CN113105306B - Device and method for synthesizing organic matters by using plasma electric field to assist methanol - Google Patents
Device and method for synthesizing organic matters by using plasma electric field to assist methanol Download PDFInfo
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- 230000005684 electric field Effects 0.000 title claims abstract description 288
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 103
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 75
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000007791 liquid phase Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 58
- 239000012467 final product Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 112
- 238000006243 chemical reaction Methods 0.000 description 89
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- 239000002184 metal Substances 0.000 description 58
- 210000002381 plasma Anatomy 0.000 description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 239000010935 stainless steel Substances 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 230000005495 cold plasma Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
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- 239000000446 fuel Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003502 gasoline Substances 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 201000009240 nasopharyngitis Diseases 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000006057 reforming reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a device and a method for synthesizing organic matters by using a plasma electric field to assist methanol. The method comprises the following steps: and (3) sending the raw material gas containing the methanol gas into a plasma electric field unit for decomposition and synthesis to obtain an organic mixture, wherein the number of electric fields in the plasma electric field unit is at least one, and the plasma electric field unit at least contains one high-voltage direct current negative electric field. The application adopts the plasma electric field unit which at least contains one high-voltage direct current negative electric field, and can adjust the feeding condition of raw material gas and the selection of the latter electric field according to the synthesis condition of the product in the former electric field and the finally obtained product, so that the synthesis of the organic matters is more flexible and the final product with high yield can be obtained.
Description
Technical Field
The application belongs to the technical field of plasma-assisted chemical reaction, and particularly relates to a device and a method for producing organic matters by using electric field-assisted methanol.
Background
The plasma is a collection of electrons, ions, atoms, radicals, molecules, and the like, which is formed by the excitation of gas molecules by heat or energy such as an electric field, and the number of positive and negative charges in the collection is substantially equal, and is called a plasma. The high temperature, hot and cold plasmas can be classified according to the plasma energy state, temperature and ion density. In cold plasma, electrons may have kinetic energy above 5eV, and molecules, radicals, atoms, etc. may range from room temperature to hundreds of degrees. Electrons having sufficient energy can collide inelastically with gas molecules to convert them into active particles such as excited state particles, free radicals (or atoms) and ions, activating the reactants, often allowing the kinetically more difficult catalytic reactions to proceed at lower temperatures.
Common cold plasma generation techniques include silent discharge, corona discharge, glow discharge, microwave discharge, radio frequency discharge, and the like. Wherein silent discharge and corona discharge are capable of generating cold plasma at normal pressure. Corona discharge utilizes asymmetric electrode discharge to generate high energy electrons at low temperature, while silent discharge is gas discharge in which an insulating medium exists between electrodes, and the insulating medium can prevent spark discharge or arc discharge between electrodes.
At present, cold plasma technology has become a leading-edge hot spot subject in the fields of environmental management, energy development and the like, and researches on purifying air, desulfurizing and denitrating, converting gas and the like by utilizing plasma reaction have been widely carried out, but no report has been made on the combination of the cold plasma generation technology, in particular to an electric field combination device and application of plasma.
In recent years, serious energy crisis is faced worldwide, and searching for new alternative energy sources has become a key for future energy strategies in various countries. The ethanol has the characteristics of being renewable, efficient, low in cost, safe and the like, can be directly used as a liquid fuel or used together with gasoline, reduces dependence on petroleum which is a non-renewable energy source, and further ensures the safety of the national energy source.
The current methods for preparing ethanol are classified into fermentation methods and chemical methods. The fermentation method for producing ethanol is mainly a process taking grains (such as grains, potatoes and sugar raw materials) as raw materials, and has the advantages of high production cost and low efficiency on one hand, and competing with people for grains on the other hand, and the fermentation method for efficiently converting non-grain biomass into ethanol is to be developed. The chemical processes are classified into an ethylene hydration process, a catalytic conversion synthesis gas process and a catalytic conversion ethyl acetate process. The ethanol is prepared by ethylene hydration, the ethylene conversion rate is low, the reaction needs to be carried out under high pressure, and the raw materials depend on fossil resources; the process for preparing ethanol by catalytic conversion of synthesis gas also needs to use a noble metal catalyst; the technology for producing ethanol by catalyzing ethyl acetate hydrogenation has the problems of high cost, high energy consumption and the like. Thus, new processes for preparing ethanol have yet to be developed further.
Methanol is the simplest saturated monohydric alcohol and the methanol industry has evolved rapidly in recent years. Currently, the capacity of coal-to-methanol is almost entirely in china. The national total capacity 8650.5 ten thousand tons was reported by 2018. However, according to the related single-site measurement, the gap of the ethanol (6000 yuan/ton) of the future fuel of the Chinese automobile is at least 1500 ten thousand tons, and the ethanol production by the whole grain fermentation is not realistic for the large-sized state of the grain shortage.
In addition, the ethyl acetate is used as a fine chemical product with wide application, is an important organic chemical raw material and industrial solvent, and is a high added value product. A common method for industrial synthesis of ethyl acetate is the ethanol oxidation process. Obviously, on the premise of high ethanol production cost and high energy consumption, the synthesis cost of ethyl acetate is always high.
How to develop a new synthetic route for preparing organic matters such as ethanol, ethyl acetate and the like by taking methanol as a main raw material, expand the downstream use of the methanol and reduce the dependence on petroleum; the method is not only used for competing with people for food, but also can fully utilize rich methanol in China, and is a technical problem to be solved urgently.
Disclosure of Invention
The application provides a method for synthesizing organic matters by using a plasma electric field to assist methanol, which comprises the following steps: and (3) sending the raw material gas containing the methanol gas into a plasma electric field unit for decomposition and synthesis to obtain an organic mixture, wherein the number of electric fields in the plasma electric field unit is at least one, and the plasma electric field unit at least contains one high-voltage direct current negative electric field.
According to embodiments of the present application, the electric field may be one, two, three or more continuous electric fields. When the plasma electric field unit contains at least two electric fields, the electric fields are continuous identical or different electric fields. For example, the plasma electric field unit may include a continuous first electric field and second electric field; the first electric field and the second electric field are the same or different and can be selected from high-voltage electric fields, for example, the high-voltage electric fields can be selected from high-frequency pulse high-voltage positive electric fields, high-frequency pulse high-voltage negative electric fields or high-voltage direct current negative electric fields; and at least one electric field of the first electric field and the second electric field is a high-voltage direct current negative electric field. For another example, the plasma electric field unit contains three continuous electric fields, wherein at least one electric field is a high voltage direct current negative electric field. "continuous" as used herein means series. Further, the electric field in each plasma electric field unit may be the same as or different from the previous or subsequent electric field, and it will be understood by those skilled in the art that the selection of the subsequent electric field may be adjusted according to the composition of the product in the previous electric field. Specifically, if the product yield in the preceding electric field has reached the requirement, the following electric field may be a high voltage dc negative field; if the product yield in the preceding electric field does not meet the requirements or if it is desired to continue synthesizing other products, the following electric field is preferably a high frequency pulsed high voltage positive electric field or a high frequency pulsed high voltage negative electric field.
According to the embodiment of the application, the plasma electric field unit only comprises one electric field, and is a high-voltage direct current negative electric field.
According to an embodiment of the present application, the plasma electric field unit contains two electric fields, wherein the first electric field may be a high voltage positive electric field (e.g., a high frequency pulsed high voltage positive electric field) and the second electric field may be a high voltage direct current negative electric field.
According to an embodiment of the present application, the plasma electric field unit contains two electric fields, the first electric field may be a high voltage negative electric field (e.g., a high frequency pulsed high voltage negative electric field), and the second electric field may be a high voltage direct current negative electric field.
According to an embodiment of the present application, the plasma electric field unit contains two electric fields, the first electric field may be a high voltage direct current negative electric field, and the second electric field may be a high voltage pulse positive electric field (e.g., a high frequency pulse high voltage positive electric field).
According to an embodiment of the present application, the plasma electric field unit contains two electric fields, the first electric field may be a high voltage direct current negative electric field, and the second electric field may be a high voltage pulse negative electric field (e.g., a high frequency pulse high voltage negative electric field).
According to an embodiment of the present application, the plasma electric field unit contains two electric fields, wherein the first electric field may be a high voltage pulse positive electric field (e.g., a high frequency pulse high voltage positive electric field) or a high voltage pulse negative electric field (e.g., a high frequency pulse high voltage negative electric field), and the second electric field may be a high voltage direct current negative electric field.
According to an embodiment of the present application, the plasma electric field unit may also contain three electric fields, the first two electric fields may be selected from any of the above listed double electric field units, and the third electric field may be a high voltage negative electric field (such as a high voltage direct current negative electric field, a high frequency pulse high voltage negative electric field) or a high voltage positive electric field (such as a high frequency pulse high voltage positive electric field).
According to the technical scheme of the application, the raw material gas can only contain methanol gas or a mixed gas containing the methanol gas, for example, the mixed gas also contains water vapor and/or carbon dioxide.
Preferably, the mixture is a mixture of methanol gas and water vapor in a molar ratio of (0.5-5): 2, e.g., (0.8-2): 2, illustratively in a molar ratio of 0.95:1, 1:1, 1.2:1, 1.55:1, 1:2. Preferably, the mixture is a mixture of methanol gas and carbon dioxide in a molar ratio of (0.5-3): 2, for example (0.8-2): 2, and illustratively in a molar ratio of 1:2. Preferably, the mixture is a mixture of methanol gas, water vapor and carbon dioxide, wherein the molar amounts of water vapor and carbon dioxide are both larger than that of methanol gas. For example, the molar ratio of methanol gas, water vapor and carbon dioxide may be 1 (1.1-24): (1.51-3), such as 1 (1.3-1.83): (1.82-2.5), with exemplary ratios of 2.31:3.6:58:4.9, 3:7.67:3.67.
According to the technical scheme of the application, the voltage of the high-frequency pulse high-voltage positive electric field or the high-frequency pulse high-voltage negative electric field can be adjusted, and the voltage is maintained at 1-25kV, such as 10-20kV and 10-15kV, in actual production. Those skilled in the art will appreciate that the frequency range of the high frequency pulses may be selected, for example, from 1kHz to 25kHz.
According to the technical scheme of the application, the voltage of the high-voltage negative direct current electric field can be adjusted, and the voltage is maintained at 1-20kV, for example 10kV, in actual production.
According to the technical scheme of the application, the decomposition and synthesis temperatures are not particularly limited, and the temperature is selected based on two aspects, so that on one hand, the water in the reaction process is maintained to be in a water vapor state at the temperature of more than 100 ℃ and the occurrence of short circuit caused by water drops in an electric field is avoided; on the other hand, the high temperature performance of the insulating silica gel material in the plasma electric field device, such as a cable material communicated with a power supply, needs to be considered. The decomposition and synthesis temperatures may be the same or different, preferably the decomposition and synthesis temperatures are greater than 100 ℃ and no greater than 150 ℃. For example, the decomposition and synthesis temperatures are the same, e.g., temperatures of 110-150 ℃, preferably 112-120 ℃, and exemplary 115 ℃.
According to the technical scheme of the application, the mixed gas obtained through the first electric field decomposition reforming effect can be condensed and collected before entering the second electric field, and the mixed ion gas after the condensed gas-liquid separation is sent into the second electric field.
Preferably, when the technical scheme of the application is used for industrial production, the mixed gas obtained through the first electric field directly enters the second electric field without condensation and collection so as to realize continuous industrial production.
According to the technical scheme of the application, the method further comprises the following steps: the organic mixture obtained from the plasma electric field is condensed to obtain a liquid phase product.
According to the technical scheme of the application, the method further comprises the following steps: and separating and purifying the liquid phase product. The components are collected separately by separation and purification.
According to the technical scheme of the application, the raw material gas can only contain methanol gas or a mixed gas containing the methanol gas, for example, the mixed gas also contains water vapor and/or carbon dioxide.
According to the technical scheme of the application, the methanol is converted by the plasma electric field containing at least one high-voltage direct current negative electric field, and the product comprises one or more of ethanol, ethyl acetate and methylal. The above-mentioned products can be obtained regardless of the arrangement of the plasma electric field, such as a single high-voltage direct-current negative electric field or a combination of the high-voltage direct-current negative electric field and an additional positive electric field or the negative electric field, but the contents of ethanol, ethyl acetate and methylal in the products may be different according to the arrangement type of the electric field and the composition and the use ratio of the raw material gas entering the electric field.
According to the technical scheme of the application, the methanol gas is subjected to a plasma electric field and is mainly used for producing ethanol-containing products and/or ethyl acetate-containing products.
Hereinafter, the electric field combination of the present application will be described by way of example, but the electric field combination of the present application is not limited to the following embodiments, and the products obtained in the following embodiments have a high content of ethanol and/or ethyl acetate, but other electric field combinations, not shown, may be obtained as long as they have a high dc negative electric field setting, although the content of ethanol and/or ethyl acetate varies.
In one embodiment of the application, the first electric field is a high frequency pulsed high voltage positive electric field and the second electric field is a high voltage direct current negative electric field; when the raw material gas is only composed of methanol gas, the main components of a liquid phase product obtained after the product is condensed are ethanol, methylal and ethyl acetate, and a small amount of toluene is also contained; when the feed gas contains methanol gas and carbon dioxide, and optionally water vapor, it is converted to an organic mixture of ethanol by a plasma electric field, and at least one of oxygen, hydrogen, acetylene gas, etc. is released by condensed gas-liquid separation.
In one embodiment of the present application, the first electric field is a high-frequency pulsed high-voltage positive electric field, and the second electric field is a high-voltage direct-current negative electric field, and when the raw material gas contains methanol gas and water vapor (for example, the molar ratio is 0.5:1.5-1.50.5, for example, 1:1), the liquid phase product obtained after condensation of the product mainly comprises ethanol, methylal and ethyl acetate. Regulating methanol and water vapor and CO 2 The main product in the liquid phase may be ethyl acetate, with minor amounts of isopropanol and acetic acid.
In one embodiment of the application, the first electric field may be free or a high voltage DC negative electric field, and the feed gas is methanol gas and water vapor with or without CO when the second electric field is a high voltage DC negative electric field 2 When the mixture gas is mixed, a liquid phase product mainly containing ethanol and acetic acid can be obtained; the liquid phase product also contains a small amount of methanol. Exemplary, when not containing CO 2 When the molar ratio of methanol gas to water vapor is 1 (0.5-2), such as 1 (0.75-1.5), exemplary are 1:1, 1:0.95; when containing CO 2 When, preferably, the molar amounts of both water vapor and carbon dioxide are greater than that of methanol gas; for example, the molar ratio of methanol gas, water vapor and carbon dioxide may be 1 (1.1-2): (1.5-3), such as 1 (1.3-1.8): (1.8-2.5), with an exemplary ratio of 2.31:3.58:4.9. In one embodiment of the application, the ethanol may be present in the liquid phase product in an amount of up to 65%.
In one embodiment of the application, the first electric field may be either no high voltage DC negative electric field or high frequency high voltage negative electric field, and the feed gas is methanol gas alone, or a mixture of methanol gas and water vapor, or methanol gas, water vapor and CO when the second electric field is a high voltage DC negative electric field 2 When the mixture gas is mixed, a liquid phase product mainly containing ethyl acetate can be obtained; the liquid phase product also contains a small amount of ethanol and/or isopropanol, etc. The molar ratio of methanol gas to water vapor is not particularly limited. Illustratively, when methanol gas and water vapor are present alone, the molar ratio is 1 (0.1-2), such as 1 (0.2-1.6), with exemplary 1:0.39, 1:0.78, 1:1.18. When methanol gas, water vapor and carbon dioxide are contained, the molar ratio of the three can be 1 (1.1-4) to 1-3. For example, in one embodiment of the application, methanol feed = 3 moles/hour, water vapor feed = 7.67 moles/hour, CO 2 Feed = 3.67 moles/hour, the ethyl acetate content in the aqueous liquid phase product may beAbove 73wt%, the liquid product failed to detect methanol, indicating that methanol may have been substantially converted. The gas components discharged after condensation and separation comprise oxygen, hydrogen and CO 2 And acetylene gas, etc.
Preferably, when the flux of methanol gas into the reactor is small, a product containing mainly ethanol is produced; when the flux of methanol gas into the reactor is increased, a product mainly containing ethyl acetate is produced. The methanol gas feed rate can be determined by simple experimentation by one skilled in the art based on the particular reactor employed.
As used herein, "feed flux" refers to the amount of feed (volume or molar amount) through the cross-sectional area of the reactor as feed gas is fed.
According to the technical scheme of the application, the raw material gas can enter under the conveying of carrier gas when entering the electric field, for example, the carrier gas is inert gas or nitrogen, and preferably nitrogen. Further, the flow rate of the carrier gas is 2 to 5mol/hr, for example, 3mol/hr.
In the present application, the overall reaction history of the reactant containing methanol gas plus water vapor in the plasma electric field is approximately as follows:
10CH 3 OH+H 2 O→C 2 H 5 OH+CH 3 OCH 2 OCH 3 +C 4 H 8 O 2 +C 2 H 2 +2O 2 +9H 2
experiments show that the mixed gas (including a small amount of entrained methanol) entering the second electric field undergoes a complex reaction process to generate organic components such as ethanol. The inventors have also experimentally confirmed that if synthesis is performed by mixing only hydrogen and carbon dioxide without using methanol and water vapor, ethanol or methanol and ethyl acetate cannot be synthesized. The inventors believe that one of the key factors is that both methanol and water molecules can be cleaved in a first electric field to produce a large amount of hydroxyl OH (alcohol functional group) as an intermediate or catalyst, which can form an ethanol mixture in a second electric field.
When methanol gas is used as raw material alone, the main components of the condensed liquid phase product are methylal and ethyl acetate, and trace toluene and ethanol. The main reaction schemes for the synthesis of ethanol mixtures may be:
16CH 3 OH→C 3 H 8 O 2 +C 4 H 8 O 2 +C 7 H 8 +C 2 H 5 OH+5.5O 2 +17H 2 。
this shows that pure methanol can be used directly by electric fields to produce high value methylal, ethyl acetate and toluene without steam addition.
For the electric field assisted methanol plus steam and carbon dioxide ethanol production process, CO can be utilized 2 The carbon element in the catalyst replaces the carbon element in the methanol, and CO discharged by a conversion section in the methanol industry is utilized 2 The use amount of methanol is reduced as much as possible, the economic benefit is improved, and the main reaction process is as follows:
CH 3 OH+CO 2 +H 2 O→C 2 H 5 OH+O 2
preferably, the process of the present application can be used to produce ethanol and other organics using the apparatus described below.
The application also provides a device for synthesizing organic matters by using the methanol assisted by the plasma electric field, which comprises at least one plasma electric field unit, wherein the plasma electric field unit at least comprises a high-voltage direct-current negative electric field reaction chamber. Wherein the high-voltage direct-current negative electric field reaction chamber contains an insulating material lining, such as glass, silica gel, ceramic and other insulating materials, preferably glass lining. The high-voltage direct current negative electric field is constructed by a stainless steel tube with a glass tube lining, the electrons sprayed by a central electrode or a central metal rod are directly sprayed on the wall of the lining glass and blocked, so that the running speed is reduced, the free electrons which are blocked and decelerated are more easily captured by polar gas molecules in a reaction chamber, energy is obtained from the electrons, the electrons interact with other molecules more effectively and are reformed into product molecules, and the combination of the product molecules is promoted to be more effective.
According to the present application, the plasma electric field unit may include a first electric field reaction chamber and a second electric field reaction chamber for providing a high voltage electric field, such as a high frequency pulse high voltage positive electric field, a high frequency pulse high voltage negative electric field, or a high voltage direct current negative electric field; and at least one of the electric field reaction chambers is provided with a high voltage DC negative electric field. Preferably, the high frequency pulsed high voltage positive electric field, the high frequency pulsed high voltage negative electric field, the high voltage negative electric field and the high voltage direct current negative electric field have the meanings as described above.
According to the device of the application, the first electric field reaction chamber is the same as or different from the second electric field reaction chamber. For example, one of the electric field reaction chambers may be a metal cylindrical reaction chamber or a metal tubular reaction chamber, preferably a metal tubular reaction chamber, such as a stainless steel tube reaction chamber.
According to the device of the application, the high-voltage direct-current negative electric field reaction chamber is an insulating cylinder type reaction chamber or an insulating tube type reaction chamber, preferably an insulating tube type reaction chamber, such as a glass tube type reaction chamber, and an exemplary stainless steel tube type reaction chamber containing a glass tube lining.
The apparatus according to the present application may further comprise a product collector, the product outlet of the second electric field reaction chamber being connected to the product collector. The final product can be obtained into ethanol mixed solution at room temperature through a water condenser, and some gases after gas-liquid separation can be obtained into different gas products (such as hydrogen, oxygen, acetylene and CO) through a traditional gas pressure swing adsorption separation process.
When the number of the electric field units is at least two, the electric field units are in a series connection mode or a parallel connection mode.
According to the device of the application, the first electric field is arranged before the second electric field, and the 'front and back' refers to the sequence of flowing through the reaction materials, namely the 'front' flowing through the reaction materials and the 'back' flowing through the reaction materials.
According to the device of the application, the device has a housing, and the first electric field reaction chamber and the second electric field reaction chamber are arranged in the housing. Electrodes or metal bars are respectively arranged at the centers of the first electric field reaction chamber and the second electric field reaction chamber, and are powered by an electric field source; the electrode or metal rod provides high energy electrons that can be adsorbed to the gas.
Preferably, the housing of the device is grounded.
Preferably, the apparatus has an air inlet for charging the reaction mass into the first electric field reaction chamber and an air outlet for removing the reacted mass.
Preferably, a condensation separator is arranged outside the device and communicated with the air outlet, and the condensation separator is provided with a liquid outlet and a gas outlet.
The strength of the plasma electric field is related to factors such as applied voltage, distance between positive and negative electrodes, whether dielectric medium is added or not, and the like. Therefore, the person skilled in the art can adjust the above-mentioned characteristics of the electric field device according to the actual production requirement to obtain a stronger electric field or a weaker electric field, so the electric field strength is not particularly limited in the present application.
According to the embodiment of the application, in the first electric field reaction chamber, a central electrode or a central metal rod is arranged at the center of a metal cylinder type reaction chamber or a metal tube type reaction chamber, and is driven by a high-frequency pulse positive voltage or a high-frequency pulse negative voltage, and a corresponding positive electrode or a corresponding negative electrode is respectively arranged on a metal shell or a metal tube of the reaction chamber to form a high-frequency pulse strong electric field. Further, the metal may be selected from metals such as stainless steel.
According to the embodiment of the application, in the second electric field reaction chamber, a central electrode or a central metal rod is arranged at the center of an insulating cylinder type reaction chamber or an insulating tube type reaction chamber, a high-voltage direct-current transformer is used for inputting direct-current high voltage, and a metal tube can be arranged around the insulating cylinder or the insulating tube of the reaction chamber as an anode and connected with the device shell to the ground. The internal electrons within this electric field may be decelerated by the barrier, forming a negative electric field of the barrier. Or, for the second electric field is a high-voltage direct current negative electric field, when a high-voltage alternating current transformer is adopted to generate a high-voltage direct current discharge electric field, when the radius of the discharge tube is smaller, in order to avoid short circuit caused by gas breakdown of a narrow gap between high-voltage electrodes, an insulating material lining, such as glass, silica gel, ceramic and other materials, preferably glass, can be added into the reaction chamber, so that the collision probability of molecules and electrons is enhanced, and the reaction yield is improved.
Preferably, the high-frequency pulse high-voltage positive electric field and the high-voltage direct current negative electric field are arranged up and down, the electric field into which the gas is firstly introduced is arranged at the lower part, namely the lower part of the device, the electric field into which the gas is introduced is arranged at the upper part, namely the upper part of the device, the gas inlet is arranged at the bottom of the device, and the gas outlet is arranged at the top of the device. However, the reactor may be arranged in reverse and may have no effect on the chemical reaction.
Preferably, the diameters and the number of the metal cylindrical reaction chambers and the metal tubular reaction chambers are not particularly limited, and may be any conventional choice by those skilled in the art, for example, 1 metal cylindrical reaction chamber may be used, or more than 2 metal cylinders or metal tubes may be used to form the reaction tube array as shown in fig. 1; when a plurality of metal cylinders or metal pipes are selected, they have no influence on each other, so that the arrangement manner thereof is not particularly limited, and may be appropriately selected according to the size and direction of the apparatus.
Preferably, the number of metal cylindrical reaction chambers or metal tubular reaction chambers in each electric field section is one or more, and a plurality of metal cylindrical reaction chambers or metal tubular reaction chambers are configured to be arranged together to form a cylinder or tubular array.
Preferably, the diameter of the metal cylinder reaction chamber or the metal tube reaction chamber is not particularly limited, and for example, a metal cylinder or a metal tube with a larger diameter (for example, 70mm or more) may be used, or a metal cylinder or a metal tube with a larger number and a smaller diameter (for example, 30-70 mm) may be used; the specific selection also needs to be reasonably selected according to the electric field intensity and the amount of the gas to be treated.
It is also known to those skilled in the art that the relative size of the diameters of the metal cylinders or tubes also affects the strength of the electric field within the reaction chamber. For example, under a certain external power supply high voltage, when a central electrode or a central metal rod is arranged at the center of the metal cylinder type reaction chamber or the metal tube type reaction chamber, and a counter electrode or a counter metal rod is arranged on the outer wall of the metal cylinder type reaction chamber or the metal tube type reaction chamber, if a metal cylinder or a metal tube with a larger size is selected, the positive and negative electrode distances of an electric field are larger than those of the metal cylinder or the metal tube with a smaller size, so that the intensity of the electric field inside the metal cylinder or the metal tube with the smaller size is smaller than that of the electric field formed inside the metal cylinder or the metal tube with the smaller size; moreover, the electric field intensity can be adjusted by introducing a medium; the thinner insulating medium layer is added into the electric field with weaker electric field strength, so that the electric field strength of the electric field can be enhanced, and the contact probability of electrons and gas molecules on the medium surface can be increased; therefore, the electric field intensity in the first electric field and the second electric field can be reasonably designed by a person skilled in the art according to the diameter of the metal cylinder type reaction chamber or the metal tube type reaction chamber, the dielectric constant of the insulating medium substance, the voltage of the external power supply and other factors.
Preferably, a baffle plate is arranged between the upper and lower bottom surfaces of the plasma electric field unit and the device shell to block and seal the gas passage only.
Preferably, the number of the central electrodes is one or more, and the electrodes may be, for example, serrated tip electrodes.
In some examples, the electrode is a linear or needle-shaped element with a sharp point at the tip of the electrode. The sharp point provides a very high charge region around it. The electrode may be nickel, iron, steel, tungsten, carbon or platinum. The present application is not limited to a specific type of electrode material, but any material that can form corona discharge to generate electrons may be used.
The electrodes within the reaction chamber generate electrons by forming a high frequency pulsed positive or negative electric field at the electrode tips. The electrons are generated in the corona at the electrode tip. These electrons are adsorbed on chemical gas molecules around the tip of the electrode, and in the electric field device of the present application, energy of about 4-6eV is required for electrons to migrate from the electrode surface for a metallic material suitable as an electrode in the device. The electrodes may be of the following materials: steel, nickel, iron, tungsten, carbon or platinum. The electrode material of the present application is not particularly limited, and any material capable of forming corona to generate electrons may be used.
The electrode may also be coated with a metal catalyst, useful noble metal catalysts are: gold, nickel, rhodium, cobalt, phosphorus, cesium and platinum. Any noble metal catalyst capable of generating electrons may be used.
Preferably the shape of the electrode may be needle-shaped or linear. If the electrode has a sharp point, the potential difference of the gas adjacent to the sharp point will be much higher than at other locations around the electrode. Eventually, the generated high potential electronegative ions will transfer charge to adjacent low potential regions, which will recombine to form gas molecules.
The principle and arrangement of the metal rods are preferably the same as those of the electrodes.
Preferably the metal rod is selected from thin metal rods.
Other sources that provide electrons with sufficient energy to transfer to the gas may also be used in the present application. Electronegative gas ions may also be generated by other non-thermal or thermal plasma techniques or negative ion sources, including high frequency methods such as radio frequency plasma, microwave plasma inductively coupled plasma, and the like, such as Electron Beam (EB). Any method that produces electronegative gas ions of sufficient energy to react with the gas may be used in the present application.
In some examples, when the product mixture generated by the electric field device contains a large amount of water vapor in addition to ethanol, the product mixture is introduced into a condensation separator for gas-liquid separation, and the gas containing residual methane and other gases which cannot be condensed are recycled to participate in reforming, and the liquid containing ethanol, organic mixture and water is separated from the gas and conveyed to the next working section, such as an atmospheric rectification tower for rectification, so as to separate ethanol and other organic matters.
According to the technical scheme of the application, the device also comprises a device for preparing methanol gas and/or a device for preparing water vapor.
According to the technical scheme of the application, the device further comprises a device for condensing the product and collecting the liquid-phase product. Still further, the apparatus also includes a means for separating and purifying the liquid phase product.
According to the technical scheme of the application, each unit, each device and each collector are connected through pipelines.
The application also provides application of the device in organic matter synthesis. Preferably, the raw material for synthesizing the organic matters is raw material gas containing methanol gas. Preferably, the organic matter includes at least one of ethanol, ethyl acetate, acetic acid, isopropyl alcohol, methylal, acetylene, toluene, etc.
The above-mentioned devices may be used in combination, for example, in series, in the synthesis of organic substances.
The application has the beneficial effects that:
the application adopts the normal-pressure electric field chemical reactor technology at normal temperature (the normal temperature refers to the normal temperature in the chemical sense, namely the temperature is between minus 20 ℃ and 200 ℃), and can respectively adopt methanol gas, methanol gas and water vapor or methanol gas and CO 2 And optionally water vapor, as a feedstock, to directly synthesize high value organics such as ethanol (about 6000 yuan/ton price), methylal (about 3500 yuan/ton price), ethyl acetate (about 5000 yuan/ton price), and acetylene, oxygen, and hydrogen. The method can completely upgrade and process the low-value industrial methanol to obtain high-value organic raw materials which are urgently needed in the market, and has excellent market application prospect.
The application adopts the plasma electric field unit which at least contains one high-voltage direct current negative electric field, and can adjust the feeding condition of raw material gas and the selection of the latter electric field according to the synthesis condition of the product in the former electric field and the finally obtained product, so that the synthesis of the organic matters is more flexible and the final product with high yield can be obtained.
Wherein, CO can be added into the mixture gas of methanol and water vapor 2 The raw materials are reformed to produce organic matters, and free CO discharged by coal chemical enterprises can be directly utilized 2 The carbon element in the furnace is used as a waste material, so that the carbon emission is reduced, the raw material cost is reduced, and the economic benefit is increased.
The method is expected to comprehensively replace the old and low-efficiency biological grain ethanol fermentation process, and a large amount of grains can be saved.
On the other hand, the method has low cost, and the electric energy consumption is about 1.0-1.5kWh/kg and the power consumption is less when 1kg of organic mixed product is obtained. If the average electricity charge is 0.7 yuan, the consumption isThe electrical cost is about 1000 yuan/ton of organic mixed product. For example, when the method of the application is used for assisting the ethanol production process by adding water vapor and carbon dioxide into methanol by using an electric field, CO can be utilized 2 The carbon element in the catalyst replaces the carbon element in the methanol, and CO discharged by a conversion section in the methanol industry is utilized 2 The amount of methanol is reduced as much as possible, and the economic benefit is improved, for example, 0.7 ton of methanol (about 2000 yuan/ton) and 1-3 ton of CO are needed for producing 1 ton of ethanol (about 6000 yuan/ton) 2 . If the average electricity price is about 0.7 yuan/degree electricity, the process consumes about 1.0 degree/kg of product, the electricity cost per ton of ethanol is about 2800 yuan/ton, and the potential profit is about 3200 yuan/ton. Obviously, the method can utilize free CO discharged in large quantity 2 As a part of methanol raw material, the cost is greatly reduced, and the economic benefit is huge.
The process of the application is initiated by the applicant, and has not been reported to be any process for directly producing organic matters, especially ethanol, by using methanol gas at normal temperature and normal pressure. Therefore, the method has unique market application value, and the future market scale of the ethanol is expected to be considerable.
Drawings
FIG. 1 is a schematic diagram of an apparatus for producing organic matters by using a plasma electric field to assist methanol provided in example 1;
reference numerals: 110-top opening, 111-glass tube reaction chamber, 112-second center electrode, 121-metal tube, 113-reactor inlet, 115-first cable electrode distribution plate, 116-first center electrode, 117-device body, 118-stainless steel tube reaction chamber, 120-opposing ground electrode, 123-second cable electrode distribution plate, 124-first port, 125-second port, 133-condenser.
FIG. 2 is a GCMS analysis spectrum of the ethanol mixture obtained in example 2.
FIG. 3 is a GCMS analysis spectrum of the mixture obtained in example 3-1.
FIG. 4 is a GCMS analysis spectrum of the mixture obtained in examples 3-5.
Detailed Description
The technical scheme of the application will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
An apparatus for producing organic matters by assisting methanol with a plasma electric field as shown in fig. 1, the apparatus comprising: the device body 117 and set up a plasma electric field unit in the device body 117, the device body 117 is the metal cylinder, and the plasma electric field unit includes first electric field reaction room and second electric field reaction room, and electric field type in first electric field reaction room and the second electric field reaction room can be adjusted according to actual production needs.
In fig. 1, the first electric field reaction chamber is a pure stainless steel tube type reaction chamber 118, and the second electric field reaction chamber is a double-layer reaction chamber 111 with an outer stainless steel tube and an additional lining glass tube. Wherein, the stainless steel tube type reaction chamber can use one or two parallel stainless steel tubes (not shown in the figure), the inner diameter of the stainless steel tube is 73+/-2 mm, and the length of the stainless steel tube is about 1.0-1.5m; the second electric field reaction chamber contained a glass liner having a thickness of about 2.+ -.1 mm within the stainless steel tube.
The first electric field is a high-frequency high-voltage direct current positive electric field, and the second electric field is a high-voltage direct current negative electric field. A first central electrode 116 is arranged in the center of the stainless steel tube type reaction chamber 118, a grounding electrode 120 which is connected with the ground is arranged opposite to the first central electrode, and the stainless steel tube type reaction chamber is driven by high-frequency pulse positive voltage to form a strong positive electric field; a second center electrode 112 is provided at the center in the glass tube type reaction chamber 111, and a metal tube 121 is provided outside the glass tube as a protection and positive electrode and is grounded to the metal housing of the device body, forming a weak negative field. The first center electrode 116 and the second center electrode 112 are both stainless steel saw tooth electrodes. The metal housing of the device body 117 may be carbon steel, stainless steel or other suitable metal materials. Positive high-frequency pulse high-voltage electricity is sent to the first central electrode 116 through the first cable electrode distribution plate 115 to discharge, and negative direct-current high-voltage electricity is sent to the second central electrode 112 through the second cable electrode distribution plate 123 to discharge.
In the operation process, when the first central electrode 116 is electrified by a high-frequency pulse high-voltage electric field source, positive corona is formed at the tip of the first central electrode 116 so as to form high-frequency positive electric field discharge, high-energy electrons hit gas molecules, and when the second central electrode 112 is electrified by a negative high-voltage direct-current electric field source, negative corona is formed at the tip of the second central electrode 112 so as to form negative corona field discharge, and the negative corona field discharge is mainly used for reduction and reforming reactions; specifically, the electrons sprayed by the central electrode are directly sprayed on the wall of the lining glass tube and blocked, so that the running speed is reduced, the free electrons which are blocked and decelerated are more easily captured by polar gas molecules in the reaction chamber, energy is obtained from the electrons, the electrons and other molecules are more effectively interacted and reformed into product molecules, and the combination of the product molecules is more effectively promoted.
A bottom opening 113 is provided in the apparatus body, the bottom opening 113 delivering the gas mixture into the plasma electric field unit within the apparatus. Some gas molecules may receive discharged electrons in a high frequency pulsed high voltage positive dc discharge electric field to decompose. A top opening 110 is provided in the device body, and when the product is removed through the top opening 110 and vapor-liquid separation is achieved by the condenser 133, wherein liquid can be vented through the second port 125 and gas can be vented through the first port 124. The first electric field and the second electric field are arranged up and down, the first electric field is firstly introduced into the gas and is arranged at the lower part, namely the lower part of the device, the second electric field is introduced into the gas and is arranged at the upper part, namely the upper part of the device, the gas inlet is arranged at the bottom of the device, and the gas outlet is arranged at the top of the device.
When the product mixture generated by the electric field device contains a large amount of water vapor in addition to ethanol, the product mixture is introduced into the condenser 133 for gas-liquid separation.
The apparatus may further comprise a product collector, the product outlet of the second electric field reaction chamber being connected to the product collector. The final product can be obtained into ethanol mixed solution at room temperature through a water condenser, and some gases after gas-liquid separation can be obtained into different gas products (such as hydrogen, oxygen, acetylene and CO) through a traditional gas pressure swing adsorption separation process.
Example 2
The method for synthesizing organic matters by adopting the plasma electric field assisted methanol of the device in the embodiment 1 comprises the following steps: three devices connected in series are adopted, methanol gas and steam with the molar ratio of 1:1 are used as raw material gas, the raw material gas firstly enters a first electric field (namely a high-frequency pulse positive high-voltage electric field, the frequency of the high-frequency pulse is 10kHz, the voltage is 10-20 kV) in a first device, the raw material gas is decomposed and reformed in a positive electric field under the condition of 115 ℃ to obtain mixed ionized gas, the mixed ionized gas is introduced into a second electric field (namely a high-voltage direct-current negative electric field, the voltage is 10-20 kV) in the device to be synthesized, and after condensation, products sequentially enter a second device and a third device, and the operation in the first device is repeated to obtain a final product.
In the preparation process, the decomposition and synthesis temperatures are 115 ℃.
The organic mixture contained methanol, ethanol, methylal and ethyl acetate as measured by GCMS (as shown in figure 2).
Example 3
The apparatus used in examples 3-1 to 3-6 was the same as that used in example 1, but the first electric field was not turned on in any of examples 3-1 to 3-5, and the first electric field "high frequency positive electric field (Table 1)" in examples 3-6 was a high frequency high voltage positive electric field. The second field "dc negative field (table 1)" in each example is a high voltage dc negative field. The feed gas, electric field conditions and main composition of the product of each example are shown in table 1.
TABLE 1
The mixture obtained in example 3-1 contained 31wt% ethanol, 62wt% methanol and 4wt% other substances (ethyl acetate, toluene, carbopol) as measured by GCMS (see FIG. 3).
The mixture obtained in examples 3-5 contained 65wt% ethanol, 30wt% methanol and 2wt% other substances (acetic acid, etc.) as measured by GCMS (as shown in FIG. 4).
Example 4
The same apparatus as in example 1 was used for examples 4-1 to 4-4 and examples 4-7, but the first electric field was not turned on in any of examples 4-1 to 4-4 and examples 4-7.
The first electric fields "high frequency negative electric field (table 2)" of examples 4-5 and examples 4-6 are both high frequency high voltage negative electric fields. The second field "dc negative field (table 2)" in each example is a high voltage dc negative field.
The feed gas, electric field conditions and main composition of the product of each example are shown in table 2.
TABLE 2
The embodiments of the present application have been described above. However, the present application is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (4)
1. A method for synthesizing organic matters by using plasma electric field to assist methanol, which is characterized by comprising the following steps: the method comprises the steps of sending raw material gas into a plasma electric field unit for decomposition and synthesis to obtain an organic mixture mainly containing ethanol and acetic acid, wherein only one electric field in the plasma electric field unit is a high-voltage direct current negative electric field;
the raw material gas is methanol gas, water vapor and CO with the mol ratio of 2.31:3.58:4.9 2 Is a mixed gas of (1);
the voltage of the high-voltage direct current negative field is maintained at 10-20kV;
the decomposition and synthesis temperatures are the same or different, the decomposition and synthesis temperatures being greater than 100 ℃ and no greater than 150 ℃.
2. A method for synthesizing organic matters by using plasma electric field to assist methanol, which is characterized by comprising the following steps: the method comprises the steps of sending raw material gas into a plasma electric field unit for decomposition and synthesis to obtain an organic mixture mainly containing ethyl acetate, wherein the number of electric fields in the plasma electric field unit is two, a first electric field is not started, and a second electric field is a high-voltage direct current negative electric field;
the raw material gas is methanol gas, water vapor and CO with the mol ratio of 3:7.67:3.67 2 Is a mixed gas of (1);
the voltage of the high-voltage direct current negative field is maintained at 10-20kV;
the decomposition and synthesis temperatures are the same or different, the decomposition and synthesis temperatures being greater than 100 ℃ and no greater than 150 ℃.
3. The method according to any one of claims 1-2, wherein the method further comprises: the organic mixture obtained from the plasma electric field is condensed to obtain a liquid phase product.
4. A method according to claim 3, characterized in that the method further comprises: and separating and purifying the liquid phase product, wherein the components are collected independently through separation and purification.
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| CN102417438A (en) * | 2011-10-27 | 2012-04-18 | 大连理工大学 | Method for converting methanol |
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| CN104003845A (en) * | 2014-06-11 | 2014-08-27 | 大连理工大学 | Method for conversion of methanol |
| CN109200969A (en) * | 2017-07-03 | 2019-01-15 | 海加控股有限公司 | The method of low-temperature plasma dual field aid in treatment carbonated and/or CO gas synthesis compound |
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