CN109020780B - System and method for preparing methanol by coal gasification coupled coal coking - Google Patents
System and method for preparing methanol by coal gasification coupled coal coking Download PDFInfo
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Abstract
The invention belongs to the technical field of energy chemical industry, and discloses a system and a method for preparing methanol by coal gasification coupled coal coking. The system comprises a coal water slurry preparation unit, a coal gasification unit, a water gas conversion unit, a synthesis gas purification unit, a coal coking unit, a coke gasification unit, a coke oven gas purification unit, a coke oven gas separation unit, a methane dry reforming unit, a gas mixer and a methanol synthesis unit. The raw synthesis gas of the coal gasification unit and the raw synthesis gas of the coke gasification unit are both connected to the water gas shift unit, the synthesis gas of the methane dry reforming unit, the purified synthesis gas of the synthesis gas purification unit and the hydrogen of the coke oven gas separation unit enter a gas mixer together, and the methanol synthesis gas obtained after mixing enters the methanol synthesis unit. The system and the method of the invention realize the coupling production of chemical products by coal gasification and coal coking, and break the limitation of the prior art.
Description
Technical Field
The invention belongs to the technical field of energy chemical industry, and particularly relates to a system and a method for preparing methanol by coal gasification coupled coal coking.
Background
The modern coal chemical industry takes synthesis gas as a core and then converts the synthesis gas into energy power and chemical products. The preparation of methanol from coal through synthesis gas is an important way for clean and efficient utilization of coal resources. Methanol is an important organic chemical raw material, and can be used as a coal resource to be introduced into a door of a chemical product to synthesize important downstream chemical products such as olefin, dimethyl ether, methyl tert-butyl ether and the like. Meanwhile, the methanol has good combustion performance, high octane number and good anti-explosion performance, and can be used as a new clean fuel in the process of developing new fuels.
Currently, coal gasification is an important way for preparing methanol from coal, and is a typical representative of modern coal chemical industry, and a process flow chart is shown in fig. 1. The system for preparing methanol by coal gasification mainly comprises four units: the system comprises a coal water slurry preparation unit, a coal gasification unit, a water gas shift unit, a synthetic gas purification unit and a methanol synthesis unit. Raw material coal and water are pretreated in a coal water slurry preparation unit to become coal water slurry, and the coal water slurry enters a coal gasification unit to react with oxygen in a gasification furnace to generate coal gasification raw synthesis gas. The coal gasification crude synthesis gas passes through a water gas shift unit, and part of CO is converted into H2With CO formation2. The transformed crude synthesis gas enters a synthesis gas purification unit to remove CO2And sulfides (H)2S) obtaining clean methanol synthesis gas. Finally, the process is carried out in a batch,the clean methanol synthesis gas enters a methanol synthesis unit to generate crude methanol, and the crude methanol is rectified by a rectification system to obtain a product methanol with purity.
The coal coking industry is another important industry for coal resource utilization, is a traditional coal chemical representative, is mainly used for producing coke and coproducing coke oven gas and coal tar, and produces 1t coke and coproducts 300-360 Nm & lt Nm & gt3Coke oven gas.
The main problem of the existing process for preparing methanol by coal gasification is CO2The utilization rate of coal resources is low due to large discharge amount. The main reason is that the H/C ratio in coal is 0.8-1, and the suitable H/C ratio for synthesizing methanol is about 2.0, so the hydrogen-carbon ratio needs to be properly adjusted in the process of preparing methanol from coal. Redundant carbon elements will be in the form of CO2The forms are discharged into the atmosphere, which on the one hand causes environmental pollution and on the other hand causes a large loss of carbon resources resulting in low resource utilization.
The coal chemical process of using coal coking as tap has the problems of waste of coke oven gas resource, excessive coke market capacity and low product value at present. The main component of the coke oven gas comprises H2(55～60％)，CH4(23～27％)，CO(5～8％)，N2(3～6％)，CO2(<2%) and the amount of coke oven gas produced as a byproduct in the coking industry per year is 900 hundred million standard cubic meters, but only 20% -40% of coke oven gas is used as coke oven fuel, most of the coke oven gas is emptied, and a large amount of resources are wasted. Researches have proposed that coke oven gas can be used for further producing chemical products such as methanol, olefin or natural gas, but the hydrogen-carbon ratio in the coke oven gas is as high as 5.6, and the hydrogen-carbon ratio of the synthesized downstream chemical products is about 2.0, so that a large amount of H is generated in the process2Cannot be fully utilized, and the excessive H2Often discharged as purge gas or combusted as fuel to provide heat, so that the highly efficient clean hydrogen can not be utilized.
According to the characteristics of more hydrogen and less carbon in the coke oven gas and less hydrogen and more carbon in the coal gasification synthesis gas, the coke oven gas and the coal gasification synthesis gas are combined to produce chemical products, so that the emission of carbon dioxide can be effectively reduced, and the coke oven gas resource can be fully utilized. Researches show that by adjusting the proportion of the coke-oven gas and the synthesis gas, the emission of carbon dioxide in the combined supply process can be reduced by 61 percent compared with the single process, and the energy efficiency is improved by 10 percent. However, this means that the coke scale is large enough to obtain a corresponding amount of coke oven gas. Meanwhile, coal gasification plants and coke-oven plants are often located in two areas which are far away from each other, long-distance transportation of coke-oven gas also becomes a big problem, and the corrosion and potential leakage of gas to pipelines limit the implementation of the combined supply process. In the period of excessive coke capacity, the operating rate of the coke oven is low, and the coke oven gas is used as a byproduct of the coking process, so that the sufficient supply of raw materials is difficult to ensure. This makes the co-generation solution very limited in terms of both raw material supply and raw material transport.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a system for preparing methanol by coal gasification coupled coal coking. The system provided by the invention is beneficial to reducing the carbon dioxide emission in the process of preparing methanol from coal, and improving the resource utilization efficiency.
The invention also aims to provide a method for preparing methanol by coal gasification coupled coal coking.
The purpose of the invention is realized by the following technical scheme:
a system for preparing methanol by coal gasification coupled coal coking comprises a coal water slurry preparation unit, a coal gasification unit, a water gas shift unit, a synthetic gas purification unit, a coal coking unit, a coke gasification unit, a coke oven gas purification unit, a coke oven gas separation unit, a methane dry reforming unit, a gas mixer and a methanol synthesis unit;
the coal water slurry preparation unit is provided with a raw material lignite inlet, a water inlet and a coal water slurry outlet, and the coal water slurry outlet is connected to the coal gasification unit; the coal gasification unit is provided with an oxygen inlet and a coal gasification crude synthesis gas outlet, and the coal gasification crude synthesis gas outlet is connected to the water gas shift unit; the water gas conversion unit is provided with a converted crude synthesis gas outlet connected to the synthesis gas purification unit; the synthetic gas purification unit is provided with a purified synthetic gas outlet, a sulfide outlet and CO2An outlet for purified syngas connected to a gas mixer, CO2The outlet is connected to a methane dry reforming unit;
the coal coking unit is provided with a raw material coking coal inlet, a coking coal outlet and a crude coke oven gas outlet, the coking coal outlet is divided into two channels, one channel is connected to the coking coal gasification unit, the other channel is used for outputting coke products, and the crude coke oven gas outlet is connected to the coke oven gas purification unit; the coke gasification unit is provided with a coke gasification crude synthesis gas outlet which is connected to the water gas shift unit; the coke-oven gas purification unit is provided with a purified coke-oven gas outlet and tar, benzene, naphthalene and sulfide outlets, and the purified coke-oven gas outlet is connected to the coke-oven gas separation unit; the coke-oven gas separation unit is provided with a methane outlet and a hydrogen outlet, the hydrogen outlet is connected to the gas mixer, and the methane outlet is connected to the methane dry reforming unit; the methane dry reforming unit is provided with a methane dry reforming gas outlet connected to the gas mixer; the gas mixer is provided with a methanol synthesis gas outlet connected to the methanol synthesis unit, and the methanol synthesis unit is provided with a methanol outlet.
A method for preparing methanol by coal gasification coupled coal coking comprises the following steps:
raw material lignite for gasification and water enter a water coal slurry preparation unit to prepare water coal slurry; the coal water slurry directly enters a coal gasification unit to be subjected to high-temperature gasification reaction with oxygen to prepare coal gasification crude synthesis gas, the coal gasification crude synthesis gas is subjected to hydrogen-carbon ratio adjustment by a water gas shift unit to obtain converted crude synthesis gas, the converted crude synthesis gas is introduced into a synthesis gas purification unit to remove sulfide and high-concentration carbon dioxide to obtain purified synthesis gas, the carbon dioxide is divided into two parts, one part of the carbon dioxide is connected with a carbon dioxide inlet of a methane dry reforming unit through a pipeline, and the other part of the remaining carbon dioxide is discharged out of the system; directly discharging the sulfide out of the system; the purified synthesis gas enters a gas mixer and is mixed to obtain methanol synthesis gas;
coking coal used as a raw material for coal coking is coked in a coal coking unit (a coking furnace) to obtain coke, crude coke-oven gas, tar and other substances; one part of the coke is made into a coke product, and the other part of the coke enters a coke gasification unit to react with oxygen and water vapor to generate coke gasification crude synthesis gas which is mixed with the coal gasification crude synthesis gas through a pipeline; the crude coke oven gas enters a coke oven gas purification unit to remove tar, benzene and naphthalene in the crude coke oven gasAnd sulfide and other impurities to obtain purified coke oven gas, sending the purified coke oven gas into a coke oven gas separation unit, and separating to obtain hydrogen and methane; hydrogen directly enters a gas mixer, methane enters a methane dry reforming unit to convert the methane in the methane dry reforming unit into methane dry reforming gas (the main components are CO and H)2) (ii) a The dry weight of methane is integrated into a forming gas, the purified forming gas and hydrogen obtained by the coke-oven gas separation unit enter a gas mixer together, the forming gas and the hydrogen are mixed to obtain methanol synthesis gas, the methanol synthesis gas enters a methanol synthesis unit, and a methanol product is obtained after reaction and purification.
Preferably, the hydrogen-carbon ratio of the coal gasification crude synthesis gas is 0.2-1.
Preferably, the hydrogen-carbon ratio of the coke gasification crude synthesis gas is 0.5-1.
Preferably, the hydrogen-carbon ratio of the purified synthesis gas is 1-3.
Preferably, the composition of the crude coke oven gas comprises 50-60% by volume of H2And 20-30% of CH4(ii) a The hydrogen-carbon ratio of the purified coke oven gas is 3-6.
Preferably, the temperature of the reaction furnace of the coke gasification unit is 1100-1600 ℃, and the pressure is 28-42 bar.
Preferably, the operation temperature of the methane dry reforming unit is 600-950 ℃, and the pressure is 4-20 bar.
Compared with the prior art, the system and the method have the following advantages and beneficial effects:
(1) the invention utilizes coke with high value through the coke gasification unit, produces chemical products and optimizes resource allocation.
(2) In the coupling process, the methane in the coke oven gas and the carbon dioxide discharged by the synthesis gas purification unit are converted into the synthesis gas by adding the methane dry reforming unit, and the purified synthesis gas is supplemented with hydrogen by the hydrogen separated from the coke oven gas to directly synthesize the methanol, so that the resource waste caused by the combustion of the hydrogen in the process of preparing the methanol from the coke oven gas is avoided.
(3) The coke oven gas is used as industrial waste gas of industrial coal coking, and has large quantity and environmental pollution. The invention fully utilizes the hydrogen-rich resource H in the waste gas2And CH4Go forward and go forwardThe synthesis of chemical products is carried out, the emission of industrial waste gas from industrial coal coking is reduced, and the utilization rate of resources and energy sources is obviously improved.
(4) The problem that coke oven gas is not convenient to transport in a long distance or corrode a pipeline exists in the conventional coal and coke oven gas combined supply process, most of coal gasification plants and coal coking plants are far away, and double-gas-head combined supply has great limitation. The invention avoids the double-gas-head matching method, realizes the coupling production of chemical products by coal gasification and coal coking, and breaks through the limitation of the prior art.
(5) A large amount of high-concentration carbon dioxide is generated in the process of producing methanol by coal gasification, and the carbon dioxide is often directly discharged into the atmosphere, so that the greenhouse effect is caused, the climate is warmed, and the utilization rate of coal resources is greatly reduced. The invention fully utilizes methane in the coke-oven gas to absorb carbon dioxide, and the carbon dioxide generated in the existing coal-to-methanol process is effectively recycled in the invention, so that the invention can reduce the carbon dioxide emission in the existing coal-to-methanol process, and the utilization rate of carbon element reaches more than 60%, which is improved by 60% compared with the existing coal gasification methanol process.
(6) The novel coupling process provided by the invention can be used for producing methanol and coke simultaneously, and the flexibility of the system is improved. The gasification amount of the coke can be adjusted between 50 percent and 90 percent according to the change of market price, and the coke is selected to be output as a product or further synthesized into methanol, thereby obtaining higher economic benefit and resource utilization efficiency.
Drawings
FIG. 1 is a flow chart of a conventional process for preparing methanol from coal. The numbering in the figures is as follows: the system comprises a coal water slurry preparation unit, a coal gasification unit, a 3-water gas shift unit, a 4-synthesis gas purification unit and a 5-methanol synthesis unit. 6 ~ 15 are the commodity circulation serial number: 6-raw material coal, 7-water, 8-coal water slurry, 9-oxygen, 10-coal gasification crude synthesis gas, 11-transformed crude synthesis gas, 12-carbon dioxide, 13-sulfide, 14-clean methanol synthesis gas and 15-methanol.
Fig. 2 is a process flow diagram of methanol production by coal gasification coupled with coal coking according to the embodiment of the invention. The numbering in the figures is as follows: 1-coal water slurry preparation unit, 2-coal gasification unit, 3-water gas shift unit, 4-synthesis gas purification unit, 5-coal coking unit, 6-coke gasification unit, 7-coke oven gas purification unit, 8-coke oven gas separation unit, 9-methane dry reforming unit, 10-methanol synthesis unit, 11-raw material lignite, 12-water, 13-oxygen, 14-coal water slurry, 15-coal gasification crude synthesis gas, 16-coke gasification crude synthesis gas, 17-converted crude synthesis gas, 18-purified synthesis gas, 19-sulfide, 20-22-carbon dioxide, 23-raw material coke coal, 24-coke, 25-tar and other substances, 26-crude coke oven gas, 27-purified coke oven gas, 28-tar, benzene, naphthalene and sulfide, 29-methane dry weight integrated gas, 30-methane, 31-hydrogen, 32-gas mixer, 33-methanol synthesis gas and 34-methanol.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The system for preparing methanol by coal gasification coupled coal coking comprises a coal water slurry preparation unit, a coal gasification unit, a water gas shift unit, a synthesis gas purification unit, a coal coking unit, a coke gasification unit, a coke oven gas purification unit, a coke oven gas separation unit, a methane dry reforming unit, a gas mixer and a methanol synthesis unit;
the coal water slurry preparation unit is provided with a raw material lignite inlet, a water inlet and a coal water slurry outlet, and the coal water slurry outlet is connected to the coal gasification unit; the coal gasification unit is provided with an oxygen inlet and a coal gasification crude synthesis gas outlet, and the coal gasification crude synthesis gas outlet is connected to the water gas shift unit; the water gas conversion unit is provided with a converted crude synthesis gas outlet connected to the synthesis gas purification unit; the synthetic gas purification unit is provided with a purified synthetic gas outlet, a sulfide outlet and CO2An outlet for purified syngas connected to a gas mixer, CO2The outlet is connected to a methane dry reforming unit;
the coal coking unit is provided with a raw material coking coal inlet, a coking coal outlet and a crude coke oven gas outlet, the coking coal outlet is divided into two channels, one channel is connected to the coking coal gasification unit, the other channel is used for outputting coke products, and the crude coke oven gas outlet is connected to the coke oven gas purification unit; the coke gasification unit is provided with a coke gasification crude synthesis gas outlet which is connected to the water gas shift unit; the coke-oven gas purification unit is provided with a purified coke-oven gas outlet and tar, benzene, naphthalene and sulfide outlets, and the purified coke-oven gas outlet is connected to the coke-oven gas separation unit; the coke-oven gas separation unit is provided with a methane outlet and a hydrogen outlet, the hydrogen outlet is connected to the gas mixer, and the methane outlet is connected to the methane dry reforming unit; the methane dry reforming unit is provided with a methane dry reforming gas outlet connected to the gas mixer; the gas mixer is provided with a methanol synthesis gas outlet connected to the methanol synthesis unit, and the methanol synthesis unit is provided with a methanol outlet.
The method for preparing methanol by adopting the system for preparing methanol by coal gasification coupled coal coking has the preparation process flow chart shown in figure 2, and comprises the following specific preparation steps:
raw materials of lignite 11 and water 12 for gasification enter a coal water slurry preparation unit 1 to prepare coal water slurry 14; the coal water slurry 14 directly enters a coal gasification unit 2 to be subjected to high-temperature gasification reaction with oxygen 13 to prepare coal gasification raw synthesis gas 15, the coal gasification raw synthesis gas 15 is subjected to hydrogen-carbon ratio adjustment by a water gas shift unit 3 to obtain shifted raw synthesis gas 17, the shifted raw synthesis gas 17 is introduced into a synthesis gas purification unit 4 to remove sulfide 19 and high-concentration carbon dioxide 20, purified synthesis gas 18 is obtained, the carbon dioxide 20 is divided into two parts, one part of carbon dioxide 22 is connected with a carbon dioxide inlet of a methane dry reforming unit 9 through a pipeline, and the other part of the remaining carbon dioxide 21 is discharged out of the system; directly discharging the sulfide 19 out of the system; the purified synthesis gas 18 enters a gas mixer 32 and is mixed to obtain methanol synthesis gas 33;
coking coal 23, a raw material for coal coking, is coked in a coal coking unit 5 (coking furnace) to obtain coke 24, crude coke-oven gas 26, tar and other substances 25; one part of the coke 24 is made into a coke product, and the other part enters the coke gasification unit 6 to react with oxygen 13 and water vapor 12 to generate coke gasification raw synthesis gas 16 and is mixed with the coal gasification raw synthesis gas 15 through a pipeline; the crude coke oven gas 26 enters a coke oven gas purification unit 7 to remove impurities 28 such as tar, benzene, naphthalene and sulfide in the crude coke oven gas 26 to obtain purified coke oven gas 27, and the purified coke oven gas is sent to a coke oven gas separation unitElement 8, hydrogen 31 and methane 30 are obtained by separation; the hydrogen 31 is directly fed to a gas mixer 32 and the methane 30 is fed to a methane dry reforming unit 9 for converting the methane 30 therein into a methane dry reforming gas 29 (the main components are CO and H)2) (ii) a The dry integrated methane forming gas 29, the purified synthesis gas 18 and the hydrogen 31 obtained by the coke oven gas separation unit 8 enter a gas mixer 32 together, the methanol synthesis gas 33 obtained after mixing enters a methanol synthesis unit 10, and a methanol product 34 is obtained after reaction and purification.
Example 2
The specific implementation of the system and the method for preparing methanol by coal gasification coupled coal coking in the embodiment 1 is as follows:
the flow rate of raw material lignite is 250t/h, and the amount of raw synthesis gas generated by the coal gasification unit is 27459kmol/h (hydrogen-carbon ratio is 0.9). The flow rate of raw coking coal is 500t/h, 375t/h coke and 16.83 ten thousand meters are produced through the coking process3H of crude coke oven gas (H)2Content of 58% CH 426 percent of the total carbon content), 9.76 ten thousand meters can be obtained after the crude coke oven gas is purified (the hydrogen-carbon ratio of the purified coke oven gas is 5.2) and separated by a coke oven gas separation unit3Hydrogen/h and 4.38 km3Methane per hour. The coke amount entering a coke gasification unit (the temperature of a reaction furnace is 1400 ℃, the pressure is 40bar) is 375t/h, the coke gasification crude synthesis gas amount generated by the coke gasification unit is 48809kmol/h (the hydrogen-carbon ratio is 0.8), the coke gasification crude synthesis gas is mixed with the coal gasification crude synthesis gas to obtain 76269kmol/h of gasification crude synthesis gas, the gasification crude synthesis gas is subjected to a water gas shift unit and a synthesis gas purification unit to obtain purified synthesis gas 58365kmol/h (the hydrogen-carbon ratio is 2.05) and carbon dioxide 24904kmol/h with the concentration of 95%, wherein the carbon dioxide of 1010kmol/h enters a methane dry reforming unit (the operation temperature is 800 ℃, the pressure is 4bar) to react with methane, the residual carbon dioxide is discharged out of the system to generate methane dry weight integrated gas amount of 4100kmol/h, the hydrogen obtained by the coke gas separation unit, the methanol synthesis gas 65483kmol/h obtained by mixing the purified synthesis gas and the methane dry weight integrated gas, synthesis of methanol 562.5 t/h. The design calculation is performed on the embodiment by chemical process simulation software Aspen, and the result is shown in table 1.
TABLE 1 results of calculation
In the existing process of preparing methanol by coal gasification single production, raw coal is prepared into water-coal slurry, and then coal gasification crude synthesis gas is generated by a coal gasification unit, and then the clean methanol synthesis gas is obtained by a water gas shift unit and a synthesis gas purification unit, and a clean methanol synthesis gas is synthesized into a methanol product. A coal gasification single-production methanol process with the raw coal processing capacity of 250t/h can produce 225t/h methanol product and generate about 28360kmol/h carbon dioxide. Compared with the process of preparing methanol by coal gasification per unit, the carbon dioxide emission reduction of the novel process is about 12% and the methanol yield is enlarged by about 2.5 times.
Example 3
The specific implementation of the system and the method for preparing methanol by coal gasification coupled coal coking in the embodiment 1 is as follows:
the flow rate of raw material lignite is 250t/h, and the amount of raw synthesis gas generated by the coal gasification unit is 27459kmol/h (hydrogen-carbon ratio is 0.9). The flow rate of raw coking coal is 500t/h, 375t/h coke and 16.83 ten thousand meters are produced through the coking process3H of crude coke oven gas (H)2Content of 58% CH 426 percent of the total carbon content), 9.76 ten thousand meters can be obtained after the crude coke oven gas is purified (the hydrogen-carbon ratio of the purified coke oven gas is 5.4) and separated by a coke oven gas separation unit3Hydrogen/h and 4.38 km3Methane per hour. The coke amount entering the coke gasification unit (the temperature of the reaction furnace is 1400 ℃, the pressure is 40bar) is 281t/h, the coke gasification crude synthesis gas amount generated by the coke gasification unit is 36607kmol/h (the hydrogen-carbon ratio is 0.8), mixing with the coal gasification crude synthesis gas to obtain the gasification crude synthesis gas 64067kmol/h, passing through a water gas shift unit and a synthesis gas purification unit, the purified synthesis gas 43773kmol/h (hydrogen-carbon ratio of 2.05) and the carbon dioxide 21218kml/h with the concentration of 95 percent are obtained, wherein 1010kmol/h of carbon dioxide enters a methane dry reforming unit (the operation temperature is 800 ℃, the pressure is 4bar) to react with methane, the rest carbon dioxide is discharged out of the system, the generated dry weight of the methane is integrated into a gas quantity of 4100kmol/h, and the hydrogen obtained by the coke oven gas separation unit, the purified synthesis gas and the dry weight of the methane are integrated into a gas mixture.The synthesized methanol synthesis gas is 57371kmol/h, and the synthesized methanol is 485 t/h. The design calculation is performed on the embodiment by chemical process simulation software Aspen, and the result is shown in table 2.
TABLE 2 calculation results
In the existing process of preparing methanol by coal gasification single production, raw coal is prepared into water-coal slurry, and then coal gasification crude synthesis gas is generated by a coal gasification unit, and then the clean methanol synthesis gas is obtained by a water gas shift unit and a synthesis gas purification unit, and a clean methanol synthesis gas is synthesized into a methanol product. A coal gasification single-production methanol process with the raw coal processing capacity of 250t/h can produce 225t/h methanol product and generate about 28360kmol/h carbon dioxide. Compared with the process of preparing methanol by coal gasification per unit, the carbon dioxide emission reduction of the novel process is about 17% and the methanol yield is enlarged by about 2.1 times.
Example 4
The specific implementation of the system and the method for preparing methanol by coal gasification coupled coal coking in the embodiment 1 is as follows:
the flow rate of raw material lignite is 250t/h, and the amount of raw synthesis gas generated by the coal gasification unit is 27459kmol/h (hydrogen-carbon ratio is 0.9). The flow rate of raw coking coal is 500t/h, 375t/h coke and 16.83 ten thousand meters are produced through the coking process3H of crude coke oven gas (H)2Content of 58% CH 426 percent of the total carbon content), 9.76 ten thousand meters can be obtained after the crude coke oven gas is purified (the hydrogen-carbon ratio of the purified coke oven gas is 5.8) and separated by a coke oven gas separation unit3Hydrogen/h and 4.38 km3Methane per hour. The coke amount entering the coke gasification unit (the temperature of the reaction furnace is 1400 ℃, the pressure is 40bar) is 187t/h, the coke gasification crude synthesis gas amount generated by the coke gasification unit is 24405kmol/h (the hydrogen-carbon ratio is 0.8), the coke gasification crude synthesis gas is mixed with the coal gasification crude synthesis gas to obtain the gasification crude synthesis gas 51865kmol/h, and the gasification crude synthesis gas is subjected to water treatmentAnd after the coal gas conversion unit and the synthesis gas purification unit, obtaining purified synthesis gas 454907kmol/h (hydrogen-carbon ratio is 2.05), and carbon dioxide 16683kml/h with the concentration of 95%, wherein 1010kmol/h of carbon dioxide enters a methane dry reforming unit (the operation temperature is 800 ℃, and the pressure is 4bar) to react with methane, the rest of carbon dioxide is discharged out of the system, the generated methane dry weight is integrated into gas with the quantity of 4100kmol/h, hydrogen obtained by the coke oven gas separation unit and methanol synthesis gas 49259kmol/h obtained by mixing the purified synthesis gas and the methane dry weight are integrated into gas, and the synthesized methanol is 409 t/h. The design calculation is performed on the embodiment by chemical process simulation software Aspen, and the result is shown in table 3.
TABLE 3 results of calculation
In the existing process of preparing methanol by coal gasification single production, raw coal is prepared into water-coal slurry, and then coal gasification crude synthesis gas is generated by a coal gasification unit, and then the clean methanol synthesis gas is obtained by a water gas shift unit and a synthesis gas purification unit, and a clean methanol synthesis gas is synthesized into a methanol product. A coal gasification single-production methanol process with the raw coal processing capacity of 250t/h can produce 225t/h methanol product and generate about 28360kmol/h carbon dioxide. Compared with the process of preparing methanol by coal gasification per unit, the carbon dioxide emission reduction of the novel process is about 21% and the methanol yield is enlarged by about 1.8 times.
In the prior process of directly producing methanol from coke-oven gas, crude coke-oven gas generated by coking coal is purified to obtain clean coke-oven gas, the clean coke-oven gas enters a methanol synthesis unit to synthesize methanol, then enters a methanol purification unit to separate unreacted hydrogen and carry out methanol rectification, and the unreacted hydrogen enters a torch system to be combusted. Compared with the process of preparing the methanol from the coke oven gas, the coupling process of the invention converts the methane in the coke oven gas and the carbon dioxide discharged by the synthetic gas purification unit into the synthetic gas by adding the methane dry reforming unit, and simultaneously supplements the hydrogen to the gasified synthetic gas by the hydrogen separated from the coke oven gas, so as to directly synthesize the methanol, thereby avoiding the resource waste caused by the combustion of the hydrogen in the process of preparing the methanol from the coke oven gas.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A coal gasification coupling coal coking methanol preparation device is characterized in that: the device comprises a coal water slurry preparation unit, a coal gasification unit, a water gas shift unit, a synthesis gas purification unit, a coal coking unit, a coke gasification unit, a coke oven gas purification unit, a coke oven gas separation unit, a methane dry reforming unit, a gas mixer and a methanol synthesis unit;
the coal water slurry preparation unit is provided with a raw material lignite inlet, a water inlet and a coal water slurry outlet, and the coal water slurry outlet is connected to the coal gasification unit; the coal gasification unit is provided with an oxygen inlet and a coal gasification crude synthesis gas outlet, and the coal gasification crude synthesis gas outlet is connected to the water gas shift unit; the water gas conversion unit is provided with a converted crude synthesis gas outlet connected to the synthesis gas purification unit; the synthesis gas purification unit is provided with a purified synthesis gas outlet, a sulfide outlet and a CO2 outlet, the purified synthesis gas outlet is connected to the gas mixer, and the CO2 outlet is connected to the methane dry reforming unit;
the coal coking unit is provided with a raw material coking coal inlet, a coking coal outlet and a crude coke oven gas outlet, the coking coal outlet is divided into two channels, one channel is connected to the coking coal gasification unit, the other channel is used for outputting coke products, and the crude coke oven gas outlet is connected to the coke oven gas purification unit; the coke gasification unit is provided with a coke gasification crude synthesis gas outlet which is connected to the water gas shift unit; the coke-oven gas purification unit is provided with a purified coke-oven gas outlet and tar, benzene, naphthalene and sulfide outlets, and the purified coke-oven gas outlet is connected to the coke-oven gas separation unit; the coke-oven gas separation unit is provided with a methane outlet and a hydrogen outlet, the hydrogen outlet is connected to the gas mixer, and the methane outlet is connected to the methane dry reforming unit; the methane dry reforming unit is provided with a methane dry reforming gas outlet connected to the gas mixer; the gas mixer is provided with a methanol synthesis gas outlet connected to the methanol synthesis unit, and the methanol synthesis unit is provided with a methanol outlet.
2. A method for preparing methanol by coal gasification coupled coal coking is characterized by comprising the following steps:
raw material lignite for gasification and water enter a water coal slurry preparation unit to prepare water coal slurry; the coal water slurry directly enters a coal gasification unit to be subjected to high-temperature gasification reaction with oxygen to prepare coal gasification crude synthesis gas, the coal gasification crude synthesis gas is subjected to hydrogen-carbon ratio adjustment by a water gas shift unit to obtain converted crude synthesis gas, the converted crude synthesis gas is introduced into a synthesis gas purification unit to remove sulfide and high-concentration carbon dioxide to obtain purified synthesis gas, the carbon dioxide is divided into two parts, one part of the carbon dioxide is connected with a carbon dioxide inlet of a methane dry reforming unit through a pipeline, and the other part of the remaining carbon dioxide is discharged out of the device; directly discharging the sulfide out of the device; the purified synthesis gas enters a gas mixer and is mixed to obtain methanol synthesis gas;
coking coal used as a raw material for coal coking in a coal coking unit to obtain coke, crude coke oven gas, tar and other substances; one part of the coke is made into a coke product, and the other part of the coke enters a coke gasification unit to react with oxygen and water vapor to generate coke gasification crude synthesis gas which is mixed with the coal gasification crude synthesis gas through a pipeline; the crude coke oven gas enters a coke oven gas purification unit to remove tar, benzene, naphthalene and sulfide impurities in the crude coke oven gas to obtain purified coke oven gas, and the purified coke oven gas is sent to a coke oven gas separation unit to be separated to obtain hydrogen and methane; hydrogen directly enters a gas mixer, and methane enters a methane dry reforming unit to convert the methane in the methane into methane dry weight reforming synthetic gas; the dry weight of methane is integrated into a forming gas, the purified forming gas and hydrogen obtained by the coke-oven gas separation unit enter a gas mixer together, the forming gas and the hydrogen are mixed to obtain methanol synthesis gas, the methanol synthesis gas enters a methanol synthesis unit, and a methanol product is obtained after reaction and purification.
3. The method for preparing methanol by coal gasification coupled coal coking according to claim 2, characterized in that: the hydrogen-carbon ratio of the coal gasification crude synthesis gas is 0.2-1.
4. The method for preparing methanol by coal gasification coupled coal coking according to claim 2, characterized in that: the hydrogen-carbon ratio of the coke gasification crude synthesis gas is 0.5-1.
5. The method for preparing methanol by coal gasification coupled coal coking according to claim 2, characterized in that: the hydrogen-carbon ratio of the purified synthesis gas is 1-3.
6. The method for preparing methanol by coal gasification coupled coal coking according to claim 2, characterized in that: the composition of the crude coke oven gas comprises 50-60% of H2 and 20-30% of CH4 by volume percentage.
7. The method for preparing methanol by coal gasification coupled coal coking according to claim 2, characterized in that: the hydrogen-carbon ratio of the purified coke oven gas is 3-6.
8. The method for preparing methanol by coal gasification coupled coal coking according to claim 2, characterized in that: the reaction furnace temperature of the coke gasification unit is 1100-1600 ℃, and the pressure is 28-42 bar.
9. The method for preparing methanol by coal gasification coupled coal coking according to claim 2, characterized in that: the operation temperature of the methane dry reforming unit is 600-950 ℃, and the pressure is 4-20 bar.
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| CN110002954B (en) * | 2019-04-30 | 2023-11-17 | 华南理工大学 | Technological method and device for preparing methanol and co-producing acid or ester by coal gasification coupled coal coking |
| CN110002955B (en) * | 2019-04-30 | 2023-12-26 | 华南理工大学 | Process method and device for preparing methanol and co-producing ethylene glycol and LNG through coal gasification coupled coal coking |
| CN110002956B (en) * | 2019-04-30 | 2023-11-17 | 华南理工大学 | Process method and device for preparing methanol and co-producing ethanol and LNG from coal-based synthesis gas and coke oven gas |
| CN112142559A (en) * | 2020-09-22 | 2020-12-29 | 吕永华 | Waste heat recovery device for methanol production |
| CN114394883A (en) * | 2021-11-02 | 2022-04-26 | 华陆工程科技有限责任公司 | Method for preparing methanol by coupling gasification of pulverized coal waste boiler with green electricity and green hydrogen to achieve near-zero carbon emission |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004547A (en) * | 2014-05-29 | 2014-08-27 | 华南理工大学 | Coal gasification and coal coking co-supply and cogeneration system and method |
| CN203938653U (en) * | 2014-05-29 | 2014-11-12 | 华南理工大学 | A kind of gasification and coal tar alliance co-generation system |
| CN104193585A (en) * | 2014-08-06 | 2014-12-10 | 华南理工大学 | System and process for preparing methyl alcohol through coke-oven gas-assisted coal gasification |
| CN204058302U (en) * | 2014-08-06 | 2014-12-31 | 华南理工大学 | A kind of coke(oven)gas assists the system of gasification methyl alcohol |
-
2018
- 2018-08-03 CN CN201810876715.1A patent/CN109020780B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004547A (en) * | 2014-05-29 | 2014-08-27 | 华南理工大学 | Coal gasification and coal coking co-supply and cogeneration system and method |
| CN203938653U (en) * | 2014-05-29 | 2014-11-12 | 华南理工大学 | A kind of gasification and coal tar alliance co-generation system |
| CN104193585A (en) * | 2014-08-06 | 2014-12-10 | 华南理工大学 | System and process for preparing methyl alcohol through coke-oven gas-assisted coal gasification |
| CN204058302U (en) * | 2014-08-06 | 2014-12-31 | 华南理工大学 | A kind of coke(oven)gas assists the system of gasification methyl alcohol |
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