CN110898848B - Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof - Google Patents

Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof Download PDF

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CN110898848B
CN110898848B CN201910749277.7A CN201910749277A CN110898848B CN 110898848 B CN110898848 B CN 110898848B CN 201910749277 A CN201910749277 A CN 201910749277A CN 110898848 B CN110898848 B CN 110898848B
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copper
catalyst
rhodium
cobalt
preparing
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CN110898848A (en
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杜波
马明水
赵锐君
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ENN Science and Technology Development Co Ltd
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ENN Science and Technology Development Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a catalyst for preparing low-carbon alcohol from synthesis gas and a preparation method thereof, wherein the catalyst comprises a composition of copper, cobalt and rhodium; the composition comprises at least one of a copper-rhodium interface structure, a cobalt-rhodium interface structure and a copper-rhodium-cobalt interface structure, wherein the mass ratio of copper element to cobalt element to rhodium element is 15-20:6-10:1, and during preparation, copper and cobalt are subjected to parallel flow precipitation to obtain a copper-cobalt catalyst precursor, and rhodium is loaded on the surface of the copper-cobalt catalyst precursor through equal volume impregnation. The invention mainly comprises oxides of copper, cobalt and rhodium, has a copper-rhodium-cobalt interface structure, introduces rhodium elements while synthesizing low-carbon alcohol by copper-cobalt interface synergistic catalysis, constructs copper-cobalt-rhodium interface synergistic catalysis, increases CO non-dissociative adsorption sites by utilizing interface interaction of copper-rhodium or rhodium-cobalt or copper-rhodium-cobalt, improves the selectivity of total alcohol, increases the carbon chain growth capacity, and improves C 2 Selectivity to +alcohol.

Description

Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof
Technical Field
The invention relates to the technical field of low-carbon alcohol preparation, in particular to a catalyst for preparing low-carbon alcohol from synthesis gas and a preparation method thereof.
Background
Aiming at the energy structure characteristics of lean oil and rich coal in China, the technology of efficient clean coal resources is utilized, and the development of the green fuel has important strategic significance and application prospect. The technology for preparing low-carbon mixed alcohol (C1-C5 alcohol) from coal-based synthesis gas is used as an important component of C1 chemical industry and is an important way for synthesizing liquid fuel, oil additives and bulk chemicals in a non-petroleum route. Meanwhile, in recent years, research shows that the use of Methyl Tertiary Butyl Ether (MTBE) threatens human health, simultaneously prevents ozone from generating, and the MTBE substitutes are actively explored in various countries. The low-carbon mixed alcohol can completely replace MTBE as a gasoline additive because of the high octane number and good blending performance with gasoline. Meanwhile, alcohol fine chemicals with high added value, such as ethanol, propanol and the like, can be prepared through separation.
The catalyst is used as a key technology for preparing low-carbon mixed alcohol from coal-based synthetic gas, the catalyst for preparing low-carbon mixed alcohol from coal-based synthetic gas at present is mainly copper-cobalt or copper-iron catalyst, the catalyst is prepared by adopting a precipitation method, and the catalyst has low total alcohol selectivity and C 2 The problem of low selectivity of +alcohol (lower alcohols containing 2 or more carbon atoms, such as ethanol, propanol, butanol, etc.) restricts the application and popularization of the technology.
Disclosure of Invention
In view of the above, the invention provides a catalyst for preparing low-carbon alcohol from synthesis gas and a preparation method thereof, which aims to solve the problems of total alcohol selectivity and C of the existing catalyst for preparing low-carbon alcohol from synthesis gas 2 The + alcohol selectivity is low.
In one aspect, the invention provides a catalyst for preparing low-carbon alcohol from synthesis gas, which comprises a composition of copper, cobalt and rhodium; the composition contains at least one of a copper-rhodium interface structure, a cobalt-rhodium interface structure and a copper-rhodium-cobalt interface structure, wherein the mass ratio of copper element to cobalt element to rhodium element is (15-20:6-10:1).
Further, in the catalyst for preparing the low-carbon alcohol from the synthetic gas, the composition consists of a copper-rhodium-cobalt interface structure.
Further, in the catalyst for producing low carbon alcohol from synthesis gas, at least one of alkali metal and transition metal element is added to the composition.
Further, in the catalyst for preparing low-carbon alcohol from synthesis gas, the alkali metal is at least one of potassium and cesium; the transition metal is at least one of manganese and zirconium.
Further, in the catalyst for preparing low-carbon alcohol from synthesis gas, the mass ratio of each element in the composition needs to satisfy the following conditions: copper: manganese: zirconium=2 to 5:1 to 2:1.
Further, in the catalyst for preparing low-carbon alcohol from synthesis gas, the mass ratio of each element in the composition also needs to satisfy the following conditions: copper: potassium or copper: cesium=6 to 10:1.
The catalyst for preparing the low-carbon alcohol from the synthesis gas mainly comprises oxides of copper, cobalt and rhodium, a copper-rhodium-cobalt interface structure exists, rhodium element is introduced while the low-carbon alcohol is synthesized by copper-cobalt interface synergistic catalysis, copper-cobalt-rhodium interface synergistic catalysis is constructed, and the CO non-dissociative adsorption position is increased by utilizing the interface interaction between copper-rhodium or rhodium-cobalt or copper-rhodium-cobalt, so that the total alcohol selectivity is improved, the carbon chain growth capacity is increased, and the C is improved 2 Selectivity to +alcohol.
On the other hand, the invention also provides a preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, which comprises the following steps: step 1, preparing a mixed solution a with a first preset concentration from metal salts of copper and cobalt according to a metering ratio; preparing a precipitant into a solution b with a second preset concentration; adding the mixed solution a and the mixed solution b into a reaction container simultaneously, keeping the pH value of the solution to be 7-10, carrying out precipitation reaction at a preset temperature until the reaction is finished, and aging, washing, drying and roasting to obtain a first catalyst precursor;
and 2, weighing rhodium metal salt to prepare a mixed solution c, soaking the mixed solution c into the first catalyst precursor in an equal volume, and drying and roasting to obtain a first catalyst finished product.
Further, in the preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, the preparation raw material of the catalyst further comprises at least one of potassium and cesium, and the step 2 is as follows: weighing rhodium, potassium or rhodium and cesium metal salts to prepare a mixed solution c ', soaking the mixed solution c' in the first catalyst precursor in an equal volume, and drying and roasting to obtain a second catalyst finished product.
Further, in the preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, the preparation raw material of the catalyst further comprises at least one of manganese and zirconium, and the step 1 is as follows: preparing a mixed solution a' with a first preset concentration from metal salts of copper, cobalt, manganese and zirconium according to a metering ratio; preparing a precipitant into a solution b' with a second preset concentration; and adding the mixed solution a 'and the mixed solution b' into a reaction container simultaneously, keeping the pH value of the solution to be 7-10, carrying out precipitation reaction at a preset temperature until the reaction is finished, and aging, washing, drying and roasting to obtain a second catalyst precursor.
In the preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, the first preset concentration is 0.3-1.2 mol/L, and the second preset concentration is 0.3-1.2 mol/L.
Further, in the preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, the precipitant is selected from any one of sodium carbonate, sodium hydroxide and ammonia water.
Further, in the preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas, the preset temperature is 50-90 ℃.
The preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas comprises the steps of firstly carrying out parallel flow precipitation on copper and cobalt to obtain a copper-cobalt catalyst precursor, then carrying rhodium on the surface of the copper-cobalt catalyst precursor through equal volume impregnation, so that the dispersibility of rhodium on the surface of the catalyst can be obviously improved, the utilization rate of noble metal is improved, the coating of auxiliary agents on rhodium is reduced, the active sites of rhodium are easier to expose, the probability and the number of interaction interfaces between copper-rhodium or rhodium-cobalt or copper-cobalt-rhodium are improved, the synergistic catalytic effect between copper, cobalt and rhodium is enhanced, and the total alcohol selectivity and C are further improved 2 Selectivity to +alcohol.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below. It should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
The catalyst for preparing the low-carbon alcohol from the synthetic gas comprises a composition of copper, cobalt and rhodium; the composition contains at least one of a copper-rhodium interface structure, a cobalt-rhodium interface structure and a copper-rhodium-cobalt interface structure, wherein the mass ratio of copper element to cobalt element to rhodium element is (15-20:6-10:1).
Specifically, the sources of the respective elements of copper, cobalt and rhodium may be soluble metal salts corresponding to each other, and are preferably any one of nitrate, sulfate and chlorate, and more preferably nitrate. Such as copper nitrate, cobalt nitrate, rhodium nitrate, etc. In practice, the mass ratio of the copper element to the cobalt element to the rhodium element may be preferably 15-20:10:1, for example, in this embodiment, the mass ratio of the copper element to the cobalt element to the rhodium element is 15:10:1, 15:6:1, 20:6:1, 20:10:1, 17:10:1, etc.
Due to the presence of at least one or more of a copper-rhodium interface structure, a cobalt-rhodium interface structure, and a copper-rhodium-cobalt interface structure in the catalyst composition. Rhodium can promote copper to generate a non-dissociative adsorption site of CO and promote cobalt to form an alcohol carbon chain, rhodium is positioned between copper atoms and cobalt atoms in a copper-rhodium-cobalt interface structure, rhodium element is introduced while copper-cobalt interface synergistic catalysis is performed to synthesize low-carbon alcohol, copper-rhodium-cobalt interface synergistic catalysis is constructed, interaction among copper-rhodium or rhodium-cobalt or copper-rhodium-cobalt interfaces is utilized, the non-dissociative adsorption site of CO is increased, the total alcohol selectivity is improved, the growth capacity of carbon chains is increased, and C is improved 2 Selectivity to +alcohol. ,
preferably, the catalyst composition consists of a copper-rhodium-cobalt interface structure, i.e., each of the smallest units in the composition is a copper-rhodium-cobalt unit, the interaction between the individual copper-rhodium-cobalt interface structural units is further enhanced, the non-dissociative adsorption sites of CO and the carbon chain growth capacity are further increased, thereby further improving the selectivity of the total alcohol and C 2 Selectivity to +alcohol.
The above clearly shows that the catalyst for preparing low carbon alcohol from synthetic gas in the embodiment of the invention mainly comprises oxides of copper, cobalt and rhodium, has a copper-rhodium-cobalt interface structure, introduces rhodium elements while synthesizing low carbon alcohol by the synergistic catalysis of copper-cobalt interface, constructs the synergistic catalysis of copper-cobalt-rhodium interface, increases the CO non-dissociative adsorption position by utilizing the interfacial interaction of copper-rhodium or rhodium-cobalt or copper-rhodium-cobalt, improves the total alcohol selectivity, and simultaneously increases the carbon chain growth capacity, thereby improvingHigh C 2 Selectivity to +alcohol.
In the above embodiment, at least one of an alkali metal and a transition metal element is further added to the catalyst composition. Wherein the alkali metal is at least one of sodium, rubidium, potassium and cesium, preferably at least one of potassium and cesium; the transition metal is at least one of manganese, zirconium, nickel and zinc; preferably at least one of manganese and zirconium.
When potassium or cesium is added to the catalyst composition, the mass ratio of each element needs to satisfy the condition: copper: potassium or copper: cesium=6 to 10:1; preferably, copper: potassium or copper: cesium mass ratio=7 to 8:1. In this example, copper: potassium or copper: the mass ratio of cesium can be 7:1, 7.6:1, 8:1, etc.
In this example, by adding the alkali metal auxiliary potassium and/or cesium to the copper, cobalt, rhodium composition, the acidity of the catalyst surface can be neutralized, suppressing side reactions such as alcohol dehydration, etc.; meanwhile, the dissociation capability of the catalyst for CO is changed, the hydrogenation reaction rate is inhibited, and the generation of hydrocarbon byproducts is reduced, so that the total alcohol selectivity of the catalyst can be improved.
When manganese and zirconium are added to the catalyst composition, the mass ratio of each element needs to satisfy the condition: copper: manganese: zirconium=2 to 5:1 to 2:1, preferably copper: manganese: zirconium mass ratio = 2-5:1:1; further preferably, copper: manganese: zirconium mass ratio=3-4:1:1.
In the embodiment, the transition metal auxiliary agent manganese and zirconium are added into the copper, cobalt and rhodium composition, so that the effect of stabilizing the grain size and the dispersity of the active components of the catalyst can be achieved through the interaction between metal oxides, the sintering of the catalyst caused by the aggregation and growth of the catalyst particles due to the thermal effect in the reaction process is effectively avoided, the thermal stability and the dispersity of the catalyst can be well improved, the interfacial contact probability between the active components can be increased, the synergistic catalytic effect between the active components is improved, and the catalytic performance is improved.
In a first embodiment of the invention, the preparation method of the catalyst for preparing the low-carbon alcohol from the synthesis gas comprises the following steps:
step 1, preparing a mixed solution a with a first preset concentration from metal salts of copper and cobalt according to a metering ratio; preparing a precipitant into a solution b with a second preset concentration; and adding the mixed solution a and the mixed solution b into a reaction container at the same time, keeping the pH value of the solution to be 7-10, carrying out precipitation reaction at a preset temperature until the reaction is finished, and aging, washing, drying and roasting to obtain a first catalyst precursor.
Specifically, the amount of the metal salts of copper and cobalt may be determined according to the mass ratio of the respective elements in the above-mentioned product examples. The first preset concentration is 0.3-1.2 mol/L, preferably 0.5-1 mol/L; the second preset concentration is 0.3 to 1.2mol/L, preferably 0.5 to 1mol/L. In this embodiment, the first preset concentration and the second preset concentration may be equal. The proper concentration of the solution can avoid uneven mixing of the precipitated components caused by too high or too low local concentration in the precipitation process.
The precipitant is selected from any one of sodium carbonate, sodium hydroxide and ammonia water, preferably sodium carbonate, and the selected precipitant is easy to form basic carbonate mixed crystal, and is easy to form solid solution in the roasting process, so that the interaction between active components is increased.
In the specific implementation, the mixed solution a and the mixed solution b can be simultaneously added into a reaction vessel with stirring and heating in a dropwise manner, and the temperature for carrying out precipitation reaction is 50-90 ℃; preferably 60-80 ℃. Suitable precipitation temperatures facilitate the formation of precipitates of uniform particle size and uniform dispersion of the active components.
During the precipitation, the pH of the solution is maintained at 7-10, preferably at 8-9, so that the precipitant reacts well with the metal salt. After the precipitation reaction is finished, aging operation is needed, the aging time is preferably kept at 60-120 minutes, and the proper pH value and aging time are favorable for stabilizing the precipitation crystal form and the grain size.
And (3) centrifugally washing the precipitate obtained by the precipitation reaction until the filtrate is neutral, and drying and roasting the precipitate to obtain the first catalyst precursor. Wherein the temperature of the calcination may be 400-450 ℃.
And 2, weighing rhodium metal salt to prepare a mixed solution c, soaking the mixed solution c into the first catalyst precursor in an equal volume, and drying and roasting to obtain a first catalyst finished product.
Specifically, the amount of the metal salt of rhodium to be used may be determined based on the mass ratio of each element in the above-mentioned product examples. In the specific implementation, ultrasonic treatment is adopted in the process of immersing the mixed solution c in the first catalyst precursor in an equal volume, so that the active components are uniformly diffused in the catalyst pore canal, and the ultrasonic treatment time can be 2-4 hours.
In this embodiment, since the amount of rhodium added is small, the synergistic catalytic effect between copper, cobalt and rhodium can be fully exerted by incorporating rhodium into the structure when copper and cobalt have formed the catalyst precursor in order to avoid the effect of the active sites being affected by the copper and cobalt being coated inside.
In the second embodiment of the present invention, step 1 is the same as step 1 in the first embodiment. Since the raw material for preparing the catalyst may further include at least one of potassium and cesium, step 2 in this embodiment is: weighing rhodium, potassium or rhodium and cesium metal salts to prepare a mixed solution c ', soaking the mixed solution c' in the first catalyst precursor in an equal volume, and drying and roasting to obtain a second catalyst finished product. The amount of rhodium, potassium or rhodium and cesium metal salts can be determined according to the mass ratio of the elements in the product embodiment, and other process conditions are the same as those in step 2 in the first embodiment.
In the third embodiment of the present invention, since the raw material for preparing the catalyst further includes at least one of manganese and zirconium, step 1 in this embodiment is:
preparing a mixed solution a' with a first preset concentration from metal salts of copper, cobalt, manganese and zirconium according to a metering ratio; preparing a precipitant into a solution b' with a second preset concentration; and (3) simultaneously dropwise adding the mixed solution a 'and the mixed solution b' into a reaction container, keeping the pH value of the solution to be 7-10, carrying out precipitation reaction at a preset temperature until the reaction is finished, and aging, washing, drying and roasting to obtain a second catalyst precursor. In this step, the amount of the copper, cobalt, manganese, zirconium metal salts may be determined according to the mass ratio of the respective elements in the above-mentioned product examples. The remaining process conditions are the same as in step 1 of the first embodiment.
In this embodiment, step 2 includes two cases, which are the same as step 2 in the first embodiment or the second embodiment, specifically:
first case: and weighing rhodium metal salt to prepare a mixed solution c1, immersing the mixed solution c1 in the second catalyst precursor in an equal volume, and drying and roasting to obtain a third catalyst finished product. The amount of raw materials and the process conditions in this step are the same as those in step 2 in the first embodiment.
Second case: and weighing rhodium, potassium or rhodium and cesium metal salts to prepare a mixed solution c2, immersing the mixed solution c2 into the second catalyst precursor in an equal volume, and drying and roasting to obtain a fourth catalyst finished product. The amount of raw materials and the process conditions in this step are the same as those in step 2 in the second example.
In the preparation method of the catalyst for preparing the low-carbon alcohol from the synthetic gas, copper and cobalt are subjected to parallel flow precipitation to obtain a copper-cobalt catalyst precursor, rhodium is loaded on the surface of the copper-cobalt catalyst precursor through equal volume impregnation, so that the dispersibility of rhodium on the surface of the catalyst can be remarkably improved, the utilization rate of noble metal is improved, the coating of the rhodium by an auxiliary agent is reduced, the active site of rhodium is easier to expose, the probability and the number of interaction interfaces between copper-rhodium or rhodium-cobalt or copper-cobalt-rhodium are improved, the synergistic catalytic effect between copper and cobalt and rhodium is enhanced, and the total alcohol selectivity and C are further improved 2 Selectivity to +alcohol.
The present invention will be described in detail with reference to the following examples.
Example 1
(1) Catalyst preparation
The mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium=20:10:1, copper nitrate, cobalt nitrate and rhodium nitrate are weighed according to a proportion, copper nitrate and cobalt nitrate are dissolved and prepared into a uniform solution a with the concentration of 0.5-1M, sodium carbonate is prepared into a solution b with the same concentration, the two solutions a and b are simultaneously and uniformly dripped into a container accompanied by heating and stirring, the PH value of the solution is kept between 8 and 9, the solution is aged for 60-120 minutes after dripping, centrifugal washing is carried out, and the solution is dried and roasted after being washed until the filtrate is neutral, so that the catalyst precursor A is obtained. Preparing weighed rhodium nitrate into a uniform solution c, dripping the solution c into the catalyst precursor A for dipping, carrying out ultrasonic treatment for 2-4 hours after dripping, and drying and roasting to obtain a catalyst finished product B.
(2) Catalyst evaluation
Adopting a fixed bed micro-reaction device, filling 5ml of catalyst, diluting the volume of quartz sand by 1:1, and reducing the catalyst: v (V) H2 ：V N2 =1:4, the amount of reduction was 500ml/min, the pressure was 0.1MPa, the reduction temperature was 400 ℃, and the reduction time was 4 hours. Cooling to 280 ℃ after the reduction of the catalyst is completed, and introducing raw gas, V H2 /V CO =2: 1, the reaction pressure is 5MPa, and the airspeed is 8000h -1 . The evaluation results are shown in Table 1 below.
Example 2
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium=15:10:1, otherwise the conditions are the same as in example 1
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 3
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium=17:10:1, otherwise the conditions are the same as in example 1
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 4
(1) Catalyst preparation
The mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 20:10:1, copper: potassium=7:1, copper nitrate, cobalt nitrate, rhodium nitrate and potassium nitrate are weighed according to a proportion, the copper nitrate and the cobalt nitrate are dissolved and prepared into a uniform solution a with the concentration of 0.5-1M, sodium carbonate is prepared into a solution b with the same concentration, the solution a and the solution b are simultaneously and uniformly dripped into a container accompanied by heating and stirring, the PH value of the solution is kept between 8 and 9, the solution is aged for 60-120 minutes after the dripping, centrifugal washing is carried out, and the solution is dried and roasted after being washed until the filtrate is neutral, so that the catalyst precursor A is obtained. Preparing weighed rhodium nitrate and potassium nitrate into a uniform solution c, dripping the solution c into the catalyst precursor A for dipping, carrying out ultrasonic treatment for 2-4 hours after dripping, and drying and roasting to obtain a catalyst finished product B.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 5
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 15:10:1, copper: potassium=8:1, otherwise the conditions are the same as in example 4.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 6
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 17:10:1, copper: potassium=7.6:1, otherwise the conditions are the same as in example 4
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 7
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 20:10:1, copper: cesium=7:1, otherwise the conditions are the same as in example 4.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 8
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 15:10:1, copper: cesium=8:1, otherwise the conditions are the same as in example 4.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 9
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 17:10:1, copper: cesium=7.6:1, otherwise the conditions are the same as in example 4.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 10
(1) Catalyst preparation
The mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 20:10:1, copper: manganese: zirconium=3:1:1, copper nitrate, cobalt nitrate, rhodium nitrate, manganese nitrate and zirconium nitrate are weighed according to a proportion, copper nitrate, cobalt nitrate, manganese nitrate and zirconium nitrate are dissolved and prepared into a uniform solution a with the concentration of 0.5-1M, sodium carbonate is prepared into a solution b with the same concentration, the two solutions a and b are simultaneously and uniformly dripped into a container accompanied by heating and stirring, the PH value of the solution is kept between 8 and 9, the solution is aged for 60-120 minutes after the dripping is finished, centrifugal washing is carried out, and drying and roasting are carried out after the filtrate is neutral, so that the catalyst precursor A is obtained. Preparing weighed rhodium nitrate into a uniform solution c, dripping the solution c into the catalyst precursor A for dipping, carrying out ultrasonic treatment for 2-4 hours after dripping, and drying and roasting to obtain a catalyst finished product B.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 11
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 15:10:1, copper: manganese: zirconium=4:1:1, other conditions were the same as in example 10.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 12
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 17:10:1, copper: manganese: zirconium=3.4:1:1, other conditions were the same as in example 10.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 13
(1) Catalyst preparation
The mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 20:10:1, copper: manganese: zirconium=3:1:1, copper: potassium=7:1, copper nitrate, cobalt nitrate, rhodium nitrate, manganese nitrate, zirconium nitrate and potassium nitrate are weighed according to a proportion, copper nitrate, cobalt nitrate, manganese nitrate and zirconium nitrate are dissolved and prepared into a uniform solution a with the concentration of 0.5-1M, sodium carbonate is prepared into a solution b with the same concentration, the two solutions a and b are simultaneously and uniformly dripped into a container accompanied by heating and stirring, the PH value of the solution is kept between 8 and 9, the solution is aged for 60-120 minutes after the dripping is finished, centrifugal washing is carried out, and drying and roasting are carried out after the filtrate is neutral, so that the catalyst precursor A is obtained. Preparing weighed rhodium nitrate and potassium nitrate into a uniform solution c, dripping the solution c into the catalyst precursor A for dipping, carrying out ultrasonic treatment for 2-4 hours after dripping, and drying and roasting to obtain a catalyst finished product B.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 14
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 15:10:1, copper: manganese: zirconium=4:1:1, copper: potassium=8:1, otherwise the conditions are the same as in example 13.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 15
(1) The preparation of the catalyst comprises the following components in percentage by mass: cobalt: rhodium = 17:10:1, copper: manganese: zirconium = 3.4:1:1, copper: potassium=7.6:1, otherwise the conditions are the same as in example 13.
(2) The catalyst was evaluated under the same conditions as in example 1, and the evaluation results are shown in Table 1 below.
Example 16
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 20:10:1, copper: manganese: zirconium=3:1:1, copper: cesium=7:1, otherwise the conditions are the same as in example 13.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 17
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 15:10:1, copper: manganese: zirconium=4:1:1, copper: cesium=8:1, otherwise the conditions are the same as in example 13.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
Example 18
(1) And (3) preparing a catalyst: the mass ratio of the elements of each component of the catalyst is copper: cobalt: rhodium = 17:10:1, copper: manganese: zirconium = 3.4:1:1, copper: cesium=7.6:1, otherwise the conditions are the same as in example 13.
(2) Catalyst evaluation: the evaluation conditions were the same as those of example 1, and the evaluation results are shown in Table 1 below.
TABLE 1 catalytic performance of synthesis gas to lower alcohols
Figure RE-GDA0002374555910000111
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Figure RE-GDA0002374555910000121
In Table C 3 +OH is an alcohol containing 3 or more carbon atoms, and the distribution of the alcohol product refers to the mass percentage of various alcohols in the mixed alcohol product obtained after the reaction of preparing low-carbon mixed alcohol from coal-based synthesis gas.
As can be seen from Table 1, total alcohols (methanol, ethanol, C in the reaction of coal-based synthesis gas to produce low carbon mixed alcohols) 3 +OH and other alcohols) space-time yield can reach more than 270mg/ml.cat.h, total alcohol selectivity reaches more than 54%, C 2 +OH Selectivity (alcohol and C in alcohol product distribution) 3 The sum of the percentages of +OH) reaches more than 70 percent, the space-time yield of the total alcohol is generally 100 to 200mg/ml.cat.h, the total alcohol selectivity is generally 30 to 50 percent, C 2 The total alcohol selectivity and C of the examples of the present invention are compared with the +OH selectivity of typically 30 to 60% 2 Higher +OH selectivity, higher total alcohol space-time yield and better catalytic effect.
In addition, the catalyst provided by the invention has stable performance after reacting for 100 hours, which indicates that the catalyst provided by the embodiment of the invention has good stability.
In summary, the catalyst for preparing low-carbon alcohol from the synthesis gas provided by the embodiment of the invention passes throughRhodium element is introduced into a copper-cobalt catalytic system, a copper-cobalt-rhodium interface structure is constructed, and the low-carbon alcohol is prepared by the synthesis gas through synergistic catalysis, so that the total alcohol selectivity and C of the low-carbon alcohol prepared by the synthesis gas are improved 2 +oh selectivity; further, potassium and cesium auxiliary agents are added to inhibit the generation of hydrocarbons, so that the selectivity of the total alcohol is increased; furthermore, manganese and zirconium auxiliary agents are added into the catalyst composition, the proportion of the catalyst components is reasonably configured, and the dispersibility and stability of the catalyst active components are improved. During preparation, copper and cobalt are subjected to parallel flow precipitation to obtain a copper-cobalt catalyst precursor, rhodium is loaded on the surface of the copper-cobalt catalyst precursor through equal volume impregnation, so that the dispersibility of rhodium on the surface of the catalyst can be remarkably improved, the utilization rate of noble metal is improved, the coating of auxiliary agent on rhodium is reduced, the active site of rhodium is easier to expose, the probability and the number of interaction interfaces between copper and rhodium or rhodium-cobalt or copper and cobalt-rhodium are improved, the synergistic catalytic effect between copper and cobalt and rhodium is enhanced, and the total alcohol selectivity and C are further improved 2 Selectivity to +alcohol.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims (10)

1. A catalyst for preparing low-carbon alcohol from synthesis gas, which is characterized by comprising a composition of copper, cobalt and rhodium; the composition contains at least one of a copper-rhodium interface structure, a cobalt-rhodium interface structure and a copper-rhodium-cobalt interface structure, wherein the mass ratio of copper element to cobalt element to rhodium element is (15-20:6-10:1); the catalyst is provided with a copper-cobalt catalyst precursor, and rhodium is loaded on the surface of the copper-cobalt catalyst precursor; at least one of alkali metals is also added into the composition; the alkali metal is at least one of potassium and cesium; the mass ratio of each element in the composition also needs to meet the following conditions: copper: potassium or copper: cesium=6 to 10:1.
2. The catalyst for preparing low-carbon alcohol from synthetic gas according to claim 1, wherein the composition is prepared from copper-rhodium-
Cobalt interface structure.
3. The catalyst for producing lower alcohols from synthesis gas according to claim 1, wherein said composition is further added with
There is at least one of transition metal elements.
4. The catalyst for producing a lower alcohol from a synthesis gas according to claim 3, wherein the transition metal is at least one of manganese and zirconium.
5. The catalyst for preparing low-carbon alcohol from synthetic gas according to claim 4, wherein the mass ratio of each element in the composition satisfies the following conditions: copper: manganese: zirconium=2 to 5:1 to 2:1.
6. A method for preparing the catalyst for preparing low-carbon alcohol from synthesis gas according to claim 1, comprising the following steps:
step 1, preparing a mixed solution a with a first preset concentration from metal salts of copper and cobalt according to a metering ratio; preparing a precipitant into a solution b with a second preset concentration; adding the mixed solution a and the mixed solution b into a reaction container at the same time, keeping the pH value of the solution to be 7-10, carrying out precipitation reaction at a preset temperature until the reaction is finished, and aging, washing, drying and roasting to obtain a first catalyst precursor, wherein the first catalyst precursor is a copper-cobalt catalyst precursor;
step 2, the preparation raw materials of the catalyst further comprise at least one of potassium and cesium, and when the catalyst composition is added with potassium or cesium, the mass ratio of each element needs to satisfy the condition: copper: potassium or copper: cesium=6 to 10:1; weighing rhodium, potassium or rhodium and cesium metal salts to prepare a mixed solution c ', soaking the mixed solution c' in the first catalyst precursor in an equal volume, and drying and roasting to obtain a second catalyst finished product.
7. The method for preparing a catalyst for preparing low-carbon alcohol from synthesis gas according to claim 6, wherein the raw materials for preparing the catalyst further comprise at least one of manganese and zirconium, and the step 1 is as follows: preparing a mixed solution a' with a first preset concentration from metal salts of copper, cobalt, manganese and zirconium according to a metering ratio; preparing a precipitant into a solution b' with a second preset concentration; and adding the mixed solution a 'and the mixed solution b' into a reaction container simultaneously, keeping the pH value of the solution to be 7-10, carrying out precipitation reaction at a preset temperature until the reaction is finished, and aging, washing, drying and roasting to obtain a second catalyst precursor.
8. The method for preparing a catalyst for preparing low-carbon alcohol from synthesis gas according to claim 6, wherein the first preset concentration is 0.3-1.2 mol/L, and the second preset concentration is 0.3-1.2 mol/L.
9. The method for preparing a catalyst for producing a lower alcohol from a synthesis gas according to claim 6, wherein the precipitant is any one selected from sodium carbonate, sodium hydroxide and aqueous ammonia.
10. The method for preparing a catalyst for preparing low carbon alcohol from synthesis gas according to claim 6, wherein the preset temperature is 50-90 ℃.
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