CN216972696U - Fixed-ratio production system for synthesis gas - Google Patents
Fixed-ratio production system for synthesis gas Download PDFInfo
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- CN216972696U CN216972696U CN202220674475.9U CN202220674475U CN216972696U CN 216972696 U CN216972696 U CN 216972696U CN 202220674475 U CN202220674475 U CN 202220674475U CN 216972696 U CN216972696 U CN 216972696U
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Abstract
The utility model discloses a fixed-ratio production system of synthesis gas, which comprises: the system comprises a first electrolytic tank (1), a coal gasification unit (2), an acid gas removal unit (3), a second electrolytic tank (4) and a gas regulation unit (5). The system also comprises a reaction unit (6), wherein the reaction unit (6) is an alcohol reaction unit, a hydrocarbon reaction unit and a synthetic oil reaction unit. According to the utility model, an air separation device and a water-gas conversion device in a traditional coal-to-methanol system are omitted, and renewable energy is used for electrolyzing water to provide green hydrogen and green oxygen; electrolysis of CO using renewable energy sources2And the water provides carbon monoxide, hydrogen and oxygen, so that the effect of water-gas shift is realized. The utility model can electrolyze water and CO without high-energy-consumption air separation device and high-emission water-gas shift device2And the renewable electric energy is fully utilized in the two processes of water and electricity.
Description
Technical Field
The utility model belongs to energy chemical industry and fuel synthesis, and particularly relates to a fixed-ratio production system of synthesis gas.
Background
Methanol (CH)3OH) is a chemical with wide application, and the yield is close to 9000 ten thousand tons/year in China by the end of 2021, and the main raw material is carbon-containing fossil raw materials such as coal.
In the traditional coal-to-methanol system in the prior art (figure 1), coal, water and oxygen (O) are mixed2) The mixture is fed into a gasification device according to a certain proportion and state to prepare carbon monoxide (CO) and hydrogen (H)2) Commonly known as syngas, by-product CO2And accompanied by hydrogen sulfide (H)2S), carbonyl sulfide (COS), and other sulfur-containing compounds.
The problems existing in the prior art are as follows:
1. the source of oxygen is an air separation unit, powered by coal and emitting a portion of the CO2Oxygen gas with a content of 23% in air is separated by means of cryogenic cooling or pressure swing adsorption and the like and used as an oxidant raw material for gasification. The pressure of the oxygen after coming out of the air separation device is usually 1-2 MPa higher than that of the gasification device, the temperature is 40 ℃, the purity is 99.5%, and simultaneously, a large amount of carbon dioxide is discharged in the step.
2. The operating pressure of the gasification device is 6.5MPa, and the reaction temperature is 1450 ℃. In the gasified crude synthesis gas product, CO and H2Is usually greater than 2, whereas the ideal methanol synthesis feedstock is CO and H in a molar ratio of 22. If the CO content is high, the temperature control is not facilitated, and the carbonyl iron is accumulated on the catalyst and is deactivated. Therefore, the gas composition needs to be adjusted so that the ratio of CO to hydrogen is 2 or less. The conventional technical means is to carry out the water gas shift reaction (CO + H)2O-->CO2+H2) Increasing hydrogen content, reducing CO content to reach proper CO to H2And (4) proportion. The synthesis gas firstly enters a medium-temperature heat exchanger, is preheated to 260 ℃ and then enters a shift converter filled with a section of sulfur-resistant catalyst to generate a water-gas shift reaction, the temperature of the shift converter discharged is about 410-420 ℃, the temperature of the shift converter is reduced by heat exchange through the medium-temperature heat exchanger, the pressure is about 6.1MPa, and simultaneously, a large amount of carbon dioxide is discharged in the step.
Because only CO and H are needed in the process of synthesizing the methanol2And sulfur-containing substances can cause the poisoning of a methanol synthesis catalyst, so that CO needs to be removed by an acid gas removal device and technical means such as low-temperature methanol washing and the like2、 H2S, COS is removed. Wherein, CO2Normally discharged or stored after separation; h2And the S and the COS are converted into sulfur for recycling after being separated. The temperature of the acid gas entering the acid gas removal device is 40 ℃, and the pressure is 5.6 MPa.
The coal-based methanol discharges a large amount of carbon dioxide, and mainly comes from two steps of an air separation device and a water-gas shift reaction. Under the aim of carbon neutralization, the existing production method cannot meet the requirement of modern chemical industry on emission, and the produced methanol product has high carbon footprint.
Meanwhile, renewable energy sources such as wind energy, solar energy and the like are vigorously developed in China and the whole world, and the cost of the renewable energy sources is reduced year by year. However, such energy sources have problems of intermittency and volatility, and waste wind and light energy sources are serious. How to utilize renewable electric energy becomes an important issue in the industry.
The present invention has been made to solve the above problems.
SUMMERY OF THE UTILITY MODEL
The method aims to solve the problem of carbon emission of the coal-to-methanol and solve the problem of utilization of renewable electric energy. Specifically, the air separation device and the water-gas shift device in the traditional coal-to-methanol system are omitted, and the renewable energy source is used for electrolyzing water to provide green hydrogen and green oxygen; electrolysis of CO using renewable energy sources2And the mixed water provides carbon monoxide, hydrogen and oxygen, so that the effect of water-gas shift is realized. The utility model can electrolyze water and CO without air separation device with high energy consumption and water-gas shift device with high discharge2And the renewable electric energy is fully utilized in the two processes of water and water.
The utility model provides a synthesis gas fixed ratio production system, which comprises: the system comprises a first electrolytic tank 1, a coal gasification unit 2, an acid gas removal unit 3, a second electrolytic tank 4, a gas regulating unit 5 and a reaction unit 6;
wherein the first electrolytic tank 1, the coal gasification unit 2, the acid gas removal unit 3 and the second electrolytic tank 4 are communicated in sequence, and the discharge ports of the first electrolytic tank 1, the acid gas removal unit 3 and the second electrolytic tank 4 are communicated with the feed port of the gas regulating unit 5;
and the discharge hole of the second electrolytic tank 4 is communicated with the feed hole of the coal gasification unit 2.
Preferably, the first electrolytic cell 1 electrolyzes water into hydrogen and oxygen, the oxygen being delivered to the coal gasification unit 2, the hydrogen being delivered to the gas conditioning unit 5;
the coal gasification unit 2 takes coal, water and oxygen as raw materials to generate carbon monoxide, hydrogen, carbon dioxide and waste acid gas, and the carbon monoxide, the hydrogen, the carbon dioxide and the waste acid gas are conveyed to the acid gas removal unit 3;
the acid gas removal unit 3 removes waste acid gas, and transmits carbon monoxide and hydrogen to the gas conditioning unit 5, and transmits carbon dioxide to the second electrolytic tank 4;
the second electrolytic tank 4 electrolyzes the carbon dioxide and water into carbon monoxide, hydrogen and oxygen, and delivers the carbon monoxide and hydrogen to a gas conditioning unit 5 and oxygen to the coal gasification unit 2;
and the carbon monoxide and the hydrogen in the gas regulating unit 5 enter a reaction unit 6 to react to generate alcohols.
Preferably, the synthesis gas fixed-ratio production system further comprises a reaction unit 6, and the discharge hole of the gas regulating unit 5 is communicated with the feed hole of the reaction unit 6; the carbon monoxide and the hydrogen in the gas regulating unit 5 enter a reaction unit 6 to react to generate a product; the reaction unit 6 is an alcohol reaction unit, a hydrocarbon reaction unit and a synthetic oil reaction unit. That is, the present invention is not limited to the compound produced in the subsequent reaction unit, as long as the raw material is a synthesis gas. When different compounds are produced, the proportion of carbon monoxide and hydrogen in the synthesis gas, the catalyst in the corresponding reaction unit and the operation condition are selected according to the concrete selection.
The method for producing the synthesis gas by fixed ratio comprises the following steps:
(1) electrolyzing water in a first electrolytic cell 1 into hydrogen and oxygen, the oxygen being fed to a coal gasification unit 2 and the hydrogen being fed to a gas conditioning unit 5;
(2) coal, water and oxygen are used as raw materials in a coal gasification unit 2 to generate carbon monoxide, hydrogen, carbon dioxide and waste acid gas, and the carbon monoxide, the hydrogen, the carbon dioxide and the waste acid gas are conveyed to an acid gas removal unit 3;
(3) removing spent acid gas in an acid gas removal unit 3 and delivering carbon monoxide and hydrogen to a gas conditioning unit 5 and carbon dioxide to the second electrolytic cell 4;
(4) the carbon dioxide and water are electrolyzed in the second electrolytic tank 4 into carbon monoxide, hydrogen and oxygen, and the carbon monoxide and hydrogen are fed to the gas conditioning unit 5, the oxygen is fed to the coal gasification unit 2, and the carbon monoxide and hydrogen are adjusted to an appropriate ratio in the gas conditioning unit 5.
Preferably, the method further comprises the step (5) of delivering carbon monoxide and hydrogen in appropriate proportions to the reaction unit 6 for reaction to generate a product; the reaction unit 6 comprises one or more of the following: alcohol reaction unit, hydrocarbon reaction unit, synthetic oil reaction unit.
Preferably, in the step (1), the first electrolytic cell 1 is a proton exchange membrane electrolytic cell, the working temperature is 20-80 ℃, and the working pressure is 1.0-1.1 bar; before entering the gas regulating unit 5, the hydrogen obtained in the step needs to be pressurized to 5-10 MPa, and 8.5MPa is preferred; the oxygen obtained in the step needs to be pressurized to 7.5-8.5 MPa, preferably 8.2MPa before entering the coal gasification unit 2.
Method for designing the first electrolytic cell 1 (oxygen enrichment premise):
the first electrolysis cell can on the one hand supply oxygen for coal gasification and on the other hand adjust the molar ratio of carbon monoxide to hydrogen by adjusting the hydrogen content produced in this step. The carbon monoxide and hydrogen supply device comprises a second electrolytic cell, a first electrolytic cell 1 and an acid gas removal unit 3 (essentially a coal gasification unit 2), wherein after the CO content generated by the second electrolytic cell and the coal gasification unit 2 is determined, the hydrogen quantity required by the synthesis of methanol is estimated, and the hydrogen quantity after the desulphurization of the crude synthesis gas is subtracted to obtain the hydrogen supply quantity of the first electrolytic cell 1, so that the scale and the quantity of the first electrolytic cell 1 are inversely calculated, and the first electrolytic cell 1 is designed. That is, the molar ratio of carbon monoxide to hydrogen in the reaction unit 6 is already secured at the time of designing the first electrolytic tank 1.
Preferably, in the step (3), before the carbon monoxide and the hydrogen obtained in the step enter the gas regulating unit 5, the pressure needs to be increased to 5-10 MPa, and 8.5MPa is preferred.
Preferably, in step (4), the cathode material of the second electrolytic cell 4 is selected from yttria-stabilized zirconia YSZ, ZrO2·Y2O3Strontium doped lanthanum manganate LSM, La1-xSrxMnO3Nickel doped yttria stabilized zirconia Ni-YSZ, nickel and samarium co-doped ceria Ni-SDC SDC Sm0.2Ce0.8O2-δThe anode material is selected from one or more of strontium-doped lanthanum manganate LSM, strontium-doped lanthanum manganate composite yttria-stabilized zirconia LSM-YSZ, strontium-doped lanthanum manganate composite gadolinium-doped ceria LSM-GDC GDC, Gd0.2Ce0.8O2-δOne ofOne or more of them.
Preferably, in step (4), CO2The temperature is 0-40 ℃, and the pressure is 6-8 bar; h2The temperature of the O entering is 150-200 ℃, and the pressure is 3.5-5.5 bar.
Preferably, the reaction unit 6 is an alcohol reaction unit, and the alcohol is methanol.
Preferably, in step (5), suitable ratios are: the molar ratio of carbon monoxide to hydrogen was 2.
Compared with the prior art, the utility model has the following beneficial effects:
1. the utility model omits a high-energy-consumption air separation device in the traditional coal-to-methanol system, and replaces the air separation device with a first electrolytic tank, hydrogen and oxygen are provided by electrolyzing water, the first electrolytic tank can provide oxygen for coal gasification on one hand, and the molar ratio of carbon monoxide and hydrogen can be adjusted by adjusting the content of hydrogen generated in the step on the other hand.
2. The utility model omits a high-emission water-gas shift device in the traditional coal-to-methanol system, and replaces the high-emission water-gas shift device with a second electrolytic tank, and carbon monoxide, hydrogen and oxygen are provided by electrolyzing carbon dioxide and water, wherein the second electrolytic tank, the first electrolytic tank 1 and the acid gas removal unit 3 (essentially the coal gasification unit 2) jointly ensure the molar ratio of the carbon monoxide and the hydrogen, on one hand, the second electrolytic tank can consume the carbon dioxide generated in the coal gasification process, the emission of the carbon dioxide is greatly reduced or even no emission, and on the other hand, the carbon monoxide and the hydrogen can be provided.
3. The CO in the reaction unit 6 of the prior art still contains a large amount of CO2The volume fraction of CO in the two can only reach more than 85 percent, however, CO hardly contains CO in the utility model2The volume fraction of CO in the two can reach more than 95 percent.
4. The utility model makes the process of preparing methanol from coal electrified from two places of energy consumption and discharge, and can be accessed to green and clean energy. In addition, the utility model can fully utilize various products generated in the electrolytic process, especially oxygen. The electrification proportion of the methanol production method is greatly increased, and the requirement of utilizing renewable electric energy at present is met.
5. The preparation process is simple and easy to implement.
Drawings
FIG. 1 is a diagram of a conventional coal-to-methanol system of the prior art;
FIG. 2 is a diagram of a coal-to-methanol system of the present invention.
Description of the reference numerals: 1-a first electrolytic tank, 2-a coal gasification unit, 3-an acid gas removal unit, 4-a second electrolytic tank, 5-a gas regulation unit and 6-a reaction unit.
Detailed Description
The present invention will be described below with reference to specific examples, but the embodiments of the present invention are not limited thereto. The experimental methods not specified in the examples are generally commercially available according to the conventional conditions and the conditions described in the manual, or according to the general-purpose equipment, materials, reagents and the like used under the conditions recommended by the manufacturer, unless otherwise specified. The starting materials required in the following examples and comparative examples are all commercially available.
The electrolytic tank 1 adopts a commercial proton exchange membrane electrolytic tank, and water is electrolyzed to obtain O at the anode2Feeding into a coal gasification unit, and obtaining H at the cathode2Input to a gas conditioning unit. The production capacity of each electrolytic cell is 0.03572t/h and 0.01786 t/h.
Obtaining CO (64 percent) and H by using coal as raw material through a coal gasification unit2(27％)，CO2(8％)H2And (1%) mixed gas of S and the like enters an acid gas removal unit.
The acid gas is removed by a low-temperature methanol washing process to obtain two streams of gas, one stream of CO with the concentration of 98.5 percent2The steam with the temperature of 150 ℃ is input into the electrolytic bath 2; the other is CO/H2The molar ratio is 2.37: the mixed gas of 1 is input into a gas regulating unit.
The electrolytic tank 2 takes Ni-YSZ as a cathode and LSM as an anode, the working temperature is 800 ℃, the working pressure is 1.1bar, and the working voltage is 1.3V. Control of CO2The feeding molar ratio of the steam to the water vapor is 0.51-1.98The molar ratio of the produced hydrogen to the produced carbon monoxide is changed within the range of 0.39-2.75. According to CO2And steam were fed at a molar ratio of 0.51.
Optimization of H in the gas conditioning unit according to the methanol synthesis reaction2The molar ratio/CO is adjusted to the requirement of 2.
Table 1 lists the variation of the parameters for the same methanol production using the conventional coal to methanol process (example 1) and the modified process (examples 2, 3, 4). Example 3 differs from example 2 in that the operating voltage is 1.0V. Example 4 differs from example 2 in that the carbon source is biomass carbon produced from wood chips.
TABLE 1
The above embodiments describe the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited by the embodiments described above, which are given by way of illustration of the principles of the utility model and are not to be taken as limiting the scope of the utility model in any way, and that various changes and modifications may be made therein without departing from the scope of the utility model as defined by the appended claims.
Claims (3)
1. A syngas fixed-ratio production system, comprising: a first electrolytic tank (1), a coal gasification unit (2), an acid gas removal unit (3), a second electrolytic tank (4) and a gas regulation unit (5);
wherein the first electrolytic tank (1), the coal gasification unit (2), the acid gas removal unit (3) and the second electrolytic tank (4) are communicated in sequence, and discharge ports of the first electrolytic tank (1), the acid gas removal unit (3) and the second electrolytic tank (4) are communicated with a feed port of the gas regulating unit (5);
and a discharge hole of the second electrolytic tank (4) is communicated with a feed inlet of the coal gasification unit (2).
2. The system according to claim 1, characterized in that the first electrolytic cell (1) electrolyzes water into hydrogen and oxygen, the oxygen being fed to the coal gasification unit (2), the hydrogen being fed to the gas conditioning unit (5);
the coal gasification unit (2) takes coal, water and oxygen as raw materials to generate carbon monoxide, hydrogen, carbon dioxide and waste acid gas, and the carbon monoxide, the hydrogen, the carbon dioxide and the waste acid gas are conveyed to the acid gas removal unit (3);
the acid gas removal unit (3) removes waste acid gas, and transmits carbon monoxide and hydrogen to the gas conditioning unit (5) and transmits carbon dioxide to the second electrolytic tank (4);
the second electrolytic cell (4) electrolyzes the carbon dioxide and water into carbon monoxide, hydrogen and oxygen, and delivers the carbon monoxide and hydrogen to a gas conditioning unit (5) and oxygen to the coal gasification unit (2).
3. The system according to claim 1, characterized in that it further comprises a reaction unit (6), the outlet of the gas conditioning unit (5) being in communication with the inlet of the reaction unit (6); carbon monoxide and hydrogen in the gas regulating unit (5) enter a reaction unit (6) to react to generate a product;
the reaction unit (6) comprises one or more of the following: alcohol reaction unit, hydrocarbon reaction unit, synthetic oil reaction unit.
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