CN114570374A - Cobalt-based catalyst, preparation method and application - Google Patents

Cobalt-based catalyst, preparation method and application Download PDF

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CN114570374A
CN114570374A CN202210211857.2A CN202210211857A CN114570374A CN 114570374 A CN114570374 A CN 114570374A CN 202210211857 A CN202210211857 A CN 202210211857A CN 114570374 A CN114570374 A CN 114570374A
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catalyst
carbon monoxide
preparation
molar ratio
reducing
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刘源
宋鹏飞
李宁焱
姜雅楠
邬怡
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Tianjin University
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    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E50/10—Biofuels, e.g. bio-diesel

Abstract

The invention provides a cobalt-based catalyst, a preparation method and application thereof; cobalt-doped CaTiO taking perovskite type composite oxide as precursor3Preparation and application of the type catalyst; the molecular formula of the catalyst is Ca1‑xLaxTi1‑xCoxO3And Ca1‑xAxTi1‑α‑βCoαBβO3(α + β ═ x); according to the invention, a series of perovskite oxide catalysts are prepared by a citric acid complexation method, metallic cobalt or other metals are separated out after reduction treatment, and the perovskite structure is still kept complete; the catalyst is used for the reaction of preparing low-carbon alcohol by carbon monoxide hydrogenation by regulating the cobalt doping amount or the relative variable of the alloy, and has higher low-carbon alcohol selectivity and good catalytic activity and stability.

Description

Cobalt-based catalyst, preparation method and application
Technical Field
The invention relates to a cobalt-based catalyst and a preparation method and application thereof; is novel cobalt-doped CaTiO taking perovskite type composite oxide as precursor3The preparation and application of the type catalyst are applied to the preparation of low-carbon alcohol by carbon monoxide hydrogenation, and belong to the application field of metal catalysts.
Background
The synthesis gas takes carbon monoxide and hydrogen as main components, can be prepared by processing shale gas, coal, biomass, carbon dioxide and carbon-containing wastes, is an important 'platform' compound in the chemical production process, and is also an important raw material for providing energy sources through non-petroleum resources[1,2]. Due to the continuous consumption of crude oil resources, the demand of people for chemicals is increasing, and the urgent requirements for realizing 'carbon neutralization and carbon peak reaching' are met, so that the conversion of the synthesis gas attracts the attention of more and more researchers[1]. Among them, hydrogenation of synthesis gas to produce lower alcohols is one of the major research directions.
The lower alcohol is alcohol containing two or more than two, mainly comprising ethanol, propanol, isobutanol and the like, is widely quoted in multiple industries such as organic synthesis, food, pesticide, fine chemical engineering and the like, mainly can be used as an intermediate of a specific commodity, can also be used as a raw material of a plasticizer and a detergent, or can be used as a gasoline additiveImprove octane number, thereby improving engine performance[3]. At present, ethanol and isobutanol are mainly prepared by further fermenting sugar extracted from starch and sugarcane, and alcohol with a large number of carbon atoms is prepared by hydrating olefin, but the former has the problem of 'competing for grains with people', and the latter has the problems of high cost and low conversion per pass, which hinder the process of industrial popularization. If the synthesis gas can be directly converted into the low-carbon alcohol, the consumption of grains in China is reduced, the abundant natural gas reserves in China are fully utilized, and the advantages of sustainable development are achieved in the future[4]。
Since the last century the synthesis of lower alcohols from synthesis gas has been proposed, four main types of catalysts have been commonly used, but all have different defects: 1. rh-based catalyst: the precious metal Rh shows the best activity and alcohol selectivity, particularly ethanol becomes the main product, but the low reserve and high price are common defects of the precious metal Rh, and the Rh is easy to sinter in the reaction process and has small application prospect[5](ii) a 2. Mo-based catalyst: compared with Rh-based catalyst, Mo-based catalyst has good carbon deposition resistance and sulfur resistance, saves huge desulphurization investment, and has good conversion rate, but the catalyst has high water gas change activity, more carbon dioxide in the product, and harsh reaction conditions, and Mo is2The loss of the sulfur component of S-based catalysts can also cause pollution problems[4,6](ii) a 3. Modified methanol synthesis catalyst: the catalyst mainly comprises metals such as Cu, Zn, Cr and the like, such as Cu-Zn-based and Zn-Cr-based catalysts, and is modified by adding other metal assistants, but the reaction temperature and the operation pressure are relatively high, methanol and isobutanol are still mainly used in the product, and the selectivity needs to be improved[7,8](ii) a 4. Modified fischer-tropsch catalyst: commonly used reactive metals include: fe. The Fischer-Tropsch synthesis catalyst modified by Co and Ni can obtain higher conversion rate and selectivity under mild conditions, but has the problem of poor stability caused by bimetallic phase separation, and although the products mainly contain methane and hydrocarbons, the catalyst is also considered to be the catalyst with the most application prospect[4,9]。
Perovskite type composite oxide (PTO)From CaTiO3Derived from the above, is a class of catalyst structures which have been extensively studied in industrial catalysis and can be expressed as ABO3. The A site is usually occupied by alkali metal, alkaline earth metal and La series metal ions, playing the role of stabilizing the structure and having no catalytic activity, while the B site is taken as an active component site and occupied by transition metal ions[10]. In addition, in the PTO structure, there is enough space for the reactant small molecules to interact with the surface metal, and when the radius of the metal ion satisfies the tolerance factor, both the a-site and B-site ions can be partially or completely substituted, resulting in the perovskite composite oxide having various compositions. While maintaining the perovskite stable structure, the catalyst generates lattice defects due to the abnormal oxidation state of B-site ions, so that the performance of the catalyst is remarkably changed[11]. In addition, the PTO structure can maintain high dispersibility of each metal ion, and the oxygen vacancy generated during the reduction process is also considered as an active site for generating a lower alcohol[12]. The stability of the PTO structure catalyst tested by Zhao, Liu and the like shows that the catalyst can still maintain stable catalyst activity after 1000h and 1500h[13,14]。
In conclusion, the research of the catalyst with excellent and stable performance is the technical key for breaking through the industrial application of preparing the low-carbon alcohol from the synthesis gas.
Disclosure of Invention
The invention aims to provide a novel cobalt-doped CaTiO taking perovskite type composite oxide as a precursor3Preparation and application of the catalyst. The catalyst can be used for preparing low-carbon alcohol by carbon monoxide hydrogenation, and has high selectivity, activity and stability.
The technical scheme of the invention is as follows:
a cobalt-based catalyst characterized in that one or more of La or Co is partially substituted, but the ratio of (Ca + A) to (Ti + Co + B) is maintained at 1: 1. The molecular formula of which is Ca1-xAxTi1-α-βCoαBβO3Alpha + beta ═ x, A is one or several of Y, La, Ce, Pr, Mg, Sr, Ba, K and Cs, B is one of Al, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo and InOne or more of them.
A cobalt-based catalyst having a characteristic molecular formula of Ca1-xLaxTi1-xCox O3Wherein the value range of x is 0-1.
The preparation method of the catalyst of the invention mainly comprises the following steps:
preparation of the catalyst
The catalyst composition is Ca1-xAxTi1-α-βCoαBβO3The preparation method comprises the following steps: according to the molar ratio of 1-x of calcium nitrate, nitrate of an element substituting Ca, tetrabutyl titanate, cobalt nitrate, nitrate of an element substituting titanium and cobalt, citric acid and glycol: x: 1- α - β: α: beta: 2.4: 0.48 was mixed and dissolved. It is noted that tetrabutyl titanate needs to be dissolved in ethanol first and then added to the mixed solution. The salt solution is put in a water bath kettle at the temperature of 60-100 ℃ and stirred to be dried by distillation, the product is dried for 6-24h in a drying box at the temperature of 80-200 ℃, the dried product is heated to 250-500 ℃ at the speed of 2-10 ℃/min and roasted for 1-6h, and is continuously heated to 600-900 ℃ and roasted for 3-10h, and the catalyst component, Ca, is obtained1-xAxTi1-α-βCoαBβO3Has a perovskite-type composite oxide structure. Wherein the relation of x, alpha and beta is alpha + beta ═ x, the range of x is 0-1, and alpha is not 0.
The catalyst composition is Ca1-xLaxTi1-xCoxO3(x is 0-0.9) the preparation method: according to the molar ratio of 1-x of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol: x: 1-x: x: 2.4: 0.48 was mixed and dissolved. It is noted that tetrabutyl titanate needs to be dissolved in ethanol first and then added to the mixed solution. The salt solution is put in a water bath kettle at the temperature of 60-100 ℃ and stirred to be dried by distillation, the product is dried for 6-24h in a drying box at the temperature of 80-200 ℃, the dried product is heated to 250-500 ℃ at the speed of 2-10 ℃/min and roasted for 1-6h, and is continuously heated to 600-900 ℃ and roasted for 3-10h, and the catalyst component, Ca, is obtained1-xLaxTi1-xCoxO3The perovskite type composite oxide has a perovskite type composite oxide structure, and the value range of x is 0-1.
Reduction of catalyst
The prepared composition is Ca1-xLaxTi1-xCoxO3Or Ca1-xAxTi1-α-βCoαBβO3The catalyst is placed in a reduction furnace, and the flow rate of the catalyst is 5-50 mL/min-1The reducing gas is used for reducing the catalyst, wherein the heating rate is 2-20 ℃/min; the temperature is 500-900 ℃; the reduction time is 0.1-6 h. The reducing gas is mainly hydrogen or carbon monoxide, and can also be a hydrogen/nitrogen or carbon monoxide/nitrogen mixed gas, wherein the volume fraction of the inert gas in the mixed gas is 1-99%.
Application of catalyst in preparation of low-carbon alcohol by carbon monoxide hydrogenation
The catalyst composition is Ca1-xLaxTi1-xCoxO3Or Ca1-xAxTi1-α-βCoαBβO3The catalyst is added into a reactor after reduction, and under the conditions that the temperature is 200-350 ℃ and the pressure is 1-10MPa, the volume space velocity is 500-30000 mL/(g-10 MPa) into the reactorcath) Introducing hydrogen and carbon monoxide to prepare the low-carbon mixed alcohol. The molar ratio of the hydrogen to the carbon monoxide is (1-4): 1.
the main method of the invention is to make Co ions enter the B site of the perovskite compound by a citric acid complexation method, because of CaTiO3The perovskite structure is difficult to reduce, and the complete perovskite structure is still kept after Co ions are reduced and separated out. Because of the retention of the perovskite structure, the reduced Co ions have high dispersity and good stability, and oxygen vacancy active sites are easily formed in the reduction process. CaTiO3The a site of the perovskite structure can also be doped with various metal ions, which makes the catalyst itself more controllable. The catalyst is used for the reaction of preparing low-carbon alcohol in the hydrogenation of carbon monoxide, and has higher selectivity, high activity and high stability for alcohols containing 2-6 carbon atoms.
Drawings
FIG. 1 shows Ca1-xLaxTi1-xCoxO3(x ═ 0 to 0.5 and 1) XRD pattern of catalyst: (a) after calcination, (b) reduction, (c) reaction and (4) Ca0.7La0.3Ti0.7Co0.3O3In three cases.
FIG. 2 shows Ca after reduction0.7La0.3Ti0.7Co0.3O3Different magnification TEM images (a, b), particle size distribution (a), high resolution TEM image (b) and corresponding EDS elemental mapping (c-g).
FIG. 3 shows Ca1-xLaxTi1-xCoxO3(x ═ 0-0.5) XPS total spectra for the catalyst (a), and high resolution XPS spectra for Co 2p (b), O1 s (c), Ti 2p (d), Ca 2p (e), and La 3d (f).
FIG. 4 is a graph at H2/CO/N28/4/1 in a syngas mixture at T270 ℃, P3 MPa 3900mLgcat -1h-1Ca after GHSV reduction of0.7La0.3Ti0.7Co0.3O3Stability test results (a, b).
Detailed Description
1. Specific preparation process of catalyst
A. Stirring and heating the prepared salt solution in a water bath kettle at 80 ℃ to form sol, heating the product at 120 ℃ for 12h, drying, heating the product to 500 ℃ at the heating rate of 2 ℃/min, calcining for 2h, heating to 600 ℃ at the heating rate of 2 ℃/min, calcining for 4h, and obtaining the catalyst.
B. Stirring and heating the prepared salt solution in a water bath kettle at 60 ℃ to form sol, heating the product at 80 ℃ for 6h, drying, heating the product to 250 ℃ at the heating rate of 2 ℃/min, calcining for 2h, heating to 600 ℃ at the heating rate of 2 ℃/min, calcining for 3h, and obtaining the catalyst.
C. Stirring and heating the prepared salt solution in a water bath kettle at 100 ℃ to form sol, heating the product at 200 ℃ for 24h, drying, heating the product to 500 ℃ at the heating rate of 10 ℃/min, calcining for 6h, heating to 900 ℃ at the heating rate of 10 ℃/min, and calcining for 10h to obtain the catalyst.
2. Specific reduction process of catalyst
A. Putting the catalyst prepared in the step 1 into a reduction furnace, and introducing H with the flow rate of 30mL/min into the reduction furnace2And the temperature is increased to 800 ℃ at the rate of 5 ℃/min and reduced for 3 h.
B. Putting the catalyst prepared in the step 1 into a reduction furnace, and introducing H with the flow rate of 50mL/min into the reduction furnace2And the temperature is raised to 500 ℃ at the heating rate of 2 ℃/min and reduced for 0.1 h.
C. Putting the catalyst prepared in the step 1 into a reduction furnace, and introducing H with the flow rate of 5mL/min into the reduction furnace2And heating to 900 ℃ at a heating rate of 20 ℃/min and reducing for 6 h.
D. And (3) placing the catalyst prepared in the step (1) in a reduction furnace, introducing CO with the flow rate of 30mL/min into the reduction furnace, and heating to 800 ℃ at the heating rate of 5 ℃/min for reduction for 3 h.
E. Putting the catalyst prepared in the step 1 into a reduction furnace, and introducing H with the flow rate of 30mL/min into the reduction furnace2/N2Mixed gas of which H2The volume fraction of (A) is 1%, and the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min and reduced for 3 h.
F. Putting the catalyst prepared in the step 1 into a reduction furnace, and introducing H with the flow rate of 30mL/min into the reduction furnace2/N2Mixed gas of which H2The volume fraction of (2) is 50%, and the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min and reduced for 3 h.
G. Putting the catalyst prepared in the step 1 into a reduction furnace, and introducing H with the flow rate of 30mL/min into the reduction furnace2/N2Mixed gas of which H2The volume fraction of the catalyst is 99 percent, and the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min for reduction for 3 h.
H. Putting the catalyst prepared in the step 1 into a reduction furnace, and introducing CO/N with the flow rate of 30mL/min into the reduction furnace2And (3) mixing the gas, wherein the volume fraction of CO is 50%, and heating to 800 ℃ at a heating rate of 5 ℃/min for reduction for 3 h.
3. Application of catalyst in preparation of low-carbon alcohol by carbon monoxide hydrogenation
A. Placing the catalyst reduced in the step 2 in a reactor, wherein the reaction temperature is 310 ℃, the operation pressure is 3MPa, and introducing 3900 mL/(g) of volume space velocity into the reactorcath) And preparing the low-carbon mixed alcohol from the carbon monoxide and the hydrogen in a molar ratio of 2: 1.
B. Placing the catalyst reduced in the step 2 in a reactor, wherein the reaction temperature is 200 ℃, the operation pressure is 1MPa, and the volume space velocity is 500 mL/(g) in the reactorcath) And preparing the low-carbon mixed alcohol from the carbon monoxide and the hydrogen in a molar ratio of 1: 1.
C. Putting the catalyst reduced in the step 2 into a reactor, wherein the reaction temperature is 350 ℃, the operation pressure is 10MPa, and the volume space velocity is 30000 mL/(g) into the reactorcath) And preparing the low-carbon mixed alcohol from the carbon monoxide and the hydrogen in a molar ratio of 4: 1.
4, preparation method of specific catalyst
[ example 1 ]
According to the molar ratio of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2A to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 2 ]
According to the molar ratio of calcium nitrate, yttrium nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1B0.7Y0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2A to obtain Co/Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 3 ] A method for producing a polycarbonate
According to the molar ratio of 0 of calcium nitrate, cerium nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and glycol.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; obtaining the catalyst Ca through the step 1C0.7Ce0.3Ti0.7Co0.3O3. Reducing the mixture in the step 2A to obtain Co/CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 4 ] A method for producing a polycarbonate
According to the molar ratio of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7Mg0.3Ti0.7Co0.3O3. Reducing the mixture in the step 2A to obtain Co/MgO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 5 ] A method for producing a polycarbonate
According to the molar ratio of 0.7: 0.3: 0.7: 0.3: 2.4: preparing a mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7Sr0.3 Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2B to obtain Co/SrO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 6 ]
According to the molar ratio of calcium nitrate, barium nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing a mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7Ba0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2C to obtain Co/BaO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 7 ] A method for producing a polycarbonate
According to the molar ratio of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7K0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2D to obtain Co/K2O-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 8 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Al0.1O3(ii) a Reducing the mixture in the step 2E to obtain Co/Al-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 9 ] A method for producing a polycarbonate
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Mn0.1O3(ii) a Reducing the mixture in the step 2F to obtain Co/Mn-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 10 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Fe0.1O3(ii) a Reducing the mixture in the step 2G to obtain Co/Fe-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 11 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, nickel nitrate, citric acid and ethylene glycol of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Ni0.1O3(ii) a Reducing the mixture by step 2H to obtain Co/Ni-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 12 ] A method for producing a polycarbonate
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing a mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Cu0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Cu-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 13 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Zn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zn-La2O3-CaTiO3A catalyst. Test condition 3B for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 14 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Ga0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ga-La2O3-CaTiO3A catalyst. Test condition 3C for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 15 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, zirconium nitrate, citric acid and ethylene glycol of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst is obtained through the step 1ACa0.6La0.4Ti0.6Co0.3Zr0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zr-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 16 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, indium nitrate, citric acid and ethylene glycol of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3In0.1O3(ii) a Reducing the mixture In the step 2A to obtain Co/In-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 17 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, ammonium molybdate, citric acid and ethylene glycol of 0.6: 0.4: 0.6: 0.3: 0.1/7: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Mo0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mo-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 18 ] A method for producing a polycarbonate
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, niobium nitrate, citric acid and ethylene glycol of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6La0.4Ti0.6Co0.3Nb0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Nb-La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 19 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: 0.48 ofPreparing a mixed salt solution according to a proportion; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Al0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Al-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 20 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Mn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mn-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 21 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Fe0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Fe-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 22 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Ni0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ni-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 23 ] to provide
According to the mol ratio of calcium nitrate, yttrium nitrate, tetrabutyl titanate, cobalt nitrate, copper nitrate, citric acid and glycol0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Cu0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Cu-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 24 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Zn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zn-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 25 ]
According to the molar ratio of calcium nitrate, yttrium nitrate, tetrabutyl titanate, cobalt nitrate, gallium nitrate, citric acid and ethylene glycol of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Ga0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ga-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 26 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Zr0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zr-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 27 ] A method for producing a polycarbonate
According to the weight ratio of calcium nitrate, yttrium nitrate, tetrabutyl titanate, cobalt nitrate and nitric acidThe molar ratio of indium to citric acid to ethylene glycol is 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3In0.1O3(ii) a Reducing the mixture In the step 2A to obtain Co/In-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 28 ] to
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1/7: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Mo0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mo-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 29 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Y0.4Ti0.6Co0.3Nb0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Nb-Y2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 30 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Al0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Al-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 31 ]
According to the formula of calcium nitrate, cerium nitrate,The molar ratio of tetrabutyl titanate, cobalt nitrate, manganese nitrate, citric acid and ethylene glycol is 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Mn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mn-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 32 ] A method for producing a polycarbonate
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Fe0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Fe-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 33 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Ni0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ni-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 34 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Cu0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Cu-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 35 ]
According to calcium nitrate, cerium nitrateTetrabutyl titanate, cobalt nitrate, zinc nitrate, citric acid and ethylene glycol in a molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Zn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zn-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 36 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Ga0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ga-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 37 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Zr0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zr-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 38 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3In0.1O3(ii) a Reducing the mixture In the step 2A to obtain Co/In-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 39 ]
According to the formula of calcium nitrate, nitric acidThe molar ratio of cerium to tetrabutyl titanate, cobalt nitrate, ammonium molybdate, citric acid and ethylene glycol is 0.6: 0.4: 0.6: 0.3: 0.1/7: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Mo0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mo-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 40 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ce0.4Ti0.6Co0.3Nb0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Nb-CeO2-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 41 ] to provide a pharmaceutical composition
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Al0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Al-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 42 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Mn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mn-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 43 ]
According to calcium nitrate, strontium nitrate and tetrabutyl titanateThe molar ratio of ester, cobalt nitrate, ferric nitrate, citric acid and ethylene glycol was 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Fe0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Fe-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 44 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Ni0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ni-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 45 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Cu0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Cu-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 46 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Zn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zn-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 47 ]
According to the formula of calcium nitrate, strontium nitrate, tetrabutyl titanate, cobalt nitrate, gallium nitrate, citric acid and ethylThe molar ratio of the diols is 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Ga0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ga-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 48 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Zr0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zr-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 49 ] to carry out the invention
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3In0.1O3(ii) a Reducing the mixture In the step 2A to obtain Co/In-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 50 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1/7: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Mo0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mo-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 51 ] A method for producing a polycarbonate
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing a mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Sr0.4Ti0.6Co0.3Nb0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Nb-SrO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 52 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Al0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Al-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 53 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Mn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mn-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 54 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing a mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Fe0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Fe-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 55 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: 0.48 of the weight percentage to prepare a mixed salt solutionLiquid; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Ni0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ni-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 56 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Cu0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Cu-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 57 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Zn0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zn-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 58 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing a mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Ga0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Ga-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 59 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Zr0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Zr-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 60 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3In0.1O3(ii) a Reducing the mixture In the step 2A to obtain Co/In-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 61 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1/7: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Mo0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Mo-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 62 ]
According to the molar ratio of 0.6: 0.4: 0.6: 0.3: 0.1: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.6Ba0.4Ti0.6Co0.3Nb0.1O3(ii) a Reducing the mixture in the step 2A to obtain Co/Nb-BaO-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 63 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2B to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 64 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2C to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation. .
[ example 65 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2D to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 66 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2E to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 67 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2F to obtain Co/La2O3-CaTiO3A catalyst. Oxygen generationTest condition 3A for preparing lower alcohols by hydrogenation of carbon.
[ example 68 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2G to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 69 ]
According to the molar ratio of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture by step 2H to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 70 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2A to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
[ example 71 ]
According to the molar ratio of calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol of 0.7: 0.3: 0.7: 0.3: 2.4: preparing mixed salt solution according to the proportion of 0.48; the catalyst Ca is obtained through the step 1A0.7La0.3Ti0.7Co0.3O3(ii) a Reducing the mixture in the step 2A to obtain Co/La2O3-CaTiO3A catalyst. Test condition 3A for the preparation of lower alcohols by carbon monoxide hydrogenation.
Reference documents:
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Figure BDA0003533475950000151
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while the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.

Claims (6)

1. A cobalt-based catalyst characterized in that one or more of La or Co is partially substituted, but the ratio of (Ca + a) to (Ti + Co + B) is maintained at 1: 1; the molecular formula of which is Ca1-xAxTi1-α-βCoαBβO3Wherein, the relation of x, alpha and beta is alpha + beta which is x, the value range of x is 0-1, alpha is not 0, A is one or more of Y, La, Ce, Pr, Mg, Sr, Ba, K and Cs, B is one or more of Al, Mn, Fe, Ni, Cu, Zn, Ga, Zr, Nb, Mo and In.
2. The catalyst of claim 1, having the formula Ca1-xLaxTi1-xCoxO3Wherein the value range of x is 0-1.
3. The process for preparing the catalyst according to claim 1, characterized by comprising the steps of:
according to the formula Ca of perovskite1-xAxTi1-α-βCoαBβO3Weighing calcium nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and glycol according to the corresponding molar ratio of 1-x: x: 1- α - β: α: beta: 2.4: 0.48. heating and stirring the mixed solution at 60-100 ℃ until sol is obtained, and then drying at 80-200 ℃ for 6-24 hours. Finally, the samples are respectively roasted for 1-6h at the temperature of 2-10 ℃/min to 250-900 ℃ and the roasting is continued to be heated to 600-10 ℃ for 3-10 h.
4. The process for preparing the catalyst according to claim 2, characterized by comprising the steps of:
a series of Ca is prepared by citrate complexation method1-xLaxTi1-xCoxO3(x is 0-0.5 and 1). Firstly, calcium nitrate, lanthanum nitrate, tetrabutyl titanate, cobalt nitrate, citric acid and ethylene glycol are mixed according to the molar ratio of 1-x: x: 1-x: x: 2.4: 0.48 was mixed and dissolved. It is to be noted that tetrabutyl titanate needs to be dissolved in ethanol and then added to the mixed solution. Then, the above mixed solution is heated and stirred at 60-100 ℃ until sol is obtained, and then dried at 80-200 ℃ for 6-24 hours. Finally, the samples are respectively roasted for 1-6h at the temperature of 2-10 ℃/min to 250-1-xLaxTi1-xCoxO3。
5. A method for reducing a catalyst prepared according to claim 1 or 2, which comprises the main steps of placing the catalyst in a reduction furnace, and introducing the catalyst into the reduction furnace at a flow rate of 5 to 50 mL-min-1The reducing gas of (a) performs reduction of the catalyst, wherein the temperature increase rate is 2-20 ° C/min; the temperature is 500-900-degree C; the reduction time is 0.1-6 h. The reducing body is mainly hydrogen or carbon monoxide, and can also be mixed gas of hydrogen/nitrogen or carbon monoxide/nitrogen, wherein the volume fraction of the mixed gas is 1-99%.
6. The use of the catalyst obtained by the reduction method in claim 5 for preparing lower alcohols by hydrogenating carbon monoxide, which comprises the main step of adding the reduced catalyst into a reactor at a volume space velocity of 500mL 30000 mL/(g) under the conditions of a temperature of 200-cath) Introducing carbon monoxide and hydrogen, wherein the molar ratio of the carbon monoxide to the hydrogen is 1: (1-4).
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