阅读说明：本技术 一种合成气制取低碳醇的方法及装置 (Method and device for preparing low-carbon alcohol from synthesis gas ) 是由 赵璐 房克功 张立功 于 2021-09-27 设计创作，主要内容包括：本发明属于醇类化学品合成及合成气化学领域,一种合成气制取低碳醇的方法,在反应温度低于150摄氏度,压力低于1 Mpa下,介质阻挡放电使合成气发生气体电离形成激发态CO分子和H自由基等离子体,在金属氧化物作为催化剂时,激发态CO分子和H自由基转化为低碳醇。本发明还涉及该合成气制取低碳醇的装置。本发明的效果和益处是：不仅实现了在低温低压下合成气高效转化为低碳醇,而且采用以电能方式实现这一过程。(The invention belongs to the field of alcohol chemical synthesis and synthesis gas chemistry, and discloses a method for preparing low-carbon alcohol from synthesis gas, which comprises the steps of ionizing the synthesis gas by dielectric barrier discharge at the reaction temperature of less than 150 ℃ and under the pressure of less than 1Mpa to form excited CO molecules and H free radical plasma, and converting the excited CO molecules and H free radicals into the low-carbon alcohol when a metal oxide is used as a catalyst. The invention also relates to a device for preparing low-carbon alcohol from the synthesis gas. The invention has the advantages that: not only realizes the high-efficiency conversion of the synthesis gas into the low-carbon alcohol at low temperature and low pressure, but also realizes the process in an electric energy mode.)

1. A method for preparing low carbon alcohol from synthesis gas is characterized by comprising the following steps: under the conditions that the reaction temperature is lower than 150 ℃ and the pressure is lower than 1Mpa, the synthesis gas is ionized by dielectric barrier discharge to form excited CO molecules and H free radical plasma, and when the metal oxide is used as a catalyst, the excited CO molecules and H free radicals are converted into low carbon alcohol.

2. The method for preparing the lower alcohol from the synthesis gas as claimed in claim 1, wherein the method comprises the following steps: the metal oxide is one or a mixture of two of molybdenum oxide, manganese oxide, chromium oxide, tungsten oxide, cerium oxide, titanium oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, vanadium oxide, zirconium oxide and lanthanum oxide, and the particle size of the oxide is 40-60 meshes.

3. The method for preparing the lower alcohol from the synthesis gas as claimed in claim 1, wherein the method comprises the following steps: the lower alcohol is a mixture of methanol, ethanol, propanol, butanol and pentanol.

4. The method for preparing the lower alcohol from the synthesis gas as claimed in claim 1, wherein the method comprises the following steps: h in synthesis gas₂The volume percentage content of the carbon dioxide is 10-90 percent, and the volume percentage content of the CO is 10-90 percent.

5. The method for preparing the lower alcohol from the synthesis gas as claimed in claim 1, wherein the method comprises the following steps: the reaction temperature is 60-150 ℃.

6. The synthesis gas-to-lower alcohol plant of the synthesis gas-to-lower alcohol method according to claim 1, characterized in that: including high voltage electrode (1), earthing pole (2), casing (3), air inlet (4), cold-trap sample thief (5), gas outlet (6), be the tube-shape reaction chamber in casing (3), be used for placing the catalyst, there is air inlet (4) casing (3) upper end, cold-trap sample thief (5) is connected to casing (3) lower extreme, cold-trap sample thief (5) lower part is gas outlet 6, the outside winding coil of casing (3) constitutes earthing pole (2), install high voltage electrode (1) on the axis of casing (3), direct current or alternating current high voltage power supply are connected to high voltage electrode (1) and earthing pole (2), anodal is connected in high voltage electrode (1), the negative pole is connected in earthing pole (2).

7. The apparatus for preparing low carbon alcohol from synthesis gas according to claim 6, wherein: in the working process, a 40-60-mesh metal oxide catalyst is placed in a shell (3), nitrogen is introduced through an air inlet (4) to remove air in a reactor, synthesis gas is introduced through the air inlet, a high-voltage power supply of a high-voltage electrode (1) and a high-voltage power supply of a grounding electrode (2) are switched on, excited CO molecules and H free radicals are converted into low carbon alcohol under the action of the metal oxide, and the low carbon alcohol is subjected to cold trap treatment by a cold trap sampler (5) to obtain the liquid low carbon alcohol.

8. The apparatus for preparing low carbon alcohol from synthesis gas according to claim 7, wherein: the flow rate of the synthesis gas is 100-10000 h^-1In which H is contained in the synthesis gas₂10-90 percent of volume percent, 10-90 percent of CO volume percent, 0.1-1 MPa of reaction pressure, 100-150 ℃ of reaction temperature, 0.8-40 kilovolt of voltage and 1-20 kilohertz of frequency.

Technical Field

The invention belongs to the field of alcohol chemical synthesis and synthesis gas chemistry, and particularly relates to a method and a device for preparing low-carbon alcohol by using synthesis gas as a raw material.

Background

Synthesis gas (H)₂And CO mixed gas) is an important way for obtaining chemicals such as liquid fuel, bulk chemical raw materials, oil additives and the like in a non-petroleum way. Because of the long-standing inherent energy structure of rich coal, little oil and poor gas in China, the synthesis gas production is lowCarbon alcohol is always a key component of the energy development strategy in China and is also an important technical method for reducing the external dependence of crude oil in China.

At present, the disclosed technology for preparing low-carbon alcohol from domestic and foreign synthesis gas adopts the traditional fixed bed process, and the existing process can realize the process under high temperature and high pressure. Reaction temperatures above 220-250 ℃ are typical, and even above 300 ℃ are reported; the reaction pressure is higher than 3-5 MPa, even higher than 8MPa has been reported. Because the conversion reaction of the synthesis gas has the characteristic of high-temperature heat release, the selectivity of the product is easily uncontrollable at high temperature, a plurality of byproducts are generated, and the energy consumption is high. But under the conditions of low reaction temperature and pressure, the CO conversion rate and the selectivity of the low-carbon alcohol of the traditional fixed bed process are low. Therefore, the technology can not realize large-scale production and application in China so far, and is a long-term key technical bottleneck in the field of synthesis gas conversion in China. Because the existing domestic and overseas low-carbon alcohol technology has the defects, a new technology for preparing the low-carbon alcohol from the synthesis gas is developed, a new method and a matched device are searched, the problems of more byproducts and high energy consumption under high temperature and high pressure are avoided, and the key for solving the neck clamping problem in the field of China is to realize the efficient conversion of the synthesis gas under low temperature and low pressure.

Disclosure of Invention

The invention aims to provide a novel method and a novel device for preparing low-carbon alcohol from synthesis gas, which are used for efficiently converting the synthesis gas into the low-carbon alcohol in a mode of coupling plasma and a catalyst at a reaction temperature of less than 150 ℃ and a pressure of less than 1 Mpa.

The technical scheme adopted by the invention is as follows: a process for preparing low-carbon alcohol from synthetic gas includes such steps as ionizing the synthetic gas by dielectric barrier discharge at 150 deg.C and 1MPa to obtain excited CO molecules and H radicals, and converting them to low-carbon alcohol by metallic oxide as catalyst.

The metal oxide is one or a mixture of two of molybdenum oxide, manganese oxide, chromium oxide, tungsten oxide, cerium oxide, titanium oxide, copper oxide, nickel oxide, cobalt oxide, iron oxide, vanadium oxide, zirconium oxide and lanthanum oxide, and the particle size of the oxide is 40-60 meshes.

The lower alcohol is a mixture of methanol, ethanol, propanol, butanol and pentanol.

The reaction temperature is 60-150 ℃.

H in synthesis gas₂The volume percentage content of the carbon dioxide is 10-90 percent, and the volume percentage content of the CO is 10-90 percent.

The utility model provides a device of low carbon alcohol is got in synthetic gas preparation, including high voltage electrode (1), earthing pole (2), casing (3), air inlet (4), cold-trap sample thief (5), gas outlet (6), be tube-shape reaction chamber in casing (3), be used for placing the catalyst, there is air inlet (4) casing (3) upper end, cold-trap sample thief (5) is connected to casing (3) lower extreme, cold-trap sample thief (5) lower part is gas outlet 6, the outside winding coil of casing (3) constitutes earthing pole (2), install high voltage electrode (1) on the axis of casing (3), direct current or alternating current high voltage power supply are connected to high voltage electrode (1) and earthing pole (2), positive pole is connected in high voltage electrode (1), negative pole is connected in earthing pole (2).

In the working process, a 40-60-mesh metal oxide catalyst is placed in a shell (3), nitrogen is introduced through an air inlet (4) to remove air in a reactor, synthesis gas is introduced through the air inlet, a high-voltage power supply of a high-voltage electrode (1) and a high-voltage power supply of a grounding electrode (2) are switched on, excited CO molecules and H free radicals are converted into low carbon alcohol under the action of the metal oxide, and the low carbon alcohol is subjected to cold trap treatment by a cold trap sampler (5) to obtain the liquid low carbon alcohol.

The flow rate of the synthesis gas is 100-10000 h^-1In which H is contained in the synthesis gas₂10-90 percent of volume percent, 10-90 percent of CO volume percent, 0.1-1 MPa of reaction pressure, 100-150 ℃ of reaction temperature, 0.8-40 kilovolt of voltage and 1-20 kilohertz of frequency.

The shell (3) is made of glass, quartz glass, ceramics or corundum.

The plasma is a fourth substance existing form except gas, liquid and solid, and is rich in a large amount of excited active species such as excited radicals, excited molecules, excited ions, excited atoms, high-energy electrons and other high-activity reactive species. The invention utilizes the non-equilibrium characteristic of the plasma in thermodynamics and simultaneously completes the enhancement of reaction kinetics by introducing the catalyst, and the synthesis gas is directly and efficiently converted into low-carbon alcohol at low temperature and low pressure by adopting the form of combining the plasma and the catalyst.

Specifically, the conversion of the synthesis gas into the low-carbon alcohol is realized by coupling dielectric barrier discharge plasma and a metal oxide catalyst: the dielectric barrier discharge ionizes the synthesis gas to form uniformly distributed low-temperature plasma, excited CO molecules and H free radicals are used as main components, when metal oxides exist in a plasma region, the CO conversion rate can be obviously improved, and the reaction temperature is measured to be below 150 ℃. The plasma discharge may be performed using an ac power supply or a dc power supply. The metal oxide catalyst filled in the plasma discharge area is solid particles or solid powder.

The invention has the advantages that: the method not only realizes the high-efficiency conversion of the synthesis gas into the low-carbon alcohol at low temperature and low pressure, but also realizes the process in an electric energy mode, and provides a new technology for national energy conservation and emission reduction and the realization of the double-carbon target of carbon peak reaching and carbon neutralization. Compared with the prior art, the method has the following advantages: 1. the invention discloses a new process method for preparing low-carbon alcohol; 2. the direct and high-efficiency preparation of low-carbon alcohol from the synthesis gas at low temperature and low pressure is realized; 3. the metal oxide catalyst is introduced to promote the conversion of the synthesis gas into lower alcohol; 4. the invention has the advantages that the CO conversion rate is higher than 90% and the selectivity of the low-carbon alcohol is higher than 90% at low temperature and low pressure.

Drawings

FIG. 1 is a schematic diagram of a plasma discharge reactor designed according to the present invention.

Detailed Description

The invention is further described in the following examples in connection with specific embodiments thereof, it being understood that these examples are given by way of illustration only and not by way of limitation, and that various equivalent modifications of the invention will occur to those skilled in the art and are intended to be within the scope of the appended claims.

Example 1

Firstly, 40-60 portions of the powder is mixed1.0mL of manganese oxide catalyst is placed in a reaction cavity of a linear barrel type reactor, the material of a discharge reactor is glass, nitrogen is introduced for 10 minutes to remove air in the reactor, and the reaction is controlled by a mass flow meter for 100 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂The volume percentage content of the catalyst is 10 percent, the volume percentage content of the CO is 90 percent, the reaction pressure is 0.1MPa, the reaction temperature is 80 ℃, a plasma power supply which is connected with a grounding electrode and a high-voltage electrode is connected, the frequency is 1 kilohertz, and the voltage is adjusted to 1 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Manganese oxide catalyst	4.5	83.0

Example 2

Firstly, 4.5mL of 40-60 mesh chromium oxide catalyst is placed in a reaction cavity in a wire barrel type reactor, the discharge reactor is made of ceramic, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 300h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂The volume percentage content is 90 percent, the volume percentage content of CO is 10 percent, the reaction pressure is 0.6MPa, the reaction temperature is 115 ℃, a plasma power supply connected with a grounding electrode and a high-voltage electrode is connected, the frequency is 3.5 kilohertz, and the voltage is adjusted to 35 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Chromium oxide catalyst	94.1	83.5

Example 3

Firstly, 2mL of catalyst of 40-60 mesh molybdenum oxide is placed in a reaction cavity of a wire-barrel type reactor, corundum is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to 6000h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂35 percent by volume, 65 percent by volume of CO, 0.8MPa of reaction pressure, 135 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 20 kilohertz and regulating the voltage to be 0.8 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Molybdenum oxide catalyst	25.1	76.6

Example 4

Firstly, 8.5mL of 40-60 mesh tungsten oxide catalyst is placed in a reaction cavity in a wire barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to 10000h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂The volume percentage content is 60 percent, the volume percentage content of CO is 40 percent, the reaction pressure is 0.4MPa, the reaction temperature is 90 ℃, a plasma power supply connected with a grounding electrode and a high-voltage electrode is connected, the frequency is 9.5 kilohertz, and the voltage is adjusted to 1.5 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Tungsten oxide catalyst	70.6	82.3

Example 5

Firstly, placing 7.0mL of 40-60 mesh lanthanum oxide catalyst in a reaction cavity of a wire-barrel type reactor, selecting corundum as a discharge reactor material, introducing nitrogen for 10 minutes to remove air in the reactor, controlling by a mass flowmeter at 7000h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂Volume percent25 percent of CO, 75 percent of CO by volume, 0.3MPa of reaction pressure, 120 ℃ of reaction temperature, connecting a plasma power supply for connecting a grounding electrode and a high-voltage electrode, controlling the frequency to be 2 kilohertz and regulating the voltage to be 17 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Lanthanum oxide catalyst	6.5	90.1

Example 6

Firstly, 9.0mL of 40-60 mesh iron oxide catalyst is placed in a reaction cavity in a wire barrel type reactor, the material of a discharge reactor is ceramic, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction for 3000 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂80 percent by volume, 20 percent by volume of CO, 0.7MPa of reaction pressure, 140 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 3 kilohertz and regulating the voltage to be 2 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Iron oxide catalyst	90.8	80.6

Example 7

Firstly, 6.5mL of 40-60 mesh vanadium oxide catalyst is placed in a reaction cavity in a wire barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 800h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂The volume percentage content of the catalyst is 43 percent, the volume percentage content of the CO is 57 percent, the reaction pressure is 0.2MPa, the reaction temperature is 100 ℃, a plasma power supply connected with a grounding electrode and a high-voltage electrode is connected, the frequency is 7.5 kilohertz, and the voltage is adjusted to 38 kilovolt.

The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Vanadium oxide catalyst	36.0	66.8

Example 8

Firstly, 5.0mL of 40-60 mesh zirconium oxide catalyst is placed in a reaction cavity of a wire barrel type reactor, corundum is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 2500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂50 percent of CO, 0.5MPa of reaction pressure, 88 ℃ of reaction temperature, switching on a plasma power supply for connecting a grounding electrode and a high-voltage electrode, controlling the frequency to be 10.5 kilohertz and regulating the voltage to be 40 kilovolts. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Zirconium oxide catalyst	46.5	70.9

Example 9

Firstly, 3.5mL of a 40-60-mesh cobalt oxide catalyst is placed in a reaction cavity in a wire-barrel type reactor, the discharge reactor is made of ceramic, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 1500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂The volume percentage content is 83 percent, the volume percentage content of CO is 17 percent, the reaction pressure is 0.95MPa, the reaction temperature is 150 ℃, a plasma power supply for connecting a grounding electrode and a high-voltage electrode is connected, the frequency is 11.5 kilohertz, and the voltage is adjusted to 23 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Cobalt oxide catalyst	95.7	83.6

Example 10

Firstly, 6.0mL of 40-60 mesh nickel oxide catalyst is placed in a reaction cavity in a wire barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction for 200 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂65 percent by volume, 35 percent by volume of CO, 0.15MPa of reaction pressure, 83 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 5 kilohertz and regulating the voltage to be 30 kilovolts.

The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Nickel oxide catalyst	76.6	90.5

Example 11

Firstly, 2.5mL of 40-60 mesh titanium oxide catalyst is placed in a reaction cavity of a wire barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction for 300 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂95 percent by volume, 5 percent by volume of CO, 0.33MPa of reaction pressure and 92 ℃ of reaction temperature, connecting a plasma power supply for connecting a grounding electrode and a high-voltage electrode, wherein the frequency is 6 kilohertz, and adjusting the voltage to 18 kilovolts.

The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Titanium oxide catalyst	99.1	74.7

Example 12

Firstly, 9.5mL of 40-60 mesh copper oxide catalyst is placed in a reaction cavity in a wire barrel type reactor, corundum is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the corundum is introducedControlling the mass flow meter for 1000h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂20 percent of volume percent, 80 percent of CO volume percent, 0.9MPa of reaction pressure, 60 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 12 kilohertz and regulating the voltage to be 4 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Copper oxide catalyst	9.8	80.8

Example 13

Firstly, 8.0mL of 40-60 mesh cerium oxide catalyst is placed in a reaction cavity in a wire barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the operation for 600 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂45 percent by volume, 55 percent by volume of CO, 0.22MPa reaction pressure, 105 ℃ reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 11 kilohertz and regulating the voltage to be 9 kilovolt.

The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Cerium oxide catalyst	36.6	82.5

Example 14

Firstly, placing 7.0mL (volume ratio of the manganese oxide to the molybdenum oxide is 0.1) of 40-60-mesh mixed catalyst in a reaction cavity of a wire-barrel type reactor, selecting quartz glass as a discharge reactor material, introducing nitrogen for 10 minutes to remove air in the reactor, controlling by a mass flow meter for 3500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂66 percent by volume, 34 percent by volume of CO, 0.85MPa of reaction pressure, 110 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 5 kilohertz and regulating the voltage to be 8 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Manganese oxide and molybdenum oxide mixed catalyst	79.6	90.1

Example 15

Firstly, 1.5mL (volume ratio of the chromium oxide to the tungsten oxide is 1) of catalyst mixed with 40-60 meshes of chromium oxide and tungsten oxide is placed in a reaction cavity in a linear barrel type reactor, corundum is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 8000h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂The volume percentage content of the catalyst is 52 percent, the volume percentage content of the CO is 48 percent, the reaction pressure is 0.5MPa, the reaction temperature is 102 ℃, a plasma power supply which is connected with a grounding electrode and a high-voltage electrode is switched on, the frequency is 4 kilohertz, and the voltage is adjusted to 8.3 kilovolts. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Mixed catalyst of chromium oxide and tungsten oxide	50.9	84.3

Example 16

Firstly, 3.0mL (volume ratio of the lanthanum oxide to the zirconium oxide is 0.5) of 40-60-mesh lanthanum oxide and zirconium oxide mixed catalyst is placed in a reaction cavity of a linear barrel type reactor, the discharge reactor is made of ceramic, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction for 500 hours^-1Passing the synthesis gas through the bed at a space velocity wherein the synthesis gasMiddle H₂72 percent of volume percent, 28 percent of CO volume percent, 0.35MPa of reaction pressure, 130 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 18 kilohertz and regulating the voltage to be 7 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Mixed lanthanum oxide and zirconium oxide catalyst	97.2	88.6

Example 17

Firstly, 5.0mL (volume ratio of the cerium oxide to the copper oxide is 0.2) of catalyst mixed with 40-60 meshes of cerium oxide and copper oxide is placed in a reaction cavity of a wire-barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to 3700 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂33 percent of volume percent, 67 percent of CO volume percent, 0.88MPa of reaction pressure, 95 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 8.5 kilohertz and regulating the voltage to be 35 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Cerium oxide and copper oxide mixed catalyst	11.8	93.1

Example 18

Firstly, 8.0mL (volume ratio of the nickel oxide to the vanadium oxide is 2) of 40-60-mesh nickel oxide and vanadium oxide mixed catalyst is placed in a reaction cavity in a linear barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 2500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂55 percent by volume, 45 percent by volume of CO, 0.18MPa of reaction pressure and 113 ℃, and a plasma power supply for connecting a grounding electrode and a high-voltage electrode is switched on, the frequency is 10 kilohertz, and the voltage is adjusted to 11 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Nickel oxide and vanadium oxide mixed catalyst	63.5	81.4

Example 19

Firstly, 2.0mL (volume ratio of the molybdenum oxide to the tungsten oxide is 3) of 40-60-mesh mixed catalyst is placed in a reaction cavity in a wire-tube reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 2000h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂30 percent of volume percent, 70 percent of CO volume percent, 0.25MPa of reaction pressure and 70 ℃ of reaction temperature, connecting a plasma power supply for connecting a grounding electrode and a high-voltage electrode, controlling the frequency to be 7 kilohertz, and regulating the voltage to be 6 kilovolts. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Mixed catalyst of molybdenum oxide and tungsten oxide	20.5	88.6

Example 20

Firstly, placing 7.5mL (volume ratio of the lanthanum oxide to the iron oxide is 7) of catalyst mixed by 40-60 meshes into a reaction cavity in a linear barrel type reactor, selecting corundum as a discharge reactor material, introducing nitrogen for 10 minutes to remove air in the reactor, controlling by a mass flowmeter, and performing 4200h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂20 percent of volume percent and CO by volumeThe percentage content is 80%, the reaction pressure is 0.65MPa, the reaction temperature is 123 ℃, a plasma power supply for connecting a grounding electrode and a high-voltage electrode is switched on, the frequency is 13 kilohertz, and the voltage is adjusted to 33 kilovolts. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Lanthanum oxide and iron oxide mixed catalyst	11.4	69.8

Example 21

Firstly, 4.0mL (volume ratio of the two is 5) of 40-60-mesh zirconium oxide and cobalt oxide mixed catalyst is placed in a reaction cavity in a linear barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and 9000h is controlled by a mass flow meter^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂15 percent by volume, 85 percent by volume of CO, 0.55MPa of reaction pressure and 65 ℃ of reaction temperature, connecting a plasma power supply for connecting a grounding electrode and a high-voltage electrode, wherein the frequency is 9 kilohertz, and adjusting the voltage to 0.9 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Zirconium oxide and cobalt oxide mixed catalyst	7.0	83.6

Example 22

Firstly, 9.0mL (volume ratio of the titanium oxide to the molybdenum oxide is 4) of 40-60-mesh mixed catalyst is placed in a reaction cavity in a wire-barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 6500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂75 percent by volume, 25 percent by volume of CO, 0.75MPa of reaction pressure and 85 ℃ of reaction temperature, connecting a plasma power supply for connecting a grounding electrode and a high-voltage electrode, wherein the frequency is 11 kilohertz, and adjusting the voltage to 20 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Titanium oxide and molybdenum oxide mixed catalyst	91.6	92.5

Example 23

No catalyst is placed in a linear barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to 6500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂75 percent by volume, 25 percent by volume of CO, 0.75MPa of reaction pressure and 85 ℃ of reaction temperature, connecting a plasma power supply for connecting a grounding electrode and a high-voltage electrode, wherein the frequency is 11 kilohertz, and adjusting the voltage to 20 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Titanium oxide and molybdenum oxide mixed catalyst	7.5	1.1

Example 24

Firstly, 9.0mL (volume ratio of the titanium oxide to the molybdenum oxide is 4) of 40-60-mesh mixed catalyst is placed in a reaction cavity in a wire-barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 6500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂75 percent by volume, 25 percent by volume of CO, 0.75MPa of reaction pressure, 85 ℃ of reaction temperature and 0V of voltage, and no discharging operation is carried out. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Titanium oxide and molybdenum oxide mixed catalyst	0.0	0.0

Example 25

Firstly, 8.0mL (volume ratio of the nickel oxide to the cobalt oxide is 9) of 40-60-mesh nickel oxide and cobalt oxide mixed catalyst is placed in a reaction cavity in a linear barrel type reactor, the discharge reactor is made of ceramic, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 4000 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂40 percent by volume, 60 percent by volume of CO, 1.0MPa of reaction pressure and 118 ℃ of reaction temperature, connecting a plasma power supply for connecting a grounding electrode and a high-voltage electrode, controlling the frequency to be 15 kilohertz and regulating the voltage to be 1.2 kilovolt. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Nickel oxide and cobalt oxide mixed catalyst	30.3	90.1

Example 26

Firstly, 5.5mL (volume ratio of the two is 10) of 40-60-mesh zirconium oxide and cerium oxide mixed catalyst is placed in a reaction cavity of a linear barrel type reactor, quartz glass is selected as a discharge reactor material, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the reaction time to be 7500h^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂85 percent by volume, 15 percent by volume of CO, 0.13MPa of reaction pressure, 75 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 8 kilohertz and regulating the voltage to be 15 kilovolts. The evaluation results are shown in the following table.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Mixed catalyst of zirconium oxide and cerium oxide	86.2	88.7

Example 27

Firstly, 10mL (6 by volume ratio) of 40-60 mesh tungsten oxide and zirconium oxide mixed catalyst is placed in a wire barrel type reactorIn the middle reaction cavity, the discharge reactor material is quartz glass, nitrogen is introduced for 10 minutes to remove air in the reactor, and the mass flow meter is used for controlling the discharge reactor material for 5000 hours^-1Passing the synthesis gas at a space velocity through the bed, wherein H in the synthesis gas₂70 percent of volume percent, 30 percent of CO volume percent, 0.2MPa of reaction pressure, 120 ℃ of reaction temperature, switching on a plasma power supply connected with a grounding electrode and a high-voltage electrode, controlling the frequency to be 17 kilohertz and regulating the voltage to be 5 kilovolt.

Catalyst and process for preparing same	Percent conversion of CO%	Selectivity to lower alcohol%
			Tungsten oxide and zirconium oxide mixed catalyst	80.9	82.6

The evaluation results are shown in the table above.

The experimental results show that the coupling of the plasma and the metal oxide can break thermodynamic equilibrium limitation, thereby realizing the high-selectivity conversion of the synthesis gas to prepare the low-carbon alcohol, and the method is a mild, high-efficiency and low-energy-consumption method for preparing the low-carbon alcohol.

The above examples include a single plasma, a single metal oxide catalyst, and a coupling of a plasma and a metal oxide catalyst, which illustrate a novel method for producing lower alcohols by high-selectivity conversion of synthesis gas through the cooperation of a metal oxide catalyst and a plasma. Modifications and improvements can be made to the invention, for example, reactor and electrode configurations, modification of metal oxides with non-metals or metals and their salts, and the like.