CN111718240B - Method for quickly converting formaldehyde into methanol - Google Patents

Method for quickly converting formaldehyde into methanol Download PDF

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CN111718240B
CN111718240B CN202010606942.XA CN202010606942A CN111718240B CN 111718240 B CN111718240 B CN 111718240B CN 202010606942 A CN202010606942 A CN 202010606942A CN 111718240 B CN111718240 B CN 111718240B
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methanol
phosphine
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CN111718240A (en
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黄涛
宋东平
藏颖
邓锦涛
苏治宇
张克
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Guizhou Hongrong Yu New Energy Technology Co ltd
Sichuan Jincheng Ruizhi Internet Technology Co ltd
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Changshu Institute of Technology
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    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
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    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention discloses a method for quickly converting formaldehyde into methanol, which comprises the following steps: respectively weighing activated carbon powder and tri (3-hydroxypropyl) phosphine, mixing and aging for 12-36 hours, and air-drying to obtain a carbon phosphine catalytic material; filling a carbon phosphine catalytic material between a low-temperature plasma processor medium baffle and a low-voltage electrode, firstly introducing argon for 5-15 min, then introducing a formaldehyde gas, hydrogen and argon mixed gas, simultaneously performing low-temperature plasma irradiation, and recovering the gas of the filled carbon phosphine catalytic material through condensation to obtain a methanol solution. The preparation method is simple in process, other chemical reagents are not required to be added in the formaldehyde reduction process, continuous conversion of formaldehyde gas is realized in a mode of introducing formaldehyde from the front end and recovering methanol from the rear end, the highest conversion rate of formaldehyde is 99.75%, and the highest purity of methanol can reach 98.24%.

Description

Method for quickly converting formaldehyde into methanol
Technical Field
The invention relates to the field of harmless disposal and resource utilization of hazardous pollutants, in particular to a method for quickly converting formaldehyde into methanol.
Background
Formaldehyde released by various interior materials is one of the most frequent pollutants that people come into contact with. Formaldehyde is a carcinogen and one of the most major causes of respiratory diseases in humans. The related indoor decoration standard of China stipulates that the concentration of formaldehyde gas in indoor air should be lower than 0.08mg/m3. If the formaldehyde is exposed to a high-concentration formaldehyde environment for a long time, the severe reaction of a human mucosal system can be caused, and the human cells can also be obviously mutated. Formaldehyde has stronger reducibility and better water solubility, so the prior disposal of formaldehyde gas mainly comprises physical adsorption and oxidation removal. The physical adsorption technology does not really realize the harmless treatment of formaldehyde, but transfers the formaldehyde to materials. This means that the technique is not only at risk of secondary contamination but is limited by the adsorption properties of the material itself and the material post-processing capacity. The oxidation technology can thoroughly oxidize the formaldehyde into carbon dioxide and water, but the oxidation technology is a technology for releasing the carbon dioxide and does not accord with the current green development trend of carbon fixation and emission reduction.
Therefore, in summary, the development of new technologies capable of rapidly converting formaldehyde gas into other energy materials is the key to solve the above-mentioned contradiction.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a method for realizing continuous conversion of formaldehyde gas in a mode of introducing formaldehyde into the front end and recovering methanol from the rear end, wherein the method is simple in process, and other chemical reagents are not required to be added in the formaldehyde reduction process.
In order to solve the technical problem, the invention adopts the following technical scheme: a process for the rapid conversion of formaldehyde to methanol comprising the steps of:
1) respectively weighing activated carbon powder and tri (3-hydroxypropyl) phosphine, mixing and aging for 12-36 hours, and air-drying to obtain a carbon phosphine catalytic material;
2) filling a carbon phosphine catalytic material between a low-temperature plasma processor medium baffle and a low-voltage electrode, firstly introducing argon for 5-15 min, then introducing a formaldehyde gas, hydrogen and argon mixed gas, simultaneously performing low-temperature plasma irradiation, and recovering the gas of the filled carbon phosphine catalytic material through condensation to obtain a methanol solution.
Wherein the activated carbon powder in the step 1) is sieved by a 200-400-mesh sieve.
Wherein the solid-to-liquid ratio of the activated carbon powder and the tris (3-hydroxypropyl) phosphine in the step 1) is 0.5-1.5: 1 mg/mL.
Wherein the volume ratio of the formaldehyde gas, the hydrogen gas and the argon gas in the mixed gas in the step 2) is 2-6: 2-4: 100.
Wherein, the low-temperature plasma irradiation action voltage in the step 2) is 3-30 kV.
Wherein the condensation recovery temperature in the step 2) is 10-30 ℃.
The low-temperature plasma processor in the step 2) comprises an electrode plate, a medium baffle and a polytetrafluoroethylene reaction tank, wherein the electrode plate comprises a high-voltage electrode plate and a low-voltage electrode plate, the high-voltage electrode plate is connected with the high-voltage end of the low-temperature plasma power supply, and the low-voltage electrode is connected with the low-voltage end of the low-temperature plasma power supply. The high-voltage electrode plate and the low-voltage electrode plate are made of stainless steel, the medium baffle plate is made of ceramic or glass, a low-temperature plasma power supply is provided by Nanjing Suman plasma technology Co., Ltd, and the medium baffle plate and the polytetrafluoroethylene reaction tank are provided by Xian Ding fluid technology Co., Ltd.
The reaction mechanism is as follows: in the aging process, the tri (3-hydroxypropyl) phosphine can be effectively loaded on the surfaces of the active carbon particles through electrostatic adsorption and capillary action. The oxygen in the apparatus was removed by passing argon before switching on the low temperature plasma. During the low temperature plasma irradiation process, the high energy electron beam can induce hydrogen gas electrolysis to generate hydrogen radicals. The hydrogen radicals can react with formaldehyde gas to promote the reduction of formaldehyde to methanol. Meanwhile, the carbon phosphine catalytic material can capture formaldehyde gas and promote the conversion of formaldehyde to methanol through the catalytic action of tris (3-hydroxypropyl) phosphine. The high-energy electron beam can accelerate the heterogeneous catalysis process of the tri (3-hydroxypropyl) phosphine. A large amount of heat is released in the low-temperature plasma irradiation process, so that the generated methanol leaves the plasma reactor in a gas form and is converted into liquid through condensation to realize recovery.
Has the advantages that: the preparation method is simple in process, other chemical reagents are not required to be added in the formaldehyde reduction process, continuous conversion of formaldehyde gas is realized in a mode of introducing formaldehyde from the front end and recovering methanol from the rear end, the highest conversion rate of formaldehyde is 99.75%, and the highest purity of methanol can reach 98.24%.
Drawings
FIG. 1 is a flow chart of the preparation process of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples. Referring to fig. 1, the low-temperature plasma processor of the invention comprises a polytetrafluoroethylene reaction tank, a high-voltage electrode plate (connected with the high-voltage end of a low-temperature plasma power supply), a medium baffle plate and a low-voltage electrode plate (connected with the low-voltage end of the low-temperature plasma power supply). The high-voltage electrode plate and the low-voltage electrode plate are made of stainless steel, the medium baffle plate is made of ceramic, a low-temperature plasma power supply is provided by Nanjing Suman plasma technology, and the medium baffle plate and the polytetrafluoroethylene reaction tank are provided by the fluid technology, Inc. of the Xian Ding industry.
Example 1 influence of solid-liquid ratio of activated carbon powder and tris (3-hydroxypropyl) phosphine on Formaldehyde conversion
Grinding the activated carbon, and sieving with a 200-mesh sieve to obtain activated carbon powder. Respectively weighing activated carbon powder and tris (3-hydroxypropyl) phosphine according to solid-to-liquid ratios of 0.25: 1mg/mL, 0.35: lmg/mL, 0.45: 1mg/mL, 0.5: 1mg/mL, 1.0: 1mg/mL, 1.5:1mg/mL, 1.55: 1mg/mL, 1.65: 1mg/mL and 1.75: 1mg/mL, mixing, aging for 12 hours, and air-drying to obtain nine groups of carbon phosphine catalytic materials. Nine groups of carbon phosphine catalytic materials are filled between a low-temperature plasma processor medium baffle and a low-voltage electrode plate as filling materials, then argon is introduced into a polytetrafluoroethylene reaction tank for 5min, then formaldehyde gas, hydrogen and argon mixed gas is introduced, low-temperature plasma irradiation is carried out simultaneously, the gas of the filled carbon phosphine catalytic materials is condensed and recovered, and nine groups of methanol solutions are obtained, wherein the volume ratio of the formaldehyde gas to the hydrogen to the argon in the mixed gas is 2: 100, the low-temperature plasma irradiation action voltage is 3kV, and the condensation recovery temperature is 10 ℃.
And (3) detecting the concentration of formaldehyde: according to a second part of a public place sanitation detection method of GB/T18204.2-2014: chemical pollutants "uses phenol reagent spectrophotometry to detect formaldehyde concentration.
Calculation of the formaldehyde conversion: the formaldehyde conversion is calculated according to equation (1), where c0The concentration of formaldehyde at the inlet of the low-temperature plasma reactor is (mg/m)3)，crIs the formaldehyde concentration (mg/m) at the outlet of the low-temperature plasma reactor3)。
Figure BDA0002559555070000031
And (3) detecting the concentration of methanol: the concentration of methanol in the liquid phase was measured by gas chromatography for measuring methanol in water (DB 61/T971-2015).
Calculation of methanol formation rate: the methanol formation rate was calculated according to equation (2) wherein coThe concentration of formaldehyde at the inlet of the low-temperature plasma reactor is (mg/m)3)，cstIs the concentration of methanol in the solution (mg/m)3)。
Figure BDA0002559555070000032
The test results of the examples of the present invention are shown in Table 1.
TABLE 1 influence of solid-liquid ratio of activated carbon powder and tris (3-hydroxypropyl) phosphine on Formaldehyde conversion
Figure BDA0002559555070000033
Figure BDA0002559555070000041
As can be seen from table 1, when the solid-to-liquid ratio of activated carbon powder and tris (3-hydroxypropyl) phosphine is less than 0.5: 1mg/mL (as in table 1, the solid-to-liquid ratio of activated carbon powder and tris (3-hydroxypropyl) phosphine is 0.45: 1mg/mL, 0.35: 1mg/mL, 0.25: 1mg/mL and lower ratios not listed in table 1), the adsorption potential is significantly reduced due to too much tris (3-hydroxypropyl) phosphine loaded on the surface of activated carbon powder, so that the formaldehyde gas capturing capability of the carbon-phosphine catalytic material is reduced, and the formaldehyde conversion rate and the methanol generation rate are both significantly reduced as the solid-to-liquid ratio of activated carbon powder and tris (3-hydroxypropyl) phosphine is reduced. When the solid-to-liquid ratio of the activated carbon powder to the tris (3-hydroxypropyl) phosphine is equal to 0.5-1.5: 1mg/mL (as shown in Table 1, the solid-to-liquid ratio of the activated carbon powder to the tris (3-hydroxypropyl) phosphine is 0.5: 1mg/mL, 1: 1mg/mL, 1.5: 1mg/mL), the carbon phosphine catalytic material can capture formaldehyde gas and promote the conversion of formaldehyde to methanol through the catalysis of the tris (3-hydroxypropyl) phosphine. The high-energy electron beam can accelerate the heterogeneous catalysis process of the tri (3-hydroxypropyl) phosphine. Finally, the formaldehyde conversion rate is greater than 83%, the methanol generation rate is greater than 81%, and when the solid-to-liquid ratio of the activated carbon powder to the tris (3-hydroxypropyl) phosphine is greater than 1.5:1mg/mL (as shown in table 1, the solid-to-liquid ratio of the activated carbon powder to the tris (3-hydroxypropyl) phosphine is 1.55: 1mg/mL, 1.65: 1mg/mL, 1.75: 1mg/mL and higher ratios not listed in table 1), the tris (3-hydroxypropyl) phosphine loaded on the surface of the activated carbon powder is less, and the catalytic performance of the carbon phosphine catalytic material is reduced, so that the formaldehyde conversion rate and the methanol generation rate are both remarkably reduced along with the further increase of the solid-to-liquid ratio of the activated carbon powder to the tris (3-hydroxypropyl) phosphine. In general, combining benefits and costs, the conversion of formaldehyde to methanol is most favored when the solid-to-liquid ratio of activated carbon powder to tris (3-hydroxypropyl) phosphine is equal to 0.5-1.5: 1 mg/mL.
Example 2 influence of Formaldehyde gas, Hydrogen, argon volume ratio on Formaldehyde conversion
And grinding the activated carbon, and sieving the ground activated carbon by using a 300-mesh sieve to obtain activated carbon powder. Respectively weighing the activated carbon powder and the tri (3-hydroxypropyl) phosphine according to the solid-to-liquid ratio of the activated carbon powder to the tri (3-hydroxypropyl) phosphine of 1.5:1mg/mL, mixing, aging for 24 hours, and air-drying to obtain the carbon phosphine catalytic material. Filling a carbon phosphine catalytic material as a filling material between a low-temperature plasma processor medium baffle and a low-voltage electrode, then introducing argon gas for 10min in a polytetrafluoroethylene reaction tank, then introducing mixed gas of formaldehyde gas, hydrogen gas and argon gas, and simultaneously performing low-temperature plasma irradiation, and recovering the gas of the filled carbon phosphine catalytic material by condensation to obtain a methanol solution, wherein the volume ratio of the formaldehyde gas, the hydrogen gas and the argon gas in the mixed gas is respectively 1: 2: 100, 1.5: 2: 100, 1.8: 2: 100, 2: 1: 100, 2: 1.5: 100, 2: 1.8: 100, 2: 100, 2: 3: 100, 2: 4:100, 4: 2: 100, 4: 3: 100, 4:100, 6: 2: 100, 6: 3: 100, 6: 4:100, 6: 5: 100, 6.5: 100, 6: 100, 6.5: 4:100, 7: 4:100, 8: 4:100, low-temperature plasma irradiation action voltage of 16.5kV, and condensation recovery temperature of 20 ℃.
The measurement of formaldehyde concentration, the calculation of formaldehyde conversion ratio, the measurement of methanol concentration and the calculation of methanol production ratio were the same as in example 1. The test results of the inventive examples are shown in table 2.
TABLE 2 influence of Formaldehyde gas, Hydrogen, argon volume ratio on Formaldehyde conversion
Figure BDA0002559555070000051
As can be seen from table 2, when the volume ratio of formaldehyde gas, hydrogen gas and argon gas is less than 2: 100 (as in table 2, the volume ratio of formaldehyde gas, hydrogen gas and argon gas is 2: 1.8: 100, 2: 1.5: 100, 2: 1: 100, 1.8: 2: 100, 1.5: 2: 100, 1: 2: 100 and lower ratios not listed in table 2), the formaldehyde gas and hydrogen gas in the mixed gas are less, the generation amount of hydrogen radicals is reduced, the formaldehyde gas captured by the phosphine catalyst material is reduced, the formaldehyde reduction efficiency is reduced, and the formaldehyde conversion rate and the methanol generation rate are both significantly reduced as the volume ratio of formaldehyde gas, hydrogen gas and argon gas is reduced. When the volume ratio of formaldehyde gas, hydrogen gas and argon gas is 2-6: 2-4: 100 (as shown in table 2, the volume ratio of formaldehyde gas, hydrogen gas and argon gas is 2: 100, 2: 3: 100, 2: 4:100, 4: 2: 100, 4: 3: 100, 4:100, 6: 2: 100, 6: 3: 100 and 6: 4: 100), in the low-temperature plasma irradiation process, the high-energy electron beam can induce hydrogen gas to be electrolyzed to generate hydrogen radicals. The hydrogen radicals can react with formaldehyde gas to promote the reduction of formaldehyde to methanol. Meanwhile, the carbon phosphine catalytic material can capture formaldehyde gas and promote the conversion of formaldehyde to methanol through the catalytic action of tris (3-hydroxypropyl) phosphine. Finally, the conversion rate of formaldehyde is more than 91 percent, and the generation rate of methanol is more than 88 percent. When the volume ratio of formaldehyde gas, hydrogen gas and argon gas is more than 6: 4:100 (as shown in table 2, the volume ratio of formaldehyde gas, hydrogen gas and argon gas is 6: 4.5: 100, 6: 5: 100, 6: 100, 6.5: 4:100, 7: 4:100, 8: 4:100 and higher ratios not listed in table 2), the formaldehyde gas and hydrogen gas are too much, the system load is too large, the generation amount of hydrogen ion free radicals is too much, the catalytic performance of the phosphine catalytic material is reduced, and the formaldehyde conversion rate and the methanol generation rate are both obviously reduced along with the further increase of the volume ratio of formaldehyde gas, hydrogen gas and argon gas. In general, the benefit and cost are combined, and when the volume ratio of formaldehyde gas, hydrogen gas and argon gas is 2-6: 2-4: 100, the conversion of formaldehyde to methanol is facilitated.
EXAMPLE 3 Effect of Low temperature plasma Exposure Voltage on Formaldehyde conversion
Grinding the activated carbon, and sieving with a 400-mesh sieve to obtain activated carbon powder. Respectively weighing the activated carbon powder and the tri (3-hydroxypropyl) phosphine according to the solid-to-liquid ratio of the activated carbon powder to the tri (3-hydroxypropyl) phosphine of 1.5:1mg/mL, mixing, aging for 36 hours, and air-drying to obtain the carbon phosphine catalytic material. Filling a carbon phosphine catalytic material serving as a filling material between a low-temperature plasma processor medium baffle plate and a low-voltage electrode, then introducing argon for 15min into a polytetrafluoroethylene reaction tank, then introducing a formaldehyde gas, hydrogen and argon mixed gas, simultaneously performing low-temperature plasma irradiation, and recovering the gas of the filled carbon phosphine catalytic material through condensation to obtain a methanol solution, wherein the volume ratio of the formaldehyde gas, the hydrogen and the argon in the mixed gas is 6: 4:100, the irradiation action voltage of the low-temperature plasma is respectively 1.5kV, 2kV, 2.5kV, 3kV, 16.5kV, 30kV, 31kV, 33kV and 35kV, and the condensation recovery temperature is 30 ℃.
The measurement of formaldehyde concentration, the calculation of formaldehyde conversion ratio, the measurement of methanol concentration and the calculation of methanol production ratio were the same as in example 1. The test results of the examples of the present invention are shown in Table 3.
TABLE 3 Effect of Low temperature plasma Exposure Voltage on Formaldehyde conversion
Figure BDA0002559555070000061
Figure BDA0002559555070000071
As can be seen from table 3, when the low temperature plasma irradiation action voltage is less than 3kV (as in table 3, the low temperature plasma irradiation action voltage is 2.5kV, 2kV, 1.5kV and lower ratios not listed in table 3), the hydrogen radicals generated by hydrogen electrolysis can be reduced by the high energy electron beam, and the heterogeneous catalytic performance of tris (3-hydroxypropyl) phosphine is weakened, resulting in that the formaldehyde conversion rate and the methanol generation rate are both significantly reduced as the low temperature plasma irradiation action voltage is reduced. When the low-temperature plasma irradiation action voltage is 3-30 kV (as in table 3, the low-temperature plasma irradiation action voltage is 3kV, 16.5kV, 30kV), the high-energy electron beam can induce hydrogen gas to generate hydrogen radicals by electrolysis during the low-temperature plasma irradiation process. The high-energy electron beam can accelerate the heterogeneous catalysis process of the tri (3-hydroxypropyl) phosphine. A large amount of heat is released in the low-temperature plasma irradiation process, so that the generated methanol leaves the plasma reactor in a gas form and is converted into liquid through condensation to realize recovery. Finally, the conversion rate of formaldehyde is more than 92%, and the generation rate of methanol is more than 90%. When the low-temperature plasma irradiation action voltage is greater than 30kV (as shown in table 3, the low-temperature plasma irradiation action voltage is 31kV, 33kV, 35kV and higher ratios not listed in table 3), the electron beam energy released from the high-voltage electrode end of the low-temperature plasma is too high, so that the phosphine catalytic material is damaged, the capturing and catalytic performance of the phosphine catalytic material to formaldehyde gas is reduced, and the formaldehyde conversion rate and the methanol generation rate are both significantly reduced with the further increase of the low-temperature plasma irradiation action voltage. In general, the benefit and the cost are combined, and when the low-temperature plasma irradiation action voltage is equal to 3-30 kV, the conversion of formaldehyde to methanol is facilitated.
Comparative example influence of different low-temperature plasma action atmosphere influences on formaldehyde conversion rate and methanol generation rate
The atmosphere influence of the mixed gas of formaldehyde gas, hydrogen and argon is as follows: grinding the activated carbon, and sieving with a 400-mesh sieve to obtain activated carbon powder. Respectively weighing the activated carbon powder and the tri (3-hydroxypropyl) phosphine according to the solid-to-liquid ratio of the activated carbon powder to the tri (3-hydroxypropyl) phosphine of 1.5:1mg/mL, mixing, aging for 36 hours, and air-drying to obtain the carbon phosphine catalytic material. Filling a carbon phosphine catalytic material serving as a filling material between a low-temperature plasma processor medium baffle and a low-voltage electrode, then introducing argon gas for 15min into a polytetrafluoroethylene reaction tank, introducing a formaldehyde gas, hydrogen gas and argon gas mixed gas, simultaneously performing low-temperature plasma irradiation, and recovering the gas of the filled carbon phosphine catalytic material through condensation to obtain a methanol solution, wherein the volume ratio of the formaldehyde gas to the hydrogen gas to the argon gas in the mixed gas is 6: 4:100, the irradiation action voltage of the low-temperature plasma is 30kV respectively, and the condensation recovery temperature is 30 ℃.
Formaldehyde gas and argon gas mixed gas atmosphere influence: and grinding the activated carbon, and sieving the ground activated carbon with a 400-mesh sieve to obtain activated carbon powder. Respectively weighing the activated carbon powder and the tri (3-hydroxypropyl) phosphine according to the solid-to-liquid ratio of the activated carbon powder to the tri (3-hydroxypropyl) phosphine of 1.5:1mg/mL, mixing, aging for 36 hours, and air-drying to obtain the carbon phosphine catalytic material. Then filling a carbon phosphine catalytic material as a filling material between a low-temperature plasma processor medium baffle and a low-voltage electrode in a polytetrafluoroethylene reaction tank, firstly introducing argon for 15min, then introducing a formaldehyde gas and argon mixed gas, simultaneously performing low-temperature plasma irradiation, and recovering the gas of the filled carbon phosphine catalytic material through condensation to obtain a methanol solution, wherein the volume ratio of the formaldehyde gas to the argon in the mixed gas is 6: 100, the low-temperature plasma irradiation action voltage is 30kV, and the condensation recovery temperature is 30 ℃.
The measurement of formaldehyde concentration, the calculation of formaldehyde conversion ratio, the measurement of methanol concentration and the calculation of methanol production ratio were the same as in example 1. The test results of the examples of the present invention are shown in Table 4.
TABLE 4 influence of different low-temperature plasma reaction atmosphere effects on the conversion of formaldehyde and the formation of methanol
Figure BDA0002559555070000081
As can be seen from Table 4, the formaldehyde conversion rate and the methanol generation rate achieved when the low-temperature plasma reaction atmosphere is a mixed gas atmosphere of formaldehyde gas, hydrogen gas and argon gas are obviously higher than those achieved when the mixed gas atmosphere of formaldehyde gas and argon gas is adopted. During the low temperature plasma irradiation process, the high energy electron beam can induce hydrogen gas electrolysis to generate hydrogen radicals. The hydrogen radicals can react with formaldehyde gas to promote the reduction of formaldehyde to methanol.

Claims (7)

1. A method for rapidly converting formaldehyde into methanol is characterized by comprising the following steps:
1) respectively weighing activated carbon powder and tri (3-hydroxypropyl) phosphine, mixing and aging for 12-36 hours, and air-drying to obtain a carbon phosphine catalytic material;
2) filling a carbon phosphine catalytic material between a medium baffle and a low-voltage electrode of a low-temperature plasma processor, firstly introducing argon for 5-15 min, then introducing a formaldehyde gas, hydrogen and argon mixed gas, simultaneously performing low-temperature plasma irradiation, and recovering the gas of the filled carbon phosphine catalytic material through condensation to obtain a methanol solution.
2. The method for rapidly converting formaldehyde into methanol according to claim 1, wherein the activated carbon powder in the step 1) is sieved by a 200-400 mesh sieve.
3. The method for rapidly converting formaldehyde into methanol according to claim 1, wherein the solid-to-liquid ratio of the activated carbon powder in the step 1) and the tris (3-hydroxypropyl) phosphine is 0.5-1.5: 1 mg/mL.
4. The method for rapidly converting formaldehyde into methanol according to claim 1, wherein the volume ratio of the formaldehyde gas, the hydrogen gas and the argon gas in the mixed gas in the step 2) is 2-6: 2-4: 100.
5. The method for rapidly converting formaldehyde into methanol according to claim 1, wherein the low-temperature plasma irradiation applied voltage in the step 2) is 3-30 kV.
6. The method for rapidly converting formaldehyde into methanol according to claim 1, wherein the condensation recovery temperature in the step 2) is 10-30 ℃.
7. The method for rapidly converting formaldehyde into methanol according to claim 1, wherein the low-temperature plasma processor of step 2) comprises electrode plates, a medium baffle plate and a polytetrafluoroethylene reaction tank, wherein the electrode plates comprise a high-voltage electrode plate and a low-voltage electrode plate, the high-voltage electrode plate is connected with the high-voltage end of the low-temperature plasma power supply, and the low-voltage electrode is connected with the low-voltage end of the low-temperature plasma power supply.
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