CN117626294A - System and method for preparing synthesis gas by coupling green electricity with melting bed - Google Patents
System and method for preparing synthesis gas by coupling green electricity with melting bed Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 73
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 73
- 230000005611 electricity Effects 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000008018 melting Effects 0.000 title claims abstract description 12
- 238000002844 melting Methods 0.000 title claims abstract description 12
- 230000008878 coupling Effects 0.000 title abstract description 8
- 238000010168 coupling process Methods 0.000 title abstract description 8
- 238000005859 coupling reaction Methods 0.000 title abstract description 8
- 238000002309 gasification Methods 0.000 claims abstract description 116
- 150000003839 salts Chemical class 0.000 claims abstract description 102
- 238000000926 separation method Methods 0.000 claims abstract description 88
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 74
- 238000003860 storage Methods 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 230000008929 regeneration Effects 0.000 claims abstract description 41
- 238000011069 regeneration method Methods 0.000 claims abstract description 41
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 25
- 238000000746 purification Methods 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000002485 combustion reaction Methods 0.000 claims abstract description 17
- -1 alkali metal salts Chemical class 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 134
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 27
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000004449 solid propellant Substances 0.000 claims description 14
- 230000005484 gravity Effects 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010248 power generation Methods 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002028 Biomass Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000011978 dissolution method Methods 0.000 claims description 3
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- 230000009466 transformation Effects 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a system and a method for preparing synthesis gas by a green electricity-coupled melting bed, a gasification furnace and a CO-rich synthesis gas purification unitThe molten salt separation unit is connected with the solid separation unit and the electrolysis unit through pipelines, and the electrolysis unit is connected with the H-rich unit respectively 2 Gas purifying unit, CO 2 The separation storage unit is connected with the fused salt regeneration unit through a pipeline, and CO 2 The separation storage unit is connected with the fused salt regeneration unit through a pipeline, and the fused salt regeneration unit is connected with the gasification furnace through a pipeline. The invention couples the green electricity heating melting bed and the electrolysis unit, overcomes the influence of the green electricity periodicity and the volatility of renewable energy production on the synthesis gas preparation process through the matching of alkali metal salts between the melting bed and the electrolysis unit, and reduces the production cost of the electrolysis unit from the system aspect, thereby realizing the coupling of the green electricity to effectively reduce the combustion heat supply reaction and the transformation reaction CO 2 Is the object of the discharge.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a system and a method for preparing synthesis gas by a green electricity-coupled melting bed.
Background
The renewable energy source of China has increasingly increased installed capacity, and the green electricity generated by the renewable energy sources becomes the main part of the energy source of China in the future, for example, the green electricity is properly combined with the industrial production process, so that the CO of the related process can be reduced 2 Emissions, thereby supporting achievement of the "two carbon" objective. In China, chemical production using coal as a source takes an important role, but chemical production process using coal as a source is often accompanied by a large amount of CO 2 Emissions, production of average CO per ton of chemical 2 Up to 3 tons or more. Both the combustion heating reaction and the shift reaction are accompanied by a large amount of CO in the coal gasification process 2 And (5) discharging. If the coal gasification process is coupled with green electricity, the combustion heat supply reaction and the shift reaction are optimized, and the CO can be effectively reduced 2 And (5) discharging.
The prior art generally optimizes the shift reaction, and realizes the shift reaction to reduce CO emission by coupling the electrolytic water hydrogen production unit 2 For example, chinese patent No. 116144401a discloses a method for increasing the hydrogen-to-carbon ratio of coal gasification synthesis gas by electrolysis of water-derived hydrogen to reduce CO additionally generated by a shift unit 2 And a method for producing methanol. It is noted that the above method is onlySolves H 2 But the problem of high cost of the electrolysis unit is difficult to solve, and green electricity is coupled to reduce CO of combustion heat supply reaction 2 The difficulty of discharging to prepare the synthesis gas is great; although chinese patent No. CN114874814a discloses a biomass pyrolysis gasification device and method based on alkali metal molten salt, which realizes the heat supply of solar energy to the pyrolysis and gasification process, the device and method are mainly used for producing fuel gas, and it is difficult to produce a synthesis gas product with relatively stable quality and yield for downstream synthesis because the solar energy supply is unstable.
In summary, the following problems exist in the production of synthesis gas by coupling green electricity: firstly, the existing mature gasification process is difficult to ensure the quality of the synthesis gas under the condition of using green electricity with the characteristics of periodicity and volatility to supply heat; secondly, although the hydrogen-carbon ratio of the synthesis gas produced by the green hydrogen regulation gasification process produced by renewable energy sources can be introduced, the waste alkali liquid produced by the alkaline electrolysis technology of the alkaline electrolysis tank which is relatively mature in technology is difficult to treat, and the cost of the proton exchange membrane electrolysis technology which is relatively environment-friendly is difficult to reduce; a system and method for green electricity coupled molten bed synthesis gas production is provided.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and provides a system and a method for preparing synthesis gas by a green electricity-coupled molten bed, which are used for solving the problems set forth in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a system for preparing synthesis gas by a green electricity-coupled melting bed at least comprises a gasification furnace, a CO-rich synthesis gas purification unit, a molten salt separation unit, an electrolysis unit and an H-rich unit 2 Gas purifying unit, CO 2 The gasification furnace is connected with the CO-rich synthetic gas purification unit and the molten salt separation unit through pipelines, the molten salt separation unit is respectively connected with the solid separation unit and the electrolysis unit through pipelines, and the electrolysis unit is respectively connected with the H-rich synthesis gas purification unit and the molten salt separation unit through pipelines 2 Gas purifying unit, CO 2 The separation storage unit is connected with the fused salt regeneration unit through a pipeline, theCO 2 The separation storage unit is connected with the fused salt regeneration unit through a pipeline, and the fused salt regeneration unit is connected with the gasification furnace through a pipeline.
As a preferable technical scheme of the invention, the gasification furnace is a molten bed gasification reactor based on alkali metal molten carbonate, the gasification furnace adopts a rotational flow or opposite spraying feeding mode to input a carbon-containing solid raw material and a gasification agent, and the gasification agent is CO 2 The method comprises the steps of carrying out a first treatment on the surface of the The gasification furnace adopts green electricity to heat alkali metal carbonate and solid fuel in an external heating or internal heating mode; the green electricity is one or more of a hydroelectric power generation device, a wind power generation device, a solar power generation device or a biomass power generation device, and a slag discharge port is further formed in the gasification furnace;
CO-rich synthesis gas and CO produced by gasification furnace 2 Separating part O from the storage unit 2 Oxygen-enriched combustion or pure oxygen combustion is carried out in the gasification furnace to be used as the supplement of gasification reaction heat supply when the renewable energy power supply fluctuates.
As a preferred embodiment of the present invention, the CO-rich syngas purification unit is used to separate methane and other hydrocarbon gases generated during pyrolysis of tar.
As a preferable technical scheme of the invention, the molten salt separation unit adopts a dissolution method to separate alkali metal carbonate which is easy to dissolve in water from unreacted carbon residue and ash which are insoluble in water and insoluble salt obtained by reaction.
As a preferable technical scheme of the invention, the electrolysis unit adopts a plurality of alkaline electrolysis tanks as electrolysis devices to electrolyze the mixture of alkali metal carbonate solution and corresponding alkali solution to prepare H 2 、O 2 And CO 2 The power of the electrolysis unit comes from green electricity, and the alkaline electrolysis tank uses a cationic membrane to separate a cathode and an anode, and the cathode obtains H 2 Anode to obtain CO 2 And O 2 Cathode generated gas enters into the H-rich part 2 The gas purifying unit purifies the gas generated by the anode and enters CO 2 The separation storage unit is used for separating, and the strong alkaline alkali liquor generated in the electrolysis unit is discharged to the molten salt regeneration unit at fixed time. Adding the molten salt from the molten salt separation unitObtaining a salt solution with lower concentration, and controlling the concentration of the solution in the electrolytic cell to ensure that no blockage occurs;
as a preferable technical scheme of the invention, the H-enriched material 2 The gas purifying unit comprises a gas purifying device and H 2 A gas storage device for reducing the periodicity and fluctuation of green electricity to H 2 Influence of preparation.
As a preferable embodiment of the present invention, the CO 2 The separation storage unit comprises a separation device and CO 2 Gas storage device and O 2 The separation device is used for separating CO generated by the anode of the electrolysis unit 2 、O 2 And a small amount of impurity gas are separated; the CO 2 Gas storage device for storing CO 2; The O is 2 Gas storage device stores O 2 And is externally supplied or used as a heat supply combustion improver for supplementing the gasification furnace, and CO from CCUS 2 Also stored in CO 2 In the separation storage unit, the CO of the whole gasification system is ensured 2 At the same time of zero emission, a certain amount of CO obtained by CCUS is consumed 2。
As a preferable technical scheme of the invention, the molten salt regeneration unit uses waste heat from gasification furnace gas to evaporate and dry, and collects condensed water obtained by evaporation and returns the condensed water to the molten salt separation unit for use so as to reduce the water consumption of the system; the solid separation unit adopts a gravity separation method to separate unreacted carbon residue, ash and insoluble salt obtained by reaction, the unreacted carbon residue with smaller specific gravity returns to the gasification furnace to be gasified, and the ash with larger specific gravity and the insoluble salt obtained by reaction are used as an ash discharge system.
A method for preparing synthesis gas by a green electricity-coupled molten bed, which is implemented in a system for preparing synthesis gas by a green electricity-coupled molten bed, and comprises the following specific steps:
s1: the solid fuel can be directly added into the gasification furnace by a feeding device, the alkali metal carbonate serving as a medium for heat transfer and catalytic gasification reaction in the molten bed is also added into the gasification furnace by a fused salt regeneration unit, and the gasifying agent used in the gasification furnace is CO 2 The gasification reaction heat of the gasification furnace is provided by green electricity produced by renewable energy sources; the gasification furnace is heated to 900 ℃ and alkali metal carbonate is formedCO as a melt liquid with good fluidity 2 Enhanced CO injection into gasifier by nozzle swirl 2 Contact with solid fuel; the solid fuel is gasified into the CO-rich synthetic gas with higher gasification strength under the catalysis of alkali carbonate, the generated tar is fully cracked in the process, and methane and other hydrocarbon gases generated in the pyrolysis process are separated in a CO-rich synthetic gas purification unit; the slag composed of unreacted carbon residue, ash content, insoluble salt obtained by reaction and alkali metal molten salt is discharged out of the gasifier from a slag discharge port so as to enter a molten salt separation unit;
s2: the molten salt separation unit utilizes hot water to dissolve alkali metal salt, unreacted carbon residue, ash and aluminosilicate for separation, other substances except the alkali metal salt are insoluble in water, an aqueous solution of the alkali metal salt enters the electrolysis unit, and the unreacted carbon residue, the ash and insoluble salt obtained by reaction which are insoluble in water enter the solid separation unit; the unreacted carbon residue and the ash and the insoluble salt obtained by the reaction have density difference, so that the unreacted carbon residue is separated into two parts of the unreacted carbon residue and the insoluble salt obtained by the ash and the reaction in a solid separation unit through a gravity separation method, the unreacted carbon residue returns to the gasification furnace for continuous gasification, and the ash and the insoluble salt obtained by the reaction are used as an ash discharge system;
S3:H 2 at the cathode of the electrolysis unit, CO 2 And O 2 Generated at anode of electrolytic unit and H generated at cathode 2 Enter into rich H 2 After the gas purifying unit, H meeting the requirement of the synthesis catalyst is obtained 2 The method comprises the steps of carrying out a first treatment on the surface of the Carbon dioxide and oxygen generated by anode in CO 2 The separation storage unit separates two gases, CO 2 For gasification furnace and fused salt regeneration unit, O 2 Can be supplied externally;
s4: the alkali metal carbonate generates corresponding alkali in the electrolysis unit, the pH value in the solution is correspondingly increased, the alkali metal carbonate solution from the molten salt separation unit continuously enters the electrolysis unit in the continuous operation process, and the alkali solution generated after ionization is continuously discharged to the molten salt regeneration unit; the discharged lye is taken from the CO in the molten salt regeneration unit 2 Separating CO in a storage unit 2 Conversion to alkali metal carbonatesAnd the alkali metal carbonate is dried to remove water, and the alkali metal carbonate after drying and regeneration is returned to the gasification furnace.
As a preferred embodiment of the present invention, the gasifying agent in step S1 is derived from CO stored in the gas obtained by the capturing means 2 CO in a storage unit 2 Also from CO generated during the electrolysis of potassium carbonate in the electrolysis unit 2 ;
Step S3, taking material loss and gas relaxation in the operation of the industrial device into consideration, adding alkali carbonate or corresponding alkali into the electrolysis unit in the synthesis process to add CO 2 Supplementing a storage Unit with CO derived from CCUS 2。
The beneficial effects of the invention are as follows: compared with the prior art, the technical scheme of the invention has the advantages that:
(1) The invention can use the green electricity produced by renewable energy sources to provide the heat required by the production of the synthesis gas, and simultaneously overcome the instability of the production of the synthesis gas caused by the periodicity and fluctuation characteristics of the green electricity, and relatively stably produce the synthesis gas, thereby effectively reducing the carbon dioxide emission in the production process of the synthesis gas;
(2) According to the invention, by coupling the alkali metal molten salt gasification, molten salt dissolution regeneration and the alkaline electrolytic tank water electrolysis hydrogen production process, most of alkali metal salt circulation is realized, the cost related to the alkali metal salt in the alkaline electrolytic tank is reduced from the system perspective, and the problem that the alkali metal molten salt is difficult to utilize in the molten bed technology is solved;
(3) The invention uses additional CO 2 The separation storage unit provides an air source for the gasification and drying regeneration unit, can regulate and control the acidity and alkalinity of alkali metal salt in the gasification furnace to weaken the corrosion to equipment, and can also regulate and control the pH value of the electrolytic tank to control the production thereof;
(4) The invention can flexibly adjust the hydrogen-carbon ratio of the synthesis gas by changing the production capacity of the gasification unit and the electrolysis unit according to the downstream demand to produce different chemicals, and eliminate the additional CO generated in the traditional process of adjusting the hydrogen-carbon ratio of the synthesis gas 2 。
Drawings
FIG. 1 is a schematic diagram of a green electricity coupled fused bed synthesis gas production system of the present invention.
In the figure: gasification furnace 1, CO-rich synthesis gas purification unit 2, molten salt separation unit 3, electrolysis unit 4 and H-rich synthesis gas 2 Gas purifying unit 5, CO 2 A separation storage unit 6, a molten salt regeneration unit 7 and a solid separation unit 8.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the attached drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making clear and defining the scope of the present invention.
Examples: referring to fig. 1, the present invention provides a technical solution: a system for preparing synthesis gas by a green electricity-coupled melting bed at least comprises a gasification furnace 1, a CO-rich synthesis gas purification unit 2, a molten salt separation unit 3, an electrolysis unit 4 and an H-rich synthesis gas purification unit 2 Gas purifying unit 5, CO 2 The gasification furnace 1 is connected with the CO-rich synthetic gas purification unit 2 and the molten salt separation unit 3 through pipelines, the molten salt separation unit 3 is respectively connected with the solid separation unit 8 and the electrolysis unit 4 through pipelines, and the electrolysis unit 4 is respectively connected with the H-rich synthetic gas purification unit 2 and the molten salt separation unit 3 through pipelines 2 Gas purifying unit 5, CO 2 The separation storage unit 6 and the fused salt regeneration unit 7 are connected through a pipeline, and CO 2 The separation storage unit 6 and the molten salt regeneration unit 7 are connected through a pipeline, and the molten salt regeneration unit 7 is connected with the gasification furnace 1 through a pipeline.
The gasification furnace 1 is a fused bed gasification reactor based on alkali metal molten carbonate, the gasification furnace 1 adopts a cyclone or opposite-spraying feeding mode to input a carbon-containing solid raw material and a gasifying agent, and the gasifying agent is CO 2 The method comprises the steps of carrying out a first treatment on the surface of the The gasification furnace 1 adopts green electricity to heat the alkali metal carbonate and the solid fuel through an external heating mode or an internal heating mode; the green electricity is one or more of a hydroelectric power generation device, a wind power generation device, a solar power generation device or a biomass power generation device, and a slag discharge port is arranged on the gasification furnace 1;
CO-rich synthesis gas and CO produced by gasification furnace 1 2 Part O obtained by separating the storage unit 6 2 Oxygen-enriched combustion or pure oxygen combustion is carried out in the gasification furnace 1And the combustion is used as the supplement of gasification reaction heat supply when the renewable energy power supply fluctuates.
The CO-rich synthesis gas purification unit 2 is used to separate methane and other hydrocarbon gases produced by tar during pyrolysis. CO-rich synthesis gas purification unit 2 and H-rich 2 The gas purifying unit 5 respectively aims at the synthesis gas mainly containing CO and the H-enriched gas 2 The gas is purified to meet the requirements of the subsequent synthesis catalyst.
The molten salt separation unit 3 separates alkali metal carbonate which is easily soluble in water and unreacted carbon residue, ash which is insoluble in water, and insoluble salt obtained by the reaction by a dissolution method.
The electrolysis unit 4 uses a plurality of alkaline electrolysis tanks as electrolysis devices to electrolyze the mixture of the alkali metal carbonate solution and the corresponding alkali solution to prepare H 2 、O 2 And CO 2 The power of the electrolysis unit 4 comes from green electricity, and the alkaline electrolysis tank uses a cationic membrane to separate a cathode and an anode, and the cathode obtains H 2 Anode to obtain CO 2 And O 2 Cathode generated gas enters into the H-rich part 2 The gas purifying unit 5 purifies the anode generated gas and enters CO 2 The separation storage unit 6 performs separation, and the strong alkaline alkali liquor generated in the electrolysis unit 4 is discharged to the molten salt regeneration unit 7 at regular time; the lower concentration salt solution obtained from the molten salt separation unit 3 is added and the solution concentration in the electrolytic cell is controlled to ensure that no clogging occurs.
Rich in H 2 The gas purifying unit 5 includes a gas purifying device and H 2 A gas storage device for reducing the periodicity and fluctuation of green electricity to H 2 Influence of preparation.
CO 2 The separation storage unit 6 comprises a separation device and CO 2 Gas storage device and O 2 Gas storage device and separation device are used for generating CO to anode of electrolysis unit 4 2 、O 2 And a small amount of impurity gas are separated; CO 2 Gas storage device for storing CO 2; O 2 Gas storage device stores O 2 And is externally supplied or used as a heat supply combustion improver for supplementing the gasification furnace 1, and CO from CCUS 2 Also stored in CO 2 In the separation and storage unit 6, the CO of the whole gasification system is ensured 2 At the same time of zero emission, a certain amount of CO obtained by CCUS is consumed 2。
The molten salt regeneration unit 7 uses the waste heat of the gas from the gasification furnace 1 to carry out evaporation drying, and condensate water obtained by evaporation is collected and returned to the molten salt separation unit 3 for use so as to reduce the water consumption of the system; the solid separation unit 8 adopts a gravity separation method to separate unreacted carbon residue, ash and insoluble salt obtained by reaction, the unreacted carbon residue with smaller specific gravity returns to the gasification furnace 1 for gasification, and the ash with larger specific gravity and the insoluble salt obtained by reaction are used as an ash discharge system.
A method for preparing synthesis gas by a green electricity-coupled molten bed, which is implemented in a system for preparing synthesis gas by a green electricity-coupled molten bed and comprises the following specific steps:
s1: the solid fuel can be directly added into the gasification furnace 1 by a feeding device, the alkali metal carbonate serving as a heat transfer and catalytic gasification reaction medium in the molten bed is also added into the gasification furnace 1 by a molten salt regeneration unit 7, and the gasifying agent used in the gasification furnace 1 is CO 2, The gasifying agent is obtained from CO obtained by capturing means and stored in CO 2 CO in storage unit 6 2 Also from the CO generated by the electrolysis of potassium carbonate in the electrolysis unit 4 2 The gasification reaction heat of the gasification furnace 1 is provided by green electricity produced by renewable energy sources; the gasification furnace 1 is heated to 900 ℃, and alkali carbonate becomes molten liquid with better fluidity, CO 2 CO is intensified by swirl injection of nozzles into gasification furnace 1 2 Contact with solid fuel; the solid fuel is gasified into the CO-rich synthetic gas with higher gasification strength under the catalysis of alkali carbonate, the generated tar is fully cracked in the process, and methane and other hydrocarbon gases generated in the pyrolysis process are separated in the CO-rich synthetic gas purification unit 2; the slag composed of unreacted carbon residue, ash content, insoluble salt obtained by reaction and alkali metal molten salt is discharged from the gasification furnace 1 through a slag discharge port so as to enter a molten salt separation unit 3;
s2: the molten salt separation unit 3 uses hot water to dissolve alkali metal salt, unreacted carbon residue, ash and aluminosilicate for separation, other substances except the alkali metal salt are insoluble in water, an aqueous solution of the alkali metal salt enters the electrolysis unit 4, and the unreacted carbon residue, ash and insoluble salt obtained by reaction which are insoluble in water enter the solid separation unit 8; the unreacted carbon residue and the ash and the insoluble salt obtained by the reaction have density difference, so that the unreacted carbon residue is separated into two parts of the unreacted carbon residue and the insoluble salt obtained by the ash and the reaction in the solid separation unit 8 by a gravity separation method, the unreacted carbon residue returns to the gasification furnace 1 for continuous gasification, and the ash and the insoluble salt obtained by the reaction are used as an ash discharge system;
S3:H 2 at the cathode of the electrolysis unit 4, CO 2 And O 2 Generated at the anode of the electrolysis unit 4 and H generated at the cathode 2 Enter into rich H 2 After the gas purifying unit 5, H meeting the requirement of the synthesis catalyst is obtained 2 The method comprises the steps of carrying out a first treatment on the surface of the Carbon dioxide and oxygen generated by anode in CO 2 The separation storage unit 6 separates two gases, CO 2 For gasification furnace 1 and fused salt regeneration unit 7, O 2 Can be supplied externally, and in consideration of material loss and gas relaxation in the operation of the industrial device, alkali carbonate or corresponding alkali is required to be supplemented into the electrolysis unit 4 in the synthesis process to supply CO 2 The storage unit 6 is supplemented with CO from CCUS 2 ;
S4: the alkali metal carbonate generates corresponding alkali in the electrolysis unit 4, the pH value in the solution is correspondingly increased, the alkali metal carbonate solution from the molten salt separation unit 3 continuously enters the electrolysis unit 4 in the continuous operation process, and the alkali solution generated after ionization is continuously discharged to the molten salt regeneration unit 7; the lye discharged is taken from the CO in the molten salt regeneration unit 7 2 Separating CO in a storage unit 6 2 Is converted into alkali metal carbonate, and is dried to remove water, and the alkali metal carbonate after drying and regeneration is returned to the gasification furnace 1.
The application of the hydrogen-carbon ratio adjustable gas forming system for producing the invention is described below by taking coal to prepare synthesis gas with the hydrogen-carbon ratio of 3 as an example to prepare oil products (Fischer Tropsch synthesis); as shown in fig. 1, a gasification furnace 1, a CO-rich synthesis gas purification unit 2, a molten salt separation unit 3, an electrolysis unit 4, and an H-rich synthesis gas purification unit 2 Gas purifying unit 5, CO 2 A storage unit 6, a molten salt regeneration unit 7, a solid separation unit 8 and necessary components and pipelines; the addition amount of the coal is 10 t/h.
The coal does not needThe treatment can be directly added into the gasification furnace 1 through a feeding device, the working temperature of the gasification furnace is 850-1100 ℃, the working pressure is normal pressure, and the gasification agent CO 2 Flow rate is 7000-14000 Nm 3 /h,O 2 The flow is 0-6000 Nm 3 /h, the flow rate of the generated CO-rich synthesis gas is 20000 Nm 3 And/h, a CO concentration of about 70%. The gasification furnace uses green electricity to supply heat, and the electricity consumption is 4-85 MW. The exhaust amount of the gasification furnace is 26-260 t/h, and the addition amount of the regenerated molten salt is 24-258 t/h. The water consumption of the fused salt separation unit 3 connected with the slag discharging port of the gasification furnace 1 is 56-612 t/h, and the solution amount of the discharged alkali metal salt is 80-870 t/h.
The electrolysis unit 4 matched with the scale gasification furnace 1 works at 65-85 ℃ and the product H thereof 2 Flow rate of 42000 and 42000 Nm 3 /h,O 2 Flow rate is 21000 Nm 3 /h,CO 2 The flow rate is 4000-42000 Nm 3 And/h. In the above gas, CO 2 In addition to the gasification furnace 1 as gasification agent, the molten salt regeneration unit 7 is also required to be applied to the regeneration of alkali metal carbonate, such as CO produced by the electrolysis unit 4 2 Insufficient to supply the gasification and regeneration unit requirements, then to the CO 2 The storage unit 6 is fed with CO from CCUS 2 To satisfy its supply; part O 2 Can be used as a combustion improver for heating the gasification furnace 1 to cope with the characteristics of green electricity periodicity and volatility, and the rest O 2 Can be externally supplied. The amount of the discharged alkali liquid of the electrolysis unit 4 is 38-750 t/h.
When the green electricity supply is reduced for a short time, O entering the gasification furnace 1 can be increased 2 Because the molten salt has better heat transfer capacity and larger heat capacity, the gasification furnace 1 can be ensured to stably run against the problem of insufficient green electricity supply.
An example of a system for producing synthesis gas with a hydrogen to carbon ratio of 3 from coal using the present invention is given above. The core of the invention is to couple the device with the characteristic of coping with the green periodic fluctuation and control CO by proper logistics and energy flow matching 2 The aim of producing synthesis gas from coupled green electricity stably and economically is achieved on the premise of emission. In practical applications, solid fuels such as biomass, organic solid waste, oil shale,Coal gangue and other various carbon-containing solid organic matters. When the solid fuel is biomass, the chemicals produced by the synthesis gas are green chemicals. In addition, since the system decouples CO and H 2 The ratio of synthesis gas hydrogen to carbon can be flexibly adjusted in a larger range, and in practical application, the ratio of synthesis gas hydrogen to carbon can be adjusted according to the requirements of downstream synthesis chemicals.
The invention realizes the coupling of the green electricity to the combustion heat supply reaction and the conversion reaction through the melting bed and the electrolysis unit respectively, and enables the alkali metal salt and the corresponding alkali used by the electrolysis unit to be used as the heat transfer medium and the catalyst of the melting bed at the same time through the material flow matching between the melting bed and the electrolysis unit, thereby reducing the production cost of the electrolysis unit from the aspect of a system. The system provided by the invention can realize the coupling of green electricity to effectively reduce the CO of combustion heat supply reaction and shift reaction 2 Is arranged in the air.
The foregoing examples merely illustrate embodiments of the invention and are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (10)
1. A system for preparing synthesis gas by a green electricity-coupled melting bed at least comprises a gasification furnace (1), a CO-rich synthesis gas purification unit (2), a molten salt separation unit (3), an electrolysis unit (4) and an H-rich synthesis gas purification unit 2 Gas purifying unit (5) and CO 2 Separation storage unit (6), fused salt regeneration unit (7) and solid separation unit (8), its characterized in that: the gasification furnace (1) is connected with the CO-rich synthetic gas purification unit (2) and the molten salt separation unit (3) through pipelines, the molten salt separation unit (3) is respectively connected with the solid separation unit (8) and the electrolysis unit (4) through pipelines, and the electrolysis unit (4) is respectively connected with the H-rich synthesis gas purification unit (3) through pipelines 2 Gas purifying unit (5) and CO 2 The separation storage unit (6) and the fused salt regeneration unit (7) are connected through a pipeline, and the CO 2 The separation storage unit (6) and the fused salt regeneration unit (7) are connected through a pipeline, theThe fused salt regeneration unit (7) is connected with the gasification furnace (1) through a pipeline.
2. A green electricity-coupled molten bed synthesis gas production system according to claim 1, wherein: the gasification furnace (1) is a molten bed gasification reactor based on alkali metal molten carbonate, the gasification furnace (1) adopts a rotational flow or opposite spraying feeding mode to input a carbon-containing solid raw material and a gasifying agent, and the gasifying agent is CO 2 The method comprises the steps of carrying out a first treatment on the surface of the The gasification furnace (1) adopts green electricity to heat the alkali metal carbonate and the solid fuel in an external heating or internal heating mode; the green electricity is one or more of a hydroelectric power generation device, a wind power generation device, a solar power generation device or a biomass power generation device, and a slag discharge port is further arranged on the gasification furnace (1);
CO-rich synthesis gas and CO produced by gasification furnace (1) 2 Separating part O obtained in the storage unit (6) 2 Oxygen-enriched combustion or pure oxygen combustion is carried out in the gasification furnace (1) and is used as the supplement of gasification reaction heat supply when the renewable energy power supply fluctuates.
3. A green electricity-coupled molten bed synthesis gas production system according to claim 1, wherein: the CO-rich synthesis gas purification unit (2) is used for separating methane and other hydrocarbon gases generated by tar in the pyrolysis process.
4. A green electricity-coupled molten bed synthesis gas production system according to claim 1, wherein: the molten salt separation unit (3) adopts a dissolution method to separate alkali metal carbonate which is easy to dissolve in water and unreacted carbon residue and ash which are insoluble in water, and insoluble salt obtained by the reaction.
5. A green electricity-coupled molten bed synthesis gas production system according to claim 1, wherein: the electrolysis unit (4) adopts a plurality of alkaline electrolysis tanks as electrolysis devices to electrolyze the mixture of alkali metal carbonate solution and corresponding alkali solution to prepare H 2 、O 2 And CO 2 Electric of the electrolysis unit (4)The force comes from green electricity, and the alkaline electrolyzer uses a cationic membrane to separate a cathode from an anode, and the cathode obtains H 2 Anode to obtain CO 2 And O 2 Cathode generated gas enters into the H-rich part 2 The gas purifying unit (5) is used for purifying, and the gas generated by the anode enters CO 2 The separation storage unit (6) is used for separating, the strong alkaline alkali liquid generated in the electrolysis unit (4) is discharged to the molten salt regeneration unit (7) at fixed time, the salt solution with lower concentration obtained from the molten salt separation unit (3) is added, and the concentration of the solution in the electrolysis tank is controlled to ensure that no blockage occurs.
6. A green electricity-coupled molten bed synthesis gas production system according to claim 1, wherein: the H is rich in 2 The gas purification unit (5) comprises a gas purification device and H 2 A gas storage device for reducing the periodicity and fluctuation of green electricity to H 2 Influence of preparation.
7. A green electricity-coupled molten bed synthesis gas production system according to claim 1, wherein: the CO 2 The separation storage unit (6) comprises a separation device and CO 2 Gas storage device and O 2 A gas storage device, the separation device is used for generating CO to the anode of the electrolysis unit (4) 2 、O 2 And a small amount of impurity gas are separated; the CO 2 Gas storage device for storing CO 2; The O is 2 Gas storage device stores O 2 And is externally supplied or used as a supplementary heat supply combustion improver of the gasifier (1), and CO from CCUS 2 Also stored in CO 2 In the separation storage unit (6), the CO of the whole gasification system is ensured 2 At the same time of zero emission, a certain amount of CO obtained by CCUS is consumed 2。
8. A green electricity-coupled molten bed synthesis gas production system according to claim 1, wherein: the molten salt regeneration unit (7) uses waste heat of gas from the gasification furnace (1) to evaporate and dry, and collects condensed water obtained by evaporation and returns the condensed water to the molten salt separation unit (3) for use so as to reduce the water consumption of the system; the solid separation unit (8) adopts a gravity separation method to separate unreacted carbon residue, ash and insoluble salt obtained by reaction, the unreacted carbon residue with smaller specific gravity returns to the gasification furnace (1) for gasification, and the ash with larger specific gravity and the insoluble salt obtained by reaction are used as an ash discharge system.
9. A method for preparing synthesis gas by a green electricity-coupled molten bed, which is characterized by comprising the following steps: the method is implemented in a system for preparing synthesis gas by a green electricity-coupled molten bed according to claims 1-8, comprising the following specific steps:
s1: the solid fuel can be directly added into the gasification furnace (1) by a feeding device, the alkali metal carbonate serving as a heat transfer and catalytic gasification reaction medium in the molten bed is also added into the gasification furnace (1) by a molten salt regeneration unit (7), and the gasifying agent used in the gasification furnace (1) is CO 2 The gasification reaction heat of the gasification furnace (1) is provided by green electricity produced by renewable energy sources; the gasification furnace (1) is heated to 900 ℃, alkali metal carbonate becomes molten liquid with better fluidity, and CO 2 CO is intensified by swirl injection of nozzles into gasification furnace (1) 2 Contact with solid fuel; the solid fuel is gasified into the CO-rich synthetic gas with higher gasification strength under the catalysis of alkali carbonate, the generated tar is fully cracked in the process, and methane and other hydrocarbon gases generated in the pyrolysis process are separated in a CO-rich synthetic gas purification unit (2); the slag composed of unreacted carbon residue, ash content, insoluble salt obtained by reaction and alkali metal molten salt is discharged from the gasification furnace (1) through a slag discharge port so as to enter a molten salt separation unit (3);
s2: the molten salt separation unit (3) utilizes hot water to dissolve alkali metal salt, unreacted carbon residue, ash and aluminosilicate for separation, other substances except the alkali metal salt are insoluble in water, an aqueous solution of the alkali metal salt enters the electrolysis unit (4), and the unreacted carbon residue, ash and insoluble salt obtained by reaction which are insoluble in water enter the solid separation unit (8); the unreacted carbon residue, ash and insoluble salt obtained by reaction have density difference, so that the unreacted carbon residue and the ash and the insoluble salt obtained by reaction are separated into two parts of the unreacted carbon residue and the insoluble salt obtained by reaction in a solid separation unit (8) through a gravity separation method, the unreacted carbon residue returns to the gasification furnace (1) for continuous gasification, and the ash and the insoluble salt obtained by reaction are used as an ash discharge system;
S3:H 2 at the cathode of the electrolysis unit (4), CO 2 And O 2 Generated at the anode of the electrolysis unit (4), H generated at the cathode 2 Enter into rich H 2 After the gas purifying unit (5), H which meets the requirement of the synthesis catalyst is obtained 2 The method comprises the steps of carrying out a first treatment on the surface of the Carbon dioxide and oxygen generated by anode in CO 2 The separation storage unit (6) separates two gases, CO 2 For gasification furnace (1) and fused salt regeneration unit (7), O 2 Can be supplied externally;
s4: the alkali metal carbonate can generate corresponding alkali in the electrolysis unit (4), the pH value in the solution can be correspondingly increased, and in the continuous operation process, the alkali metal carbonate solution from the molten salt separation unit (3) continuously enters the electrolysis unit (4), and alkali liquid generated after ionization is continuously discharged to the molten salt regeneration unit (7); the discharged lye is taken from the CO in a molten salt regeneration unit (7) 2 Separating CO in a storage unit (6) 2 Is converted into alkali metal carbonate, and is dried to remove water, and the alkali metal carbonate after drying and regeneration is returned to the gasification furnace (1).
10. A method for producing synthesis gas from a green electricity-coupled molten bed according to claim 9, wherein: the gasifying agent in step S1 is derived from CO stored in the gas obtained by the capturing means 2 CO in the storage unit (6) 2 Also from CO generated during the electrolysis of potassium carbonate in the electrolysis unit (4) 2 ;
Step S3 takes into account material losses and gas emissions during operation of the industrial plant, during the synthesis process alkali carbonate or corresponding alkali is added to the electrolysis unit (4) to CO 2 The storage unit (6) is supplemented with CO from CCUS 2。
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