CN109293540A - Utilize the technique of coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide - Google Patents
Utilize the technique of coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide Download PDFInfo
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- CN109293540A CN109293540A CN201811335101.9A CN201811335101A CN109293540A CN 109293540 A CN109293540 A CN 109293540A CN 201811335101 A CN201811335101 A CN 201811335101A CN 109293540 A CN109293540 A CN 109293540A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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Abstract
The present invention relates to technical field of waste gas treatment, specifically disclose a kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide, prepare vulcanized sodium；By dimethyl ether and H2S produces the sulfur trioxide in sulfuric acid apparatus and carries out synthetic reaction production dimethyl suflfate crude product；Dimethyl suflfate purification；Prepare methyl sulfide；Pure nitric oxide is obtained with sodium nitrite and dilute sulfuric acid；Dimethyl sulfoxide is prepared, dimethyl sulfoxide is known as " alembroth ", and the current market price is about 10200 yuan/ton, relative to the H for facing environmental protection treatment2S exhaust gas, nitrite waste water etc., appreciation space are apparent.
Description
Technical field
It is specifically a kind of to be produced using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide the present invention relates to technical field of waste gas treatment
The technique of dimethyl sulfoxide.
Background technique
For a long time, not only technologic stabilization and equipment of puzzlement domestic coal-ethylene glycol enterprise is intact
Rate, it is prior, it is environmental issue, the H discharged in synthesis gas production process2In S gas and dimethyl oxalate production process
High-salt wastewater discharge (main component is sodium nitrite), above two treatment of wastes produced abilities can almost determine coal second two
The life and death of alcohol enterprise.
In the existing industrial technology of coal-ethylene glycol, synthesis gas preparing ethylene glycol technique generally use nitric oxide, oxygen and
Methanol reaction generates methyl nitrite, then generates intermediate product dimethyl oxalate by methyl nitrite and reaction of carbon monoxide, so
It afterwards by adding hydrogen to obtain ethylene glycol product, and synthesizes in the reaction system of methyl nitrite, there are a kind of pair for generating nitric acid is anti-
It answers.
Waste water is produced for DMO workshop section, contains a large amount of NO3-N and NO2-N class, nitrate nitrogen and cultured water pair
It can be removed in the processing of coal chemical industry sewage at this stage AO technique, but salts substances are to inhibit even to poison to microorganism
Effect.
Summary of the invention
Dimethyl sulfoxide is produced using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide the object of the present invention is to provide a kind of
Technique.
Core of the invention content is:
A kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide, comprising the following steps:
(1) hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, washing, the purification of the processes such as gas-liquid separation, removal of impurities
Afterwards, it into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, is closed through examining
It is concentrated by evaporation after lattice, is sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, is packed and stored after sheet is made,
Reserves registration is carried out as production raw material；
(2) by dimethyl ether and H2S produces the sulfur trioxide in sulfuric acid apparatus and carries out synthetic reaction production dimethyl suflfate crude product；
(3) dimethyl suflfate semifinished product is put into evaporation boiler, when vacuum degree reaches -0.1~-0.08MPa, temperature reaches 120
At~130 DEG C, start heated vaporization, with the continuation of process, material composition changes in pot, and evaporating temperature is gradually increasing, wait rise
When to 140~145 DEG C or so, material has steamed substantially, and the raffinate of sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate stays in pot, distills maximum temperature
It is liquid after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature less than 160 DEG C, into receiving slit, is closed through analysis
It is stored after lattice, raffinate contains part of sulfuric acid dimethyl ester in pot, can be steamed recycling sulfuric acid two therein after centralized recovery raffinate again
Methyl esters, higher beat to crude of the dimethyl ester acidity recycled at this time are reacted again, are contained by raffinate its acid that second distillation is handled
Amount is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake and be evaporated next time again；
(4) solid sodium sulfide is heated by steam melt in advance, is then pumped into the reactor of enamel, dimethyl suflfate is by a high position
Slot, which slowly instills, to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, and reaction generates first sulphur
Ether, through cooling and static separation water outlet and methyl sulfide；
(5) sodium nitrite that evaporative crystallization obtains in dimethyl oxalate waste water react with dilute sulfuric acid and generate nitric oxide simultaneously
By sodium hydroxide solution, by being dried to obtain pure nitric oxide；
(6) reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, and it is crude that methyl sulfide is oxidized generation
Dimethyl sulfoxide, will oxidation generate crude dimethyl sulfoxide heating, drive extra nitrogen dioxide away, with lye be neutralized to pH=
8, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, it then send rectifying column to carry out rectifying, purification diformazan can be obtained
Base sulfoxide.
Preferably, the temperature of evaporation and concentration is 100~105 DEG C.
Preferably, the production method of dimethyl ether are as follows: be vaporized into methanol steam, methanol after methanol is preheated in vaporization tower
Steam is warming up to 240~260 DEG C and enters reactor, and methanol steam carries out intermolecular under the conditions of catalyst and certain temperature and pressure
Dehydration, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%.
Preferably, the temperature of dehydration is 135~145 DEG C, and pressure is 0.6~1.0Mpa.
Preferably, the catalyst is CNM-3 methanol dehydration catalyst, and surface area is 150~300m2/ g, average pore size
It is 4~6 × 10-6mm。
Preferably, the concentration of dilute sulfuric acid is 20~30%.
Preferably, the mass concentration of sodium hydroxide solution is 15~30%.
The working principle of the invention and advantage are:
To H2S carries out deep processing, the byproducts such as nitrogen, the oxygen in existing air separation unit is rationally utilized, by H2The deep processing of S is made
It is comprehensively utilized for three wastes and is extended to medicine intermediate or other people's livelihood projects, should belong to pioneering, H at home2S
About 99.3% element sulphur is recycled in gas, the production waste for not needing to bury or be further processed, simple production process
Flexibly, dimethyl sulfoxide is known as " alembroth ", and the current market price is about 10200 yuan/ton, relative to facing environmentally friendly place
The H of reason2S exhaust gas, nitrite waste water etc., appreciation space are apparent.
Specific embodiment
Embodiment 1:
A kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide is as follows:
The hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, and washing, the processes such as gas-liquid separation purify, after removal of impurities,
It into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, qualified through examining
100 DEG C of evaporation and concentration are carried out afterwards, are sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, are packaged into after sheet is made
Library carries out reserves registration as production raw material；Methanol steam, methanol steam are vaporized into after methanol is preheated in vaporization tower
It is warming up to 250 DEG C and enters reactor, methanol steam is 150~300m in surface area2/ g, average pore size are 4~6 × 10-6Mm's
CNM-3 methanol dehydration catalyst and temperature are 140 DEG C, and pressure carries out intermolecular dehydration under conditions of being 0.8Mpa
Dimethyl ether, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%, by dimethyl ether and H2S produces sulphur
Sulfur trioxide in sour device carries out synthetic reaction and produces dimethyl suflfate crude product；Dimethyl suflfate semifinished product is put into evaporation boiler
It is interior, when temperature reaches 130 DEG C when vacuum degree reaches -0.1MPa, start heated vaporization, with the continuation of process, material in pot
Composition variation, evaporating temperature is gradually increasing, and when rising to 144 DEG C or so, material has steamed substantially, sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate
Raffinate stays in pot, distills maximum temperature less than 160 DEG C, is after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature
Liquid stores, raffinate contains part of sulfuric acid dimethyl ester in pot, can after centralized recovery raffinate into receiving slit after analysis is qualified
Recycling dimethyl suflfate therein is steamed again, and higher beat to crude of the dimethyl ester acidity recycled at this time is reacted again.By
Its acid content of the raffinate of second distillation processing is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake
It is evaporated next time again；Solid sodium sulfide is heated by steam in advance to be melted, and is then pumped into the reactor of enamel, sulfuric acid two
Methyl esters is slowly instilled by head tank to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, instead
Methyl sulfide should be generated, through cooling and static separation water outlet and methyl sulfide；By the Asia that evaporative crystallization obtains in dimethyl oxalate waste water
Sodium nitrate and concentration are that 30% dilute sulfuric acid react and generates nitric oxide and be 30% sodium hydroxide solution by mass concentration, are passed through
It crosses and is dried to obtain pure nitric oxide；Reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, first
Thioether, which is oxidized, generates crude dimethyl sulfoxide, and the crude dimethyl sulfoxide that oxidation is generated heats, and drives extra titanium dioxide away
Nitrogen is neutralized to pH=8 with lye, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, and rectifying column is then sent to carry out essence
It evaporates, purification dimethyl sulfoxide can be obtained.
Embodiment 2:
A kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide is as follows:
The hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, and washing, the processes such as gas-liquid separation purify, after removal of impurities,
It into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, qualified through examining
100 DEG C of evaporation and concentration are carried out afterwards, are sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, are packaged into after sheet is made
Library carries out reserves registration as production raw material；Methanol steam, methanol steam are vaporized into after methanol is preheated in vaporization tower
It is warming up to 240 DEG C and enters reactor, methanol steam is 150~300m in surface area2/ g, average pore size are 4~6 × 10-6Mm's
CNM-3 methanol dehydration catalyst and temperature are 135 DEG C, and pressure carries out intermolecular dehydration under conditions of being 0.6Mpa
Dimethyl ether, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%, by dimethyl ether and H2S produces sulphur
Sulfur trioxide in sour device carries out synthetic reaction and produces dimethyl suflfate crude product；Dimethyl suflfate semifinished product is put into evaporation boiler
It is interior, when temperature reaches 120 DEG C when vacuum degree reaches -0.1MPa, start heated vaporization, with the continuation of process, material in pot
Composition variation, evaporating temperature is gradually increasing, and when rising to 140 DEG C or so, material has steamed substantially, sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate
Raffinate stays in pot, distills maximum temperature less than 160 DEG C, is after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature
Liquid stores, raffinate contains part of sulfuric acid dimethyl ester in pot, can after centralized recovery raffinate into receiving slit after analysis is qualified
Recycling dimethyl suflfate therein is steamed again, and higher beat to crude of the dimethyl ester acidity recycled at this time is reacted again.By
Its acid content of the raffinate of second distillation processing is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake
It is evaporated next time again；Solid sodium sulfide is heated by steam in advance to be melted, and is then pumped into the reactor of enamel, sulfuric acid two
Methyl esters is slowly instilled by head tank to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, instead
Methyl sulfide should be generated, through cooling and static separation water outlet and methyl sulfide；By the Asia that evaporative crystallization obtains in dimethyl oxalate waste water
Sodium nitrate and concentration are that 20% dilute sulfuric acid react and generates nitric oxide and be 15% sodium hydroxide solution by mass concentration, are passed through
It crosses and is dried to obtain pure nitric oxide；Reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, first
Thioether, which is oxidized, generates crude dimethyl sulfoxide, and the crude dimethyl sulfoxide that oxidation is generated heats, and drives extra titanium dioxide away
Nitrogen is neutralized to pH=8 with lye, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, and rectifying column is then sent to carry out essence
It evaporates, purification dimethyl sulfoxide can be obtained.
Embodiment 3:
A kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide is as follows:
The hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, and washing, the processes such as gas-liquid separation purify, after removal of impurities,
It into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, qualified through examining
105 DEG C of evaporation and concentration are carried out afterwards, are sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, are packaged into after sheet is made
Library carries out reserves registration as production raw material；Methanol steam, methanol steam are vaporized into after methanol is preheated in vaporization tower
It is warming up to 260 DEG C and enters reactor, methanol steam is 150~300m in surface area2/ g, average pore size are 4~6 × 10-6Mm's
CNM-3 methanol dehydration catalyst and temperature are 145 DEG C, and pressure carries out intermolecular dehydration under conditions of being 1.0Mpa
Dimethyl ether, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%, by dimethyl ether and H2S produces sulphur
Sulfur trioxide in sour device carries out synthetic reaction and produces dimethyl suflfate crude product；Dimethyl suflfate semifinished product is put into evaporation boiler
It is interior, when temperature reaches 130 DEG C when vacuum degree reaches -0.08MPa, start heated vaporization, with the continuation of process, material in pot
Composition variation, evaporating temperature is gradually increasing, and when rising to 145 DEG C or so, material has steamed substantially, sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate
Raffinate stays in pot, distills maximum temperature less than 160 DEG C, is after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature
Liquid stores, raffinate contains part of sulfuric acid dimethyl ester in pot, can after centralized recovery raffinate into receiving slit after analysis is qualified
Recycling dimethyl suflfate therein is steamed again, and higher beat to crude of the dimethyl ester acidity recycled at this time is reacted again.By
Its acid content of the raffinate of second distillation processing is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake
It is evaporated next time again；Solid sodium sulfide is heated by steam in advance to be melted, and is then pumped into the reactor of enamel, sulfuric acid two
Methyl esters is slowly instilled by head tank to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, instead
Methyl sulfide should be generated, through cooling and static separation water outlet and methyl sulfide；By the Asia that evaporative crystallization obtains in dimethyl oxalate waste water
Sodium nitrate and concentration are that 30% dilute sulfuric acid react and generates nitric oxide and be 30% sodium hydroxide solution by mass concentration, are passed through
It crosses and is dried to obtain pure nitric oxide；Reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, first
Thioether, which is oxidized, generates crude dimethyl sulfoxide, and the crude dimethyl sulfoxide that oxidation is generated heats, and drives extra titanium dioxide away
Nitrogen is neutralized to pH=8 with lye, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, and rectifying column is then sent to carry out essence
It evaporates, purification dimethyl sulfoxide can be obtained.
Embodiment 4:
A kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide is as follows:
The hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, and washing, the processes such as gas-liquid separation purify, after removal of impurities,
It into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, qualified through examining
100 DEG C of evaporation and concentration are carried out afterwards, are sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, are packaged into after sheet is made
Library carries out reserves registration as production raw material；Methanol steam, methanol steam are vaporized into after methanol is preheated in vaporization tower
It is warming up to 240 DEG C and enters reactor, methanol steam is 150~300m in surface area2/ g, average pore size are 4~6 × 10-6Mm's
CNM-3 methanol dehydration catalyst and temperature are 145 DEG C, and pressure carries out intermolecular dehydration under conditions of being 0.6Mpa
Dimethyl ether, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%, by dimethyl ether and H2S produces sulphur
Sulfur trioxide in sour device carries out synthetic reaction and produces dimethyl suflfate crude product；Dimethyl suflfate semifinished product is put into evaporation boiler
It is interior, when temperature reaches 120 DEG C when vacuum degree reaches -0.08MPa, start heated vaporization, with the continuation of process, material in pot
Composition variation, evaporating temperature is gradually increasing, and when rising to 145 DEG C or so, material has steamed substantially, sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate
Raffinate stays in pot, distills maximum temperature less than 160 DEG C, is after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature
Liquid stores, raffinate contains part of sulfuric acid dimethyl ester in pot, can after centralized recovery raffinate into receiving slit after analysis is qualified
Recycling dimethyl suflfate therein is steamed again, and higher beat to crude of the dimethyl ester acidity recycled at this time is reacted again.By
Its acid content of the raffinate of second distillation processing is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake
It is evaporated next time again；Solid sodium sulfide is heated by steam in advance to be melted, and is then pumped into the reactor of enamel, sulfuric acid two
Methyl esters is slowly instilled by head tank to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, instead
Methyl sulfide should be generated, through cooling and static separation water outlet and methyl sulfide；By the Asia that evaporative crystallization obtains in dimethyl oxalate waste water
Sodium nitrate and concentration are that 30% dilute sulfuric acid react and generates nitric oxide and be 30% sodium hydroxide solution by mass concentration, are passed through
It crosses and is dried to obtain pure nitric oxide；Reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, first
Thioether, which is oxidized, generates crude dimethyl sulfoxide, and the crude dimethyl sulfoxide that oxidation is generated heats, and drives extra titanium dioxide away
Nitrogen is neutralized to pH=8 with lye, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, and rectifying column is then sent to carry out essence
It evaporates, purification dimethyl sulfoxide can be obtained.
Embodiment 5:
A kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide is as follows:
The hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, and washing, the processes such as gas-liquid separation purify, after removal of impurities,
It into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, qualified through examining
102 DEG C of evaporation and concentration are carried out afterwards, are sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, are packaged into after sheet is made
Library carries out reserves registration as production raw material；Methanol steam, methanol steam are vaporized into after methanol is preheated in vaporization tower
It is warming up to 260 DEG C and enters reactor, methanol steam is 150~300m in surface area2/ g, average pore size are 4~6 × 10-6Mm's
CNM-3 methanol dehydration catalyst and temperature are 135 DEG C, and pressure carries out intermolecular dehydration under conditions of being 1.0Mpa
Dimethyl ether, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%, by dimethyl ether and H2S produces sulphur
Sulfur trioxide in sour device carries out synthetic reaction and produces dimethyl suflfate crude product；Dimethyl suflfate semifinished product is put into evaporation boiler
It is interior, when temperature reaches 130 DEG C when vacuum degree reaches -0.1MPa, start heated vaporization, with the continuation of process, material in pot
Composition variation, evaporating temperature is gradually increasing, and when rising to 140 DEG C or so, material has steamed substantially, sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate
Raffinate stays in pot, distills maximum temperature less than 160 DEG C, is after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature
Liquid stores, raffinate contains part of sulfuric acid dimethyl ester in pot, can after centralized recovery raffinate into receiving slit after analysis is qualified
Recycling dimethyl suflfate therein is steamed again, and higher beat to crude of the dimethyl ester acidity recycled at this time is reacted again.By
Its acid content of the raffinate of second distillation processing is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake
It is evaporated next time again；Solid sodium sulfide is heated by steam in advance to be melted, and is then pumped into the reactor of enamel, sulfuric acid two
Methyl esters is slowly instilled by head tank to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, instead
Methyl sulfide should be generated, through cooling and static separation water outlet and methyl sulfide；By the Asia that evaporative crystallization obtains in dimethyl oxalate waste water
Sodium nitrate and concentration are that 25% dilute sulfuric acid react and generates nitric oxide and be 30% sodium hydroxide solution by mass concentration, are passed through
It crosses and is dried to obtain pure nitric oxide；Reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, first
Thioether, which is oxidized, generates crude dimethyl sulfoxide, and the crude dimethyl sulfoxide that oxidation is generated heats, and drives extra titanium dioxide away
Nitrogen is neutralized to pH=8 with lye, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, and rectifying column is then sent to carry out essence
It evaporates, purification dimethyl sulfoxide can be obtained.
Embodiment 6:
A kind of technique using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide is as follows:
The hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, and washing, the processes such as gas-liquid separation purify, after removal of impurities,
It into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, qualified through examining
101 DEG C of evaporation and concentration are carried out afterwards, are sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, are packaged into after sheet is made
Library carries out reserves registration as production raw material；Methanol steam, methanol steam are vaporized into after methanol is preheated in vaporization tower
It is warming up to 250 DEG C and enters reactor, methanol steam is 150~300m in surface area2/ g, average pore size are 4~6 × 10-6Mm's
CNM-3 methanol dehydration catalyst and temperature are 140 DEG C, and pressure carries out intermolecular dehydration under conditions of being 0.6Mpa
Dimethyl ether, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%, by dimethyl ether and H2S produces sulphur
Sulfur trioxide in sour device carries out synthetic reaction and produces dimethyl suflfate crude product；Dimethyl suflfate semifinished product is put into evaporation boiler
It is interior, when temperature reaches 125 DEG C when vacuum degree reaches -0.1MPa, start heated vaporization, with the continuation of process, material in pot
Composition variation, evaporating temperature is gradually increasing, and when rising to 142 DEG C or so, material has steamed substantially, sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate
Raffinate stays in pot, distills maximum temperature less than 160 DEG C, is after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature
Liquid stores, raffinate contains part of sulfuric acid dimethyl ester in pot, can after centralized recovery raffinate into receiving slit after analysis is qualified
Recycling dimethyl suflfate therein is steamed again, and higher beat to crude of the dimethyl ester acidity recycled at this time is reacted again.By
Its acid content of the raffinate of second distillation processing is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake
It is evaporated next time again；Solid sodium sulfide is heated by steam in advance to be melted, and is then pumped into the reactor of enamel, sulfuric acid two
Methyl esters is slowly instilled by head tank to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, instead
Methyl sulfide should be generated, through cooling and static separation water outlet and methyl sulfide；By the Asia that evaporative crystallization obtains in dimethyl oxalate waste water
Sodium nitrate and concentration are that 30% dilute sulfuric acid react and generates nitric oxide and be 30% sodium hydroxide solution by mass concentration, are passed through
It crosses and is dried to obtain pure nitric oxide；Reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, first
Thioether, which is oxidized, generates crude dimethyl sulfoxide, and the crude dimethyl sulfoxide that oxidation is generated heats, and drives extra titanium dioxide away
Nitrogen is neutralized to pH=8 with lye, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, and rectifying column is then sent to carry out essence
It evaporates, purification dimethyl sulfoxide can be obtained.
Claims (7)
1. it is a kind of using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide technique, which is characterized in that including with
Lower step:
(1) hydrogen sulfide discharged from boiler or gasification installation process is through overpickling, washing, the purification of the processes such as gas-liquid separation, removal of impurities
Afterwards, it into process is absorbed, is absorbed with sodium hydroxide solution, tail gas is extracted out with jet pump and is vented, and absorption reaches terminal, is closed through examining
It is concentrated by evaporation after lattice, is sent into pelleter after vulcanized sodium mass concentration reaches 60-70%, is packed and stored after sheet is made,
Reserves registration is carried out as production raw material；
(2) by dimethyl ether and H2S produces the sulfur trioxide in sulfuric acid apparatus and carries out synthetic reaction production dimethyl suflfate crude product；
(3) dimethyl suflfate semifinished product is put into evaporation boiler, when vacuum degree reaches -0.1~-0.08MPa, temperature reaches 120
At~130 DEG C, start heated vaporization, with the continuation of process, material composition changes in pot, and evaporating temperature is gradually increasing, wait rise
When to 140~145 DEG C or so, material has steamed substantially, and the raffinate of sulfuric acid and methyl-hydrogen-sulfate monomethyl-sulfate stays in pot, distills maximum temperature
It is liquid after the water cooled device of dimethyl suflfate after vaporization is cooled to room temperature less than 160 DEG C, into receiving slit, is closed through analysis
It is stored after lattice, raffinate contains part of sulfuric acid dimethyl ester in pot, can be steamed recycling sulfuric acid two therein after centralized recovery raffinate again
Methyl esters, higher beat to crude of the dimethyl ester acidity recycled at this time are reacted again, are contained by raffinate its acid that second distillation is handled
Amount is higher, can beat to crude and use with hydrogen manufacturing methyl esters, after raffinate centralized recovery, continue to feed intake and be evaporated next time again；
(4) solid sodium sulfide is heated by steam melt in advance, is then pumped into the reactor of enamel, dimethyl suflfate is by a high position
Slot, which slowly instills, to be reacted, and synthetic reaction heat release is water-cooled, and reaction temperature is controlled at 90-110 DEG C, and reaction generates first sulphur
Ether, through cooling and static separation water outlet and methyl sulfide；
(5) sodium nitrite that evaporative crystallization obtains in dimethyl oxalate waste water react with dilute sulfuric acid and generate nitric oxide simultaneously
By sodium hydroxide solution, by being dried to obtain pure nitric oxide；
(6) reactor is added by middle part in methyl sulfide, oxygen and nitric oxide are added by tower bottom, and it is crude that methyl sulfide is oxidized generation
Dimethyl sulfoxide, will oxidation generate crude dimethyl sulfoxide heating, drive extra nitrogen dioxide away, with lye be neutralized to pH=
8, then send evaporator to be evaporated desalination thick dimethyl sulfoxide, it then send rectifying column to carry out rectifying, purification diformazan can be obtained
Base sulfoxide.
2. the technique according to claim 1 using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide,
It is characterized in that, the temperature of evaporation and concentration is 100~105 DEG C.
3. the technique according to claim 1 using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide,
It is characterized in that, the production method of dimethyl ether are as follows: be vaporized into methanol steam, methanol steam liter after methanol is preheated in vaporization tower
Temperature enters reactor to 240~260 DEG C, and methanol steam carries out intermolecular dehydration under the conditions of catalyst and certain temperature and pressure
Reaction, conversion per pass >=80% of methanol in the reactor, dimethyl ether selectivity >=99%.
4. the technique according to claim 3 using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide,
It is characterized in that, the temperature of dehydration is 135~145 DEG C, and pressure is 0.6~1.0Mpa.
5. the technique according to claim 3 using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide,
It is characterized in that, the catalyst is CNM-3 methanol dehydration catalyst, and surface area is 150~300m2/ g, average pore size are 4~6
×10-6mm。
6. the technique according to claim 1 using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide,
It is characterized in that, the concentration of dilute sulfuric acid is 20~30%.
7. the technique according to claim 1 using coal-ethylene glycol synthesis exhaust gas hydrogen sulfide production dimethyl sulfoxide,
It is characterized in that, the mass concentration of sodium hydroxide solution is 15~30%.
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