CN114522734A - Catalyst, preparation thereof and application thereof in preparation of mixed aldol from synthesis gas - Google Patents

Catalyst, preparation thereof and application thereof in preparation of mixed aldol from synthesis gas Download PDF

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CN114522734A
CN114522734A CN202011320099.5A CN202011320099A CN114522734A CN 114522734 A CN114522734 A CN 114522734A CN 202011320099 A CN202011320099 A CN 202011320099A CN 114522734 A CN114522734 A CN 114522734A
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catalyst
component
cobalt
hours
carbon
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赵子昂
丁云杰
李怡蕙
朱何俊
卢巍
姜淼
龚磊峰
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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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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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    • C07C29/157—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 containing platinum group metals or compounds thereof
    • C07C29/158—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 containing platinum group metals or compounds thereof containing rhodium or compounds thereof
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
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    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B01J2531/82—Metals of the platinum group
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B01J2531/845—Cobalt
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Abstract

The invention relates to a catalyst, a preparation method thereof and application thereof in preparing mixed aldol from synthesis gas. The catalyst comprises two components: wherein, the first component is a supported catalyst, the carrier is one or more than two of alumina, titanium dioxide, silicon dioxide, active carbon and ordered mesoporous carbon, and the active component is one or more than two of metallic cobalt, metallic iron, cobalt carbide and iron carbide; the second component is also a supported catalyst, the carrier is one or more than two of active carbon, functionalized silicon dioxide and porous organic polymer, and the active component is one or more than two of metal cobalt, rhodium and iridium; the two components are matched for use, so that the preparation of oxygen-containing compounds such as alcohol, aldehyde and the like from synthesis gas is realized. The catalyst provided by the invention can obviously improve the selectivity of oxygen-containing compounds (alcohol and aldehyde) in reaction products. The selectivity of the oxygen-containing compound in the product is more than 60 percent, so that the preparation of high-value chemicals such as alcohol, aldehyde and the like from the synthesis gas is of great significance.

Description

Catalyst, preparation thereof and application thereof in preparation of mixed aldol from synthesis gas
Technical Field
The invention belongs to the technical field of industrial catalyst development, and particularly relates to a catalyst, preparation thereof and application thereof in preparation of mixed aldol from synthesis gas. More specifically, the catalyst comprises two components, wherein the first component is one or more than two of active carbon or ordered mesoporous carbon supported metallic cobalt, metallic iron, cobalt carbide and iron carbide, and the second component is one or more than two of functionalized silicon dioxide or porous organic polymer supported metallic cobalt, rhodium and iridium. By adopting the catalyst provided by the invention, two different components of the catalyst are coupled, so that the one-step preparation of oxygen-containing compounds such as mixed alcohol, aldehyde and the like from synthesis gas can be realized, the process flow is simplified, and the process has higher economical efficiency. The invention provides a new way for clean and efficient utilization of non-petroleum-based carbonaceous resources such as coal and the like.
Background
The petroleum resources in China are relatively deficient, the external dependence degree is over 70 percent at present, the carbon resources such as coal, biomass and the like are relatively rich, and the problems of petroleum resource shortage, environmental pollution and the like in China can be relieved to a certain extent by cleanly and efficiently utilizing the carbon resources such as coal and the like. Various carbonaceous resources such as coal, natural gas and biomass can be converted into Synthesis gas (a mixed gas of carbon monoxide and hydrogen with adjustable proportion) by using different technical means, and a Fischer-Tropsch Synthesis (FTS) process for producing clean liquid fuel by taking the Synthesis gas as a raw material and adopting an iron-based or cobalt-based catalyst is one of important platform technologies in the field of Synthesis gas conversion. The traditional Fischer-Tropsch synthesis reaction products are mainly straight-chain alkanes, the content of organic oxygen-containing compounds is relatively low, and oxygen elements in synthesis gas are generally converted into water or carbon dioxide, so that the formed industrial wastewater and waste gas have large amount. With the rapid development of the field of synthesis gas conversion, a new reaction process for producing oxygen-containing compounds such as alcohol and aldehyde from synthesis gas can realize the efficient utilization of oxygen element in synthesis gas, and has recently attracted extensive attention of researchers and gradually become the research focus in the future carbon-chemical field.
Olefins are an important commodity chemical, and the annual production and consumption is enormous. Hydroformylation (also known as oxo synthesis) of olefins coupled with synthesis gas over a catalyst to produce linear/branched aldehydes having one more carbon atom is the most widely used method for producing aldehyde compounds. The reaction raw materials are easy to obtain, the requirements of atom economy are met, and the product aldehyde can be further converted into chemical raw materials such as alcohol and acid, and further synthesized into high-value fine chemicals such as medicines, spices and the like. The butanol-octanol process is one of the largest applications of hydroformylation reaction scale, and refers to the reaction of propionaldehyde and synthesis gas under the action of a catalyst to generate butyraldehyde, the butyraldehyde can be directly hydrogenated to obtain butanol, the butyraldehyde can be subjected to alkali-catalyzed condensation and dehydration to obtain octenal, and the octanol can be obtained through hydrogenation.
Higher alcohols (C)2+OH) refers to a linear aliphatic primary alcohol having two or more carbon atoms, and has wide applications in various fields of the national civilian population. Lower mixed alcohol (C)2～C5OH) is usually used as a solvent, and methyl tert-butyl ether (MTBE) can be replaced as a gasoline additive with excellent quality. The high carbon mixed alcohol is a synthetic plasticizer (C)6～C9OH), detergent (C)10～C18OH), surfactants and other important raw materials of various fine chemicals, and has wide application in the fields of food, medicine, textile, paper making and the like. Currently, there are two major industrial methods for producing higher fatty alcohols, the Ziegler process (Ziegler process) and the OXO process (OXO process). The Ziegler method takes ethylene as a raw material and triethyl aluminum as a catalyst to realize carbon chain growth, and then processes such as oxidation, hydrolysis, separation and the like are carried out to obtain C6～C16Linear primary alcohols of even number of carbon atoms in the range. The Ziegler method uses aluminium ethyl trioxide as a catalyst, and is very easy to explode. More importantly, the method has the advantages of complex technology, great development difficulty, long process flow, great catalyst consumption and poor safety. The oxo process is also called as hydroformylation process, and is a process in which olefins and synthesis gas are subjected to hydroformylation reaction to produce aldehydes, and the aldehydes are hydrogenated to produce corresponding alcohols under the action of a catalyst. According to estimation, the market price of the higher fatty alcohol is more than 1 ten thousand yuan/ton, the market demand exceeds 1600 ten thousand tons/year, and the market demand is increased year by year. Therefore, the development of a new technology for producing the high-carbon fatty alcohol/aldehyde, which has the advantages of simple process, mild reaction conditions, easily obtained raw materials and wide sources, has great theoretical and practical significance.
In the process of preparing liquid fuel by using synthesis gas through a Fischer-Tropsch synthesis path, a large amount of olefins are usually generated, and the olefins are usually hydrogenated and saturated to generate alkane, but under the current large environment with low oil price, how to realize high-value utilization of Fischer-Tropsch synthesis byproduct olefins becomes the focus of attention of a plurality of researchers. The patent CN111646884A discloses a hydroformylation method based on Fischer-Tropsch synthesis products, which adopts a homogeneous hydroformylation process technology, firstly, reacting the Fischer-Tropsch synthesis products and synthesis gas with a catalyst solution in a reaction zone at the reaction temperature of 20-150 ℃ and the reaction pressure of 1.0-8.0 MPa to generate aldehyde, returning gas-phase products to the reaction zone after the gas-phase products are refluxed by a condenser, and feeding the gas which cannot be condensed into a tail gas collection system; then the liquid phase material flow in the reaction area is sent to a separation area, the product aldehyde and the catalyst solution are separated, the separated catalyst solution is sent back to the reaction area, and the aldehyde is discharged and collected from the top of the separation area. Patent CN111646885A discloses a method for preparing aldehyde compounds by hydroformylation of low carbon olefins in Fischer-Tropsch synthesis products, which comprises the steps of reacting the low carbon olefins in the Fischer-Tropsch synthesis products with synthesis gas in a reaction zone with a catalyst to generate the aldehyde compounds by the same homogeneous hydroformylation process technology, feeding the generated liquid phase material flow into a first separation zone, condensing the catalyst and then feeding the condensed catalyst back to the reaction zone, and condensing the aldehyde and the alkane which does not participate in the reaction and then feeding the condensed catalyst into a second reaction zone to obtain the aldehyde products with higher purity. The two processes adopt homogeneous hydroformylation technology, reactants and a catalyst need to be dissolved in a reaction solvent, the catalyst and a reaction product are separated after reaction, the separation difficulty is high, active components of the hydroformylation catalyst are usually noble metals, the active components of the catalyst in the homogeneous process are easy to lose, the process flow is also complex, and the large-scale development of the catalyst is restricted.
A series of porous organic polymer self-supported noble metal hydroformylation catalysts are developed at the early stage of the institute of chemical and physical university of Chinese academy of sciences, wherein the porous organic polymer not only serves as a ligand of noble metal, but also can serve as a catalyst carrier, and the noble metal is supported on the porous organic polymer in a solid manner, so that the heterogeneous hydroformylation process of homogeneous hydroformylation is realized. The reaction conditions required by the catalytic system are mild (less than or equal to 100 ℃, less than or equal to 1.0MPa, 500-3000 h)-1，H21/1), and due to coordination of the carrier, the noble metal is dispersed on the carrier in a single site, the activity of the catalyst is close to that of a homogeneous catalyst, and the problem of low activity of the heterogeneous hydroformylation catalyst is greatly improved. The heterogeneous hydroformylation process adopting the technology has short flow and simple process, saves the separation step between the product and the catalyst, and improves the overall economy of the process. Meanwhile, a cobalt-based catalyst loaded with carbon materials is also developed in the macro-linked compound for the catalytic process of synthesizing straight-chain mixed alcohol by synthesis gas in one step, and the reaction conditions required by the catalytic system are mild (not more than 220 ℃, not more than 3.0MPa, 1000-4000 h)-1，H22/1/CO). In a series of catalysts disclosed in patents US 7670985, US 7468396 and CN101310856, C is contained in the liquid product of carbon monoxide hydrogenation2～C18The selectivity of alcohol is up to 60 percent, andthe distribution of methanol in the alcohol is only about 2-4%. The reason that the catalytic system can directly prepare the higher alcohol from the synthesis gas is that Co is formed in situ in the reaction process2C species, Co2C species can adsorb CO without dissociation, promoting CO insertion; and CO dissociation and adsorption are carried out on the metal Co, so that the carbon chain growth is promoted. Co-Co2The C interface structure constitutes a double active center formed by higher alcohols. Patents CN108014816A and CN108067235A disclose a series of catalysts for producing mixed alcohols and co-producing olefins from syngas, and a hydroformylation technology is adopted to make high-value use of olefins produced as byproducts in the process, so as to realize in-situ conversion into fine chemical products such as alcohols/aldehydes, and improve the overall economy of the process of producing mixed alcohols from syngas.
Disclosure of Invention
The invention aims to develop a catalyst for preparing mixed alcohol and aldehyde and other oxygen-containing compounds by using synthesis gas, aiming at the defects in the prior art, wherein the selectivity of the alcohol, aldehyde and other oxygen-containing compounds reaches more than 65 percent (by carbon number), the proportion of olefin and oxygen-containing compounds in a liquid-phase product is not less than 85 percent (by mass), and the alcohol, aldehyde and other oxygen-containing compounds are prepared in one step from the synthesis gas.
In order to achieve the above object, the technical solution adopted by the present invention specifically includes:
a catalyst comprising two components: the first component is a supported catalyst, the carrier is one or more than two of alumina, titanium dioxide, silicon dioxide, activated carbon and ordered mesoporous carbon (preferably one or two of activated carbon and ordered mesoporous carbon), the active component is one or more than two of metal cobalt, metal iron, cobalt carbide and iron carbide (preferably one or two of cobalt carbide and iron carbide), and the content of the active component is 5-35 wt% (preferably 10-25 wt%) of the weight of the catalyst; the auxiliary agent is one or more than two of alkali metal, alkaline earth metal, rare earth metal and transition metal (preferably one or more than two of sodium, magnesium, chromium, manganese, zirconium and nickel), and the content of the auxiliary agent is 0.1-10 wt% (preferably 0.3-5 wt%) of the weight of the catalyst; the second component is also a supported catalyst, the carrier is one or more than two of active carbon, functionalized silica and porous organic polymer (preferably one or two of functionalized silica and porous organic polymer), the active component is one or more than two of metal cobalt, rhodium and iridium (preferably one or two of cobalt and rhodium), and the content of the active component is 0.01-10 wt% (preferably 0.1-5 wt%) of the weight of the catalyst.
The preparation method of the catalyst specifically comprises the following steps:
(1) the first component was prepared as follows:
boiling an activated carbon raw material or an ordered mesoporous carbon raw material in a nitric acid or hydrochloric acid solution with the mass concentration of 5-30% (preferably 10-20%), refluxing for 2 hours to remove impurities and ash, boiling and washing with deionized water for 1 hour, and repeating the boiling and washing with the deionized water until the conductivity of the washed waste liquid is reduced to 20 mu s/cm; drying the washed activated carbon or the washed ordered mesoporous carbon in an air atmosphere at the temperature of 110-130 ℃ for 12-24 hours, and crushing the activated carbon or the ordered mesoporous carbon into particles of 20-200 meshes for later use;
the alumina, titanium dioxide or silicon dioxide carrier is directly applied subsequently without the treatment;
soaking the carrier with one or more soluble salts of the active component and one or more soluble salts of the assistant X in mixed water solution at room temperature; drying the impregnated catalyst precursor in the shade at room temperature for 6-12 hours, and then drying in an air atmosphere at 45-120 ℃ (preferably 50-80 ℃) for 8-48 hours to prepare a semi-dry catalyst;
thirdly, roasting the semi-dry catalyst in inert atmosphere, wherein the inert atmosphere is one or more of nitrogen, argon or helium, the roasting temperature is 180-450 ℃ (preferably 200-380 ℃), the pressure is 0.1-1.5 MPa (preferably 0.1-0.5 MPa), and the gas space velocity is 100-3000 h-1(preferably 1000 to 2500 h)-1) Roasting for 8-24 hours to obtain a dry-based catalyst;
activating the dry catalyst in hydrogen-containing atmosphere, wherein the hydrogen content in the hydrogen-containing atmosphere is 5-100% (preferably 10-100%), and the gas except hydrogen in the hydrogen-containing mixed gas is one or two of nitrogen, argon or heliumThe activation temperature is 200-600 ℃ (preferably 400-550 ℃), the pressure is 0.1-2.5 MPa (preferably 0.1-1.0 MPa), and the gas space velocity is 300-6000 h-1(preferably 1000 to 3000 hours)-1) Activating for 6-72 hours to prepare an activated catalyst;
activating catalyst with synthetic gas (H)2And CO) to achieve stable activity and selectivity; h in the mixed gas2The molar ratio of the carbon dioxide to CO is 0.4-4.0 (preferably 1.0-3.0), the pretreatment temperature is 170-250 ℃ (preferably 190-220 ℃), the pressure is 0.1-10.0 MPa (preferably 0.5-5.0 MPa), and the space velocity is 100-10000 h-1(preferably 1000 to 5000 hours)-1) The treatment time is 2-96 hours;
sixthly, passivating the pretreated catalyst in an oxygen-containing atmosphere, wherein the oxygen content in the oxygen-containing atmosphere is 0.1-10 percent (preferably 0.5-2 percent), the gas except oxygen in the oxygen-containing mixed gas is one or more of nitrogen, argon or helium, the passivating temperature is room temperature, the pressure is 0.1-1.0 MPa (preferably 0.1-0.5 MPa), and the gas airspeed is 300-6000 h-1(preferably 500 to 2000 h)-1) And activating for 1-6 hours to prepare the passivated first component catalyst.
(2) The second component was prepared as follows:
firstly, impregnating and modifying active carbon, functional silicon dioxide or porous organic polymer by adopting organic ligand, and then using the modified active carbon, functional silicon dioxide or porous organic polymer as a catalyst carrier, wherein the organic ligand is one or more than two of organic phosphine ligand or organic nitrogen ligand;
dissolving one or more than two active component precursors in water or an organic solvent, and soaking the treated active carbon, functionalized silicon dioxide or porous organic polymer at room temperature, wherein the organic solvent is one or more than two of methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide; and drying the impregnated catalyst precursor in the shade at room temperature for 2-6 hours, and then pumping out the residual organic solvent by using a vacuum pump to prepare the second component catalyst.
The soluble salt of the active component in the first component is one or more than two of cobalt formate, cobalt acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, ferric nitrate, ferric chloride, ferric sulfate and ferric acetate, wherein the preferable soluble salt of the active component is one or more than two of cobalt nitrate, cobalt acetate, ferric nitrate and ferric acetate; the soluble salt of the auxiliary agent is one or more than two of metal formate, acetate, oxalate, nitrate, sulfate, citrate, malate, ammonium salt and chloride, wherein the preferable soluble salt of the auxiliary agent is one or more than two of formate, acetate and nitrate;
the precursor of the active component in the second component is one or more than two of cobalt chloride, cobalt nitrate, cobalt formate, cobalt acetate, cobalt acetylacetonate, rhodium chloride and rhodium acetylacetonate, wherein the preferable soluble salt of the active component is one or more than two of cobalt chloride, rhodium chloride, cobalt acetylacetonate and rhodium acetylacetonate; the organic phosphine ligand is one or more than two of trimethylphosphine, triphenylphosphine oxide, tri-tert-butylphosphine, triphenylphosphine sodium tri-m-sulfonate, tri-m-methyl triphenylphosphine, tri-m-methoxyl triphenylphosphine and tri-p-methoxyl triphenylphosphine; the organic nitrogen ligand is one or more than two of dimethyl bipyridine, dimethyl imidazole, o-phenanthroline and dimethyl piperazine.
The catalyst is applied to preparing mixed alcohol and aldehyde by using synthesis gas, a fixed bed reactor or a slurry bed reactor is adopted as a reactor, the filling modes of the two components of the catalyst in the fixed bed reactor are that the first component is arranged at the upper layer and the second component is arranged at the lower layer, or the second component is arranged at the upper layer and the first component is arranged at the lower layer, or the two components are physically mixed, and the filling modes of the two components of the catalyst in the slurry bed reactor are that the two components of the catalyst are dispersed in slurry liquid.
Reaction conditions are as follows: the temperature is 170-240 ℃ (preferably 190-220 ℃), the reaction pressure is 0.5-5.0 MPa (preferably 1.0-4.0 MPa), and the space velocity is 550-5500 h-1(preferably 500 to 2500 h)-1) Of starting material H2The mol ratio of the carbon dioxide to the CO is 0.5-5.0 (preferably 1.0-3.0).
Raw syngas (H)2Mixed gas with CO) by continuous feeding, continuously reacting in a catalyst bed layer or slurry liquid to generateAnd continuously discharging the gas product and the liquid product, collecting heavy components with high boiling point by using a hot tank, collecting light components with low boiling point by using a cold tank, and maintaining the heating temperature of the hot tank at 100-120 ℃ and the temperature of the cold tank at 0-5 ℃.
The product is straight-chain alkane with the carbon number of 1-30, straight-chain olefin with the carbon number of 2-20, and oxygen-containing compounds are mixed alcohol and aldehyde with the straight chain and the branched chain with the carbon number of 2-20; the proportion of oxygen-containing compounds in the product is not less than 65 percent (calculated by carbon number); the proportion of the olefin and the oxygen-containing compound in the liquid-phase product is not less than 85 wt% (by mass).
Compared with the prior art, the invention has the following advantages:
the catalyst provided by the invention can simultaneously improve the selectivity of olefin and oxygen-containing compound (especially oxygen-containing compound) in the synthetic product, the proportion of the oxygen-containing compound in the product is not less than 65 percent (carbon number selectivity), and the proportion of the total mass of the olefin and the oxygen-containing compound in the liquid product is not less than 85 percent by weight. While reducing the selectivity of the product alkane.
The catalyst provided by the invention utilizes the unique properties of two components of the catalyst to realize the coupling of Fischer-Tropsch synthesis reaction and hydroformylation reaction, and realizes the direct synthesis of oxygen-containing compounds such as alcohol, aldehyde and the like from synthesis gas.
The catalyst provided by the invention can carry out the reactions which need to be respectively carried out in two reactors in the same reactor, thereby simplifying the reaction process flow and improving the overall economy of the process.
Compared with the supported cobalt-based Fischer-Tropsch synthesis catalyst disclosed in the earlier stage of the institute of chemical and physical university of the Chinese academy of sciences, the supported cobalt-based Fischer-Tropsch synthesis catalyst has the advantages that the bifunctional catalyst is designed, the coupling of Fischer-Tropsch synthesis reaction and hydroformylation reaction is realized, and oxygen-containing compounds with high additional values, such as alcohol, aldehyde and the like, are directly prepared from synthesis gas.
Detailed Description
The present invention will be further illustrated with reference to the following examples and the accompanying tables, without any limitation thereto.
Example 1
Preparation of Cat1, comprising a first component a and a second component B.
Preparing a first component:
4.94g of cobalt nitrate hexahydrate, 0.91g of zirconium nitrate tetrahydrate and 0.23g of manganese acetate tetrahydrate were dissolved in 10g of water to prepare a solution. Soaking 8.73g of purified activated carbon carrier in the soaking solution at the room temperature of 298K, drying in shade for about 10 hours until no mobile water exists on the surface of the catalyst, placing the catalyst in a 313K oven for drying for 24 hours, taking out the catalyst, and gradually heating to 573K in argon gas for roasting for 20 hours to obtain a dry-based catalyst precursor. Then the dry-based catalyst precursor is gradually heated up to 673K in hydrogen to be reduced for 15 hours, the filling amount is 2mL, and the space velocity is 2000h-1. Reducing the temperature to room temperature after reduction, and switching to 1% O2Passivating the mixed gas of/Ar for 1 hour to obtain a first component A of the catalyst.
Preparing a second component:
0.15g of rhodium acetylacetonate was dissolved in 2.5g of tetrahydrofuran to prepare an impregnation solution, and then the porous organic polymer modified with 1.5g of an organophosphine ligand was dried in the shade at room temperature for about 10 hours using the impregnation solution, and then the excess solvent was removed by a rotary evaporator to obtain a second component B of the catalyst.
The catalyst evaluation method comprises the following steps:
the two components A, B of the catalyst (B below A) were sequentially fed into a fixed bed reactor and the synthesis gas (H) was switched2and/CO is 2.0), the pressure is adjusted to 3.0MPa, and the temperature is increased to 493K for reaction. After 12 hours of stabilization, sampling and analyzing the concentration of each component, the composition of the liquid-phase product and the yield of the liquid-phase product in the tail gas every 24 hours. The results obtained are shown in the attached Table 1.
Example 2
Preparation of Cat2, comprising a first component a and a second component B.
Preparing a first component:
4.94g of cobalt nitrate hexahydrate, 1.54g of chromium nitrate nonahydrate and 0.21g of sodium nitrate were dissolved in 10g of water to prepare a dipping solution. Soaking 8.57g of the purified mesoporous carbon carrier in the soaking solution at the room temperature of 298K, drying in shade for about 10 hours until no mobile water exists on the surface of the catalyst, placing the catalyst in a 313K oven for drying for 24 hours, taking out the catalyst, and gradually rising in argon gasAnd the temperature is up to 573K, and the catalyst is roasted for 20 hours to obtain a dry-based catalyst precursor. Then the dry-based catalyst precursor is gradually heated to 673K in hydrogen for reduction for 15 hours, the filling amount is 2mL, and the space velocity is 2000h-1. Reducing the temperature to room temperature after reduction, and switching to 1% O2Passivating the mixed gas of/Ar for 1 hour to obtain a first component A of the catalyst.
Preparing a second component:
0.75g of cobalt acetylacetonate was dissolved in 2.5g of tetrahydrofuran to prepare an impregnation solution, and then the porous organic polymer modified with 1.5g of an organophosphine ligand was dried in the shade at room temperature for about 10 hours using the impregnation solution, and then excess solvent was removed by a rotary evaporator to obtain a second component B of the catalyst.
The catalyst evaluation method comprises the following steps:
the two components A, B of the catalyst (B below A) were sequentially fed into a fixed bed reactor and the synthesis gas (H) was switched2and/CO is 2.0), the pressure is adjusted to 3.0MPa, and the temperature is increased to 493K for reaction. After 12 hours of stabilization, sampling and analyzing the concentration of each component, the composition of the liquid-phase product and the yield of the liquid-phase product in the tail gas every 24 hours. The results obtained are shown in the attached Table 1.
Example 3
Cat3 was prepared, comprising a first component a and a second component B.
Preparing a first component:
4.94g of cobalt nitrate hexahydrate, 0.84g of nickel nitrate hexahydrate and 0.38g of magnesium nitrate were dissolved in 10g of water to prepare a dipping solution. Soaking 8.40g of the purified mesoporous carbon carrier in the soaking solution at the room temperature of 298K, drying in the shade for about 10 hours until no mobile water exists on the surface of the catalyst, placing the catalyst in a 313K drying oven for drying for 24 hours, taking out the catalyst, and gradually heating to 573K in argon gas for roasting for 20 hours to obtain a dry-based catalyst precursor. Then the dry-based catalyst precursor is gradually heated to 673K in hydrogen for reduction for 15 hours, the filling amount is 2mL, and the space velocity is 2000h-1. Reducing the temperature to room temperature after reduction, and switching to 1% O2Passivating the mixed gas of/Ar for 1 hour to obtain a first component A of the catalyst.
Preparing a second component:
0.45g of iridium chloride was dissolved in 2.5g of tetrahydrofuran to prepare an impregnation solution, and then the porous organic polymer modified with 1.5g of an organophosphine ligand was dried in the shade at room temperature for about 10 hours using the impregnation solution, and then excess solvent was removed using a rotary evaporator to obtain a second component B of the catalyst.
The catalyst evaluation method comprises the following steps:
the two components A, B of the catalyst (B above A) were sequentially fed into a fixed bed reactor and synthesis gas (H) was switched22.0) and the pressure was adjusted to 3.0MPa, the temperature was raised to 493K, and the reaction was carried out. After 12 hours of stabilization, sampling and analyzing the concentration of each component, the composition of the liquid-phase product and the yield of the liquid-phase product in the tail gas every 24 hours. The results obtained are shown in the attached Table 1.
Example 4
Preparation of Cat4, comprising a first component a and a second component B.
Preparing a first component:
4.94g of cobalt nitrate hexahydrate, 0.84g of nickel nitrate hexahydrate and 0.38g of magnesium nitrate were dissolved in 10g of water to prepare a solution for impregnation. Soaking 8.40g of the purified mesoporous carbon carrier in the soaking solution at the room temperature of 298K, drying in the shade for about 10 hours until no mobile water exists on the surface of the catalyst, placing the catalyst in a 313K drying oven for drying for 24 hours, taking out the catalyst, and gradually heating to 573K in argon gas for roasting for 20 hours to obtain a dry-based catalyst precursor. Then the dry-based catalyst precursor is gradually heated up to 673K in hydrogen to be reduced for 15 hours, the filling amount is 2mL, and the space velocity is 2000h-1. Reducing the temperature to room temperature after reduction, and switching to 1% O2Passivating the mixed gas of/Ar for 1 hour to obtain a first component A of the catalyst.
Preparing a second component:
0.15g of rhodium acetylacetonate was dissolved in 2.5g of tetrahydrofuran to prepare an impregnation solution, and then the porous organic polymer modified with 1.5g of an organophosphine ligand was dried in the shade at room temperature for about 10 hours using the impregnation solution, and then the excess solvent was removed by a rotary evaporator to obtain a second component B of the catalyst.
The catalyst evaluation method comprises the following steps:
the two components A, B of the catalyst (B below A) were sequentially fed into a fixed bed reactor and the synthesis gas (H) was switched2/CO＝2.0)，The pressure is adjusted to 3.0MPa, and the temperature is increased to 493K for reaction. After 12 hours of stabilization, sampling and analyzing the concentration of each component, the composition of the liquid-phase product and the yield of the liquid-phase product in the tail gas every 24 hours. The results obtained are shown in the attached Table 1.
Example 5
Preparation of Cat5, comprising a first component a and a second component B.
Preparing a first component:
4.94g of cobalt nitrate hexahydrate, 0.64g of zirconium nitrate tetrahydrate and 0.25g of magnesium nitrate were dissolved in 10g of water to prepare a dipping solution. And (3) soaking 8.40g of purified activated carbon carrier in the soaking solution at the room temperature of 298K, drying in shade for about 10 hours until no flowable water exists on the surface of the catalyst, drying in a 313K drying oven for 24 hours, taking out, gradually heating to 573K in argon gas, and roasting for 20 hours to obtain a dry-based catalyst precursor. Then the dry-based catalyst precursor is gradually heated up to 673K in hydrogen to be reduced for 15 hours, the filling amount is 2mL, and the space velocity is 2000h-1. Reducing the temperature to room temperature after reduction, and switching to 1% O2Passivating the mixed gas of/Ar for 1 hour to obtain a first component A of the catalyst.
Preparing a second component:
0.75g of cobalt acetylacetonate was dissolved in 2.5g of tetrahydrofuran to prepare an impregnation solution, and then the porous organic polymer modified with 1.5g of an organophosphine ligand was dried in the shade at room temperature for about 10 hours using the impregnation solution, and then excess solvent was removed by a rotary evaporator to obtain a second component B of the catalyst.
The catalyst evaluation method comprises the following steps:
the two components A, B of the catalyst (B below A) were sequentially fed into a fixed bed reactor and the synthesis gas (H) was switched2and/CO is 2.0), the pressure is adjusted to 3.0MPa, and the temperature is increased to 493K for reaction. After 12 hours of stabilization, sampling and analyzing the concentration of each component, the composition of the liquid-phase product and the yield of the liquid-phase product in the tail gas every 24 hours. The results obtained are shown in the attached Table 1.
Example 6
Cat6 was prepared, comprising a first component a and a second component B.
Preparing a first component:
6.65g of nine waterIron nitrate, 0.23g of sodium nitrate and 0.54g of a 50 wt% manganese nitrate solution were dissolved in 10g of water to prepare an impregnation solution. Soaking 8.55g of purified activated carbon carrier in the soaking solution at the room temperature of 298K, drying in shade for about 10 hours until no mobile water exists on the surface of the catalyst, placing the catalyst in a 313K oven for drying for 24 hours, taking out the catalyst, and gradually heating to 573K in argon gas for roasting for 20 hours to obtain a dry-based catalyst precursor. Then the dry-based catalyst precursor is gradually heated to 673K in hydrogen for reduction for 15 hours, the filling amount is 2mL, and the space velocity is 2000h-1. Reducing the temperature to room temperature after reduction, and switching to 1% O2Passivating the mixed gas of/Ar for 1 hour to obtain a first component A of the catalyst.
Preparing a second component:
0.20g of rhodium acetylacetonate was dissolved in 2.5g of tetrahydrofuran to prepare an impregnation solution, and then the porous silica modified with 1.5g of an organic nitrogen ligand was dried in the shade at room temperature for about 10 hours using the impregnation solution, and then the excess solvent was removed by a rotary evaporator to obtain a second component B of the catalyst.
The catalyst evaluation method comprises the following steps:
two components A, B of the catalyst (B above A) were sequentially packed into a fixed bed reactor and synthesis gas (H) was switched2and/CO is 2.0), the pressure is adjusted to 3.0MPa, and the temperature is increased to 493K for reaction. After 12 hours of stabilization, sampling and analyzing the concentration of each component, the composition of the liquid-phase product and the yield of the liquid-phase product in the tail gas every 24 hours. The results obtained are shown in the attached Table 1.
Example 7
Preparation of Cat7, comprising a first component a and a second component B.
Preparing a first component:
6.65g of iron nitrate nonahydrate, 0.45g of magnesium nitrate and 1.84g of chromium nitrate nonahydrate were dissolved in 10g of water to prepare a dipping solution. Soaking 8.48g of purified activated carbon carrier in the soaking solution at the room temperature of 298K, drying in shade for about 10 hours until no mobile water exists on the surface of the catalyst, placing the catalyst in a 313K oven for drying for 24 hours, taking out the catalyst, and gradually heating to 573K in argon gas for roasting for 20 hours to obtain a dry-based catalyst precursor. Then the dry-based catalyst precursor is gradually heated up to 673K in hydrogen to be reduced for 15 hours, and the filling amount isIs 2mL, and the space velocity is 2000h-1. Reducing the temperature to room temperature after reduction, and switching to 1% O2Passivating the mixed gas of/Ar for 1 hour to obtain a first component A of the catalyst.
Preparing a second component:
0.80g of cobalt acetylacetonate was dissolved in 2.5g of tetrahydrofuran to prepare an impregnation solution, and then silica modified with 1.5g of an organophosphine ligand was used for the impregnation solution at room temperature, dried in the shade at room temperature for about 10 hours, and then excess solvent was removed by a rotary evaporator to obtain a second component B of the catalyst.
The catalyst evaluation method comprises:
the two components A, B of the catalyst (B above A) were sequentially fed into a fixed bed reactor and synthesis gas (H) was switched2and/CO is 2.0), the pressure is adjusted to 3.0MPa, and the temperature is increased to 493K for reaction. After 12 hours of stabilization, sampling and analyzing the concentration of each component, the composition of the liquid-phase product and the yield of the liquid-phase product in the tail gas every 24 hours. The results obtained are shown in the attached Table 1.
Comparative example
The catalyst was prepared by changing the formulation and method provided in patent CN108014816A, and its reaction was evaluated in a similar manner and compared with the examples. The results obtained are shown in the attached Table 1.
The comparison result shows that the catalyst provided by the patent utilizes the Fischer-Tropsch synthesis and hydroformylation catalysts for coupling on the basis of keeping higher activity, realizes high-value utilization of Fischer-Tropsch synthesis products, greatly improves the selectivity of oxygen-containing compounds in the products, simultaneously inhibits the formation of methane, improves the comprehensive value of the Fischer-Tropsch synthesis products, and has higher atom economy and added value.
Attached table 1
Catalyst performance for combined production of synthetic gas oil and alcohol on catalyst
Figure BDA0002792603800000101

Claims (8)

1. A catalyst comprising two components:
the first component is a supported catalyst, the carrier is one or more than two of alumina, titanium dioxide, silicon dioxide, activated carbon and ordered mesoporous carbon (preferably one or two of activated carbon and ordered mesoporous carbon), the active component is one or more than two of metal cobalt, metal iron, cobalt carbide and iron carbide (preferably one or two of cobalt carbide and iron carbide), and the content of the active component is 5-35 wt% (preferably 10-25 wt%) of the weight of the catalyst; the auxiliary agent is one or more than two of alkali metal, alkaline earth metal, rare earth metal and transition metal (preferably one or more than two of sodium, magnesium, chromium, manganese, zirconium and nickel), and the content of the auxiliary agent is 0.1-10 wt% (preferably 0.3-5 wt%) of the weight of the catalyst;
the second component is also a supported catalyst, the carrier is one or more than two of active carbon, functionalized silica and porous organic polymer (preferably one or two of functionalized silica and porous organic polymer), the active component is one or more than two of metal cobalt, rhodium and iridium (preferably one or two of cobalt and rhodium), and the content of the active component is 0.01-10 wt% (preferably 0.1-5 wt%) of the weight of the catalyst.
2. A method for preparing the catalyst of claim 1, comprising the steps of:
(1) the first component was prepared as follows:
boiling an activated carbon raw material or an ordered mesoporous carbon raw material in a nitric acid or hydrochloric acid solution with the mass concentration of 5-30% (preferably 10-20%), refluxing for 2 hours to remove impurities and ash, boiling and washing with deionized water for 1 hour, and repeating the boiling and washing with the deionized water until the conductivity of the washed waste liquid is reduced to 20 mu s/cm; drying the washed activated carbon or the washed ordered mesoporous carbon in an air atmosphere at the temperature of 110-130 ℃ for 12-24 hours, and crushing the activated carbon or the ordered mesoporous carbon into particles of 20-200 meshes for later use;
the alumina, titanium dioxide or silicon dioxide carrier is directly applied subsequently without the treatment;
soaking the carrier with one or more soluble salts of the active component and one or more soluble salts of the assistant X in mixed water solution at room temperature; drying the impregnated catalyst precursor in the shade at room temperature for 6-12 hours, and then drying in an air atmosphere at 45-120 ℃ (preferably 50-80 ℃) for 8-48 hours to prepare a semi-dry catalyst;
thirdly, roasting the semi-dry catalyst in inert atmosphere, wherein the inert atmosphere is one or more of nitrogen, argon or helium, the roasting temperature is 180-450 ℃ (preferably 200-380 ℃), the pressure is 0.1-1.5 MPa (preferably 0.1-0.5 MPa), and the gas space velocity is 100-3000 h-1(preferably 1000 to 2500 h)-1) Roasting for 8-24 hours to obtain a dry-based catalyst;
activating the dry-based catalyst in a hydrogen-containing atmosphere, wherein the hydrogen content in the hydrogen-containing atmosphere is 5-100% (preferably 10-100%), the gas except hydrogen in the hydrogen-containing mixed gas is one or more of nitrogen, argon or helium, the activation temperature is 200-600 ℃ (preferably 400-550 ℃), the pressure is 0.1-2.5 MPa (preferably 0.1-1.0 MPa), and the gas airspeed is 300-6000 h-1(preferably 1000 to 3000 hours)-1) Activating for 6-72 hours to prepare an activated catalyst;
activation of catalyst requires synthesis gas (H)2And CO) to achieve stable activity and selectivity; h in the mixed gas2The molar ratio of the carbon dioxide to CO is 0.4-4.0 (preferably 1.0-3.0), the pretreatment temperature is 170-250 ℃ (preferably 190-220 ℃), the pressure is 0.1-10.0 MPa (preferably 0.5-5.0 MPa), and the space velocity is 100-10000 h-1(preferably 1000 to 5000 hours)-1) The treatment time is 2-96 hours;
sixthly, passivating the pretreated catalyst in an oxygen-containing atmosphere, wherein the oxygen content in the oxygen-containing atmosphere is 0.1-10 percent (preferably 0.5-2 percent), the gas except oxygen in the oxygen-containing mixed gas is one or more of nitrogen, argon or helium, the passivating temperature is room temperature, the pressure is 0.1-1.0 MPa (preferably 0.1-0.5 MPa), and the gas airspeed is 300-6000 h-1(preferably 500 to 2000 h)-1) Activating for 1-6 hours to prepare a passivated first component catalyst;
(2) the second component was prepared as follows:
firstly, impregnating and modifying active carbon, functional silicon dioxide or porous organic polymer by adopting organic ligand, and then using the modified active carbon, functional silicon dioxide or porous organic polymer as a catalyst carrier, wherein the organic ligand is one or more than two of organic phosphine ligand or organic nitrogen ligand;
dissolving one or more than two active component precursors in water or an organic solvent, and soaking the treated active carbon, functional silicon dioxide or porous organic polymer at room temperature, wherein the organic solvent is one or more than two of methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide and N, N-dimethylformamide; and drying the impregnated catalyst precursor in the shade at room temperature for 2-6 hours, and then pumping out the residual organic solvent by using a vacuum pump to prepare the second component catalyst.
3. The method for preparing a catalyst according to claim 2, wherein:
the soluble salt of the active component in the first component is one or more than two of cobalt formate, cobalt acetate, cobalt nitrate, cobalt chloride, cobalt sulfate, ferric nitrate, ferric chloride, ferric sulfate and ferric acetate, wherein the preferable soluble salt of the active component is one or more than two of cobalt nitrate, cobalt acetate, ferric nitrate and ferric acetate; the soluble salt of the auxiliary agent is one or more than two of metal formate, acetate, oxalate, nitrate, sulfate, citrate, malate, ammonium salt and chloride, wherein the preferable soluble salt of the auxiliary agent is one or more than two of formate, acetate and nitrate;
the precursor of the active component in the second component is one or more than two of cobalt chloride, cobalt nitrate, cobalt formate, cobalt acetate, cobalt acetylacetonate, rhodium chloride and rhodium acetylacetonate, wherein the preferable soluble salt of the active component is one or more than two of cobalt chloride, rhodium chloride, cobalt acetylacetonate and rhodium acetylacetonate; the organic phosphine ligand is one or more than two of trimethylphosphine, triphenylphosphine oxide, tri-tert-butylphosphine, triphenylphosphine sodium tri-m-sulfonate, tri-m-methyl triphenylphosphine, tri-m-methoxyl triphenylphosphine and tri-p-methoxyl triphenylphosphine; the organic nitrogen ligand is one or more than two of dimethyl bipyridine, dimethyl imidazole, o-phenanthroline and dimethyl piperazine.
4. Use of the catalyst of claim 1 in the preparation of mixed alcohols and aldehydes from synthesis gas.
5. Use according to claim 4, characterized in that:
the reactor for preparing the mixed alcohol/aldehyde by the synthesis gas adopts a fixed bed reactor or a slurry bed reactor, the two components of the catalyst are filled in the fixed bed reactor in a mode that the first component is at the upper layer and the second component is at the lower layer, or the second component is at the upper layer and the first component is at the lower layer, or the two components are physically mixed, and the two components of the catalyst are filled in the slurry bed reactor in a mode that the two components of the catalyst are dispersed in slurry liquid.
6. Use according to claim 4, characterized in that: reaction conditions are as follows: the temperature is 170-240 ℃ (preferably 190-220 ℃), the reaction pressure is 0.5-5.0 MPa (preferably 1.0-4.0 MPa), and the space velocity is 550-5500 h-1(preferably 500 to 2500 h)-1) Of starting material H2The mol ratio of the carbon dioxide to the CO is 0.5-5.0 (preferably 1.0-3.0).
7. Use according to claim 4, 5 or 6, characterized in that:
raw syngas (H)2And CO) in a catalyst bed layer or slurry liquid, continuously discharging gas products and liquid products generated by the reaction, collecting heavy components with high boiling point by using a hot tank, collecting light components with low boiling point by using a cold tank, and maintaining the heating temperature of the hot tank at 100-120 ℃ and the temperature of the cold tank at 0-5 ℃.
8. Use according to claim 4, 5 or 6, characterized in that:
the product is straight-chain alkane with the carbon number of 1-30, straight-chain olefin with the carbon number of 2-20, and oxygen-containing compounds are mixed alcohol and aldehyde with the straight chain and the branched chain with the carbon number of 2-20;
the proportion of oxygen-containing compounds in the product is not less than 65 percent (calculated by carbon number);
the proportion of the olefin and the oxygen-containing compound in the liquid-phase product is not less than 85 wt% (by mass).
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