CN117867522A - Synthesis gas and bicarbonate co-production system and co-production method - Google Patents
Synthesis gas and bicarbonate co-production system and co-production method Download PDFInfo
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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 64
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 63
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 286
- 238000000926 separation method Methods 0.000 claims abstract description 115
- 239000007789 gas Substances 0.000 claims abstract description 100
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 58
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- 230000001502 supplementing effect Effects 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000012530 fluid Substances 0.000 claims description 24
- 239000006260 foam Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000002637 fluid replacement therapy Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 6
- 239000003014 ion exchange membrane Substances 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000009736 wetting Methods 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 30
- 235000017557 sodium bicarbonate Nutrition 0.000 description 15
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 15
- 238000001802 infusion Methods 0.000 description 11
- 230000008901 benefit Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical group [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Abstract
The invention belongs to the technical field of carbon dioxide neutralization and utilization, and discloses a system and a method for co-production of synthesis gas and bicarbonate, wherein carbon dioxide and low-value alkali solution are used as raw materials to realize co-production of the synthesis gas and the bicarbonate, and the system and the method can realize the neutralization and utilization of the carbon dioxide at the same time; the co-production system mainly comprises a gas supply device, a liquid circulation device, an electrolysis device and a product collection device, and the co-production method comprises a gas-liquid circulation process, an electrolysis process and a separation process. The invention takes alkali solution and carbon dioxide with lower value as raw materials to realize controllable synthesis of synthesis gas with different hydrogen/carbon monoxide ratios; meanwhile, high-value chemicals such as oxygen, bicarbonate and the like with high value are generated, the reaction cost is covered, and the economic value is improved. On the other hand, the conversion and the utilization of the carbon dioxide can be effectively realized, and the environment is friendly.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide neutralization and utilization, and particularly relates to a co-production system and a co-production method of synthesis gas and bicarbonate.
Background
Carbon Capture, utilization and sequestration (Utilization and Storage, abbreviated CCUS) is becoming increasingly important as an effective and sustainable method for limiting Carbon dioxide emissions. However due to the lack of effective CO 2 Conversion route, CO at present 2 The main direction of the trapped water is to directly use the water in beverage, mining and other industries, and to store the water in underground landfill and finally discharge the water into the atmosphere. It is therefore of particular importance how to utilize the carbon dioxide directly or to convert it into a more valuable product.
The synthesis gas is a raw material gas which takes hydrogen and carbon monoxide as main components for chemical synthesis, and the synthesis gas with different hydrogen/carbon monoxide ratios has different application values in the chemical industry field. Currently, most synthesis gas production processes are developed based on processes that treat both natural gas and coal. However, the process for preparing the synthesis gas by converting the natural gas has the defects of high investment, sensitivity to the price of the natural gas, expensive catalyst, easy deactivation at high temperature and the like. Coal gasification causes environmental pollution and resource consumption. Therefore, the synthesis gas produced by the electroreduction of carbon dioxide is applied to the recycling of carbon dioxide because the synthesis gas does not pollute the environment and has ideal application conditions.
It is worth noting that the method for preparing the synthesis gas by electrocatalytic reduction of carbon dioxide at present usually adopts noble metal catalysts such as gold and silver, and meanwhile, more expensive electrolyte raw materials are consumed or more complex preparation technology of a membrane electrode is used, so that the reaction cost is increased, and the value of a synthesis gas product cannot cover the reaction cost, so that the industrial practical application of the synthesis gas preparation has a larger problem.
Thus, co-production of other high value chemicals is achieved while synthesis gas is being produced.
Disclosure of Invention
The invention provides a co-production system and a co-production method for synthesis gas and bicarbonate, which are based on the technical purpose of effectively improving economy while solving the problem of the neutralization and utilization of carbon dioxide.
In order to solve the technical problems, the invention is realized by the following technical scheme:
according to one aspect of the present invention there is provided a synthesis gas and bicarbonate co-production system comprising a gas supply means, a liquid circulation means, an electrolysis means and a product collection means;
the gas supply device comprises CO 2 An air source and a rotameter;
the liquid circulation device comprises a cathode circulation pump, an anode circulation pump, a cathode gas-liquid separation tank, an anode gas-liquid separation tank, a cathode fluid supplementing pump, an anode fluid supplementing pump, a cathode fluid supplementing tank and an anode fluid supplementing tank; deionized water is stored in the cathode gas-liquid separation tank and the cathode fluid replacement tank, and alkali solution is stored in the anode gas-liquid separation tank and the anode fluid replacement tank;
the electrolysis device comprises a direct current power supply and an electrolysis unit, wherein the direct current power supply is used for providing electric power energy for the electrolysis unit; the electrolysis unit comprises a cathode chamber, an anode chamber and an ion exchange membrane; a cathode catalytic electrode is arranged in the cathode chamber and stores cathode liquid, and the cathode catalytic electrode is used for catalyzing water and CO 2 Is capable of absorbing CO 2 And combine with metal ions in the solution to formBicarbonate; an anode catalytic electrode is arranged in the anode chamber and is used for catalyzing the oxidation reaction of the alkali solution to generate oxygen, and the anode liquid can be catalyzed to generate the oxidation reaction to generate oxygen;
the product collecting device comprises a cathode overflow collecting tank, an anode overflow collecting tank, a drying device, a bicarbonate collecting device, a synthetic gas collecting device and an oxygen collecting device;
the CO 2 The air source is connected with a cathode air inlet of the cathode chamber through the rotameter, and a cathode liquid inlet of the cathode chamber is connected with a liquid outlet of the cathode gas-liquid separation tank through the cathode circulating pump; the cathode circulating pump is communicated with a pipeline between the rotameter and the cathode air inlet through another branch and is used for carrying out CO 2 Wetting of the gas; the cathode gas-liquid outlet of the cathode chamber is connected with the liquid inlet of the cathode gas-liquid separation tank; the cathode liquid supplementing box is connected with a liquid inlet of the cathode gas-liquid separation tank through the cathode liquid supplementing pump; the overflow port of the cathode gas-liquid separation tank is connected with the inlet of the cathode overflow liquid collection tank, and the gas outlet of the cathode gas-liquid separation tank is connected with the synthesis gas collection device; the outlet of the cathode overflow liquid collecting tank is connected with the inlet of the drying device, and the outlet of the drying device is connected with the bicarbonate collecting device;
the anode gas-liquid outlet of the anode chamber is connected with the liquid inlet of the anode gas-liquid separation tank; the anode liquid supplementing box is connected with a liquid inlet of the anode gas-liquid separation tank through the anode liquid supplementing pump; the overflow port of the anode gas-liquid separation tank is connected with the anode overflow liquid collection tank; the gas outlet of the anode gas-liquid separation tank is connected with the oxygen collecting device.
Further, the cathode catalytic electrode consists of a conductive matrix and a cathode catalyst, wherein the conductive matrix is at least one of foam nickel, foam copper, foam zinc, carbon felt and carbon cloth, and the cathode catalyst is at least one of Ag, au, zn, cu, ni, fe; the anode catalytic electrode is at least one of foam nickel, foam iron, foam copper, foam cobalt and foam silver.
Further, the anode overflow liquid collecting tank is internally provided with a low-concentration alkali solution, and the low-concentration alkali solution is taken out to be mixed with a high-concentration alkali solution until the pH value is=5-6 mol/L, and then the mixture can be poured into the anode overflow liquid collecting tank for repeated use.
Further, a pressure sensor is arranged on a connecting pipeline between the cathode circulating pump and the cathode liquid inlet of the cathode chamber, and a pressure sensor is arranged on a connecting pipeline between the anode circulating pump and the anode liquid inlet.
Further, the overflow port of the cathode gas-liquid separation tank is higher than the liquid inlet of the cathode gas-liquid separation tank, and the overflow port of the anode gas-liquid separation tank is higher than the liquid inlet of the anode gas-liquid separation tank.
According to another aspect of the invention, a method for co-producing synthesis gas and bicarbonate is provided, wherein carbon dioxide and low-value alkali solution are used as raw materials, so that co-production of the synthesis gas and the bicarbonate is realized, and meanwhile, the neutralization and the utilization of the carbon dioxide are realized; comprising a gas-liquid circulation process, an electrolysis process and a separation process:
the gas-liquid circulation process is that carbon dioxide and cathode liquid are respectively introduced into a cathode chamber of an electrolysis device through a rotameter and a cathode circulating pump; simultaneously, anode liquid is introduced into an anode chamber of the electrolysis device through an anode circulating pump; the cathode liquid supplementing box supplements liquid to the cathode gas-liquid separation tank through a cathode liquid supplementing pump; the anode liquid supplementing box supplements liquid to the anode gas-liquid separation tank through the cathode liquid supplementing pump and the anode liquid supplementing pump;
the electrolysis process is to provide direct current to the electrolysis device, and in the cathode chamber of the electrolysis device, the carbon dioxide and the cathode liquid are catalyzed to generate reduction reaction to generate synthesis gas, and the cathode liquid absorbs part of the carbon dioxide; in an anode chamber of the electrolysis device, anode liquid is catalyzed to generate oxidation reaction to generate oxygen;
the separation process is that the synthesis gas and the cathode liquid absorbing carbon dioxide enter a cathode gas-liquid separation tank from a cathode chamber of an electrolysis device, the synthesis gas is collected after separation, and the liquid flows into a cathode overflow liquid collection tank and then is dried by a drying device to form bicarbonate solid products; simultaneously, anode liquid and oxygen enter an anode gas-liquid separation tank, liquid flows into an anode overflow liquid collection tank for recovery, and the oxygen is collected after separation.
Preferably, the pH value in the cathode gas-liquid separation tank is 8-9, and the concentration of the alkali solution in the anode gas-liquid separation tank is 5-6 mol/L.
Preferably, a heater and a temperature sensor are respectively arranged in the cathode gas-liquid separation tank and the anode gas-liquid separation tank, so that the liquid temperature is 45-55 ℃.
Preferably, the electrolysis pressure of the electrolysis device is 10kPa-10 MPa, and the voltage of the electrolysis device when the reaction occurs is 1.8-3.5V.
Preferably, the alkali solution is sodium hydroxide and potassium hydroxide, and the concentration of metal ions in the alkali solution is 1-8mol/L.
The beneficial effects of the invention are as follows:
the invention takes alkali solution and carbon dioxide with lower value as raw materials to realize controllable synthesis of synthesis gas with different hydrogen/carbon monoxide ratios; meanwhile, high-value chemicals such as oxygen, bicarbonate and the like with high value are generated, the reaction cost is covered, and the economic value is improved. On the other hand, the conversion and the utilization of the carbon dioxide can be effectively realized, and the environment is friendly.
Drawings
FIG. 1 is a schematic structural view of a syngas and bicarbonate co-production system of the present invention;
FIG. 2 is a schematic diagram of the structure of a cathode gas-liquid separator tank in the co-production system of the present invention;
FIG. 3 is a schematic view of the structure of an anode gas-liquid separator tank in the co-production system of the present invention;
FIG. 4 is a schematic view of the structure of an electrolyzer in the co-production system of the present invention;
FIG. 5 is a diagram of sodium bicarbonate (baking soda) produced in the example of the present invention;
fig. 6 is an infrared spectrum of sodium bicarbonate (baking soda) produced in the example of the present invention.
In the figure: 101-CO 2 A gas source; 102-rotameter; 103-a cathode circulation pump; 104-an anode circulation pump; 105-cathode gas-liquid separation tank; 106-an anode gas-liquid separation tank; 107-cathode fluid infusion pump; 108-an anode fluid infusion pump; 109-cathode fluid infusion tank; 110-an anode fluid supplementing box; 1051-a cathode gas-liquid separation tank gas outlet; 1052-liquid inlet of cathode gas-liquid separating tank; 1053-the liquid outlet of the cathode gas-liquid separation tank; 1054-overflow port of cathode gas-liquid separating tank; 1061-anode gas-liquid separation tank gas outlet; 1062-anode gas-liquid separation tank liquid inlet; 1063-an anode gas-liquid separation tank liquid outlet; 1064-overflow port of anode gas-liquid separation tank;
2-an electrolysis device; 201-a direct current power supply; 202-a cathode chamber; 203-an anode chamber; 204-a cathode catalytic electrode; 205-anode catalytic electrode; 206-ion exchange membrane; 2021-cathode inlet; 2022-cathode liquid inlet; 2023-cathode gas-liquid outlet; 2031-anode liquid inlet; 2032-anode gas-liquid outlet;
301-a cathode overflow collection tank; 302-an anode overflow collection tank; 303-a drying device; 304-bicarbonate collection means; 305-a syngas collection device; 306-oxygen collection means.
Detailed Description
The present invention is described in further detail below by way of specific examples, which will enable those skilled in the art to more fully understand the invention, but are not limited in any way.
As shown in fig. 1, an embodiment of the present invention provides a syngas and bicarbonate co-production system, mainly comprising a gas supply device, a liquid circulation device, an electrolysis device 2 and a product collection device.
The gas supply means comprises CO 2 A gas source 101 and a rotameter 102 for providing a system with a controllable flow rate of CO 2 And (3) a gas raw material.
The liquid circulation device comprises a catholyte circulation unit and an anolyte circulation unit. The catholyte circulation unit receives the electrolyte of the cathode chamber 202 and is used for catholyte circulation, and the anolyte circulation unit receives the electrolyte of the anode chamber 203 and is used for anolyte circulation. Specifically, the liquid circulation device comprises a cathode circulation pump 103, an anode circulation pump 104, a cathode gas-liquid separation tank 105, an anode gas-liquid separation tank 106, a cathode fluid infusion pump 107, an anode fluid infusion pump 108, a cathode fluid infusion tank 109 and an anode fluid infusion tank 110, and the liquid circulation device can controllably convey necessary liquid raw materials to the electrolysis device 2, separate gas-liquid products, ensure the circulation of the liquid and maintain the relative stability of the liquid raw materials in the system.
Wherein deionized water is stored in the cathode gas-liquid separation tank 105 and the cathode fluid replacement tank 109, and alkali solution is stored in the anode gas-liquid separation tank 106 and the anode fluid replacement tank 110.
As shown in fig. 2, the cathode gas-liquid separator 105 is provided with a cathode gas-liquid separator gas outlet 1051, a cathode gas-liquid separator liquid inlet 1052, a cathode gas-liquid separator liquid outlet 1053, and a cathode gas-liquid separator overflow 1054.
As shown in fig. 3, the anode gas-liquid separation tank 106 is provided with an anode gas-liquid separation tank gas outlet 1061, an anode gas-liquid separation tank liquid inlet 1062, an anode gas-liquid separation tank liquid outlet 1063, an anode gas-liquid separation tank overflow port 1064, and an anode gas-liquid separation tank liquid supplementing port 1065.
As shown in fig. 4, the electrolysis apparatus 2 comprises at least one dc power supply 201 and at least one electrolysis unit.
The dc power supply 201 is used to provide electrical energy for the electrolysis unit.
The electrolysis unit comprises a cathode chamber 202, an anode chamber 203, and an ion exchange membrane 206. Wherein, a cathode catalytic electrode 204 is arranged in the cathode chamber 202 and is used for catalyzing water and CO 2 Is reduced to produce synthesis gas. The cathode chamber 202 is provided with a cathode gas inlet 2021, a cathode liquid inlet 2022, and a cathode gas-liquid outlet 2023. The anode chamber 203 is provided with an anode liquid inlet 2031 and an anode gas-liquid outlet 2032.
The cathode catalytic electrode 204 is generally composed of a conductive substrate, which may be one of nickel foam, copper foam, zinc foam, carbon felt, carbon cloth, and a cathode catalyst, which may be one or more of Ag, au, zn, cu, ni, fe.
An anode catalytic electrode 205 is disposed in the anode chamber 203 for catalyzing the oxidation reaction of the alkaline solution to generate oxygen.
The anode catalytic electrode 205 is one or more of foam nickel, foam iron, foam copper, foam cobalt and foam silver.
During the electrolytic reaction, the catholyte absorbs CO 2 And bind the metal ions in the solution to form bicarbonate. The electrolysis unit 2 may be multi-layered in series to meet the demand for greater production.
The product collection device comprises separation, drying and collection of the synthesis gas, oxygen and bicarbonate. Specifically, the product collection device comprises a cathode overflow liquid collection tank 301, an anode overflow liquid collection tank 302, a drying device 303, a bicarbonate collection device 304, a synthesis gas collection device 305 and an oxygen collection device 306, and is used for collecting and storing different products. Wherein, the cathode overflow liquid collecting tank 301 contains saturated solution of bicarbonate, the solution is taken out and dried in the drying device 303 to obtain solid powder, and the solid powder is collected and stored by the bicarbonate collecting device 304. The anode overflow liquid collecting tank 302 stores low-concentration alkali solution, and after the low-concentration alkali solution is taken out and mixed with high-concentration alkali solution to the pH value of 5-6 mol/L, the mixture can be poured into the anode overflow liquid tank 110 for repeated use.
CO 2 The air source 101 is connected with the cathode air inlet 2021 through the rotameter 102, the liquid outlet 1053 of the cathode gas-liquid separation tank is connected with the cathode liquid inlet 2022 through the cathode circulating pump 103, and a pressure sensor is further arranged on a connecting pipeline between the cathode circulating pump 103 and the cathode liquid inlet 2022. And, the cathode circulation pump 103 is communicated with the pipeline between the rotameter 102 and the cathode air inlet 2021 through the other branch for CO 2 Wetting of the gas.
The cathode gas-liquid outlet 2023 is connected with the liquid inlet 1052 of the cathode gas-liquid separation tank, the overflow 1054 of the cathode gas-liquid separation tank is connected with the cathode overflow collecting tank 301, and the gas outlet 1051 of the cathode gas-liquid separation tank is connected with the synthesis gas collecting device 305. Wherein the overflow 1054 of the cathode gas-liquid separator is higher than the inlet 1052 of the cathode gas-liquid separator to prevent gas leakage.
The outlet of the cathode fluid supplementing box 109 is connected with a liquid inlet 1052 of the cathode gas-liquid separation tank through a cathode fluid supplementing pump 107, and the cathode fluid supplementing box 109 supplements deionized water in the cathode gas-liquid separation tank 105 through the cathode fluid supplementing pump 107.
The liquid outlet 1063 of the anode gas-liquid separation tank is connected with the anode liquid inlet 2031 through the anode circulating pump 104, and a pressure sensor is further arranged on the connecting pipeline between the anode circulating pump 104 and the anode liquid inlet 2031.
The anode gas-liquid outlet 2032 is connected with the anode gas-liquid separation tank liquid inlet 1062, the anode gas-liquid separation tank overflow port 1064 is connected with the anode overflow liquid collection tank 302, and the anode gas-liquid separation tank gas outlet 1061 is connected with the oxygen collection device 306. Wherein the anode gas-liquid separator overflow port 1064 should be higher than the anode gas-liquid separator inlet 1062 to prevent gas leakage.
The outlet of the anode fluid infusion tank 110 is connected with the liquid inlet 1062 of the anode gas-liquid separation tank through the anode fluid infusion pump 108, and the anode fluid infusion tank 110 supplements the alkaline solution into the anode gas-liquid separation tank 106 through the anode fluid infusion pump 108.
In the production of synthesis gas and bicarbonate, a voltage, CO, is applied to the DC power supply 201 2 The gas source 101 is controlled by the rotameter 102 to be introduced into the cathode chamber 202 of the electrolyzer 2 through the cathode inlet 2021. Cathode liquid in the cathode gas-liquid separation tank 105 is discharged from a liquid outlet 1053 of the cathode gas-liquid separation tank, the flow rate is controlled by a cathode circulating pump 103, and enters the electrolysis device 2 from a cathode liquid inlet 2022, and a branch liquid is used for wetting CO 2 And (3) gas. After electrolysis, the gas-liquid and unreacted gas-liquid generated in the cathode chamber are discharged from the cathode gas-liquid outlet 2023, and flow into the cathode gas-liquid separation tank 105 through the cathode gas-liquid separation tank liquid inlet 1052. The synthesis gas produced by the cathode gas-liquid separator tank 105 will exit through the cathode gas-liquid separator tank outlet 1051 and enter the synthesis gas collection apparatus 305. After the liquid is filled to the overflow 1054 of the cathode gas-liquid separator, it overflows to the cathode overflow collecting tank 301, and then is dried and collected. The anode liquid in the anode gas-liquid separation tank 106 is discharged from the anode gas separation tank liquid outlet 1063, and the flow rate is controlled by the anode circulation pump 104, and enters the electrolysis device 2 through the anode liquid inlet 2031. After electrolysis, the gas-liquid and unreacted gas-liquid generated in the anode chamber 203 are discharged from the anode gas-liquid outlet 2032 and flow into the anode gas-liquid separation tank through the liquid inlet 1062 of the anode gas-liquid separation tank106. Oxygen generated by the anode gas-liquid separator tank 106 will be discharged through the anode gas-liquid separator tank outlet 1061 and into the oxygen collection device 306. After the liquid fills the anode gas-liquid separator overflow port 1064, it overflows to the anode overflow collection tank 302. In this process, the cathode replenishing tank 109 replenishes deionized water into the cathode gas-liquid separation tank 105 through the cathode replenishing pump 107, and the anode replenishing tank 110 replenishes alkaline solution into the anode gas-liquid separation tank 106 through the anode replenishing pump 108, so as to maintain the stability of the solution in the system.
Based on the synthesis gas and bicarbonate co-production system, the embodiment of the invention also provides a synthesis gas and bicarbonate co-production method, which takes carbon dioxide and low-value alkali solution as raw materials to realize the co-production of the synthesis gas and the bicarbonate and the neutralization and the utilization of the carbon dioxide; including gas-liquid circulation processes, electrolysis processes and separation processes.
Gas-liquid circulation process: introducing carbon dioxide and catholyte into a cathode chamber 202 of the electrolysis device 2 through the rotameter 102 and the cathode circulation pump 103, respectively; at the same time, anode liquid is introduced into the anode chamber 203 of the electrolysis apparatus 2 through the anode circulation pump 104. The cathode replenishing tank 109 and the anode replenishing tank 110 are replenished with liquid in the cathode gas-liquid separation tank 105 and the anode gas-liquid separation tank 106 by the cathode replenishing pump 107 and the anode replenishing pump 108, respectively.
The electrolysis process comprises the following steps: the electrolysis device 2 is supplied with direct current. In the cathode chamber 202 of the electrolysis device 2, the carbon dioxide and the catholyte are catalytically reduced to synthesis gas, while the catholyte absorbs part of the carbon dioxide. In the anode chamber 203 of the electrolysis device 2, the anode liquid is catalyzed to undergo an oxidation reaction to generate oxygen.
The separation process comprises the following steps: the synthesis gas and the cathode liquid absorbing carbon dioxide enter the cathode gas-liquid separation tank 105 from the cathode chamber 202 of the electrolysis device 2, the synthesis gas is collected after separation, and the liquid flows into the cathode overflow liquid collection tank 301 and is dried by the drying device 303 to form bicarbonate solid products. Simultaneously, anode liquid and oxygen enter the anode gas-liquid separation tank 106, the liquid flows into the anode overflow liquid collection tank 302 for recovery, and the oxygen is collected after separation.
During the gas-liquid cycle, the carbon dioxide may be from commercially available carbon dioxide or industrial carbon dioxide off-gas. Preferably, the flow rate of carbon dioxide is 1-10L/min, the flow rate of cathode liquid is 300-800mL/min, the flow rate of anode liquid is 100-500mL/min, and the temperatures of the cathode liquid and the anode liquid are 45-55 ℃.
As a preferred embodiment, the pH value in the cathode gas-liquid separation tank 105 is maintained at 8 to 9, and the concentration of the alkali solution 106 in the anode gas-liquid separation tank is maintained at 5 to 6mol/L.
As a preferred embodiment, a heater and a temperature sensor are provided in each of the cathode gas-liquid separation tank 105 and the anode gas-liquid separation tank 106, so that the liquid temperature is maintained at 45 to 55 ℃.
In the electrolytic process: the temperature of the environment in which the electrolysis apparatus 2 reacts is preferably stabilized at 30 to 40 ℃.
The anode liquid is alkali solution, and the cathode liquid is deionized water. Wherein, the alkali solution is preferably sodium hydroxide and potassium hydroxide, and the concentration of metal ions in the alkali solution is 1-8mol/L. When the alkali solution is sodium hydroxide, the corresponding bicarbonate is sodium bicarbonate (baking soda), and when the alkali solution is potassium hydroxide, the corresponding bicarbonate is potassium bicarbonate.
As a preferred embodiment, the electrolysis pressure of the electrolysis apparatus 2 is 10kPa to 10 MPa, and the voltage at which the reaction of the electrolysis apparatus 2 occurs is 1.8 to 3.5V.
In the separation process, the ratio of hydrogen to carbon monoxide in the synthesis gas is 1:2-3:1, controllable adjustment.
Example 1
The catholyte was water at a flow rate of 450mL/min, the anolyte was 5mol/L sodium hydroxide at a flow rate of 600mL/min. Carbon dioxide enters the cathode chamber 202 of the electrolyzer 2 through the rotameter 102 at a flow rate of 5L/min. Applying 2.4V DC, CO in the cathode chamber 202 2 And water is reduced to synthesis gas by a cathode selective catalyst while a portion of the CO 2 Is absorbed by water; in the anode chamber 203, sodium hydroxide is oxidized to oxygen by a selective catalyst, and at the same time, na + Migration is performed through an ion exchange membrane. The specific reaction process is as follows:
anode: 4OH - ＝2H 2 O+O 2 +4e -
And (3) cathode: CO 2 +H 2 O+2e - ＝CO+2OH - 2H 2 O+2e - ＝H 2 +2OH -
Total reaction: CO 2 +H 2 O→CO+H 2 +O 2
The water in the cathode chamber 202 absorbs carbon dioxide and combines with sodium ions to form a sodium bicarbonate (baking soda) solution, which upon drying produces a white solid powder, as shown in fig. 5. Phase analysis was performed on the synthesis gas and bicarbonate product, with a hydrogen/carbon monoxide ratio of 2: the bicarbonate can be identified as sodium bicarbonate (baking soda) as shown in fig. 6.
It can be seen that in this example 1, the main product benefits can be derived from syngas, oxygen, sodium bicarbonate and carbon quota benefits, and the main costs are derived from NaOH, electricity charges, CO consumed by the anode 2 Cost, separation cost of sodium bicarbonate, separation cost of gas, and the like. When 1 ton of synthesis gas is produced, the product yield is about 2.5 ten thousand yuan, the cost is about 1.8 ten thousand yuan, and the profit is 0.7 ten thousand yuan. Of which more than 85% benefit is derived from sodium bicarbonate.
Example 2
The catholyte was water at a flow rate of 380mL/min, the anolyte was sodium hydroxide at a flow rate of 450mL/min. Carbon dioxide enters the cathode chamber of the electrolytic reactor through the gas flowmeter at the same time, and the flow rate is 3L/min. Applying 2.8V DC to the electrolytic reactor, CO in the cathode chamber 2 And water is reduced to synthesis gas by a cathode selective catalyst while a portion of the CO 2 Is absorbed by water; in the anode chamber, sodium hydroxide is oxidized into oxygen by a selective catalyst, and meanwhile Na + Migration occurs through the membrane. The specific reaction process is as follows:
anode: 4OH - ＝2H 2 O+O 2 +4e -
And (3) cathode: CO 2 +H 2 O+2e - ＝CO+2OH - 2H 2 O+2e - ＝H 2 +2OH -
Total reaction: CO 2 +H 2 O→CO+H 2 +O 2
The water in the cathode absorbs carbon dioxide and combines with sodium ions, forming a sodium bicarbonate (baking soda) solution. The gas is discharged from the gas outlet above the pot and collected, and the cathode gas is subjected to gas component analysis every 20 min. Phase analysis was performed on the synthesis gas and bicarbonate product, the ratio of hydrogen/carbon monoxide in the synthesis gas being 1:1, the dried solid product is NaHCO 3 。
In this example 2, the main product benefits can be from syngas, oxygen, sodium bicarbonate, carbon quota benefits, etc., and the main costs are from NaOH, electricity, CO consumed by the anode 2 Cost, separation cost of sodium bicarbonate, separation cost of gas, and the like. When 1 ton of synthesis gas is produced, the product yield is about 1.7 ten thousand yuan, the cost is about 1.1 ten thousand yuan, and the profit is about 0.6 ten thousand yuan. Of which more than 85% benefit is derived from sodium bicarbonate.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative, not restrictive, and many changes may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the appended claims, which are to be construed as falling within the scope of the present invention.
Claims (10)
1. A co-production system of synthesis gas and bicarbonate, which is characterized by comprising a gas supply device, a liquid circulation device, an electrolysis device and a product collection device;
the gas supply device comprises CO 2 An air source and a rotameter;
the liquid circulation device comprises a cathode circulation pump, an anode circulation pump, a cathode gas-liquid separation tank, an anode gas-liquid separation tank, a cathode fluid supplementing pump, an anode fluid supplementing pump, a cathode fluid supplementing tank and an anode fluid supplementing tank; deionized water is stored in the cathode gas-liquid separation tank and the cathode fluid replacement tank, and alkali solution is stored in the anode gas-liquid separation tank and the anode fluid replacement tank;
the electrolysis device comprises a direct current power supply and an electrolysis unit, wherein the direct current power supply is used for providing electric power energy for the electrolysis unit; the electrolysis unit comprises a cathode chamber, an anode chamber and an ion exchange membrane; a cathode catalytic electrode is arranged in the cathode chamber and stores cathode liquid, and the cathode catalytic electrode is used for catalyzing water and CO 2 Is capable of absorbing CO 2 And combining metal ions in the solution to form bicarbonate; an anode catalytic electrode is arranged in the anode chamber and is used for catalyzing the oxidation reaction of the alkali solution to generate oxygen, and the anode liquid can be catalyzed to generate the oxidation reaction to generate oxygen;
the product collecting device comprises a cathode overflow collecting tank, an anode overflow collecting tank, a drying device, a bicarbonate collecting device, a synthetic gas collecting device and an oxygen collecting device;
the CO 2 The air source is connected with a cathode air inlet of the cathode chamber through the rotameter, and a cathode liquid inlet of the cathode chamber is connected with a liquid outlet of the cathode gas-liquid separation tank through the cathode circulating pump; the cathode circulating pump is communicated with a pipeline between the rotameter and the cathode air inlet through another branch and is used for carrying out CO 2 Wetting of the gas; the cathode gas-liquid outlet of the cathode chamber is connected with the liquid inlet of the cathode gas-liquid separation tank; the cathode liquid supplementing box is connected with a liquid inlet of the cathode gas-liquid separation tank through the cathode liquid supplementing pump; the overflow port of the cathode gas-liquid separation tank is connected with the inlet of the cathode overflow liquid collection tank, and the gas outlet of the cathode gas-liquid separation tank is connected with the synthesis gas collection device; the outlet of the cathode overflow liquid collecting tank is connected with the inlet of the drying device, and the outlet of the drying device is connected with the bicarbonate collecting device;
the anode gas-liquid outlet of the anode chamber is connected with the liquid inlet of the anode gas-liquid separation tank; the anode liquid supplementing box is connected with a liquid inlet of the anode gas-liquid separation tank through the anode liquid supplementing pump; the overflow port of the anode gas-liquid separation tank is connected with the anode overflow liquid collection tank; the gas outlet of the anode gas-liquid separation tank is connected with the oxygen collecting device.
2. The co-production system of synthesis gas and bicarbonate according to claim 1, wherein the cathode catalytic electrode is composed of a conductive substrate and a cathode catalyst, wherein the conductive substrate is at least one of nickel foam, copper foam, zinc foam, carbon felt and carbon cloth, and the cathode catalyst is at least one of Ag, au, zn, cu, ni, fe; the anode catalytic electrode is at least one of foam nickel, foam iron, foam copper, foam cobalt and foam silver.
3. The co-production system of synthesis gas and bicarbonate according to claim 1, wherein the anode overflow liquid collecting tank is filled with a low-concentration alkaline solution, and the low-concentration alkaline solution is taken out and mixed with a high-concentration alkaline solution until the pH value is between 5 and 6mol/L, and then the mixture can be poured into the anode overflow liquid tank for repeated use.
4. The co-production system of synthesis gas and bicarbonate according to claim 1, wherein a pressure sensor is provided on a connection line between the cathode circulation pump and a cathode liquid inlet of the cathode chamber, and a pressure sensor is provided on a connection line between the anode circulation pump and the anode liquid inlet.
5. The co-production system of synthesis gas and bicarbonate according to claim 1, wherein the overflow port of the cathode gas-liquid separation tank is higher than the liquid inlet thereof, and the overflow port of the anode gas-liquid separation tank is higher than the liquid inlet thereof.
6. The co-production method of the synthesis gas and the bicarbonate is characterized in that the co-production of the synthesis gas and the bicarbonate is realized by taking carbon dioxide and low-value alkali solution as raw materials, and meanwhile, the neutralization and the utilization of the carbon dioxide are realized; comprising a gas-liquid circulation process, an electrolysis process and a separation process:
the gas-liquid circulation process is that carbon dioxide and cathode liquid are respectively introduced into a cathode chamber of an electrolysis device through a rotameter and a cathode circulating pump; simultaneously, anode liquid is introduced into an anode chamber of the electrolysis device through an anode circulating pump; the cathode liquid supplementing box supplements liquid to the cathode gas-liquid separation tank through a cathode liquid supplementing pump; the anode liquid supplementing box supplements liquid to the anode gas-liquid separation tank through the cathode liquid supplementing pump and the anode liquid supplementing pump;
the electrolysis process is to provide direct current to the electrolysis device, and in the cathode chamber of the electrolysis device, the carbon dioxide and the cathode liquid are catalyzed to generate reduction reaction to generate synthesis gas, and the cathode liquid absorbs part of the carbon dioxide; in an anode chamber of the electrolysis device, anode liquid is catalyzed to generate oxidation reaction to generate oxygen;
the separation process is that the synthesis gas and the cathode liquid absorbing carbon dioxide enter a cathode gas-liquid separation tank from a cathode chamber of an electrolysis device, the synthesis gas is collected after separation, and the liquid flows into a cathode overflow liquid collection tank and then is dried by a drying device to form bicarbonate solid products; simultaneously, anode liquid and oxygen enter an anode gas-liquid separation tank, liquid flows into an anode overflow liquid collection tank for recovery, and the oxygen is collected after separation.
7. The method for co-production of synthesis gas and bicarbonate according to claim 6, wherein the pH value in the cathode gas-liquid separation tank is 8-9, and the concentration of the alkaline solution in the anode gas-liquid separation tank is 5-6 mol/L.
8. The method for co-production of synthesis gas and bicarbonate according to claim 6, wherein a heater and a temperature sensor are respectively arranged in the cathode gas-liquid separation tank and the anode gas-liquid separation tank, so that the liquid temperature is 45-55 ℃.
9. The method for co-production of synthesis gas and bicarbonate according to claim 6, wherein the electrolysis pressure of the electrolysis device is 10kPa to 10 MPa, and the voltage at which the electrolysis device reacts is 1.8 to 3.5V.
10. The method for co-production of synthesis gas and bicarbonate according to claim 6, wherein the alkaline solution is sodium hydroxide and potassium hydroxide, and the concentration of metal ions in the alkaline solution is 1-8mol/L.
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