CN114849725B - 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

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CN114849725B
CN114849725B CN202210530831.4A CN202210530831A CN114849725B CN 114849725 B CN114849725 B CN 114849725B CN 202210530831 A CN202210530831 A CN 202210530831A CN 114849725 B CN114849725 B CN 114849725B
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catalyst
red mud
low
carbon alcohol
carrier
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CN114849725A (en
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关倩
徐海燕
杨树华
张竟月
何晓峰
师新广
尚延峰
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Henan Academy of Sciences
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    • 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
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    • 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
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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 agent is one or more of Rh, mo, zr, la, ce, mn, co, cr; the mass content of the active ingredients in the catalyst is 10-80%, the mass content of the auxiliary agent is 10-50%, and the other is a carrier. The invention takes the red mud as the carrier to prepare the catalyst, and applies the catalyst to the reaction for preparing the low-carbon alcohol from the biomass synthetic gas, thereby improving the utilization rate of biomass resources, and solving the problems of high catalyst cost, low CO conversion rate and C in the reaction for preparing the low-carbon alcohol from the synthetic gas in the prior art 2+ The problem of low alcohol selectivity has potential for industrial application.

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 traditional fossil energy sources are causing the development of new clean energy sources to be increasingly important. The synthesis gas is CO and H 2 The chemical raw material gas which is the 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 an energy source. At present, the conversion of synthesis gas into low-carbon alcohol for liquid fuel is becoming an environment-friendly energy utilization mode, however, the existing low-carbon alcohol synthesis reaction has the problems of low CO conversion rate and low-carbon alcohol selectivity, wherein the catalyst and the catalytic activity thereof are key points of the problems, and the research and development of efficient and stable catalyst is one of hot spots in the research of preparing low-carbon alcohol from synthesis gas. The Cu@Fe core-shell structure catalyst for preparing the low-carbon alcohol from the synthesis gas is prepared by the Chinese invention CN104841432B, but the selectivity of hydrocarbons is higher. Chinese patent CN108465468B uses carbon nano tube as carrier to prepare catalyst for preparing low-carbon alcohol from synthetic gas, and the selectivity of C2+ alcohol in the obtained product is not high. The red mud is used as a pollution 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 application potential of catalyzing CO dissociation, and can be used as a basic raw material for preparing the low-carbon alcohol catalyst from the synthesis gas. The red mud discharge amount of China tends to increase year by year, and the red mud discharge amount is about 6000 ten thousand tons per year, but the utilization rate is very low. Therefore, the red mud is used as a catalyst carrier for preparing the low-carbon alcohol from the biomass synthesis gas, so that the pollution problem of the red mud to the environment can be reduced, and the utilization rate of biomass can be improved.
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+ The alcohol has high selectivity, stable performance, easily available carrier raw materials, simple preparation process and low cost.
In order to solve the technical problems, the invention adopts the following technical scheme:
the red mud-based catalyst for synthesizing the low-carbon alcohol takes red mud as a carrier, cu as an active ingredient and one or more of Rh, mo, zr, la, ce, mn, co, cr as an auxiliary agent; the mass content of the active ingredient in the catalyst is 10-80%, the mass content of the auxiliary agent is 10-50%, and the rest is the carrier.
Preferably, the carrier is dealkalized red mud.
The invention further provides a preparation method of the red mud-based catalyst for synthesizing the low-carbon alcohol, which comprises the steps of preparing a carrier, fusing a mixed solution of salt dissolved with active components and auxiliary agents with the carrier by a vacuum impregnation method, and filtering, drying and roasting to obtain the catalyst.
The preparation of the carrier is as follows: mixing the red mud with ethanol solution, performing ultrasonic treatment for 1-3h, then replacing the ethanol solution with water, and drying after the pH value of the replaced 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 a volume concentration of 95%.
The red mud-based catalyst has good application in synthesizing low-carbon alcohol, and after the catalyst is placed in a fixed bed reactor, the catalyst is firstly put in H 2 The catalyst is reduced under the atmosphere and normal pressure, and then the reaction for synthesizing the low-carbon alcohol is carried out.
Further, when the catalyst is reduced, the reduction temperature is 300-400 ℃ and the reduction time is 2-5h. Preferably, the reduction temperature is 350 ℃ and the reduction time is 4 hours.
Further, the reaction pressure is 2-6MPa, the reaction temperature is 220-500 ℃, and the volume space velocity of the reaction gas is 1000-4000h -1 Under the reaction condition of (1) synthesizing low-carbon alcohol, H in raw material gas 2 And the volume ratio of CO is 0.5-3.5:1.
preferably, the synthetic lower alcohols are reacted at a pressure of 3.0MPa, a temperature of 280 ℃ and a space velocity of 4000h -1 Is carried out under the reaction conditions of H in the raw material gas 2 And the volume ratio of CO is 2:1.
The invention prepares the catalyst by taking red mud as a carrier and applies the catalyst toIn the reaction of preparing low-carbon alcohol from biomass synthesis gas, the utilization rate of biomass resources is improved, and the problems of high catalyst cost, low CO conversion rate and C in the reaction of preparing low-carbon alcohol from synthesis gas in the prior art are solved 2+ The problem of low alcohol selectivity has potential for industrial application. Particularly, the carrier is treated red mud, so that the activity of the catalyst and the dispersity of active components of the catalyst are improved, and the selectivity of C2+ alcohol is increased. The carrier has the advantages of cheap and easily obtained raw materials, simple preparation process and stable performance.
Detailed Description
The following specific embodiments are used to illustrate the technical solution of the present invention, 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 ethanol solution (volume concentration is 95%, the same applies below), performing ultrasonic treatment for 2 hours, washing with distilled water for 5 times to neutrality, 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: copper, zirconium and cerium nitrate and ammonium molybdate were dissolved in water to prepare a mixed solution according to the molar ratio of Cu to Mo to Zr to ce=1:0.3:0.064:0.072. Under vacuum condition, 1g of the red mud carrier obtained in the step 1) is immersed in the mixed solution, then suction filtration is carried out, and then the immersed catalyst precursor is dried at 100 ℃ and baked at 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%, and the molar ratio of several metal elements is Cu to Mo to Zr to Ce=1 to 0.3 to 0.064 to 0.072.
The red mud-based catalyst is used for synthesizing low-carbon alcohol:
the prepared red mud-based catalyst is placed in a fixed bed reactor, firstly in H 2 Atmospheric reduction (temperature is 350 ℃ C., time is 4 h) is carried out in atmosphere, then the reaction mode is switched, the catalyst dosage is 2g, the reaction pressure is 3.0MPa, the reaction temperature is 280 ℃ C., and the space velocity is 4000h -1 Is used for preparing synthesis gas under the reaction conditionReaction of low-carbon alcohol 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 ethanol solution, performing ultrasonic treatment at 50 ℃ for 2 hours, washing with distilled water for 6 times to neutrality, and 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: the nitrate of copper, cobalt, chromium and cerium is dissolved in water according to the mol ratio of Cu to Co to Cr to Ce=1:0.2:0.055:0.064 to prepare a mixed solution. Under the vacuum condition, 1g of the red mud carrier obtained in the step 1) is immersed in the mixed solution, then suction filtration is carried out, and then the immersed catalyst precursor is dried at 100 ℃ and baked at 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 support 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 used was Cu: mo: zr: la=1:0.3:0.055:0.064.
Example 4
The catalyst support preparation, catalyst impregnation preparation and low carbon alcohol synthesis reactions were the same as in example 2, except that the molar ratio of the metal elements was Cu to Rh to Cr la=1:0.2:0.067:0.05.
Example 5
The catalyst support 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=1: 0.3:0.064:0.072.
example 6
The catalyst support preparation, catalyst impregnation preparation and low carbon alcohol synthesis reactions were the same 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: directly washing the collected red mud with distilled water for 5 times to neutrality, and carrying out suction filtration and drying to obtain the treated red mud carrier. The other steps are the same as in example 1.
The results of evaluation of the catalysts obtained in examples and comparative examples are shown in the following table.

Claims (7)

1. The application of the red mud-based catalyst in synthesizing low-carbon alcohol is characterized in that the catalyst takes dealkalized 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, cr; the mass content of the active ingredients in the catalyst is 10-80%, the mass content of the auxiliary agent is 10-50%, and the other is a carrier; the carrier is prepared by mixing red mud with ethanol solution, performing ultrasonic treatment for 1-3h, then replacing the ethanol solution with water, and drying after the pH value of the replaced water is reduced to be neutral; the volume concentration of the ethanol solution is 95%, and the lower alcohol is C 2+ An alcohol.
2. The process according to claim 1, wherein the catalyst is obtained by preparing a support, then fusing the mixed solution of the salt in which the active ingredient and the auxiliary agent are dissolved with the support by vacuum impregnation, and then filtering, drying and calcining.
3. The use according to claim 1, wherein the mass ratio of red mud to ethanol solution is 1:3-5.
4. The process according to claim 1, wherein after the catalyst has been placed in the fixed bed reactor, it is carried out first in H 2 Reducing the catalyst under the atmosphere and normal pressure, and then carrying out a reaction for synthesizing the low-carbon alcohol; feeding the catalystWhen in reduction, the reduction temperature is 300-400 ℃ and the reduction time is 2-5h.
5. The method according to claim 4, wherein the reduction temperature is 350℃and the reduction time is 4h.
6. The process according to claim 4, wherein the reaction pressure is 2-6MPa, the reaction temperature is 220-500 ℃ and the volume space velocity of the raw material gas is 1000-4000h -1 Under the reaction condition of (1) synthesizing low-carbon alcohol, H in raw material gas 2 And the volume ratio of CO is 0.5-3.5:1.
7. the process according to claim 6, wherein the synthesis of the lower alcohols is carried out at a pressure of 3.0MPa, a temperature of 280℃and a volume space velocity of 4000h -1 Is carried out under the reaction conditions of H in the raw material gas 2 And the volume ratio of CO is 2:1.
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