CN111003690A - Decarburization process of synthesis gas - Google Patents
Decarburization process of synthesis gas Download PDFInfo
- Publication number
- CN111003690A CN111003690A CN201911178479.7A CN201911178479A CN111003690A CN 111003690 A CN111003690 A CN 111003690A CN 201911178479 A CN201911178479 A CN 201911178479A CN 111003690 A CN111003690 A CN 111003690A
- Authority
- CN
- China
- Prior art keywords
- solution
- decarbonization
- decarburization
- gas
- carbon dioxide
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a decarburization process of synthesis gas, which comprises hydrogen, carbon monoxide and carbon dioxide, wherein the synthesis gas is precooled to 20-30 ℃, introduced into a pre-decarburization device, and a pre-decarburization solution is sprayed from the upper part of the pre-decarburization device, so that part of the carbon dioxide and H2S in the synthesis gas are dissolved in the pre-decarburization solution, then continuously cooled to 0-10 ℃, introduced from the lower part of the decarburization device, and a decarburization solution is sprayed from the upper part of the decarburization device, so that the carbon dioxide in the synthesis gas is dissolved in the decarburization solution, and the carbon dioxide is removed, and the pre-decarburization solution and the decarburization solution contain polyethylene glycol dimethyl ether. The decarbonization process of the invention removes CO in the synthesis gas2Thereby adjusting the hydrogen-carbon ratio of the synthesis gas to hydrogenThe carbon ratio is qualified, so that precious volatile components and coal quality in the low-rank coal are fully utilized; the decarburization process disclosed by the invention is simple and feasible to operate, uses more existing equipment, is low in operation cost and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of clean utilization of coal substances, in particular to a decarburization process of synthesis gas.
Background
More than half of the coal reserves already explored in China are low-rank coals, and the volatile components in the low-rank coals are equivalent to 1000 hundred million tons of oil and gas resources. The low-rank coal mainly has the characteristics of high moisture and high volatility, flame is long and has smoke during combustion, the coalification degree is low, and typical coal types are brown coal and long flame coal. The coal-rich, oil-less and gas-deficient coal in China becomes a major subject of the clean coal technology at present by how to efficiently utilize low-rank coal. However, both combustion power generation and modern coal chemical utilization have extremely low comprehensive utilization efficiency due to the three characteristics of high water content, high ash content and low calorific value.
At present, the utilization mode of low-rank coal is mainly direct combustion or gasification. Direct combustion power generation is one of the most common utilization modes, and more than 90% of lignite in China is used for power station boilers and various industrial boilers according to incomplete statistics. The direct combustion of the low-rank coal not only wastes rich oil and gas resources contained in the coal, has low efficiency, but also pollutes the environment, easily causes a large amount of greenhouse gases such as SOx and NOx, and causes severe weather environments such as acid rain. The modern coal chemical technology uses coal gasification as a technical tap, and primary raw materials CO and H required by chemical synthesis are obtained by gasification2However, the coal gasification technology has not developed to date, and a mature large-scale commercial low-rank coal gasification technology has not yet been formed. In the prior art, low-rank coal gasification is used for preparing CO and H2Generally, low-rank coal is pyrolyzed to obtain raw coal gas and upgraded coal, and the pyrolysis is generally carried out in the presence of a large amount of oxygen (or air), wherein a part of coal is reacted with oxygen to supply heat and generate a large amount of CO2. Due to CO2Can not be combusted, belongs to ineffective gas, and has over high nitrogen content due to aerobic combustion, thereby reducing crude coalThe energy density of gas; and the crude gas contains a large amount of CH4Reducing CO and H in the synthesis gas2The content of the (C) in the raw gas reduces the calorific value of the raw gas, the raw gas cannot be used as a first-grade raw material for chemical synthesis, the mixed gas produced by pyrolysis has no other economic value except for return combustion, and the utilization rate of the coal raw material is low; and no related integrated equipment can utilize low-rank coal to continuously produce gas and can realize continuous large-scale production.
At present, the decarbonization is usually performed by using an NHD solution, the water content of a decarbonization system is continuously increased due to the strong water absorption of the NHD solution, the water content in the decarbonization system needs to be extracted, an air extraction method is usually adopted, but the air water content is high, and especially in summer, when the NHD solution and air stripping air are in countercurrent contact in an air stripping tower, the absorption effect of a decarbonized lean solution is influenced. And a dehydration system is adopted, 1.3MPa steam is used for heating, water is evaporated according to different boiling points of water and the NHD solution, ether components in the NHD solution are evaporated, and the loss of the solution is increased.
Furthermore, particularly to the synthesis gas prepared from low-rank coal, the decarbonization process removes carbon dioxide and other component gases, mainly H2S, carbon dioxide can become a resource gas and can also become an environmental pollution, and when the concentration of the carbon dioxide is high enough and is higher than 95% (V/V), the higher the concentration is, the higher the value is, especially the value is more than 98% (V/V), the carbon dioxide is needed by the chemical industry and is also obtained by the existing decarburization technology of the synthesis gas.
Disclosure of Invention
In view of the above, the present invention provides a decarbonization process of syngas, which prepares the low-rank coal containing CO and H under the condition of no oxygen or micro oxygen2Introducing the synthesis gas into a pre-decarbonization device to remove part of carbon dioxide and H2S and other impurities are introduced into a decarbonizing device to remove carbon dioxide so as to obtain decarbonized gas, and hydrocarbons are reformed to prepare the carbon dioxide-containing carbon dioxide2The synthesis gas increases the path for preparing the synthesis gas, and fully and effectively utilizes the volatile components and the coal quality in the low-rank coal.
In order to solve the technical problems, the invention provides the following technical scheme:
a decarburization process of synthesis gas, wherein the synthesis gas contains hydrogen, carbon monoxide and carbon dioxide, the synthesis gas is introduced into a pre-decarburization device after being precooled to 20-30 ℃, and a pre-decarburization solution is sprayed out from the upper part of the pre-decarburization device, so that part of the carbon dioxide and H in the synthesis gas2S is dissolved in the pre-decarbonization solution, then the pre-decarbonization solution and the decarbonization solution are continuously cooled to 0-10 ℃, then the decarbonization solution is introduced from the lower part of a decarbonization device, the decarbonization solution is sprayed from the upper part of the decarbonization device, so that carbon dioxide in the synthesis gas is dissolved in the decarbonization solution, the carbon dioxide is removed, and decarbonization gas is obtained, wherein the pre-decarbonization solution and the decarbonization solution contain polyethylene glycol dimethyl ether.
The raw material low-rank coal can be pulverized coal or lump coal, and when the low-rank coal adopts the lump coal, the pulverized coal with smaller granularity can be obtained by crushing and screening the oversize lump coal. The low-rank coal dried by the drying process enters the gasification reduction process for reaction, and for one-step optimization process, a gasification feeding process can be added before the dried low-rank coal enters the gasification reduction process, so that the dried low-rank coal can rapidly enter the gasification reduction process, the surface area of the material is increased, and the gasification reduction reaction can be accelerated.
Wherein, the gasification reduction process is a chemical reaction process for heating the dried low-rank coal under the condition of no oxygen or micro oxygen. The dried low-rank coal enters a gasification reduction process, under the heating of heating media such as flue gas and the like, additives and other substances are not needed to be added in the reaction process, the temperature is generally 350-800 ℃, and the pressure is less than or equal to 30Kpa, a complex chemical reaction process is carried out, so that solid carbon and high-temperature rich gas are obtained, wherein the solid carbon is upgraded coal, and the volatile matter in the upgraded coal is 8-15 wt%. The high-temperature rich gas comprises CO and H2、CO2Hydrocarbon, coal tar, naphthalene, halide, dust, sulfur compounds, and the like.
The sulfur compounds are liable to cause poisoning and deactivation of reforming conversion catalyst and methane synthesis catalyst, so that the sulfur compounds need to be removed and purified before the reforming conversion processSulfide in the later rich gas. The purified rich gas enters a coarse desulfurization process for treatment, and H in the purified rich gas is removed2S removal to 20mg/Nm3The following.
After the desulfurization process, the synthesis gas is often subjected to a conversion process to increase H in the synthesis gas2The molar ratio of/CO; however, the effective component in the methane synthesis gas required for natural gas synthesis is H2、CO、CO2The requirement for the hydrogen to carbon ratio in methane synthesis gas is expressed as follows: r ═ H2-CO2)/(CO+CO2) Wherein, the theoretical value of the hydrogen-carbon ratio R value of the methane synthetic gas is 3.0, and the optimal value is 2.95-3.05. And the R value of the hydrogen-carbon ratio in the prepared synthetic gas can not just meet the condition that the R value is between 2.95 and 3.05, so that the R value of the hydrogen-carbon ratio in the methane synthetic gas is adjusted to be between 2.95 and 3.05, the upgraded coal and/or the rich gas are prepared by gasifying and reducing low-rank coal to obtain upgraded coal and rich gas, and the upgraded coal and/or the rich gas are prepared to contain CO and CO2And H2The decarbonization gas enters a methane synthesis process to synthesize methane.
Preferably, before the synthesis gas is introduced into the pre-decarbonization device, the synthesis gas is compressed under the pressure of 0.3-1.0MPa to remove the water in the synthesis gas.
Preferably, part of the carbon dioxide and H are dissolved2And (S) carrying out a first regeneration process on the pre-decarbonization solution to obtain a pre-decarbonization barren solution, wherein the first regeneration process comprises a dehydration process, so that the water content of the pre-decarbonization barren solution is lower than 4 wt%, the decarbonization solution for dissolving carbon dioxide is subjected to a second regeneration process, and then the decarbonization solution, namely a decarbonization barren solution, is subjected to a regeneration decarbonization process to remove carbon dioxide, and the pre-decarbonization barren solution and the decarbonization barren solution are communicated and are subjected to liquid guiding mutually.
Further, to dissolve H2And introducing a stripping gas into the pre-decarburization solution of S for stripping, wherein the stripping gas is selected from at least one of air, nitrogen or oxygen, so that the sulfur in the pre-decarburization solution is removed.
Further, the gas stripping gas is cooled by water cooling or low-temperature solution to remove water.
Further, the water content of the stripping gas is not higher than 50 ppm. Further, heating the pre-decarbonization barren solution or the decarbonization barren solution to 120-150 ℃, introducing the heated pre-decarbonization barren solution or the decarbonization barren solution into a lower section packing layer of a second dehydration device, introducing pressurized gas into the second dehydration device, pressurizing the mixture to 1.5-3.0 MPa, and pressurizing and evaporating to obtain light components.
Further, the pressurized gas is selected from one of air, hydrogen-rich gas, carbon monoxide-rich gas and nitrogen gas, and the water content of the pressurized gas is not higher than 50 ppm.
Further, precooling the synthesis gas to 20-30 ℃, and introducing the synthesis gas into a first dehydration device to remove moisture in the synthesis gas.
Preferably, the weight ratio of the pre-decarbonization solution to the decarbonization solution is 1: (2-15).
Based on the technical scheme, the method provided by the invention prepares the dried low-rank coal into the coal mainly containing CO and H under the anaerobic or micro-aerobic condition2By the decarbonation process of the invention, by removing CO from the synthesis gas2Thereby adjusting the hydrogen-carbon ratio of the synthesis gas to make the synthesis gas become decarbonized gas with qualified hydrogen-carbon ratio, and fully utilizing precious volatile components and coal quality in the low-rank coal; the decarburization process disclosed by the invention is simple and feasible to operate, uses more existing equipment, is low in operation cost and is suitable for industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Preparation example
The invention provides a process for decarbonising a synthesis gas, which comprises hydrogen, carbon monoxide and carbon dioxide, and is pre-treatedCooling to 20-30 ℃, introducing into a pre-decarbonization device, and spraying a pre-decarbonization solution from the upper part of the pre-decarbonization device to ensure that part of carbon dioxide and H in the synthesis gas2S is dissolved in the pre-decarbonization solution, then the pre-decarbonization solution and the decarbonization solution are continuously cooled to 0-10 ℃, then the decarbonization solution is introduced from the lower part of a decarbonization device, the decarbonization solution is sprayed from the upper part of the decarbonization device, so that carbon dioxide in the synthesis gas is dissolved in the decarbonization solution, the carbon dioxide is removed, and decarbonization gas is obtained, wherein the pre-decarbonization solution and the decarbonization solution contain polyethylene glycol dimethyl ether.
The raw material low-rank coal can be pulverized coal or lump coal, and when the low-rank coal adopts the lump coal, the pulverized coal with smaller granularity can be obtained by crushing and screening the oversize lump coal. The pulverized coal is preferably used as a raw material, on one hand, the pulverized coal does not need to be crushed and screened, so that the process steps are saved, the heating area is large during drying, the drying efficiency is high, and on the other hand, the pulverized coal is low in price compared with lump coal. Pulverized coal having a particle size of less than 20mm is preferably used, and pulverized coal having a particle size of less than 6mm is still more preferably used.
The low-rank coal generally has 20-55% of volatile components, about 3-15% of tar, 30-60% of fixed carbon, 10-40% of water and the balance of other impurities such as dust. The low-rank coal has low coalification degree but contains abundant oil and gas resources, and the volatile components in the low-rank coal are very beneficial to extracting the synthesis gas, so that the low-rank coal with the volatile components between 30% and 55% is preferred.
If the low-rank coal contains a large amount of moisture, the heat consumption in the gasification reduction reaction process is large, so the technical scheme of the invention preferably treats the low-rank coal through a drying process.
The low-rank coal dried by the drying process is conveyed to the gasification reduction process for reaction, and a gasification feeding process can be added before the dried low-rank coal enters the gasification reduction process, so that the dried low-rank coal can rapidly enter a gasification reduction device, the surface area of the material is increased, and the gasification reduction reaction is accelerated.
Wherein the gasification reduction process is carried out under the condition of no oxygen or micro oxygenAnd (3) heating the dried low-rank coal. The dried low-rank coal is conveyed to a gasification reduction process, under the heating of heating media such as flue gas and the like, additives and other substances are not needed to be added in the reaction process, the temperature is generally 350-800 ℃, the pressure is less than or equal to 30Kpa, a complex chemical reaction process is carried out, solid carbon and a high-temperature oil-gas mixture are obtained, wherein the solid carbon is upgraded coal, the temperature of the upgraded coal is 350-800 ℃, and the volatile matter in the upgraded coal is 8-15 wt%. The high-temperature oil-gas mixture contains CO and H2、CO2Hydrocarbon, coal tar, dust, sulfur compounds, and the like.
The sulfur compounds are liable to cause poisoning and deactivation of the reforming conversion catalyst and the methane synthesis catalyst, so that the sulfur compounds in the purified rich gas need to be removed before the reforming conversion process. The purified rich gas enters a coarse desulfurization process for treatment, and H in the purified rich gas is removed2S removal to 20mg/Nm3The following.
After the desulfurization process, the synthesis gas is often subjected to a conversion process to increase H in the synthesis gas2The molar ratio of/CO;
however, the effective component in the methane synthesis gas required for natural gas synthesis is H2、CO、CO2The requirement for the hydrogen to carbon ratio in methane synthesis gas is expressed as follows: r ═ H2-CO2)/(CO+CO2) Wherein, the theoretical value of the hydrogen-carbon ratio R value of the methane synthetic gas is 3.0, and the optimal value is 2.95-3.05. And the R value of the hydrogen-carbon ratio in the prepared synthetic gas can not just meet the condition that the R value is between 2.95 and 3.05, so that the R value of the hydrogen-carbon ratio in the methane synthetic gas is adjusted to be between 2.95 and 3.05, the upgraded coal and/or the rich gas are prepared by gasifying and reducing low-rank coal to obtain upgraded coal and rich gas, and the upgraded coal and/or the rich gas are prepared to contain CO and CO2And H2The decarbonization gas enters a methane synthesis process to synthesize methane.
Preferably, the synthesis gas is compressed under a pressure of 0.3 to 1.0MPa before being introduced into the decarbonation device.
Preferably, part of the carbon dioxide and H are dissolved2The pre-decarbonization solution of S is subjected to a first regeneration stepAnd after the first regeneration process, removing the carbon dioxide from the decarbonized solution, namely the decarbonized lean solution, which is obtained by carrying out regeneration decarbonization process, wherein the decarbonized solution is obtained by carrying out the first regeneration process, and the decarbonized solution is communicated with the decarbonized lean solution to conduct liquid conduction.
Further, to dissolve H2And introducing a stripping gas into the pre-decarburization solution of S for stripping, wherein the stripping gas is selected from at least one of air, nitrogen or oxygen, so that the sulfur in the pre-decarburization solution is removed.
Further, the gas stripping gas is cooled by water cooling or low-temperature solution to remove water.
Further, the water content of the stripping gas is not higher than 50 ppm. Further, heating the pre-decarbonization barren solution or the decarbonization barren solution to 120-150 ℃, introducing the heated pre-decarbonization barren solution or the decarbonization barren solution into a lower section packing layer of a second dehydration device, introducing pressurized gas into the second dehydration device, pressurizing the mixture to 1.5-3.0 MPa, and pressurizing and evaporating to obtain light components.
Further, the pressurized gas is selected from one of air, hydrogen-rich gas, carbon monoxide-rich gas and nitrogen gas, and the water content of the pressurized gas is not higher than 50 ppm.
Further, precooling the synthesis gas to 20-30 ℃, and introducing the synthesis gas into a first dehydration device to remove moisture in the synthesis gas.
Preferably, the weight ratio of the pre-decarbonization solution to the decarbonization solution is 1: (2-15).
The technical progress of the shift process of the present invention was analyzed by analyzing the composition of the pre-decarbonization apparatus desorbed gas and the decarbonization apparatus desorbed gas obtained, and the sulfur content and the carbon dioxide content of the decarbonized gas, through comparative experiments.
Experimental example 1
A decarburization process of synthesis gas, wherein the synthesis gas contains hydrogen, carbon monoxide and carbon dioxide, the synthesis gas is introduced into a pre-decarburization device after being precooled to 20-30 ℃, and a pre-decarburization solution is sprayed out from the upper part of the pre-decarburization device, so that H in the synthesis gas is removed2S is dissolved in the pre-decarbonization solution, then the pre-decarbonization solution is continuously cooled to 0-10 ℃, then the pre-decarbonization solution and the decarbonization solution are compressed under the pressure of 0.3-1.0MPa, and then the pre-decarbonization solution and the decarbonization solution are introduced from the lower part of a decarbonization device, the decarbonization solution is sprayed from the upper part of the decarbonization device, so that carbon dioxide in the synthesis gas is dissolved in the decarbonization solution, and then the carbon dioxide is removed to obtain decarbonization gas, wherein the pre-decarbonization solution and the decarbonization solution both contain polyethylene glycol dimethyl ether.
In experimental example 1, in the decarburization apparatus, the pre-decarburization solution adsorbs part of carbon dioxide and H in the syngas2S, the pre-decarbonized rich solution is formed, and the carbon dioxide and H are separated out from the pre-decarbonized rich solution in a first regeneration device2S and other light components become the gas analyzed by the pre-decarbonization device, and the NHD solution flows out at the bottom of the first regeneration device to become pre-decarbonization barren solution.
In experimental example 1, the decarbonizing solution adsorbs carbon dioxide in the synthesis gas in the decarbonizing device to form a decarbonized rich solution, the decarbonized rich solution desorbs carbon dioxide in the second regenerating device to form a decarbonizing device analysis gas, and the NHD solution flows out at the bottom of the second regenerating device to form a decarbonized lean solution.
In experimental example 1, the weight ratio of the pre-decarburization solution to the decarburization solution was 1: 8.
experimental example 1 Synthesis gas selected as the raw Material for the composition of CH427.67% of CO, 14.7% of H2Content 28.53%, CO2Content 18.91%, H2The S content is less than 0.1 ppm.
Experimental example 2
Experimental example 2 reference was made to Experimental example 1 except that, in the decarburization process of Experimental example 2, part of carbon dioxide and H were dissolved2The pre-decarbonization solution of S is subjected to a first regeneration process to obtain a pre-decarbonization barren solution, the first regeneration process comprises a dehydration process, the water content of the pre-decarbonization barren solution is lower than 4 wt%, the pre-decarbonization solution for dissolving carbon dioxide is subjected to a second regeneration process, and the decarbonization solution is subjected to a regeneration decarbonization process to remove carbon dioxide, namely the decarbonization barren solutionAnd the pre-decarbonization barren solution is communicated with the decarbonization barren solution and mutually drained.
In the dehydration process in Experimental example 2, in the pre-decarburization device, the pre-decarburization solution adsorbs part of carbon dioxide and H in the synthesis gas2S and other impurities are formed into a pre-decarbonized rich solution, the pre-decarbonized rich solution is in a first regeneration device, part of the pre-decarbonized rich solution is heated from about 20 ℃ to about 140 ℃ by a solution heat exchanger and enters a lower packing layer of a dehydration tower, the other part of the pre-decarbonized rich solution directly enters a condenser coil at the top of the dehydration tower to exchange heat with rising steam and then enters the lower packing layer of the dehydration tower, the temperature of the top of the tower is controlled, a condenser reflux liquid contacted by an upper packing layer is converged with a lower preheated rich solution and enters a heating section of the dehydration tower, steam of a U-shaped pipe at the bottom of the tower is introduced into a reboiler to be heated by 2.0-3.0Mpa steam, an adsorption material flow is evaporated and enters a water cooler of the dehydration tower, light components such as water, benzene and the like in the adsorption material flow and a small amount of NHD are condensed and flow. The heated and rectified NHD solution is led out from the bottom of the tower, and the temperature of the solution is reduced from about 145 ℃ to about 40 ℃ through a solution heat exchanger and returns to the bottom of the stripping tower to become pre-decarbonized barren solution, so that the water content of the pre-decarbonized barren solution is lower than 4 wt%.
Experimental example 3
Experimental example 3 reference was made to experimental example 1, except that in the decarburization process of experimental example 3, the synthesis gas was compressed at a pressure of 0.3 to 1.0MPa, specifically about 0.6MPa, before being introduced into the decarburization apparatus. The aim is, on the one hand, to facilitate the control of the decarbonization effect and to reserve a certain amount of CO in the synthesis gas2On the other hand, the purity of the gas to be analyzed in the decarburization device is improved.
Comparative example 1
A decarburization process of synthesis gas, wherein the synthesis gas contains hydrogen, carbon monoxide and carbon dioxide, the synthesis gas is introduced from the lower part of a decarburization device after being precooled to 0-10 ℃, a decarburization solution is sprayed from the upper part of the decarburization device, so that the carbon dioxide in the synthesis gas is dissolved in the decarburization solution, the carbon dioxide is removed, and the decarburization gas is obtained, and the decarburization solution contains polyethylene glycol dimethyl ether.
In comparative example 1, the decarburization solution in the decarburization device adsorbed impurities such as carbon dioxide in the synthesis gas to become a rich decarburization solution, the rich decarburization solution in the second regeneration device desorbed carbon dioxide to become the gas of the decarburization device, and the NHD solution in the bottom of the second regeneration device flown out to become a lean decarburization solution.
TABLE 1 carbon dioxide and Sulfur contents in the decarburized gas produced in test examples 1 to 3 and comparative example 1*1
| Composition of | Experimental example 1 | Experimental example 2 | Experimental example 3 | Comparative example 1 |
| CO2 | 0.45％ | 0.86％ | 2.35％ | 1.41％ |
| Sulfur content | Less than 0.1ppm | Less than 0.1ppm | Less than 0.1ppm | Less than 0.1ppm |
Note: 1. the content is volume percentage content.
From the results in table 1, we can obtain that the carbon dioxide and sulfur contents in the decarbonized gas are firstly pre-decarbonized at 20-30 ℃ and then decarbonized at 0-10 ℃, the decarbonization effect is more remarkable, which is reduced from 1.41% of the comparative example to 0.86% of experimental example 1 and experimental example 2, and secondly, the amount of carbon dioxide in the obtained synthetic gas can be controlled by controlling the synthetic gas to be introduced into the decarbonization device and passing through the pressure of 0.3-1.0 MPa.
TABLE 2 carbon dioxide and Sulfur contents of the gas analyzed by the Pre-decarbonizing apparatuses of test examples 1 to 3 and comparative example 1*1
| Composition of | Experimental example 1 | Experimental example 2 | Experimental example 3 | Comparative example 1 |
| CO2 | 90.58％ | 90.58％ | 90.58％ | 90.26％ |
| Sulfur content | 21.6ppm | 21.6ppm | 21.6ppm | 8.5ppm |
Note: 1. the content is volume percentage content.
2. Since comparative example 1 has no pre-desulfurization stage, the pre-decarbonization apparatus gas is referred to the decarbonization apparatus gas.
From the results in table 2, we can see that the synthesis gas of the present invention is subjected to pre-decarburization at 20-30 ℃ and then to decarburization at 0-10 ℃, and the concentration of the desorbed carbon dioxide in the pre-decarburization device is equivalent to that of comparative example 1, but the desulfurization effects of experimental examples 1-3 are more significant, and there is an obvious sulfur enrichment effect, so that hydrogen sulfide can be treated in a centralized manner.
TABLE 3 carbon dioxide and Sulfur contents of the decarbonizing apparatus solutions of test examples 1 to 3 and comparative example 1*1
Note: 1. the content is volume percentage content.
From the results of Table 3, it can be seen that the carbon dioxide and sulfur contents in the decarbonized gas were previously decarbonized at 20 to 30 ℃ and then decarbonized at 0 to 10 ℃, the concentration of the desorbed carbon dioxide in the decarbonizing apparatus was higher than that of comparative example 1, the carbon dioxide concentration of the decarbonized gas in the decarbonizing apparatus was increased from 90.26% in the comparative example to 95.26% in examples 1 and 2, and the sulfur content was as low as less than 0.1 ppm; but the sulfur content of examples 1-3 was also lower.
In experimental example 2, we have unexpectedly found that the decarbonizing solution containing more than 4% of water can be reduced to less than 3% by communicating the pre-decarbonizing lean solution with the decarbonizing lean solution and conducting the pre-decarbonizing lean solution with the decarbonizing lean solution to form a circulation process, so that the water brought into the decarbonizing process system by the process operations of synthesis gas, air and the like is removed, and the water content balance of the decarbonizing solution is ensured. For a small part, one ninth to Experimental example 2 without the need for a wholeThe decarbonized solution was dehydrated, and the rich solution was enriched with H in the case of one ninth of the experimental example 22S, so that hydrogen sulfide can be removed simultaneously, thereby achieving the objective effects of simplifying the process and increasing the work efficiency.
In conclusion, the dried low-rank coal is prepared to mainly contain CO and H under the anaerobic or micro-aerobic condition2The synthesis gas of (2) is subjected to the decarbonization process of the invention to remove CO in the synthesis gas2Thereby adjusting the hydrogen-carbon ratio of the synthesis gas to make the synthesis gas become decarbonized gas with qualified hydrogen-carbon ratio, and fully utilizing precious volatile components and coal quality in the low-rank coal; the decarburization process is simple and feasible to operate, uses the existing equipment, has low operation cost and is suitable for industrial production.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. The decarburization process of the synthesis gas is characterized in that the synthesis gas contains hydrogen, carbon monoxide and carbon dioxide, the synthesis gas is precooled to 20-30 ℃, then introduced into a pre-decarburization device, and a pre-decarburization solution is sprayed out from the upper part of the pre-decarburization device, so that part of the carbon dioxide and H in the synthesis gas2S is dissolved in the pre-decarbonization solution, then the pre-decarbonization solution and the decarbonization solution are continuously cooled to 0-10 ℃, then the decarbonization solution is introduced from the lower part of a decarbonization device, the decarbonization solution is sprayed from the upper part of the decarbonization device, so that carbon dioxide in the synthesis gas is dissolved in the decarbonization solution, the carbon dioxide is removed, and decarbonization gas is obtained, wherein the pre-decarbonization solution and the decarbonization solution contain polyethylene glycol dimethyl ether.
2. The decarbonization process of claim 1, wherein the syngas is compressed at a pressure of 0.3 to 1.0MPa prior to being passed into the decarbonization device.
3. Decarburization process according to claim 1, wherein part of the carbon dioxide and H is dissolved2And (S) carrying out a first regeneration process on the pre-decarbonization solution to obtain a pre-decarbonization barren solution, wherein the first regeneration process comprises a dehydration process, so that the water content of the pre-decarbonization barren solution is lower than 4 wt%, the decarbonization solution for dissolving carbon dioxide is subjected to a second regeneration process, and then the decarbonization solution, namely a decarbonization barren solution, is subjected to a regeneration decarbonization process to remove carbon dioxide, and the pre-decarbonization barren solution and the decarbonization barren solution are communicated and are subjected to liquid guiding mutually.
4. The decarburization process of claim 3, wherein the first regeneration process includes feeding dissolved H2And introducing a stripping gas into the pre-decarburization solution of S for stripping, wherein the stripping gas is selected from at least one of air, nitrogen or oxygen, so that the sulfur in the pre-decarburization solution is removed.
5. The decarbonization process of claim 4, wherein the stripping gas has a water content of not greater than 50 ppm.
6. The decarburization process according to claim 3, wherein the dehydration process comprises heating the pre-decarbonized lean solution to 120-150 ℃, introducing the heated pre-decarbonized lean solution into a lower packing layer of a dehydration device, introducing pressurized gas into the lower packing layer, pressurizing the gas to 1.5-3.0 MPa, and pressurizing and evaporating light components.
7. The decarburization process of claim 1, wherein the weight ratio of the pre-decarburization solution to the decarburization solution is 1: (2-15).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911178479.7A CN111003690A (en) | 2019-11-27 | 2019-11-27 | Decarburization process of synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911178479.7A CN111003690A (en) | 2019-11-27 | 2019-11-27 | Decarburization process of synthesis gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111003690A true CN111003690A (en) | 2020-04-14 |
Family
ID=70112022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911178479.7A Pending CN111003690A (en) | 2019-11-27 | 2019-11-27 | Decarburization process of synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111003690A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356158A (en) * | 2001-09-26 | 2002-07-03 | 南化集团研究院 | Physical process for removing sulfur and carbon by solvent |
| CN1546206A (en) * | 2003-12-09 | 2004-11-17 | 南化集团研究院 | Method for removing sulfides and carbon dioxide by high pressure |
| CN101254388A (en) * | 2008-04-03 | 2008-09-03 | 清华大学 | Carbon elimination technique using dimethyl carbonate as absorbing agent |
| CN103007748A (en) * | 2013-01-04 | 2013-04-03 | 济南承乾工程技术有限公司 | System for removing H2S in acid gas |
| CN103146447A (en) * | 2013-03-20 | 2013-06-12 | 神华集团有限责任公司 | System for producing CH4-enriched gas and method for producing CH4-enriched gas by employing system |
| CN104275083A (en) * | 2013-07-05 | 2015-01-14 | 中国石油天然气股份有限公司 | Method for capture and separation of CO2 from gas mixture |
| CN107057767A (en) * | 2017-03-17 | 2017-08-18 | 北京交通大学 | One kind is based on CO before chemical chain making oxygen by air separation and burning2The electricity generation system of trapping |
-
2019
- 2019-11-27 CN CN201911178479.7A patent/CN111003690A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1356158A (en) * | 2001-09-26 | 2002-07-03 | 南化集团研究院 | Physical process for removing sulfur and carbon by solvent |
| CN1546206A (en) * | 2003-12-09 | 2004-11-17 | 南化集团研究院 | Method for removing sulfides and carbon dioxide by high pressure |
| CN101254388A (en) * | 2008-04-03 | 2008-09-03 | 清华大学 | Carbon elimination technique using dimethyl carbonate as absorbing agent |
| CN103007748A (en) * | 2013-01-04 | 2013-04-03 | 济南承乾工程技术有限公司 | System for removing H2S in acid gas |
| CN103146447A (en) * | 2013-03-20 | 2013-06-12 | 神华集团有限责任公司 | System for producing CH4-enriched gas and method for producing CH4-enriched gas by employing system |
| CN104275083A (en) * | 2013-07-05 | 2015-01-14 | 中国石油天然气股份有限公司 | Method for capture and separation of CO2 from gas mixture |
| CN107057767A (en) * | 2017-03-17 | 2017-08-18 | 北京交通大学 | One kind is based on CO before chemical chain making oxygen by air separation and burning2The electricity generation system of trapping |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101649232B (en) | Synthesis process of natural gas employing methanation of coke oven gas | |
| CN103275777A (en) | Method for preparing hydrogen and liquefied natural gas through using gas retort raw gas | |
| CN104803819B (en) | A kind of method and system utilizing fine coal preparing ethylene | |
| CN112897464B (en) | Process for producing hydrogen and coproducing LNG (liquefied natural gas) by using raw gas with methanation | |
| CN103407963A (en) | Coke oven gas hydrogen generation process | |
| CN101239702B (en) | High temperature coke oven crude gas hydrogen generating system device and technique | |
| CN102199433A (en) | Coal carbonization technology with treating CO2 as temperature control component in combustion process | |
| CN103952197A (en) | Process for co-producing LNG (Liquefied Natural Gas) by using pyrolysis gas generated in power generation system | |
| CN102642810A (en) | Combined process for preparing Fischer-Tropsch synthetic oil raw material gas by utilizing coke-oven gas | |
| CN217459345U (en) | Device for producing low-carbon methanol by using coke oven gas | |
| CN102827620A (en) | Methane-rich gas production combined internal heat coal dry distillation poly-production technology | |
| CN110631326B (en) | Fischer-Tropsch synthesis tail gas recycling system process | |
| CN102626580A (en) | Two-step pressure swing adsorption separation method of multicomponent gas containing hydrogen and hydrogen sulfide | |
| CN204529700U (en) | A kind of system utilizing fine coal preparing ethylene | |
| CN104192845A (en) | Comprehensive utilization technology for producing distillate gas in liquid carbon dioxide purifying tower from pressure swing adsorption decarbonization tail gas | |
| CN105001899A (en) | Method for preparing clean coal-based synthetic wax | |
| CN110862841B (en) | Method for preparing natural gas from coal water slurry | |
| CN102320568A (en) | Method and device for preparing synthetic gas or hydrogen with BGL pressuring slag gasification and pure oxygen non-catalytic partial oxidation | |
| CN110804468A (en) | Dry desulfurization process for synthesis gas | |
| CN215250677U (en) | System for burnt tail gas transform of gasification, decarbonization system LNG | |
| CN107311173B (en) | Preparation method of high-pressure gas-phase carbon dioxide for pulverized coal gasification unit | |
| CN111003690A (en) | Decarburization process of synthesis gas | |
| CN202208705U (en) | Device for preparing synthesis gas or hydrogen through BGL pressurizing molten slag gasification with pure oxygen non-catalytic partial oxidation | |
| CN115717090A (en) | Method for preparing synthesis gas from semi-coke oven gas | |
| CN104593079A (en) | Process for producing clean synthesis gas from crushed coal |
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 |