CN116102402A - Method and device for synthesizing methanol by double-carbon hydrogenation - Google Patents
Method and device for synthesizing methanol by double-carbon hydrogenation Download PDFInfo
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Abstract
The invention discloses a method for preparing high-concentration CO and CO by using two kinds of carbon oxides 2 Method for synthesizing methanol, realizing CO 2 The original effluent is changed to achieve the purpose of high conversion rate into methanol. The coal synthesis gas, the natural gas conversion gas, the coke oven or converter conversion gas or various petrochemical production devices after removing harmful substances and oxygen to the catalyst contain H 2 、CO、CO 2 One or more gas distribution in the purge gas containing high CO 2 Raw material synthesis gas with concentration, and then supplementing H 2 Or H 2 And CO 2 To condition raw synthesis gasIn the ratio of hydrogen to carbon, the catalyst is heated to a temperature higher than the reaction activity temperature of the catalyst, and then enters a solid catalyst with high activity of a plurality of chemical reactions between a heat exchange water pipe and a reactor shell to perform heat exchange reaction of byproduct steam to synthesize methanol so as to greatly reduce CO 2 And (5) discharging. The invention also discloses a device for synthesizing methanol by double-carbon hydrogenation and a device for co-producing electric power and ammonia by using the device.
Description
Technical Field
The invention relates to a plurality of fields of coal chemical industry, energy and environmental protection, mainly comprising the steps of producing synthetic gas by gasifying solid fuel coal and liquid fuel, producing natural gas or coke oven gas, producing the synthetic gas by converting steam of converter gas, and synthesizing methanol by purifying and distributing gas.
Background
The invention relates to the field of coal chemical industry for producing methanol or a large amount of CO in flue gas generated by coal-fired power generation 2 IGCC energy field for emission recovery and methanol synthesis power CO-production and global carbon reduction CO 2 Environmental protection field of emission.
Methanol is an important chemical basic raw material, except for synthesizing ammonia, the methanol raw material is synthesized by gasifying and purifying synthesis gas which takes coal as a main raw material in China, the synthesis gas is mainly converted into the methanol by natural gas in foreign countries, and then the methanol is further processed into various main products such as olefin, and the like, because the CO and the H are considered under the existing copper-based methanol synthesis catalysts and the design and design process conditions in the home and abroad 2 Methanol synthesis speed ratio CO 2 Much larger. At the same time due to CO 2 The synthesis of methanol consumes 1mol H more than CO 2 Due to CO 2 Unlike CO, H 2 The method has high effective energy and heat value, but is zero, thus, no matter the method is used for preparing the methanol by converting the natural gas abroad, 10000 tons/day large methanol design raw material gas mainly comprises CO and H2 gas, wherein the CO is more than 23 percent (see PEP Report 43D MeGA Methanol Plant), and the method is used for introducing the raw material gas into a large device abroad for preparing the methanol by coal in China, and the CO in the raw material gas for synthesizing the methanol 2 The content is lower. Technical guidelines for preparing methanol from carbon dioxide, which are put into practice in 2018, 4, china (5.1)The feed gas meets the requirements of GB/T6052, and the hydrogen feed gas for preparing methanol meets the requirements of GB/T3634.1), the industrial pure hydrogen and liquid CO are used 2 The raw material flow of synthesizing methanol requires raw material gas H 2 、CO 2 The purity is high, the purity of industrial hydrogen and carbon dioxide is required to be more than 99%, and the corresponding production cost is a problem in actual factory construction.
At present, a large amount of CO is produced by methanol synthesis enterprises 2 The synthesis of methanol is not efficiently utilized but a large amount of CO is discharged 2 There is a problem that the chemical mechanism of the methanol synthesis process is researched in a further step, and a catalyst with higher activity is developed, for example, besides the existing copper-based catalyst, the catalyst such as noble metal, nanotechnology, colloidal mass and other suspended beds, and the like, and also the existing technical problem, for example, the existing coal-to-large methanol synthesis device commonly adopts the technology that the coal gasification outlet gas is high in CO and low in H 2 Gas, CO/H 2 2-3 times of H 2 CO conversion to H by O gas 2 And CO 2 Conversion of CO in export dry gas 2 30-40%, and then is subjected to low-temperature methanol washing decarburization (CO) 2 ) Removing more than 30% of the total dry gas, and delivering the total dry gas to CO in the methanol synthesis feed gas 2 About 2%, for example, 1.95% according to DAVY method and 2.65% according to Lurgi method, it is seen that a large amount of CO is discharged from the synthetic methanol 2 。
For CO 2 Adding H 2 Synthesis of methanol CO 2 The problem of low conversion rate is that patent developers at home and abroad adopt the method of firstly adding CO into a pre-reactor 2 The water-gas reverse conversion is carried out to form CO, and the CO is sent into a methanol synthesis tower which is connected in series to form methanol, but the process has a large number of equipment, and if the temperature is 1MPa570 ℃ at low pressure and high temperature for CO conversion and 200-280 ℃ at high temperature of 6-5MPa for methanol synthesis according to the patent, the energy consumption is high, and pure H is used 2 And pure CO 2 The cost for synthesizing methanol is far higher than that of synthesis gas H 2 、CO、CO 2 The mixture gas is high.
Disclosure of Invention
Based on the CO conversion in the prior process of preparing methanol from coal gasification synthetic gas to discharge a large amount of CO 2 Or with CO 2 The invention proposes that the conversion rate of synthesized methanol is low and the like by two kinds of carbonThe oxide adopts high concentration CO and CO 2 The technical scheme of synthesizing methanol, namely double-carbon synthesis methanol, realizes the CO 2 The original effluent is changed to achieve the purpose of high conversion rate into methanol.
A process for synthesizing methanol by double-carbon hydrogenation includes such steps as removing sulfur, chlorine, cyanide and oxygen from catalyst, preparing synthetic gas, natural gas, coke oven or converter, or preparing H from petrochemical equipment 2 、CO、CO 2 One or more gas distribution in the purge gas containing high CO 2 Raw material synthesis gas with concentration, and then supplementing H 2 Or H 2 And CO 2 To adjust the hydrogen-carbon ratio in the raw material synthesis gas, boost the pressure to be more than 4MPa, then heat the raw material synthesis gas to be higher than the reaction activity temperature of the catalyst, and enter the solid catalyst with high activity performance of a plurality of chemical reactions between a heat exchange water pipe and a reactor shell to perform heat exchange reaction of byproduct steam to synthesize methanol so as to greatly reduce CO 2 The emission is changed into a carbon greening method, and chemical co-production or energy-saving chemical-power poly-production of single-product methanol or methanol-ammonia products is realized;
said high CO 2 The raw synthesis gas being enriched in CO 2 And CO gas are used for synthesizing methanol in the same reactor, and the synthesis process is different from the synthesis process of coal-to-methanol, and is mainly used for synthesizing methanol by CO hydrogenation, CO 2 Hydrogenation to methanol is pure CO 2 Synthesizing methanol by hydrogenation.
Said high CO 2 CO in the concentration of synthesis gas 2 Concentration > 10% or CO+CO 2 ＞20％。
The granular solid catalyst is a double-carbon hydrogenation methanol synthesis catalyst prepared by a copper-based methanol synthesis catalyst and a carbon oxide conversion catalyst according to the weight ratio of 1-9.
Said adjusting H in raw material synthesis gas 2 +CO+CO 2 Mole percent > 95%, hydrogen-carbon ratio
CO 2 More than or equal to 10 percent or CO+CO 2 More than or equal to 20 percent, compressing to 4 to 10MPa, carrying out double-carbon hydrogenation on a copper-based high-activity catalyst under medium pressure to synthesize methanol, preparing a methanol product, carrying out medium pressure synthesis on the unreacted gas part after separating the methanol by pressurizing the raw material mixture through a circulator and a compressor, carrying out partial purge gas or hydrogen recovery device, or carrying out parameter optimization again, regulating the composition of the unreacted gas by CO or sending the un-regulated unreacted gas part to be connected in series in the subsequent stage of double-carbon hydrogenation to synthesize methanol, or re-compressing to more than 10MP a Synthesizing methanol by double-carbon hydrogenation under high pressure, and further improving CO and CO 2 The total conversion rate reduces the raw material gas unit consumption of ton methanol products, carries out the project of methanol-synthetic ammonia CO-production on the raw material gas of coal synthesis, and further reduces the CO+CO at the outlet of the methanol synthesis by the equal-pressure double-carbon hydrogenation 2 Concentration, realizing CO+CO output through high-pressure methanation 2 Less than 10ppm, and ensures the safety of the ammonia synthesis catalyst.
Setting a mixer gas component automatic regulator in the double-carbon methanol synthesis process, detecting the crude methanol yield and the methanol concentration, the purge gas quantity and the molar composition, the gas quantity and the composition of an inlet and an outlet of a methanol synthesis tower and the gas composition and the gas quantity of an inlet compressor of an outlet of a synthesis gas mixing cylinder in real time, and regulating the opening degree of an inlet and an outlet bypass valve of a CO shift converter of a front working section and the H on the mixer according to the gas composition of the methanol synthesis tower 2 Cylinder and CO 2 And the opening and closing degree of a valve on the cylinder air inlet pipe line is used for adjusting the hydrogen-carbon ratio of the mixed synthesis gas.
The device for synthesizing the methanol by double-carbon hydrogenation comprises three working sections of raw material synthesis gas preparation, synthesis gas purification and distribution and methanol synthesis, wherein the raw material synthesis gas preparation working section converts one or more raw material gases to prepare and obtain the hydrogen-containing gas 2 、CO、CO 2 More than 95% of raw material synthesis gas, wherein the raw material gas is one or more of coal synthesis gas, natural gas conversion gas, coke oven or converter conversion gas; the synthetic gas purifying and distributing section purifies raw material synthetic gas to remove harmful substances, then the raw material synthetic gas is sent into a CO shift converter according to the requirement, or is partially sent into the CO shift converter, or is directly sent to a methanol washing tower without being sent into the CO shift converter, and is sent into a distributing cylinder after removing the toxic substances to a methanol synthesis catalyst,make-up from H 2 Cylinder and CO 2 CO of cylinder 2 Or H 2 And CO 2 To adjust the hydrogen to carbon ratio of the mixed synthesis gas;
the methanol synthesis working section comprises a synthesis raw material gas compressor, a tower inlet and outlet gas heat exchanger, a methanol synthesis reactor, a methanol tower outlet gas cooling condenser, a methanol gas-liquid separator, a circulator, a methanol synthesis tower steam boiler and a boiler water pump, wherein the boiler water pump is connected with a heat exchange water pipe in the synthesis tower and the steam boiler to form water vapor circulation, the raw material gas compressor, the tower inlet and outlet gas heat exchanger, the methanol synthesis reactor, the methanol tower outlet gas cooling condenser, the methanol gas-liquid separator, the circulator and the compressor form a circulation loop which is connected front and back, a methanol synthesis product is sent to be rectified by the lower part of the alcohol separator, and when the alcohol component gas is in power CO-production, CO and H are generated 2 The high heat value and more gas are sent to a gas turbine for power generation, the gas is supplied for the self-use or the external sending of a pump of a methanol device, when the medium pressure is lower than 10MPa, the methanol is synthesized again after the pressure is increased by a circulating machine and the synthesis gas of the raw material of a compression outlet is combined with a small amount of purge gas for hydrogen recovery; when the pressure of the high-pressure double-carbon hydrogenation is more than or equal to 10MPa, the methanol is synthesized at high pressure by feeding the methanol to an inlet of a high-pressure compressor for compression to be more than 10 MPa.
The raw material gas is coal dust raw material, the raw material synthesis gas preparation section comprises a coal gasifier and a tubular waste boiler, after coal dust oxygenation and steam gasification are completed in the pressurized high-temperature coal gasifier, the prepared high-carbon oxide low-hydrogen-carbon ratio synthesis gas enters the communicated tubular waste boiler to cool and transfer heat, and the boiler in the heat exchange tube is used for producing high-pressure steam;
the synthetic gas purifying and distributing section comprises a CO shift converter, a low-temperature methanol washing tower and a distributing tank.
The raw material gas is a dual raw material of coal and gaseous hydrocarbon, the raw material synthesis gas preparation section comprises a coal gasification furnace and a reformer, and the synthesis gas purification and distribution section comprises a CO converter, a methanol scrubber and a distribution tank;
the gaseous hydrocarbon is firstly purified to remove harmful substances such as sulfide and the like to the catalyst, then enters a heat exchange reformer shell side to exchange heat with high-temperature coal-made synthetic gas,the high-temperature coal synthesis gas in the heat exchange tube is transferred to the gaseous hydrocarbon of the catalytic reaction in the reforming catalyst bed layer of the reformer to generate reforming endothermic reaction CH 4 +H 2 O→CO+3H 2 Carrying out natural gas water vapor endothermic reaction to obtain
The cooled coal-made synthetic gas enters a CO shift converter to carry out CO partial gas shift, partial crude synthetic gas does not enter the shift converter but enters a gas distribution tank after being converged with the CO shift synthetic gas through a short circuit communicated with an inlet and an outlet of the shift converter to remove toxic substances on a methanol synthesis catalyst by a methanol eluting tower, and is supplemented from H 2 Tank and CO 2 H of tank 2 Or H 2 And CO 2 。
The device for co-producing the electric power by adopting the device for synthesizing the methanol through double-carbon hydrogenation comprises a raw material synthesis gas preparation section, a synthesis gas purification and distribution section, a methanol synthesis section, and a gas and steam power generation section. When methanol synthesis and power CO-production are carried out, CO in the flue gas in the gas power generation outlet gas can be used 2 Recovering heat and then using the heat as CO 2 CO of synthetic methanol 2 A source.
A device for CO-producing ammonia by adopting the device for synthesizing methanol by double-carbon hydrogenation comprises a raw material synthesis gas preparation working section, a synthesis gas purification and distribution working section and a methanol synthesis working section, wherein the device also comprises the ammonia synthesis working section, the coal synthesis gas is firstly subjected to double-carbon hydrogenation to synthesize methanol under the pressure of less than 10MPa, the gas of a methanol product is separated, part of circulating gas is returned to a circulating machine to be synthesized into gas except the methanol again, the gas is pressurized to the synthesis pressure of 12-32MPa by a compressor, and the composition of the gas is regulated to perform double-carbon hydrogenation to synthesize the methanol under the high pressure, so that CO and CO are obtained 2 The conversion rate is more than 90%, and the gas after separating the methanol product is subjected to isobaric methanation to enable CO+CO 2 Less than 10ppm, adding nitrogen to achieve
And synthesizing ammonia to obtain the synthetic ammonia product.
The clean coal synthesis gas with high CO prepared by taking coal as raw material does not undergo CO conversion and CO 2 Decarbonization is not carried out by adopting H 2 、CO 2 Adjusting hydrogen-to-carbon ratio
After methanol synthesis, the mixture is sent to a gas turbine to generate electricity for a methanol synthesizer pump to use or send out.
High CO at the outlet of the shift converter after CO shift 2 Sent for sale as a refrigerant.
The invention discharges a large amount of CO in the prior coal chemical methanol synthesis technology 2 Greenhouse gas effect, which increases global air temperature to turn CO 2 Adding H 2 The methanol is generated or further processed into products such as ethers, hydrocarbons and the like, thereby realizing zero emission basically, becoming the carbon neutralization target even in advance in the same year as the period of 2060 in China, and reducing the CO conversion after the raw material coal is gasified and the CO of the products 2 And the removing device reduces and lowers a great amount of equipment investment cost. Meanwhile, the process of preparing gas from coal is simplified and optimized, the energy loss is greatly reduced, and the production cost is greatly reduced. The process design technique is similar to coal gasification when heavy oil is gasified with liquid fuel.
The invention uses the synthesis gas H prepared from the existing domestic and external coal gas or hydrocarbon conversion gas 2 、CO、CO 2 Based on the methanol synthesis formed on the basis, the combination optimization or further combining the methanol synthesis with the gas power generation, namely, the chemical energy-power cogeneration is carried out by a chemical energy-power IGCC system, the purge gas in the system is preferentially used for recycling hydrogen as a hydrogen source, and the gas power generation flue gas is used for recycling CO 2 As CO 2 The source adjusts the composition of the methanol mixed gas, greatly reduces the cost compared with the prior art of preparing methanol by using carbon dioxide or preparing methanol by using hydrogen with purity of more than 99 percent and CO2, and is beneficial to large-area popularization.
Drawings
FIG. 1 is a schematic diagram of an apparatus for synthesizing methanol from two carbons by mixing a raw material synthesis gas from a coal gas and an electrolytic hydrogen gas.
Fig. 2 is a schematic diagram of a process for producing raw synthesis gas from coal gas.
FIG. 3 is a schematic diagram of a process for co-producing synthetic ammonia from two-carbon synthetic methanol with coal gas as raw material.
FIG. 4 is a schematic diagram of a medium pressure synthesis and high pressure methanol synthesis unit with compressors in series.
FIG. 5 is a schematic diagram of CO for distribution of autothermal reformed gas from coal-derived synthesis gas and natural gas 2 And a device diagram for preparing methanol by synthesizing CO double carbon.
Reference numerals illustrate:
1. alcohol separator of condenser 4 of heat exchanger 3 of outgoing tower of methanol synthesis tower 2
5. Mix tank 8H of circulator 6 steam boiler 7 2 Tank
9 CO 2 Tank 10 gas composition automatic regulator 11 preheater 12 purifier
13. Cyclone separator of compressor 14 coal gasification furnace 15 heat recovery boiler 16
17. Heat exchange reformer
1-1 first-stage methanol synthesis tower 1-2 first-stage heat exchanger 1-3 first-stage condenser 1-4 first-stage alcohol separator
1-5-stage circulating machine 1-6-stage steam boiler 1-10-stage gas composition automatic regulator
2-1 second-level methanol synthesis tower 2-2 second-level heat exchanger 2-3 second-level condenser 2-4 second-level alcohol separator
2-10 secondary gas component automatic regulator of 2-5 secondary circulation machine 2-6 secondary steam boiler
18 N 2 19. Coal 22O 2 23. Slag of furnace
24. Ash 25 natural gas 27 mixed gas 28 raw material synthesis gas
29. Methanol 30 boiler water 31 steam 32 recycle gas
Detailed Description
The invention is described in detail below with reference to fig. 1 and the examples.
Example 1 two-carbon methanol synthesis with the aid of FIG. 1, in the prior art (Wang Genbao, chemical engineering, vol 48 No 8, P68-72, table 6, 8 months in 2020), gasification of pulverized coal under pressure at 3MPa and > 1300 ℃ in a coal gasifier gave a synthesis gas dry basis composition of 62.4 mol% CO, CO 2 8.1％、H 2 27.7% of the high-carbon-hydrogen ratio coal gas is subjected to heat recovery and temperature reductionThe post CO shift converter carries out water vapor adding shift: CO+H 2 O＝H 2 +CO 2 The exothermic reaction and the dry gas at the outlet of the shift converter are 19.8 percent of CO and 19.8 percent of CO 2 32.7％、H 2 46.2% of the CO is removed from the converted gas 2 The latter is the raw material gas for synthesizing methanol, for example, DAVY methanol technology is 30.4% CO and CO 2 1.95％、H 2 67% of Lurgi methanol technology is CO 28.3%, CO 2 2.65％、 H 2 67.8% of methanol is synthesized into raw material gas. It can be seen that a large amount of CO is discharged in the synthesis of methanol from coal 2 。
For this purpose, the invention uses coal as raw material, double carbon CO and CO 2 Synthesizing methanol (shown in figures 1 and 2) by using pure oxygen and high-temperature water vapor and using CO 2 The pulverized coal is gasified by feeding the gas into the coal gasifier, the components are as before, but the dry gas discharged from the gasifier does not adopt a large CO conversion, but adopts a part of the crude gas which is not converted by a bypass valve (see figure 2), and then the sulfide and chloride which are toxic to the methanol synthesis catalyst are removed by purifying the synthesis gas, so as to carry out high-concentration CO 2 Double carbon synthesis under CO, then preparing hydrogen from electrolyzed water to high concentration CO 2 Methanol synthesis was performed with a hydrogen to carbon ratio of 2.06 (see fig. 1).
In FIG. 1, a raw material gas with the hydrogen-carbon ratio regulated is mixed with recycle gas, and is heated to 210 ℃ by a tower heat exchanger 2, and a methanol synthesis tower 1 for byproduct steam of a winding pipe is filled with para-CO 2 On a solid catalyst with high activity for the inverse CO synthesis of methanol and CO steam transformation reaction, the reaction is fast carried out at the temperature of 210-280 ℃:
synthesis of methanol CO+2H from CO 2 ＝CH 3 OH
CO 2 Synthesis of methanol CO 2 +3H 2 ＝CH 3 OH
CO 2 Inverse transform CO 2 +H 2 O＝CO+H 2
At a diameter of 3M 30M 3 77KM under 7.5MPa pressure with a catalyst 3 220KM tower gas inlet for synthesizing gas amount of raw material/h 3 /h、 CO7.6％、CO 2 13.5% of synthesized methanol has a net value of 10.1%, annual refined methanol yield of 21 ten thousand tons, and CO emission reduction 2 Greater than 29 ten thousand tons/yearThe conversion rate of the CO synthesized methanol is 97%, CO 2 The conversion was 72%. The scheme is provided with an automatic gas component regulator 10 which can automatically and continuously monitor the purge amount and composition and automatically regulate the methanol yield and concentration H 2 And a hydrogen supplementing valve of the tank 8.
Example 2
See figure 3, a process diagram of the dual-carbon synthesis of methanol and co-production of synthetic ammonia by using coal gas as raw material, and figure 4 is a schematic diagram of a medium-pressure synthesis and high-pressure methanol synthesis device connected in series by a compressor.
In connection with fig. 3 and 4, which are also coal-based synthesis gas, the former part is as in example 1:77KM 3 Methanol is synthesized by hydrogen-carbon ratio f=2.06 of the synthesis gas at the medium pressure of 7.5MPa, 21 tons/year of methanol is prepared, and 14KM is also obtained 3 The purge gas is compressed to 12MPa at 15M 3 High-pressure synthesis is carried out on the catalyst, the CO conversion rate is 99.6%, the CO2 conversion rate is 99.7%, and the (CO+CO) conversion rate is 99.7% 2 ) =0.43% and separating methanol to obtain refined alcohol of 2.8 ten thousand tons/year, reducing CO emission 2 More than 3.8 ten thousand tons/year, 5KM is still available after the synthesis of medium-high pressure methanol 3 Hydrogen 98%, CO+CO 2 12MPa isobaric methanation of =0.4% gas followed by co+co 2 Less than 10ppm nitrogen
Ammonia synthesis, ammonia production 2 ten thousand tons/year.
Example 3
See FIG. 5, for CO for distribution of coal-derived synthesis gas and natural gas autothermal reforming gas 2 And synthesizing the methanol by using CO double carbon. The coal gasifier 14 is used for gasifying coal powder at high temperature of 3MPa and 1300 ℃ or above, and CO is used for coal powder 2 The gas is fed through nozzles symmetrically arranged on the side surface of the upper shell of the gasification furnace and is mixed with O 2 、H 2 O steam reaction.
The outlet of the coal gasifier 14 is high-carbon hydrogen specific heat coal gas CO 66.5%, CO 2 8％、H 2 25％。
Example 4
FIG. 4 is a schematic diagram of a series connection of two devices for synthesizing methanol by ammonia with two carbons, which can be used for new devices and energy saving reconstruction of old devices, wherein the front and rear systems are respectively provided with a synthesis reactor with a byproduct steam boiler, a heat exchanger of an inlet tower, a heat exchanger of an outlet tower, a cooling condenser, a methanol separator and a pipeline connection between the front and rear of a circulator. In fig. 4, after the alcohol is compressed in the front system, part of the gas is boosted by the compressor 13 to the rear system to high-pressure synthesize methanol, but the compressor is not needed, the front and rear systems can be connected with the front pipeline of the rear system entering the tower heat exchanger through the outlet of the front system circulator, the front and rear systems are synthesized at equal pressure, or connected with the inlet of the rear system circulator, the pressure is increased for the rear system to synthesize methanol, and if the front pipeline of the front system circulator is connected to the front of the rear system entering the tower heat exchanger, the rear system is decompressed to synthesize methanol.
The medium pressure two-carbon methanol synthesis was carried out using FIG. 4, and the amount and composition of the raw material were the same as those in example 3 above, but methanol was synthesized under 8.5MPa with a space velocity of 7300h -1 The methanol content of the hot spot 271 ℃ of the inlet tower 210 ℃ is 12.1%, the CO conversion rate is 94%, the CO2 is 60%, the annual output of the methanol is reduced to 53.5 ten thousand tons, and the first-stage methanol synthesis has purge gas 63KM 3 And/h, the content of CO is 2.68%, the content of CO2 is 16.7%, the pressure is increased to 9.8MPa, the methanol content of the second-stage synthesis tower is 10%, the CO conversion rate is 95%, and the CO is converted 2 The conversion rate is 92%, the annual yield of refined methanol is 12.5 ten thousand tons, and the emission of CO is reduced 2 12.5 ten thousand tons/year. In the method, 66 ten thousand tons of methanol are produced in total year under the medium pressure of 8.5MPa and 9.8MPa in order, and CO is reduced 2 91 ten thousand tons.
The method aims at methanol synthesis and carbon neutralization, and aims at energy conservation and consumption reduction, and specific flow equipment for converting natural gas hydrocarbons is sequentially arranged, and the connection sequence of the reactor, the heat recovery boiler and the heat exchanger is reasonably selected according to the temperature.
The method is based on a methanol synthesis reaction mechanism, scientifically designs a double-carbon synthesis process and a reactor, realizes that the synthesis rate of the hydrogenated methanol of carbon dioxide reaches more than 90 percent, can be applied to a large-scale methanol engineering device, and is far higher than the recording level of the existing literature.
Claims (10)
1. A method for synthesizing methanol by double-carbon hydrogenation is characterized by comprising the following steps: the coal-made synthetic gas, natural gas conversion gas, coke oven or converter conversion gas or various petrochemical production devices after removing sulfur, chlorine, cyanide and oxygen harmful to the catalyst contain H 2 、CO、CO 2 One or more gas distribution in the purge gas containing high CO 2 Raw material synthesis gas with concentration, and then supplementing H 2 Or H 2 And CO 2 To adjust the hydrogen-carbon ratio in the raw material synthesis gas, boost the pressure to be more than 4MPa, and then heat upThe catalyst is heated to be higher than the reaction activity temperature of the catalyst, and enters a solid catalyst with high activity of a plurality of chemical reactions between a heat exchange water pipe and a reactor shell to perform heat exchange reaction of byproduct steam to synthesize methanol so as to greatly reduce CO 2 The emission is changed into a carbon greening method, and chemical co-production or energy-saving chemical-power poly-production of single-product methanol or methanol-ammonia products is realized;
said high CO 2 The raw synthesis gas being enriched in CO 2 And CO gas are used for synthesizing methanol in the same reactor, and the synthesis process is different from the synthesis process of coal-to-methanol, and is mainly used for synthesizing methanol by CO hydrogenation, CO 2 Hydrogenation to methanol is pure CO 2 Synthesizing methanol by hydrogenation.
2. The method for synthesizing methanol by double-carbon hydrogenation according to claim 1, wherein: said high CO 2 CO in the concentration of synthesis gas 2 Concentration > 10% or CO+CO 2 ＞20％。
3. The method for synthesizing methanol by double-carbon hydrogenation according to claim 1, wherein: the granular solid catalyst is a double-carbon hydrogenation methanol synthesis catalyst which is prepared from a copper-based methanol synthesis catalyst and a carbon oxide conversion catalyst according to a weight ratio of 1-9.
4. The method for synthesizing methanol by double-carbon hydrogenation according to claim 1, wherein: said adjusting H in raw material synthesis gas 2 +CO+CO 2 Mole percent > 95%, hydrogen-carbon ratio
CO 2 More than or equal to 10 percent or CO+CO 2 More than or equal to 20 percent, compressing to 4 to 10MPa, carrying out medium-pressure double-carbon hydrogenation on a copper-based high-activity catalyst to synthesize methanol, preparing a methanol product, carrying out medium-pressure synthesis on the unreacted gas part after separating the methanol by pressurizing the raw material mixed gas through a circulator and a compressor, carrying out partial purge gas or hydrogen recovery device, or carrying out parameter optimization again, regulating the composition of the unreacted gas by CO or carrying out non-regulation on the unreacted gas part after the unreacted gas part is sentThe two carbons are serially connected in the subsequent stage to hydrogenate and synthesize the methanol, or compressed to more than 10MPa to hydrogenate and synthesize the methanol under high pressure, so as to further improve CO and CO 2 The total conversion rate reduces the raw material gas unit consumption of ton methanol products, carries out the project of methanol-synthetic ammonia CO-production on the raw material gas of coal synthesis, and further reduces the CO+CO at the outlet of the methanol synthesis by the equal-pressure double-carbon hydrogenation 2 Concentration, realizing CO+CO output through high-pressure methanation 2 Less than 10ppm, and ensures the safety of the ammonia synthesis catalyst.
5. The method for synthesizing methanol by double-carbon hydrogenation according to claim 1, wherein: setting a mixer gas component automatic regulator in the double-carbon methanol synthesis process, detecting the crude methanol yield and the methanol concentration, the purge gas quantity and the molar composition, the gas quantity and the composition of an inlet and an outlet of a methanol synthesis tower and the gas composition and the gas quantity of an inlet compressor of an outlet of a synthesis gas mixing cylinder in real time, and regulating the opening degree of an inlet and an outlet bypass valve of a CO shift converter in a front working section and the H on the mixer according to the gas composition of the methanol synthesis tower 2 Cylinder and CO 2 And the opening and closing degree of a valve on the cylinder air inlet pipe line is used for adjusting the hydrogen-carbon ratio of the mixed synthesis gas.
6. The device for synthesizing the methanol by double-carbon hydrogenation comprises three working sections of raw material synthesis gas preparation, synthesis gas purification and distribution and methanol synthesis, and is characterized in that: the raw material synthesis gas preparation working section converts one or more raw material gases to prepare the H-containing gas 2 、CO、CO 2 More than 95% of raw material synthesis gas, wherein the raw material gas is one or more of coal synthesis gas, natural gas conversion gas, coke oven or converter conversion gas; the synthetic gas purifying and distributing section purifies raw material synthetic gas to remove harmful substances, then the raw material synthetic gas is sent into a CO shift converter according to the requirement, or is partially sent into the CO shift converter, or is not sent into the CO shift converter to directly go to a methanol washing tower, and after removing toxic substances to a methanol synthesis catalyst, the raw material synthetic gas is sent into a distributing cylinder to supplement H 2 Cylinder and CO 2 CO of cylinder 2 Or H 2 And CO 2 To adjust the hydrogen to carbon ratio of the mixed synthesis gas;
the methanol synthesis working section comprises a synthesis raw material gas compressor and an inlet tower and an outlet towerThe device comprises a gas heat exchanger, a methanol synthesis reactor, a methanol outlet tower gas cooling condenser, a methanol gas-liquid separator, a circulator, a methanol synthesis tower steam boiler and a boiler water pump, wherein the boiler water pump is connected with a heat exchange water pipe in the synthesis tower and the steam boiler to form water vapor circulation, a raw gas compressor, an inlet tower gas heat exchanger, an outlet tower gas heat exchanger, the methanol synthesis reactor, the methanol outlet tower gas cooling condenser, the methanol gas-liquid separator, the circulator and the compressor form a circulation loop which is connected with one another, the methanol synthesis product is sent to rectification by the lower part of the alcohol separator, and CO and H are generated when the alcohol gas is produced in power cogeneration 2 The high heat value and more gas are sent to a gas turbine for power generation, the gas is supplied to a methanol device pump for self-use or external delivery, when methanol is synthesized under the pressure of only less than 10MPa, a small amount of purge gas is sent to hydrogen for recovery, and the purge gas is fully mixed with the raw material synthesis gas at the compression outlet before through the rising pressure of a circulating machine to synthesize methanol again; when the pressure of the high-pressure double-carbon hydrogenation is more than or equal to 10MPa, the methanol is synthesized at high pressure by feeding the methanol to an inlet of a high-pressure compressor for compression to be more than 10 MPa.
7. The device for synthesizing methanol by double-carbon hydrogenation according to claim 6, wherein the raw material gas is pulverized coal, the raw material synthesis gas preparation section comprises a coal gasifier and a tubular waste boiler, after pulverized coal oxygenation and steam gasification are completed in the pressurized high-temperature coal gasifier, the prepared high-carbon oxide low-hydrogen carbon ratio synthesis gas enters the communicated tubular waste boiler to cool and transfer heat, and the boiler in the heat exchange tube is used for producing high-pressure steam for water production;
the synthetic gas purifying and distributing section comprises a CO shift converter, a low-temperature methanol washing tower and a distributing tank.
8. The apparatus for synthesizing methanol by double-carbon hydrogenation according to claim 6, wherein the raw material gas is a double raw material of coal and gaseous hydrocarbon, the raw material synthesis gas preparation section comprises a coal gasification furnace and a reformer, and the synthesis gas purification and distribution section comprises a CO shift furnace, a methanol scrubber and a distribution tank;
the gaseous hydrocarbon is purified to eliminate sulfide and other harmful matters to catalyst, and the catalyst is further heat exchanged to produce synthetic gas with high temperature coalHeat exchange, high temperature coal synthesis gas in the heat exchange pipe transfers heat to gaseous hydrocarbon in catalytic reaction in a reforming catalyst bed layer of a reformer to generate reforming endothermic reaction CH 4 +H 2 O→CO+3H 2 Carrying out natural gas water vapor endothermic reaction to obtain
The cooled coal-made synthetic gas enters a CO shift converter to carry out CO partial gas shift, partial crude synthetic gas does not enter the shift converter but enters a gas distribution tank after being delivered to a methanol washing tower to remove toxic substances on a methanol synthesis catalyst through a short-circuit communicated with an inlet and an outlet of the shift converter and the CO shift synthetic gas is converged, and the H is supplemented 2 Tank and CO 2 H of tank 2 Or H 2 And CO 2 。
9. A device for co-producing electric power by adopting the double-carbon hydrogenation methanol synthesis device as claimed in claim 6, comprising a raw material synthesis gas preparation section, a synthesis gas purification and distribution section and a methanol synthesis section, and is characterized in that: the device also comprises a gas and steam power generation section.
10. A device for co-producing synthetic ammonia by adopting the double-carbon hydrogenation methanol synthesis device as claimed in claim 6, comprising a raw material synthetic gas preparation section, a synthetic gas purification and distribution section and a methanol synthesis section, and is characterized in that: the device also comprises an ammonia synthesis section, the coal synthesis gas is hydrogenated to synthesize methanol at the double carbon pressure of less than 10MPa, the gas of separated methanol products is returned to the circulating machine to synthesize the gas except part of the circulating gas, the gas is pressurized to the synthesis pressure of 12-32MPa by a compressor, and the composition of the gas is regulated to perform double carbon hydrogenation to synthesize the methanol under high pressure, so that CO and CO are obtained 2 The conversion rate is more than 90%, and the gas after separating the methanol product is subjected to isobaric methanation to enable CO+CO 2 Less than 10ppm, adding nitrogen to achieve
And synthesizing ammonia to obtain the synthetic ammonia product. />
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