性组分后 浸催化剂助剂组分， 或先浸催化剂助剂组分后浸催化剂活性组分， 也可以采用共浸的 方法。 浸渍后样品在室温下阴干， 在 323 353 K温度下空气气氛中烘 8~24小时制得 催化剂可溶性盐前驱体。 该前驱物在 373 393 K氩气或氮气中干燥 2~10小时， 随后 在 473 773 K氩气或氮气气氛中焙烧 4~20小时， 获得催化剂氧化物前驱物。 最后在 含氢混合气中 (氢含量为 10~100%， 含氢混合气中氢气以外的其他气体为氮气或氩 气) 473 873 K还原活化 2~48小时， 还原压力为 0.1 1 MPa， 空速为 300 2000 h , 获 得催化剂主催化组分为金属态的前驱体。 催化剂在使用前， 进行 H2/CO预处理， 其中 H2/CO摩尔比为 0.5 4.0 : 1。 在固定床和浆态床中反应的催化剂采用原位预处理方式， 预处理温度为 453-553 K, H2/CO混合气空速为 100-10000 h"1 , 压力为 0.1-10.0 MPa 的条件下预处理 1~24小时。 制备得到高碳醇合成催化剂， 所述催化剂包括活性组分、 助剂和载体， 其中， 所述活性组分为金属 Co及 Co2C的混合相， 所述助剂为 Al、 B或 Ga中的一种或多种， 并且所述载体为活性炭。 由于预处理所用的气体为 H2/CO混合 气并且催化剂的载体为活性炭， 预处理过程中金属钴会有一部分被碳化成 Co2C。碳化 程度取决于碳化的条件， 如温度、 压力、 时间、 活性炭载体以及 H2/CO混合气的比率 等。在金属 Co及 Co2C的混合相中， Co与 Co2C的比率是变化的， 因此不需要进行限 定。 另外， 由于载体为活性炭， 元素分析也不能用于确定碳化钴的含量。 但是， 通常， 取决于碳化的条件， 如温度、 压力、 时间、 活性炭载体以及 H2/CO混合气的比率等， 在金属 Co及 Co2C的混合相中， Co/Co2C摩尔比为约 0.5-99.5: 1，更优选为约 1-99: 1， 并且最优选为约 5~95： 1。
金属 Co活性中心具有解离 CO以及增长碳链的催化作用， Co2C活性位具有较强 的 CO非解离吸附活化以及 CO线性插入的性能。
本发明的反应可以采用浆态床反应器， 也可以采用固定床反应器， 其中优选采用 浆态床反应器。 反应温度： 473 500 K、 反应压力： 0.5 8.0 MPa、 空速 500 3000！^1。 具体实施方式
下面通过具体实施例对本发明做进一步说明。 除非另有具体说明， 本申请中所用 的 "百分比"和 "份"都基于重量。
在下面的实施例中， 所有的原料如下：
椰壳活性炭： 唐山联合炭业有限公司
杏壳活性炭： 唐山联合炭业有限公司
Co(N03)2-6H20: 中国医药（集团）上海化学试齐忪司， 分析纯
CoC204-2H20: 中国医药（集团）上海化学试剂公司， 分析纯
二水柠檬酸钴： 中国医药（集团）上海化学试齐忪司， 分析纯
Α1(Ν03)3·9Η20: 中国医药（集团）上海化学试剂公司， 分析纯
Ga(N03)3 : 中国医药（集团）上海化学试齐忪司， 分析纯
H3B03: 中国医药（集团）上海化学试剂公司， 分析纯
Zr(N03)2-5H20: 中国医药（集团）上海化学试剂公司， 分析纯
S102: 青岛海洋化工厂， 纯度 99.5 %
¾： 大连大特气体有限公司， 纯度 ^99.999体积％
Ar: 大连大特气体有限公司， 纯度 ^99.999体积％
H2/CO混合气（含有 66.6 体积 ％H2、 33.4 体积 ％CO): 大连大特气体有限公司， 纯度 ^99.999体积％ 实施例 1 椰壳活性炭的比表面积和孔径分布测定在 QUANTACHROME公司的 AS-1型吸附 仪上进行。 样品先在 573 K下脱气处理 3 h， 在液氮温度下进行氮吸附测试， N2分子 横截面积取 0.162 nm2。 用 BET法计算样品的比表面积， 用 BJH法计算孔分布。 所测 得的椰壳活性炭比表面积为 1012 m2/g， 平均孔径为 3.5 nm， 孔容为 0.42 mL/g。
取 1000克椰壳活性炭载体， 采用去离子水煮沸洗涤方法进行处理 3次， 具体方法 为： 取 1000克椰壳活性炭， 加入 5000克去离子水， 一起煮沸 0.5小时， 随后将活性 炭与沸水分离， 再次加入去离子水进行下一次煮沸洗涤。 洗好的活性炭在 393 K温度 下干燥 8小时， 备用， 标记为 AC1。 采用以上方法测定 AC1活性炭比表面积为 1053 m2/g， 平均孔径为 3.7 nm， 孔容为 0.46 mL/g。
催化剂 A的组成为 15Co0.1Al/ACl。 以 20~40目处理过的活性炭为载体， 催化剂 按照下述步骤制备。 称取 10克处理好活性炭。 称取 0.163克 Α1(Ν03)3·9Η20和 8.7克 Co(N03)2-6H20, 将它们溶解于 10 mL去离子水中制成溶液。 用常规浸渍法将制得的 溶液担载在活性炭上， 即在室温下， 将活性炭浸泡在制得的溶液中， 搅拌 1~2分钟， 使得溶液均匀浸渍在活性炭载体上。 室温下阴干， 时间以催化剂达到干爽状态耗费时 间为准， 随后在空气气氛 333 K温度下干燥 24小时， 随后在氩气气氛中 393 K温度下 烘干 4小时； 最后在氩气气氛中 623 K温度下焙烧 8小时， 得到 Co重量含量为 15%、 A1重量含量为 0.1%的催化剂 A氧化物前驱物。催化剂 A氧化物前驱物的 BET测定同 上， 其比表面积为 778 m2/g， 平均孔径为 3.8 nm， 孔容为 0.35 mL/g。 采用 PHILIPS公 司的 Magix型 X-射线荧光 (XRF)仪测定催化剂 A氧化物前驱物的活性组分和助剂含量， 实际测量 Co含量为 14.83重量％， A1含量为 0.12重量％。 实施例 2
催化剂 B组成为 15Co0.5Al/ACl。 以实施例 1中处理好的椰壳活性炭为载体， 催 化剂按照下述步骤制备。 称取 10 克处理好活性炭， 置于抽滤瓶中。 称取 0.822 克 Α1(Ν03)3·9Η20和 8.7克 Ο)(Ν03;)2·6Η20， 将它们溶解于 10mL去离子水中制成溶液， 并置于分液漏斗中。 用中间开孔的橡皮塞将分液漏斗与锥形抽滤瓶密封连接。 用真空 浸渍法将制得的溶液浸渍在活性炭上， 即在室温下， 关闭分液漏斗活塞， 先将活性炭 在真空条件下 （O.OlMPa) 处理 20分钟， 然后打开活塞将分液漏斗中的溶液流入抽滤 瓶中的活性炭， 使之浸泡在溶液中。 将制得的样品在室温下阴干， 阴干时间以催化剂 达到干爽状态耗费时间为准， 随后在空气气氛 353 K温度下干燥 24小时， 随后在氩气 气氛中 383 K温度下烘干 8小时； 最后在氩气气氛中 603 Κ温度下焙烧 8小时， 得到 Co重量含量为 15%、 A1重量含量为 0.5%的催化剂 B氧化物前驱物。催化剂 B氧化物 前驱物的 BET测定同上， 其比表面积为 810 m2/g， 平均孔径为 3.8 nm， 孔容为 0.345 mL/g。 催化剂 B氧化物前驱物的活性组分和助剂含量测量方法同上， 实际测量 Co含 量为 14.75重量％， A1含量为 0.54重量％。 采用 XRD检测反应后催化剂中 Co的晶相， XRD测试在 PANalytical公司 X'Pert PRO型 X射线衍射仪上进行。 Cu ι辐射源，管压 40 KV, 管流 40 mA， 扫描范围为 2θ=5°-75°， 扫描速度为 0.2°/s。 实施例 3
催化剂 C组成为 15ColAl/ACl。 以实施例 1中处理好的椰壳活性炭为载体， 催化 剂按照下述步骤制备。 称取 10克处理好活性炭， 称取 1.65克 Α1(Ν03)3·9Η20和 5.53 克 CoC2(V2H20于 13 mL去离子水中制成溶液，采用上述常规浸渍法将制得的溶液浸 渍在活性炭上。 室温下阴干， 阴干时间以催化剂达到干爽状态的时间为准， 随后在空 气气氛 343 K温度下干燥 24小时， 随后在氩气气氛中 383 K温度下烘干 4小时； 最后 在氩气气氛中 623 K温度下焙烧 4小时，得到 Co重量含量为 15%、 A1重量含量为 1% 的催化剂 C氧化物前驱物。 催化剂 C氧化物前驱物的 BET测定同上， 其比表面积为 804 m2/g， 平均孔径为 3.9 nm， 孔容为 0.33 mL/g。 催化剂 C氧化物前驱物的活性组分 和助剂含量方法测量同上， 实际测量 Co含量为 14.62重量％， A1含量为 1.13重量％。 实施例 4
催化剂 D组成为 15Co2Al/ACl。 以实施例 1中处理好的椰壳活性炭为载体， 催化 剂按照下述步骤制备。 称取 10克处理好活性炭， 称取 3.34克 Α1(Ν03)3·9Η20和 5.67 克二水柠檬酸钴于 10 mL去离子水中制成溶液， 采用上述常规浸渍法将制得的溶液浸 渍在活性炭上。 室温下阴干， 阴干时间以催化剂达到干爽状态耗费时间为准， 随后在 空气气氛 333 K温度下干燥 24小时， 随后在氩气气氛中 393 K温度下烘干 2小时； 最 后在氩气气氛中 623 K温度下焙烧 6小时， 得到 Co重量含量为 15%、 A1重量含量为 2%的催化剂 D氧化物前驱物。催化剂的 BET测定方法同上， 其比表面积为 804 m2/g， 平均孔径为 3.9 nm， 孔容为 0.32 mL/g。 催化剂 D氧化物前驱物的活性组分和助剂含 量测量方法同上， 实际测量 Co含量为 14.55重量％， A1含量为 2.31重量％。 实施例 5
催化剂 E组成为 30Co4Al/AC2。 催化剂按照下述步骤制备。
杏壳活性炭的比表面积和孔径分布测定在 QUANTACHROME公司的 AS-1型吸附 仪上进行。 样品先在 573 K下脱气处理 3 h， 在液氮温度下进行氮吸附测试， N2分子 横截面积取 0.162 nm2。 用 BET法计算样品的比表面积， 用 BJH法计算孔分布用 BET 法计算样品的比表面积， 用 BJH法计算孔分布。 杏壳活性炭比表面积为 646 m2/g， 平 均孔径为 3.7 nm， 孔容为 0.60 mL/g。
1000克杏壳活性炭载体采用去离子水煮沸洗涤方法进行处理 3次， 具体方法为： 取 1000克杏壳活性炭， 加入 5000克去离子水， 一起煮沸 0.5小时， 随后将活性炭与 沸水分离， 再次加入去离子水进行下一次煮沸洗涤。 洗好的活性炭在 393 K温度下干 燥 8小时， 393 K温度下干燥 8小时， 备用， 标记为 AC2。 采用以上方法测定 AC2活 性炭的比表面积和孔分布， AC2杏壳活性炭比表面积为 673 m2/g，平均孔径为 3.8 nm， 孔容为 0.64 mL/g。
以 20 40目 AC2活性炭为载体， 催化剂制备步骤如下。 称取 10克 AC2活性炭， 称取 8.41克 Α1(Ν03)3·9Η20和 22.41克 Co(N03;> 6H20于 20mL去离子水中制成溶液， 采用上述常规浸渍法将制得的溶液浸渍在活性炭上， 即在室温下， 将活性炭浸泡在制 得的溶液中， 搅拌 1~2分钟， 使得溶液均匀浸渍在活性炭载体上。 室温下阴干， 时间 以催化剂达到干爽状态耗费时间为准， 随后在空气气氛 353 K温度下干燥 12小时， 随 后在氩气气氛中 393 K温度下烘干 8小时； 最后在氩气气氛中 623 K温度下焙烧 4小 时， 得到 Co重量含量为 30%、 A1重量含量为 4%的催化剂 E氧化物前驱物。催化剂 E 氧化物前驱物的 BET测定同上， 其比表面积为 561 m2/g， 平均孔径为 3.8 nm， 孔容为 0.51 mL/g。 催化剂 E氧化物前驱物的活性组分和助剂含量测量方法同上， 实际测量 Co含量为 29.21重量％， A1含量为 4.2重量％。 实施例 6
催化剂 F组成为 15Co0.5B/ACl。 以实施例 1中处理好的椰壳活性炭为载体， 催化 剂按照下述步骤制备。 称取 10 克处理好活性炭， 称取 0.328 克 H3B03和 8.7 克 Co(N03)2-6H20于 10 mL去离子水中， 加热至 333 K制成溶液， 采用上述常规浸渍法 将制得的溶液浸渍在活性炭上。 室温下阴干， 阴干时间以催化剂达到干爽状态耗费时 间为准， 随后在空气气氛 333 K温度下干燥 24小时， 随后在氩气气氛中 393 K温度下 烘干 6小时； 最后在氩气气氛中 623 K温度下焙烧 4小时， 得到 Co重量含量为 15%、 B重量含量为 0.5%的催化剂 F氧化物前驱物。 催化剂 F氧化物前驱物的 BET测定方 法同上， 其比表面积为 812m2/g， 平均孔径为 3.8 nm， 孔容为 0.34 mL/g。 催化剂 F氧 化物前驱物的活性组分和助剂含量测量方法同实施例 1， 实际测量 Co含量为 14.8重 量％， B含量为 0.42重量％。 催化剂 F氧化物前驱物的活性组分和助剂含量测量方法 同上， 实际测量 Co含量为 14.86重量％， B含量为 0.46重量％。 实施例 7
催化剂 G组成为 1CO0.01B/AC1。 以实施例 1中处理好的椰壳活性炭为载体， 催化 剂按照下述步骤制备。 称取 10 克处理好活性炭， 称取 0.007 克 H3B03和 0.498 克 Ο)(Ν03)2·6Η20于 10mL去离子水中， 加热至 333 K制成溶液， 采用上述常规浸渍法 将制得的溶液浸渍在活性炭上。 室温下阴干， 阴干时间以催化剂达到干爽状态耗费时 间为准， 随后在空气气氛 333 K温度下干燥 24小时， 随后在氩气气氛中 393 K温度下 烘干 4小时； 最后在氩气气氛中 623 K温度下焙烧 6小时， 得到 Co重量含量为 1%、 B重量含量为 0.01%的催化剂 G氧化物前驱物。 催化剂 G氧化物前驱物的 BET测定 方法同上， 其比表面积为 853m2/g， 平均孔径为 3.8 nm， 孔容为 0.37 mL/g。 催化剂 G 氧化物前驱物的活性组分和助剂含量测量方法同上， 实际测量 Co含量为 0.87重量％， B含量为 0.01重量％。 实施例 8
催化剂 H组成为 15Co0.5Ga/ACl。 以实施例 1中处理好的椰壳活性炭为载体， 催 化剂按照下述步骤制备。 称取 10克处理好活性炭， 称取 0.216克 Ga(N03)3和 8.7克 Ο)(Ν03)2·6Η20于 10 mL去离子水中制成溶液， 采用上述常规浸渍法将制得的溶液浸 渍在活性炭上。 室温下阴干， 阴干时间以催化剂达到干爽状态耗费时间为准， 阴干时 间以催化剂达到干爽状态的实际时间为准，随后在空气气氛 333 K温度下干燥 24小时， 随后在氩气气氛中 393 K温度下烘干 4小时； 最后在氩气气氛中 623 K温度下焙烧 6 小时， 得到 Co重量含量为 15%、 Ga重量含量为 0.5%的催化剂 H氧化物前驱物。 催 化剂 H氧化物前驱物的 BET测定方法同上，其比表面积为 785m2/g，平均孔径为 3.8 nm， 孔容为 0.35mL/g。催化剂 H氧化物前驱物的活性组分和助剂含量测量方法同上， 实际 测量 Co含量为 14.83重量％， Ga含量为 0.51重量％。 采用 XRD测定反应后催化剂中 Co的晶相， XRD测试在 PANalytical公司 X'Pert PRO型 X射线行射仪 行。 Cu ι辐射源， 管压 40 KV, 管流 40 mA， 扫描范围为 2θ=5°-75°， 扫描速度为 0.2°/s。 实施例 9
催化剂 I组成为 15ColA10.5B/ACl。 以实施例 1中处理好的椰壳活性炭为载体， 催 化剂按照下述步骤制备。
称取 10克处理好活性炭， 称取 1.66克 AlCN03;) 9H20、 0.33克 H3B03和 8.7克 Ο)(Ν03)2·6Η20于 10mL去离子水中， 加热至 333 K制成溶液， 采用上述常规浸渍法 将制得的溶液浸渍在活性炭上。 室温下阴干， 阴干时间以催化剂达到干爽状态耗费时 间为准， 随后在空气气氛 343 K温度下干燥 24小时， 随后在氩气气氛中 393 K温度下 烘干 2小时； 最后在氩气气氛中 673 K温度下焙烧 2小时， 得到 Co重量含量为 15%、 A1重量含量为 1%、 B重量含量为 0.5%的催化剂 I氧化物前驱物。 催化剂 I氧化物前 驱物的 BET测定方法同上， 其比表面积为 812 m2/g， 平均孔径为 3.8 nm， 孔容为 0.34 mL/g。 催化剂 I氧化物前驱物的活性组分和助剂含量测量方法同上， 实际测量 Co含 量为 14.76重量％， A1含量为 1.07重量％。 B含量为 0.47重量％。 采用 XRD测定反应 后催化剂中 Co的晶相， XRD测试在 PANalytical公司 X'Pert PRO型 X射线衍射仪 行。 Cu koa辐射源， 管压 40 KV, 管流 40 mA， 扫描范围为 2θ=5°-75°， 扫描速度为 0.2°/s。 对比例 1
催化剂 J组成为 15Co2Zr/ACl。 以实施例 1中处理好的椰壳活性炭为载体，催化剂 按照下述步骤制备。
称取 10克处理好活性炭， 称取 8.7克 Co(N03;) 6H20和 1.13克 Ζι<Ν03;)2·5Η20于 lOmL 去离子水中制成溶液， 采用上述常规浸渍法将制得的溶液浸渍在活性炭上。 室 温下阴干， 阴干时间以催化剂达到干爽状态耗费时间为准， 随后在空气气氛 333 K温 度下干燥 24小时， 随后在氩气气氛中 393 K温度下烘干 4小时； 最后在氩气气氛中 623 K温度下焙烧 2小时， 得到 Co重量含量为 15%、 Zr重量含量为 2%的催化剂 J氧 化物前驱物。 催化剂 J氧化物前驱物的 BET测定方法同上， 其比表面积为 802m2/g， 平均孔径为 3.7 nm， 孔容为 0.35 mL/g。催化剂 J氧化物前驱物的活性组分和助剂含量 测量方法同上， 实际测量 Co含量为 14.73重量％， Zr含量为 1.95重量％。 采用 XRD 测定反应后催化剂中 Co的晶相， XRD测试在 PANalytical公司 X'Pert PRO型 X射线衍射仪上 进行。 Cukoa辐射源， 管压 40KV， 管流 40 mA， 扫描范围为 2θ=5°-75°， 扫描速度为 0.2°/s。 对比例 2
催化剂 K组成为 15Co/ACl。 以实施例 1中处理好的椰壳活性炭为载体， 催化剂按 照下述步骤制备。
称取 10克处理好活性炭， 称取 8.7克 Ο)(Ν03)2·6Η20于 10mL去离子水中制成溶 液， 采用上述常规浸渍法将制得的溶液浸渍在活性炭上。 室温下阴干， 阴干时间以催 化剂达到干爽状态耗费时间为准， 随后在空气气氛 333 K温度下干燥 24小时， 随后在 氩气气氛中 393 K温度下烘干 4小时； 最后在氩气气氛中 623 K温度下焙烧 2小时， 得到 Co重量含量为 15%的催化剂 K氧化物前驱物。 催化剂 K氧化物前驱物的 BET 测定方法同上， 其比表面积为 810m2/g， 平均孔径为 3.8 nm， 孔容为 0.37 mL/g。 催化 剂 K氧化物前驱物的活性组分和助剂含量测量方法同上， 实际测量 Co含量为 14.82 重量％。采用 XRD测定反应后催化剂中 Co的晶相， XRD测试在 PANalytical公司 X'Pert PRO 型 X射线衍射仪上进行。 Cu koa辐射源， 管压 40 KV, 管流 40 mA， 扫描范围为 2θ=5。-75。， 扫描速度为 0.2°/s。 对比例 3
催化剂 L组成为 15Co/Si02。 催化剂按照下述步骤制备。
100克 Si02采用去离子水煮沸洗涤方法进行处理 3次， 具体方法： 取 100克 Si02， 加入 500克去离子水， 一起煮沸 0.5小时， 随后将活性炭与沸水分离， 再次加入去离 子水进行下一次处理， 洗好的 Si02在 393 K温度下干燥 8小时， 备用。 Si02的比表面 积和孔分布测定在 QUANTACHROME公司的 AS-1型吸附仪上进行。样品先在 573 K 下脱气处理 3 h，在液氮温度下进行氮吸附测试， N2分子横截面积取 0.162 nm2。用 BET 法计算样品的比表面积， 用 BJH法计算孔分布。 经处理的 Si02比表面积为 276 m2/g， 平均孔径为 10.8 nm,孔容为 0.85 mL/g。采用 XRD测定反应后催化剂中 Co的晶相， XRD 测试在 PANalytical公司 X'Pert PRO型 X射线衍射仪上进行。 Cu i ^ M, 管压 40 KV， 管 流 40 mA， 扫描范围为 2θ=5°-75°， 扫描速度为 0.2%。 称取 10克处理好 Si02，称取 8.7克 Ο)(Ν03)2·6Η20于 10mL去离子水中制成溶液， 采用上述常规浸渍法将制得的溶液浸渍在活性炭上。 室温下阴干， 阴干时间以催化剂 达到干爽状态耗费时间为准， 随后在空气气氛 393 K温度下烘干 8小时； 最后在空气 气氛中 623 K温度下焙烧 2小时，得到 Co重量含量为 15%的催化剂 L氧化物前驱物。 催化剂 L氧化物前驱物的 BET测定方法同上， 其比表面积为 247 m2/g， 平均孔径为 10.1 nm， 孔容为 0.78 mL/g。 催化剂 L氧化物前驱物的活性组分和助剂含量测量方法 同上， 实际测量 Co含量为 14.86重量％。 催化剂 A-L反应评价在固定床反应器中进行。各取催化剂 4mL装填在固定床反应 器中， 固定床反应器的直径为 9mm， 长度为 40mm。 催化剂反应前需还原活化， 还原 活化的条件为纯氢气氛， 压力为常压， 空速为 500 h—1 , 温度 703 K， 时间为 6小时。 即得主活性组分为金属态的前驱体。 活化以后催化剂床层温度降至 373Κ 以下， 切换 合成气 (含有 66.6 体积％Η2、 33.4 体积％CO， 其中催化剂 D所使用的合成气组分为： 60.0 体积％H2、 40.0 体积％CO， 并且其中催化剂 G所使用的的合成气组分为： 75.0 体积％¾、 25.0 体积％CO)， 在温度为 493 K， 反应压力为 3.0 MPa， 空速为 500 h—1连 续进料的条件下进行预处理 24小时， 即得高碳混合醇催化剂。 继续在温度为 493 K, 反应压力为 3.0 MPa， 空速为 500 h—1连续进料的条件下进行反应， 反应尾气和气相产 物持续出料， 用冷阱收集液相产物， 冷阱温度维持在 273 293 K。 反应前期 (TOS=24 小时)为预处理期及稳定期， 稳定期后收集 48小时样品进行分析并计算。 反应尾气采 用 HP-6890气相色谱仪 (Porapark QS填充柱， TCD检测器)在线分析， 液体产物包括油 相和水相产品， 采用 HP-6890气相色谱仪 (HP-5毛细管， FID检测器)离线分析油相和 水相产品， 水相产物分析以仲丁醇为内标。 根据分析结果计算 CO的转化率和产物的 选择性。 催化剂 A-L的组成和评价结果列于表 1。
分别取上述实施例 3和 9中制备所得催化剂 C和 I氧化物前驱物各 5 mL，研磨至 150目以下粉末， 分别置于流化床反应器中， 流化床反应器的直径为 20 mm， 体积为 100 mL， 通入氢气在流化状态下进行还原活化， 在温度为 703 K、 常压、 空速 800 h—1 的条件下活化 10小时。 催化剂评价在浆态床反应器中进行。 待催化剂温度降至 333 K 以后， 将所述活化后的催化剂采用吹扫的方式转移至预先装有 300 mL液体石蜡的 1 升浆态床反应器 (不锈钢高压反应釜， 体积 1升)中， 吹扫气体为 H2， 体积空速为 3000 h"1 , 吹扫时间为 2小时； 转移完成后在高压釜中通入 H2和 CO混合气 (含有 66.6 体 积％1¾、 33.4 体积％CO)进行预处理， 预处理温度为 493 K， 压力为 3.0 MPa， 空速为 500 h"1 , 合成气连续进料预处理 24小时。 预处理结束后继续在浆态床反应器中进行 CO加氢反应， 反应条件与预处理条件相同。 反应尾气和产物持续出料， 用冷阱收集 液相产物， 冷阱温度维持在 273 293 K， 液相产物经过滤器过滤催化剂后连续出料。 经 24小时预处理气和稳定期后， 每 48小时取反应样品分析。 反应尾气采用 ΗΡ-6890 气相色谱仪 (Porapark Q S填充柱， TCD检测器)在线分析， 液体产物包括油相和水相 产品，采用 HP-6890气相色谱仪 (HP-5毛细管， FID检测器)离线分析油相和水相产品， 水相产物分析以仲丁醇为内标。 根据分析结果计算 CO的转化率和产物的选择性， 评 价结果列于表 1。
由表 1可见， 实施例中采用 Al、 B或 Ga中的一种或多种助剂调变的催化剂具有 较高的的活性和合成 C2~C18高碳醇选择性， 所生成的醇中 C6~C18高碳醇分布高于 50%, 最高可达 56.4%。 专利 US 7670985和 CN101310856公开了 Zr等助剂调变的活 性炭负载催化剂合成 c2~c18醇的活性和选择性， 未给出 ^~ 8高碳醇的分布。 本申 请对比例 1 以专利 US 7670985和 CN101310856中具有代表性的 Zr助剂研制催化剂 15Co2Zr/ACl , 表 1显示， 其合成产物醇中。6~ 8醇分布为 47.3%， 低于本申请实施 例中催化剂合成产物醇中 C6~C18高碳醇的分布。本申请对比例 2未用助剂制备了活性 炭负载的 15Co/ACl。 由表可见， 其合成产物醇中 C6~C18醇选择性较低。 表 1显示， 对比例 3采用 Si02载体负载 15Co/ Si02催化剂合成 C2~C18醇的选择性极低， 且合成 产物醇为 d~C5低碳醇， 没有生成 C6~C18高碳醇。
表 1： 催化剂 (A-L)催化 CO加氢合成混合伯醇反应性能
Figure imgf000017_0001
反应条件： 温度 493 Κ; 压力 3.0MPa; 空速 500h— 时间为 48小时。 * 浆态床反应

Claims

权 利 要 求
1、 一种用于提高 CO加氢生成混合伯醇中高碳伯醇选择性的催化剂， 所述催化剂包 括活性组分、 助剂和载体， 其中， 所述活性组分为金属 Co及 Co2C的混合相， 所述助剂 为 Al、 B或 Ga中的一种或多种， 并且所述载体为活性炭， 其中所述高碳伯醇是指碳数为 6以上的伯醇。
2、 按照权利要求 1所述的催化剂， 其中， 所述载体为杏壳活性炭或椰壳活性炭， 所 述活性炭的比表面积为 200 2000 m2/g， 平均孔径为 1~10 nm， 并且孔容为 0.1 2 mL/g。
3、 按照权利要求 1或 2所述的催化剂， 其中， 所述活性组分重量含量以 Co计为催 化剂重量的 1~30 %， 并且所述助剂重量含量为催化剂重量的 0.01 5 %。
4、 一种制备按照权利要求 1至 3中任何一项所述的催化剂的方法， 所述方法包括以 下步骤：
(1) 活性炭经过去离子水煮沸洗涤处理；
(2) 采用湿式浸渍方法将主活性组分和助剂的可溶性盐或酸的水溶液浸渍在活性炭 载体上， 在室温下阴干； 在 323 353 K温度下空气气氛中烘干 8~24小时， 制得催化剂可 溶性盐前驱物； 和
(3) 所述前驱物在氮气或氩气惰性气氛下 373 393 K干燥 2~10小时， 在氮气或氩气 惰性气氛下 473 773 K焙烧 4~20小时， 制备得到催化剂氧化物前驱物。
5、 按照权利要求 4所述的制备方法， 所述方法还包括以下步骤：
(4) 将上述催化剂氧化物前驱物还原活化成主活性组分为金属态的催化剂前驱体， 还 原所用的还原气体为含氢混合气， 氢含量为 10 100 %， 含氢混合气中氢气以外的其他气 体为氮气或氩气， 并且还原所用的温度为 473 873 K， 压力为 0.1 1.0 MPa， 空速为 300-2000 h"1, 且时间为 2~48小时。
6、 按照权利要求 4所述的制备方法， 所述方法还包括以下步骤：
(5) 主活性组分为金属态的催化剂前驱体经 H2/CO混合气进行预处理，制备得到所述 催化剂， 其中 H2/CO摩尔比为 0.5~4.0： 1。
7、 按照权利要求 6所述的制备方法， 其中所述催化剂用于固定床反应， 并且用于固 定床反应的催化剂采用原位还原方式进行； 或者
所述催化剂用于浆态床反应， 并且用于浆态床反应的催化剂采用流化床还原进行，还 原后通过气体吹扫转移至浆态床反应器。
8、 按照权利要求 6所述的制备方法， 其中所述预处理为原位预处理， 并且所述预处 理在 H2/CO混合气空速为 100 10000 h"1,预处理温度为 453 553 K,压力为 0.1 10.0 MPa 的条件下进行 1~24小时， 其中 H2/CO摩尔比为 0.5~4.0： 1。
9、 一种用于提高 CO加氢生成混合伯醇中高碳伯醇选择性的方法， 所述方法包括在 权利要求 1至 3中任何一项所述的催化剂存在下， CO由 H2加氢生成 d-C18混合伯醇， 其中所述高碳伯醇是指碳数为 6以上的伯醇，
其中所述方法在如下条件下进行： 反应温度 473 500 K、 反应压力 0.5 8.0 MPa、 空 速 500 3000 IT1, H2/CO摩尔比为 0.5 4.0： 1， 并且
其中 H2和 CO混合气连续进料， 得到反应尾气、 气相产物和液相产物， 其中 H2/CO 摩尔比为 0.5-4.0： 1。
10、按照权利要求 9所述的方法， 其中所述方法采用固定床进行， 其中反应尾气和气 相产物持续出料， 并且用冷阱收集液相产物； 或
其中所述方法采用浆态床进行，其中反应尾气和气相产物持续出料，用冷阱收集液相 产物， 并且液相产物经过滤器过滤催化剂后连续出料。
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