CN114849725A - Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof - Google Patents

Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof Download PDF

Info

Publication number
CN114849725A
CN114849725A CN202210530831.4A CN202210530831A CN114849725A CN 114849725 A CN114849725 A CN 114849725A CN 202210530831 A CN202210530831 A CN 202210530831A CN 114849725 A CN114849725 A CN 114849725A
Authority
CN
China
Prior art keywords
red mud
catalyst
low
based catalyst
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210530831.4A
Other languages
Chinese (zh)
Other versions
CN114849725B (en
Inventor
关倩
徐海燕
杨树华
张竟月
何晓峰
师新广
尚延峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan Academy of Sciences
Original Assignee
Henan Academy of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan Academy of Sciences filed Critical Henan Academy of Sciences
Priority to CN202210530831.4A priority Critical patent/CN114849725B/en
Publication of CN114849725A publication Critical patent/CN114849725A/en
Application granted granted Critical
Publication of CN114849725B publication Critical patent/CN114849725B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8871—Rare earth metals or actinides
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J23/894—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 rare earths or actinides
    • 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
    • B01J23/8993—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 chromium, molybdenum or tungsten
    • 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
    • C07C29/154—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 copper, silver, gold, or compounds thereof
    • 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
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the technical field of biomass energy utilization, and particularly relates to a red mud-based catalyst for synthesizing low-carbon alcohol, and preparation and application thereof. The catalyst takes red mud as a carrier, the active ingredient is Cu, and the auxiliary agents are Rh, Mo and ZrOne or more of La, Ce, Mn, Co and Cr; the mass content of the active component in the catalyst is 10-80%, the mass content of the auxiliary agent is 10-50%, and the rest is a carrier. The invention uses the red mud as a carrier to prepare the catalyst, and applies the catalyst to the reaction of preparing the low carbon alcohol from the biomass synthesis gas, thereby improving the utilization rate of biomass resources, and solving the problems of high cost of the catalyst, low CO conversion rate and C in the reaction of preparing the low carbon alcohol from the synthesis gas in the prior art 2+ Low alcohol selectivity and industrial application potential.

Description

Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof
Technical Field
The invention belongs to the technical field of biomass energy utilization, and particularly relates to a red mud-based catalyst for synthesizing low-carbon alcohol, and preparation and application thereof.
Background
The crisis and problems faced by the traditional fossil energy sources are driving the development of new clean energy sources to be increasingly important. The synthesis gas is CO and H 2 The chemical raw material gas as a main component is derived from coal, biomass and the like, can be directly converted into oxygen-containing compounds such as alcohols and the like under the action of a catalyst, and has practical significance as a chemical raw material source and energy. At present, the conversion of synthesis gas into lower alcohol for liquid fuel is gradually becoming a utilization mode of green energy, however, the existing synthesis reaction of lower alcohol has the problems of low CO conversion rate and low selectivity of lower alcohol, wherein the catalyst and the catalytic activity thereof are the key points of the above problems, and the exploration and development of a high-efficiency and stable catalyst is one of the hot spots of research on synthesis gas preparation of lower alcohol. The Cu @ Fe core-shell structure catalyst for preparing low-carbon alcohol from synthesis gas is prepared by CN104841432B in China, but the selectivity of hydrocarbons is higher. The chinese patent CN108465468B uses carbon nanotubes as a carrier to prepare a catalyst for preparing low-carbon alcohol from synthesis gas, and the selectivity of C2+ alcohol in the obtained product is not high. The red mud is used as polluting waste residue discharged in the aluminum industrial process and contains metal elements such as iron, aluminum, potassium, gallium, lanthanum, vanadium, titanium, scandium and the like. Therefore, the red mud has the application potential of catalyzing CO dissociation, and can be used as a basic raw material for preparing a low-carbon alcohol catalyst from synthesis gas. The discharge amount of the red mud in China tends to increase year by year, about 6000 million tons of red mud are discharged per year, but the utilization rate is very low. Therefore, the red mud is used as a catalyst carrierThe method is used for preparing low-carbon alcohol from biomass synthesis gas, can reduce the pollution problem of red mud to the environment, and can improve the utilization rate of biomass.
Disclosure of Invention
The invention aims to provide a red mud-based catalyst for synthesizing low-carbon alcohol and a preparation method thereof, and the catalyst prepared by the method has high catalytic activity and C 2+ High alcohol selectivity, stable performance, easily obtained carrier raw materials, simple preparation process and low cost.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the red mud-based catalyst for synthesizing the low-carbon alcohol takes red mud as a carrier, the active ingredient is Cu, and the auxiliary agent is one or more of Rh, Mo, Zr, La, Ce, Mn, Co and Cr; the mass content of the active component in the catalyst is 10-80%, the mass content of the auxiliary agent is 10-50%, and the rest is a carrier.
Preferably, the carrier is red mud after dealkalization treatment.
The invention further provides a preparation method of the red mud-based catalyst for synthesizing the low-carbon alcohol, which comprises the steps of firstly preparing a carrier, then fusing the mixed solution dissolved with the active components and the salt of the auxiliary agent with the carrier by a vacuum impregnation method, and then filtering, drying and roasting to obtain the catalyst.
The preparation of the carrier was as follows: mixing the red mud and an ethanol solution, carrying out ultrasonic treatment for 1-3h, then replacing the ethanol solution with water, and drying after the pH value of the replacement water is reduced to be neutral.
Preferably, the mass ratio of the red mud to the ethanol solution is 1: 3-5.
The ethanol solution is preferably absolute ethanol with the volume concentration of 95 percent.
The red mud-based catalyst has good application in synthesizing low-carbon alcohol, and after being placed in a fixed bed reactor, the catalyst is firstly placed in H 2 Reducing the catalyst in atmosphere and normal pressure, and then carrying out the reaction for synthesizing the low-carbon alcohol.
Further, when the catalyst is reduced, the reduction temperature is 300-400 ℃, and the reduction time is 2-5 h. Preferably, the reduction temperature is 350 ℃ and the reduction time is 4 h.
Further, the reaction pressure is 2-6MPa, the reaction temperature is 220- -1 Under the reaction condition of (1), carrying out the reaction of synthesizing low-carbon alcohol, wherein H in the raw material gas 2 And CO in a volume ratio of 0.5-3.5: 1.
preferably, the synthesis of the low-carbon alcohol is carried out under the conditions that the pressure is 3.0MPa, the temperature is 280 ℃, and the space velocity is 4000h -1 Under the reaction conditions of (1), H in the feed gas 2 And CO at a volume ratio of 2: 1.
The invention uses the red mud as a carrier to prepare the catalyst, and applies the catalyst to the reaction of preparing the low carbon alcohol from the biomass synthesis gas, thereby improving the utilization rate of biomass resources, solving the problems of high cost of the catalyst, low CO conversion rate and C in the reaction of preparing the low carbon alcohol from the synthesis gas in the prior art 2+ Low alcohol selectivity and industrial application potential. Particularly, the used carrier is the treated red mud, so that the activity of the catalyst and the dispersion degree of active components of the catalyst are improved, and the selectivity of C2+ alcohol is increased. The raw materials of the carrier are cheap and easy to obtain, the preparation process is simple, and the performance is stable.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
A red mud-based catalyst for synthesizing low-carbon alcohol is prepared by the following steps:
1) preparing a catalyst carrier: soaking the collected red mud in an ethanol solution (with the volume concentration of 95 percent, the same below), carrying out ultrasonic treatment for 2 hours, then washing the red mud with distilled water for 5 times until the red mud is neutral, carrying out suction filtration and drying to obtain the treated red mud carrier. The mass ratio of the red mud to the ethanol solution is 1: 4.
2) Preparing a catalyst by impregnation: according to the mol ratio of Cu, Mo, Zr and Ce, namely 1:0.3:0.064:0.072, nitrates of copper, zirconium and cerium and ammonium molybdate are dissolved in water to prepare a mixed solution. Under the vacuum condition, 1g of the red mud carrier obtained in the step 1) is soaked in the mixed solution, then, the mixed solution is subjected to suction filtration, and then, the soaked catalyst precursor is dried at the temperature of 100 ℃ and roasted at the temperature of 450 ℃ to obtain 2.5g of the red mud-based catalyst for synthesizing the low-carbon alcohol, wherein the red mud carrier accounts for 40 percent, and the molar ratio of the metal elements is Cu, Mo, Zr and Ce is 1:0.3:0.064: 0.072.
The reaction for synthesizing the low-carbon alcohol by using the red mud-based catalyst comprises the following steps:
placing the prepared red mud-based catalyst in a fixed bed reactor, firstly in H 2 Reducing at normal pressure in the atmosphere (the temperature is 350 ℃ and the time is 4h), then switching to a reaction mode, wherein the catalyst dosage is 2g, the reaction pressure is 3.0MPa, the reaction temperature is 280 ℃ and the space velocity is 4000h -1 Under the reaction condition of (1), the reaction for preparing low carbon alcohol from synthesis gas is carried out, and H in raw material gas 2 : the volume ratio of CO is 2: 1.
example 2
A red mud-based catalyst for synthesizing low-carbon alcohol is prepared by the following steps:
1) preparing a catalyst carrier: soaking the collected red mud in an ethanol solution, performing ultrasonic treatment for 2 hours at 50 ℃, then washing the red mud for 6 times to be neutral by using distilled water, performing suction filtration and drying to obtain the treated red mud carrier. The mass ratio of the red mud to the ethanol solution is 1: 4.
2) Preparing a catalyst by impregnation: nitrates of copper, cobalt, chromium and cerium were dissolved in water in a molar ratio of Cu to Co to Cr to Ce of 1 to 0.2 to 0.055 to 0.064 to prepare a mixed solution. Under the vacuum condition, 1g of the red mud carrier obtained in the step 1) is soaked in the mixed solution, then, the mixed solution is filtered, and then, the soaked catalyst precursor is dried at the temperature of 100 ℃ and roasted at the temperature of 400 ℃ to obtain 2g of the red mud-based catalyst for synthesizing the low carbon alcohol, wherein the red mud carrier accounts for 50 percent.
The reaction for synthesizing lower alcohols using the red mud-based catalyst was the same as in example 1.
Example 3
The catalyst carrier preparation, catalyst impregnation preparation and synthesis of lower alcohols were carried out as in example 1, except that the molar ratio of the metal elements Cu: Mo: Zr: La was 1:0.3:0.055: 0.064.
Example 4
Catalyst support preparation, catalyst impregnation preparation and synthesis of lower alcohols the reaction was the same as in example 2 except that the molar ratio of the metal elements Cu: Rh: Cr: La was 1:0.2:0.067: 0.05.
Example 5
The catalyst carrier preparation, catalyst impregnation preparation and low carbon alcohol synthesis reactions were the same as in example 1, except that the molar ratio of the metal elements was Cu: co: ce: mn is 1:0.3:0.064: 0.072.
example 6
The catalyst carrier preparation, catalyst impregnation preparation and reaction for synthesizing lower alcohols were performed as in example 2, except that the molar ratio of the metal elements was Cu: Co: Ce: Rh 1:0.2:0.055: 0.064.
comparative example 1
Step 1) of preparing the catalyst support is as follows: and directly washing the collected red mud with distilled water for 5 times until the red mud is neutral, and performing suction filtration and drying to obtain the treated red mud carrier. The other steps are the same as in example 1.
The results of the evaluation of the examples and of the catalysts obtained in comparative examples are shown in the following table.
Figure BDA0003645948700000051

Claims (10)

1. The red mud-based catalyst for synthesizing the low-carbon alcohol is characterized in that the catalyst takes red mud as a carrier, an active ingredient is Cu, and an auxiliary agent is one or more of Rh, Mo, Zr, La, Ce, Mn, Co and Cr; the mass content of the active component in the catalyst is 10-80%, the mass content of the auxiliary agent is 10-50%, and the rest is a carrier.
2. The red mud-based catalyst for synthesizing lower alcohols according to claim 1, wherein the carrier is red mud after dealkalization treatment.
3. The method for preparing a red mud-based catalyst for synthesizing lower alcohols according to claim 1, wherein the catalyst is obtained by preparing a carrier, fusing a mixed solution of salts dissolved with active components and auxiliaries and the carrier by a vacuum impregnation method, and then filtering, drying and roasting.
4. The method for preparing the red mud-based catalyst according to claim 3, wherein the support is prepared by: mixing the red mud and an ethanol solution, carrying out ultrasonic treatment for 1-3h, then replacing the ethanol solution with water, and drying after the pH value of the replacement water is reduced to be neutral.
5. The method for preparing the red mud-based catalyst according to claim 4, wherein the mass ratio of the red mud to the ethanol solution is 1: 3-5.
6. The application of the red mud-based catalyst in the synthesis of lower alcohols according to claim 1, wherein the catalyst is placed in a fixed bed reactor and then is firstly placed in H 2 Reducing the catalyst in atmosphere and normal pressure, and then carrying out the reaction for synthesizing the low-carbon alcohol.
7. The application of the red mud-based catalyst in the synthesis of lower alcohols according to claim 6, wherein the reduction temperature is 300-400 ℃ and the reduction time is 2-5h when the catalyst is reduced.
8. The application of the red mud-based catalyst in the synthesis of lower alcohols according to claim 7, wherein the reduction temperature is 350 ℃ and the reduction time is 4 h.
9. The application of the red mud-based catalyst in the synthesis of low carbon alcohol according to claim 6, wherein the reaction pressure is 2-6MPa, the reaction temperature is 220-4000 ℃, and the volume space velocity of the reaction gas is 1000-4000h -1 Under the reaction condition of (1), carrying out the reaction of synthesizing low-carbon alcohol, wherein H in the raw material gas 2 And CO in a volume ratio of 0.5-3.5: 1.
10. the erythro of claim 9The application of the mud-based catalyst in the synthesis of low-carbon alcohol is characterized in that the low-carbon alcohol is synthesized by reaction under the conditions that the pressure is 3.0MPa, the temperature is 280 ℃ and the space velocity is 4000h -1 Under the reaction conditions of (1), H in the feed gas 2 And CO in a volume ratio of 2: 1.
CN202210530831.4A 2022-05-16 2022-05-16 Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof Active CN114849725B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210530831.4A CN114849725B (en) 2022-05-16 2022-05-16 Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210530831.4A CN114849725B (en) 2022-05-16 2022-05-16 Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114849725A true CN114849725A (en) 2022-08-05
CN114849725B CN114849725B (en) 2024-01-23

Family

ID=82638216

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210530831.4A Active CN114849725B (en) 2022-05-16 2022-05-16 Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114849725B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110156595A (en) * 2019-05-27 2019-08-23 河南省科学院能源研究所有限公司 A kind of method of red mud base catalyst Production of Levulinic Acid from Biomass ester
CN110152675A (en) * 2019-05-22 2019-08-23 国家能源投资集团有限责任公司 The method of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas
CN112495384A (en) * 2020-11-26 2021-03-16 中国科学院山西煤炭化学研究所 CuCo-based composite catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof
US20210229995A1 (en) * 2020-01-28 2021-07-29 Saudi Arabian Oil Company Catalyst carrier for bi-reforming processes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110152675A (en) * 2019-05-22 2019-08-23 国家能源投资集团有限责任公司 The method of low carbon alcohol by synthetic gas catalyst, preparation method and low carbon alcohol by synthetic gas
CN110156595A (en) * 2019-05-27 2019-08-23 河南省科学院能源研究所有限公司 A kind of method of red mud base catalyst Production of Levulinic Acid from Biomass ester
US20210229995A1 (en) * 2020-01-28 2021-07-29 Saudi Arabian Oil Company Catalyst carrier for bi-reforming processes
CN112495384A (en) * 2020-11-26 2021-03-16 中国科学院山西煤炭化学研究所 CuCo-based composite catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
胡忠攀等: "赤泥在催化工业领域中的应用", 《石油学报（石油加工）》, vol. 35, no. 1, pages 183 - 195 *
陈高峰;雷廷宙;徐海燕;杨延涛;朱金陵;何晓峰;: "CoCu-K/ZrO_2-Al_2O_3催化剂的制备及其在合成气制备低碳醇中的应用", 河南科学, vol. 34, no. 10, pages 1691 - 1695 *

Also Published As

Publication number Publication date
CN114849725B (en) 2024-01-23

Similar Documents

Publication Publication Date Title
CN112973718B (en) Kerosene co-hydrogenation catalyst and preparation method thereof
CN103589446B (en) A kind of method of iron-based liquid hydrocarbon
CN111167459A (en) Catalyst for preparing methanol from mixed gas and preparation method and application thereof
CN101428229A (en) Catalyst for synthesis of gas produced low-carbon mixed alcohol and production method thereof
CN102908957A (en) Method for Fischer-Tropsch synthesis
CN110329992B (en) Catalyst for preparing hydrogen by reforming methanol with low temperature water vapor and preparation method thereof
CN114849725B (en) Red mud-based catalyst for synthesizing low-carbon alcohol and preparation method and application thereof
CN112108138B (en) Biomass hydrothermal carbon carrier catalyst and preparation method and application thereof
CN110093179A (en) A kind of method that the upgrading of lignin mink cell focus prepares biological oxygenated fuel
CN108465468B (en) Preparation method of catalyst for preparing low-carbon alcohol from synthesis gas
CN110560137A (en) Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof
CN102911693A (en) Fischer-Tropsch synthesis method by employing mixed catalyst
CN105727977B (en) A kind of synthesis gas methanation substitutes the method for preparing catalyst of natural gas
CN102649746A (en) Method for producing glycolic acid ester through adding hydrogen in oxalic ester
CN101463016B (en) Method for synthesizing 2,6-dimethyl piperazine
CN113713809A (en) Catalyst suitable for catalyzing guaiacol to prepare oxygen-containing product through low-temperature selective hydrogenation, and preparation and application thereof
CN102911695A (en) Fischer-Tropsch synthetic method of mixed system by using different catalysts
CN112062673A (en) Method for directionally synthesizing methyl lactate by catalytically converting fructose by one-pot method
CN105727974B (en) A kind of method for preparing catalyst for synthesis gas methanation
CN1736594A (en) Synthetic gas conversion catalyst and its preparing process
CN107224980B (en) Preparation method of carbon dioxide methanation catalyst without reduction activation
CN116272976B (en) Method for preparing pentanediol by catalyzing furfural to hydrogenate through antibiotic fungus dreg derived bimetallic catalyst
CN115584283B (en) Method for preparing adamantane high-density fuel from crude fluorene
CN114250079B (en) Method for producing biodiesel by catalyzing selective hydrodeoxygenation of methyl oleate
CN114797878B (en) Method for preparing tar catalytic cracking reforming hydrogen production and carbon dioxide adsorption dual-function catalyst by using biomass ash

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant