CN110698320A - Continuous recovery device and continuous recovery process for glyphosate hydrolyzed gas phase - Google Patents
Continuous recovery device and continuous recovery process for glyphosate hydrolyzed gas phase Download PDFInfo
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- CN110698320A CN110698320A CN201911070121.2A CN201911070121A CN110698320A CN 110698320 A CN110698320 A CN 110698320A CN 201911070121 A CN201911070121 A CN 201911070121A CN 110698320 A CN110698320 A CN 110698320A
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 57
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 57
- 238000011084 recovery Methods 0.000 title claims abstract description 57
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 498
- 229940050176 methyl chloride Drugs 0.000 claims abstract description 155
- 238000010521 absorption reaction Methods 0.000 claims abstract description 111
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002250 absorbent Substances 0.000 claims abstract description 53
- 230000002745 absorbent Effects 0.000 claims abstract description 53
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 50
- 230000007062 hydrolysis Effects 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 306
- 239000007788 liquid Substances 0.000 claims description 165
- 238000010992 reflux Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 27
- 239000006096 absorbing agent Substances 0.000 claims description 22
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 10
- 238000006386 neutralization reaction Methods 0.000 abstract description 10
- 230000018044 dehydration Effects 0.000 abstract description 9
- 238000006297 dehydration reaction Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 abstract description 6
- 239000002920 hazardous waste Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 186
- 239000012071 phase Substances 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 14
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 14
- 239000003507 refrigerant Substances 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- KCGLPGCUKWUTGF-UHFFFAOYSA-N chloromethane dimethoxymethane Chemical compound COCOC.ClC KCGLPGCUKWUTGF-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004063 acid-resistant material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- 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
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Treating Waste Gases (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a continuous recovery device and a continuous recovery process for a glyphosate hydrolysis gas phase. Compared with the prior art which adopts the mode of adding alkali for neutralization and deacidification, the method avoids the hydrolysis of methyl chloride in high-temperature alkaline environment in the alkali-adding neutralization process, reduces the loss of methyl chloride, improves the yield of the methyl chloride, and does not generate salt-containing wastewater; the deacidification and the dehydration are completed in one step, and the operation is simple; the invention also recovers the chloromethane in the glyphosate hydrolysis gas by an absorption and rectification mode, can avoid hazardous waste generated by drying concentrated sulfuric acid in the prior art, and improves the product yield; the methylal component separated from the glyphosate hydrolysis gas is used as an absorbent and is put into a methyl chloride absorption tower to absorb and separate methyl chloride, so that the absorbent is not required to be additionally introduced, and the cost is reduced; and materials with other new components are not introduced for absorption, so that impurities can be prevented from being introduced, and the purity of the methyl chloride product is improved.
Description
Technical Field
The invention relates to the field of recovery of glyphosate byproducts in chemical production, in particular to a continuous recovery device and a continuous recovery process for glyphosate hydrolysis gas phase.
Background
Glyphosate is a nonselective and residue-free biocidal herbicide, is particularly effective on perennial rooted weeds, and particularly has the characteristics of high efficiency, low toxicity, broad spectrum, residue-free property and the like, so that the glyphosate is more and more concerned by people. It was developed by monsanto corporation in the early seventies of the twentieth century and is generally prepared as an isopropylamine salt or sodium salt at the time of use. Wherein, a large amount of chloromethane is produced as a byproduct in the process of producing glyphosate by a glycine method, and the preparation route is approximately as follows: glycine, paraformaldehyde and dialkyl phosphite (such as dimethyl phosphite) are used as raw materials and are subjected to condensation reaction under the action of a methanol solvent and a triethylamine catalyst to obtain a condensation liquid; then the condensation liquid is acidified and hydrolyzed to form glyphosate products and byproducts such as methylal, methanol, chloromethane, hydrogen chloride and the like. After the acidification hydrolysis reaction, two routes are adopted, wherein one route is that the main product is crystallized to obtain a glyphosate product; and secondly, respectively recovering the gas byproducts through a gas recovery process.
Most of industrial glyphosate hydrolyzed gas phase recovery is direct condensation, condensate is neutralized by adding alkali, then methanol and methylal are separated and recovered, and non-condensable gas methyl chloride after hydrolyzed gas phase condensation is sent to a water washing tower, an alkali washing tower, concentrated sulfuric acid drying and compressed condensation to recover methyl chloride, so that the route is long and the operation is complex. For example, patent application 201510258999.4 discloses a recovery apparatus and process for producing glyphosate solvent by glycine method, which comprises continuously adding alkali to neutralize and hydrolyze gas phase, after completing the neutralization of hydrogen chloride, dehydrating and removing methanol, washing the non-condensable gas methyl chloride with water, alkali washing, drying with concentrated sulfuric acid, compressing and condensing to recover methyl chloride. However, in the above process, the hydrolysis of methyl chloride in a high-temperature alkaline environment occurs in the gas phase neutralization hydrolysis process by adding alkali, methyl chloride is consumed, and a byproduct loss is caused.
Disclosure of Invention
In view of the above, the present invention provides a continuous recycling apparatus and a continuous recycling process for hydrolyzed gas phase of glyphosate. The recovery device or the recovery process provided by the invention can reduce the loss of byproduct chloromethane, improve the product recovery rate, avoid the generation of salt-containing wastewater, avoid the generation of hazardous waste due to the drying of concentrated sulfuric acid, and simplify the process flow.
The invention provides a continuous recovery device of glyphosate hydrolyzed gas phase, comprising:
a deacidification tower;
the gas inlet of the first condensing device is communicated with the gas outlet at the top of the deacidification tower; the liquid outlet of the first condensing device is communicated with the liquid return port of the deacidification tower;
the gas inlet of the methanol removing tower is communicated with the non-condensable gas exhaust port of the first condensing device;
the gas inlet of the second condensing device is communicated with the gas outlet at the top of the methanol removing tower; the liquid outlet of the second condensing device is communicated with the liquid return port of the methanol removing tower;
a gas inlet of the chloromethane absorption tower is communicated with a non-condensable gas exhaust port of the second condensing device; and the liquid inlet of the absorbent of the chloromethane absorption tower is communicated with the liquid outlet of the second condensing device;
the gas inlet is communicated with the top gas outlet of the chloromethane absorption tower;
the feed inlet of the methyl chloride rectifying tower is communicated with the discharge outlet at the bottom of the methyl chloride absorption tower;
the air inlet of the third condensing device is communicated with the tower top air outlet of the chloromethane rectifying tower; a liquid outlet of the third condensing device is respectively communicated with a liquid inlet of the chloromethane receiving tank and a liquid return port of the chloromethane rectifying tank; and the non-condensable gas exhaust port of the third condensing unit is communicated with the gas inlet of the adsorber;
and the feeding port of the methylal receiving tank is communicated with the liquid outlet at the bottom of the chloromethane rectifying tower.
In one embodiment of the present invention, further comprising:
a cooler;
and the liquid inlet of the cooler is communicated with the liquid outlet of the second condensing device, and the liquid outlet of the cooler is communicated with the liquid inlet of the absorbent of the chloromethane absorption tower.
In one embodiment of the present invention, the liquid outlet of the chloromethane rectification tower is further communicated with the liquid inlet of the cooler.
In one embodiment of the present invention, further comprising:
an acid liquid absorber; a feed inlet of the acid liquid absorber is communicated with a tower bottom liquid outlet of the deacidification tower;
a methanol receiving tank; and a feed inlet of the methanol receiving tank is communicated with a liquid outlet at the bottom of the methanol removing tower.
In one embodiment of the present invention, further comprising:
a material transfer pump of the deacidification tower; communicating a feed inlet of the acid liquid absorber with a tower bottom liquid outlet of the deacidification tower through a material transferring pump of the deacidification tower;
a material transfer pump of the methanol removing tower; a feed inlet of the methanol receiving tank is communicated with a tower bottom liquid outlet of the methanol removing tower through the material transferring pump of the methanol removing tower;
a chloromethane rectifying tower material transfer pump; and a tower bottom liquid outlet of the methyl chloride rectifying tower is communicated with a feed inlet of a methylal receiving tank through the methyl chloride rectifying tower material transferring pump.
In one embodiment of the invention, the number of theoretical plates of the deacidification tower is 15-20;
the number of theoretical plates of the methanol removing tower is 20-25;
the number of theoretical plates of the chloromethane absorption tower is 15-20;
the number of theoretical plates of the chloromethane rectifying tower is 15-20.
The invention also provides a continuous recovery process of the glyphosate hydrolyzed gas phase, which is carried out on the continuous recovery device of the glyphosate hydrolyzed gas phase in the technical scheme; the continuous recovery process comprises:
a) feeding the glyphosate hydrolysis gas into a deacidification tower, discharging part of gas phase through the tower top of the deacidification tower, condensing the gas phase through a first condensing device, refluxing condensate to the deacidification tower, and feeding non-condensable gas into a methanol removing tower; acid water is produced at the bottom of the deacidification tower and is extracted;
the tower top temperature of the deacidification tower is 60-64 ℃, and the tower bottom temperature is 100-105 ℃;
b) the non-condensable gas entering the methanol removing tower in the step a) is rectified by the methanol removing tower; in the rectification process, gas phase discharged from the top of the tower is condensed by a second condensing device, one part of condensate liquid reflows, the other part of condensate liquid is used as an absorbent and is sent into a methyl chloride absorption tower, and non-condensable gas is also sent into the methyl chloride absorption tower; methanol liquid is generated at the bottom of the methanol removing tower and is extracted;
c) the absorbent fed into the methyl chloride absorption tower is contacted with the non-condensable gas to absorb the methyl chloride in the non-condensable gas; in the absorption process, gas phase discharged from the tower top is sent to an adsorber for adsorption treatment, and tower bottom liquid generated at the tower bottom is extracted;
d) feeding the tower bottom liquid obtained in the step c) into a methyl chloride rectifying tower for rectification treatment, condensing gas phase discharged from the tower top in the rectification process through a third condensing device, refluxing one part of condensate, feeding the other part of condensate into a methyl chloride receiving tank, and feeding non-condensable gas into an absorber for adsorption treatment; and (4) extracting a methylal liquid generated at the bottom of the tower.
Preferably, in step b): the temperature of the top of the methanol removing tower is 36-42 ℃, and the temperature of the bottom of the methanol removing tower is 63-66 ℃; the reflux ratio of the reflux is 2-5.
Preferably, in step b): cooling the condensate serving as an absorbent before feeding the condensate into a methyl chloride absorption tower, and then feeding the condensate into the methyl chloride absorption tower after cooling;
the cooling temperature is below 10 ℃;
the absorbent is fed from the upper part or the top of the methyl chloride absorption tower, the non-condensable gas is fed from the lower part or the bottom of the methyl chloride absorption tower, and the absorbent is in reverse mass transfer contact with the non-condensable gas to absorb the methyl chloride in the non-condensable gas.
Preferably, in step d):
the operating pressure of the chloromethane rectifying tower is 10-15 bar;
the temperature of the top of the chloromethane rectifying tower is 45-64 ℃, and the temperature of the bottom of the chloromethane rectifying tower is 125-148 ℃;
the reflux ratio of the reflux is 1.5-4.5.
The invention provides a continuous recovery device and a continuous recovery process for a glyphosate hydrolysis gas phase. By the recovery device or the recovery process provided by the invention, the following effects can be realized: (1) compared with the prior art that the hydrogen chloride and water in the glyphosate hydrolysis gas are removed by a water washing and rectifying mode, the method has the advantages that on one hand, the hydrolysis of the chloromethane in a high-temperature alkaline environment in the process of alkali neutralization is avoided, the chloromethane loss is reduced, the recovery rate of the chloromethane is favorably improved, and salt-containing wastewater cannot be generated; on the other hand, the deacidification and the dehydration can be completed in one step, the operation is simple, and the obtained dilute acid can be recovered. (2) The method recovers the methyl chloride in the glyphosate hydrolysis gas by an absorption and rectification mode, can avoid hazardous waste generated by drying concentrated sulfuric acid in the prior art, and improves the product yield. (3) The methylal component separated from the glyphosate hydrolysis gas is used as an absorbent and is put into a methyl chloride absorption tower to absorb and separate methyl chloride, on one hand, the absorbent does not need to be additionally introduced, and the cost is reduced; on the other hand, substances in the glyphosate hydrolysis gas system are used as an absorbent, and materials with other new components are not introduced for absorption, so that impurities can be prevented from being introduced, and the purity of the methyl chloride product is improved. (4) The invention can also adopt low-cost circulating water as the refrigerant in the tower top condensing device by controlling the operation conditions of the chloromethane rectifying tower, and can greatly reduce the energy consumption compared with cold brine refrigerant.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic diagram of a continuous recovery apparatus for a glyphosate hydrolysis vapor phase provided by one embodiment of the present invention.
Detailed Description
The invention provides a continuous recovery device of glyphosate hydrolyzed gas phase, comprising:
a deacidification tower;
the gas inlet of the first condensing device is communicated with the gas outlet at the top of the deacidification tower; the liquid outlet of the first condensing device is communicated with the liquid return port of the deacidification tower;
the gas inlet of the methanol removing tower is communicated with the non-condensable gas exhaust port of the first condensing device;
the gas inlet of the second condensing device is communicated with the gas outlet at the top of the methanol removing tower; the liquid outlet of the second condensing device is communicated with the liquid return port of the methanol removing tower;
a gas inlet of the chloromethane absorption tower is communicated with a non-condensable gas exhaust port of the second condensing device; and the liquid inlet of the absorbent of the chloromethane absorption tower is communicated with the liquid outlet of the second condensing device;
the gas inlet is communicated with the top gas outlet of the chloromethane absorption tower;
the feed inlet of the methyl chloride rectifying tower is communicated with the discharge outlet at the bottom of the methyl chloride absorption tower;
the air inlet of the third condensing device is communicated with the tower top air outlet of the chloromethane rectifying tower; a liquid outlet of the third condensing device is respectively communicated with a liquid inlet of the chloromethane receiving tank and a liquid return port of the chloromethane rectifying tank; and the non-condensable gas exhaust port of the third condensing unit is communicated with the gas inlet of the adsorber;
and the feeding port of the methylal receiving tank is communicated with the liquid outlet at the bottom of the chloromethane rectifying tower.
Referring to fig. 1, fig. 1 is a schematic diagram of a continuous recovery apparatus for a glyphosate hydrolyzed gas phase according to an embodiment of the present invention. Wherein, 1 is a deacidification tower, 1a is an acid liquid absorber, and 1b is a material transfer pump of the deacidification tower; 2 is a first condensing device; 3 is a methanol removing tower, 3a is a methanol receiving tank, and 3b is a material transferring pump of the methanol removing tower; 4 is a second condensing device; 5 is a chloromethane absorption tower, and 5a is a chloromethane absorption tower material transfer pump; 6 is a cooler; 7 is an absorber; 8 is a chloromethane rectifying tower; 9 is a third condensing device, and 10 is a chloromethane receiving tank; 11 is a methylal receiving tank.
The deacidification tower 1 is used for receiving the glyphosate hydrolysis gas and removing hydrogen chloride and water in the glyphosate hydrolysis gas. Specifically, the hydrolysis gas (comprising chloromethane, methylal, methanol, water and hydrogen chloride) enters the deacidification tower in a gas phase form, and self-reflux is formed in the tower by using the water and the methanol in the hydrolysis gas to achieve the processes of deacidification and dehydration.
In the present invention, the acid removing tower 1 is preferably an acid-resistant tower, and in some embodiments of the present invention, the acid removing tower 1 is a tetrafluoro tower or a glass lining tower.
In some embodiments of the invention, the number of theoretical plates in the deacidification tower 1 is 15-20. In some embodiments, the number of theoretical plates in the deacidification column 1 is 18. In the invention, the hydrolysis gas inlet of the deacidification tower 1 is preferably arranged in the middle of the deacidification tower, and particularly can be arranged at the 7 th to 12 th tower plates.
In the invention, in the operation process of the deacidification tower 1, the temperature of the top of the tower is 60-64 ℃, and the temperature of the bottom of the tower is 100-105 ℃. In operation, the chloromethane, methylal and methanol in the hydrolysis gas are discharged from the tower top in a gas state (namely, no hydrogen chloride and water exist at the tower top), the hydrogen chloride and the water flow to the tower bottom to form tower bottom liquid, and deacidification and dehydration are completed.
In some embodiments of the invention, the continuous recovery apparatus further comprises: and a feed inlet of the acid liquid absorber 1a is communicated with a liquid outlet at the bottom of the deacidification tower 1. And (3) absorbing the dilute hydrochloric acid solution at the bottom of the deacidification tower 1 through the acid solution absorber 1 a.
In some embodiments of the invention, the continuous recovery apparatus further comprises: a material transfer pump 1b of the deacidification tower; a feed inlet of the acid liquid absorber 1a is communicated with a liquid outlet at the bottom of the deacidification tower 1 through a material transfer pump 1b of the deacidification tower; namely, the bottom liquid of the deacidification tower 1 is transferred into the acid liquid absorber 1a through the deacidification tower material transfer pump 1 b.
The air inlet of the first condensing device 2 is communicated with the exhaust port at the top of the deacidification tower 1 and is used for condensing the gas phase discharged from the top of the deacidification tower 1, the liquid discharge port of the first condensing device 2 is communicated with the liquid return port of the deacidification tower 1, the condensed methanol flows back to the deacidification tower 1, and the non-condensable gas is sent to the methanol removing tower. In some embodiments of the invention, the liquid return port is disposed at the top or upper portion of the deacidification column 1.
In some embodiments of the invention, the first condensation device 2 is a primary condenser. In some embodiments of the invention, the condenser is a vertical condenser. In some embodiments of the invention, the air inlet of the vertical condenser is arranged at the upper part or the top part, the liquid outlet is arranged at the lower part or the bottom part, and the non-condensable gas exhaust port is arranged at the lower part or the bottom part.
According to the invention, the deacidification tower and the first condensing device are arranged, and hydrogen chloride and water in the glyphosate hydrolysis gas are removed by using a water washing rectification mode through the matching of the deacidification tower and the first condensing device, compared with the mode of adding alkali for neutralization and deacidification in the prior art, on one hand, the hydrolysis of methyl chloride in a high-temperature alkaline environment in the alkali-adding neutralization process is avoided, the loss of methyl chloride is reduced, the recovery rate of methyl chloride is favorably improved, and salt-containing wastewater is not generated; on the other hand, deacidification and dehydration are completed in one step, the operation is simple, and the obtained dilute acid can be recovered.
And the gas inlet of the methanol removing tower 3 is communicated with the non-condensable gas exhaust port of the first condensing device 2 and is used for rectifying the received non-condensable gas and removing methanol. Specifically, after the non-condensable gas (including methanol, methylal and methyl chloride) from the first condensing device 2 enters the methanol removing tower 3, the methylal and the methyl chloride are converted into gas and discharged from the top of the methanol removing tower 3 in the rectification process, and the methanol flows to the bottom of the tower in a liquid form, so that the methanol is removed.
In the present invention, the methanol removing tower 3 may be a tower made of non-acid-resistant material, and in particular, in some embodiments of the present invention, the methanol removing tower 3 is a carbon steel tower or a stainless steel tower.
In some embodiments of the invention, the number of theoretical plates of the demethanizer 3 is between 20 and 25. In one embodiment, the number of theoretical plates in the demethanizer 3 is 18. In the invention, the gas inlet of the methanol removing tower 3 is preferably arranged in the middle of the methanol removing tower 3, and particularly can be arranged at 9 th to 13 th tower plates.
In some embodiments of the invention, the continuous recovery apparatus further comprises: and a methanol receiving tank 3a, wherein a feed inlet of the methanol receiving tank 3a is communicated with a tower bottom liquid outlet of the methanol removing tower 3.
In some embodiments of the invention, the continuous recovery apparatus further comprises: a material transfer pump 3b of the methanol removing tower; a feed inlet of the methanol receiving tank 3a is communicated with a tower bottom liquid outlet of the methanol removing tower 3 through a material transferring pump 3b of the methanol removing tower; namely, the bottom liquid of the demethanizer 3 is transferred to the methanol receiver tank 3a by the demethanizer transfer pump 3 b.
And the air inlet of the second condensing device 4 is communicated with the top air outlet of the methanol removing tower 3, and the liquid outlet of the second condensing device 4 is communicated with the liquid return port of the methanol removing tower 3 and is also communicated with the absorbent liquid inlet of the methyl chloride absorption tower. The second condensing device 4 is used for condensing the gas phase discharged from the top of the methanol removing tower 3, wherein one part of the condensed methylal liquid flows back to the methanol removing tower 3, and the other part of the condensed methylal liquid is used as an absorbent and is sent to a methyl chloride absorption tower 5; the non-condensable gas methyl chloride is also fed into the methyl chloride absorption tower 5. Wherein, the liquid return port is arranged at the top or the upper part of the methanol removing tower 3.
In some embodiments of the present invention, the second condensing device 4 is a primary condenser. In some embodiments of the invention, the condenser is a vertical condenser. In some embodiments of the invention, the air inlet of the vertical condenser is arranged at the upper part or the top part, the liquid outlet is arranged at the lower part or the bottom part, and the non-condensable gas exhaust port is arranged at the lower part or the bottom part.
In some embodiments of the invention, the continuous recovery apparatus further comprises: a cooler 6; and the liquid inlet of the cooler 6 is communicated with the liquid outlet of the second condensing device 4, and the liquid outlet of the cooler is communicated with the liquid inlet of the absorbent of the chloromethane absorption tower 5. That is, the condensate discharged from the second condensing unit 4 is cooled by the cooler 6 before being fed to the methyl chloride absorption tower 5, and then is fed to the methyl chloride absorption tower 5 as an absorbent. In the present invention, the cooling temperature of the cooler 6 is 10 ℃ or less, preferably 0 to 10 ℃.
The air inlet of the methyl chloride absorption tower 5 is communicated with the non-condensable gas exhaust port of the second condensing device 4, and the liquid inlet is communicated with the liquid outlet of the second condensing device 4, namely, the methyl chloride absorption tower 5 simultaneously receives the non-condensable gas (mainly methyl chloride) and the condensate (mainly methylal) discharged by the second condensing device 4, wherein the condensate is used as an absorbent to absorb the methyl chloride component in the non-condensable gas.
In some embodiments of the present invention, the gas inlet of the methyl chloride absorption tower 5 is disposed at the lower part or bottom of the methyl chloride absorption tower 5, and the absorbent liquid inlet is disposed at the upper part or top of the methyl chloride absorption tower 5; namely, the non-condensable gas is introduced from the lower part or the bottom of the methyl chloride absorption tower 5, the absorbent is fed from the upper part or the top of the methyl chloride absorption tower 5, the absorbent and the non-condensable gas are in reverse contact in the methyl chloride absorption tower 5, the methyl chloride component in the non-condensable gas is fully absorbed, the formed methyl chloride methylal solution flows to the bottom of the tower, and the gas which is not absorbed is discharged from the top of the tower.
In some embodiments of the invention, the number of theoretical plates of the methyl chloride absorption tower 5 is 15-20; in one embodiment, the number of theoretical plates of the methyl chloride absorption column 5 is 15. In some embodiments of the invention, the gas inlet of the methyl chloride absorption column 5 is provided at tray 15 and the absorbent liquid inlet is provided at tray 1.
According to the invention, the liquid outlet of the second condensing device 4 is communicated with the liquid inlet of the chloromethane absorption tower 5, namely, a condensate liquid conveying pipeline leading the second condensing device 4 to the chloromethane absorption tower 5 is arranged, so that a methylal component separated from glyphosate hydrolysis gas is used as an absorbent to separate chloromethane, on one hand, the absorbent is not required to be additionally introduced, and the cost is reduced; on the other hand, substances in the glyphosate hydrolysis gas system are used as an absorbent, and materials with other new components are not introduced for absorption, so that impurities can be prevented from being introduced, and the purity of the methyl chloride product is improved.
The gas inlet of the adsorber 7 is communicated with the gas outlet at the top of the methyl chloride absorption tower 5, and gas components which are not absorbed in the methyl chloride absorption tower 5 are discharged through the gas outlet at the top of the tower, absorbed by the adsorber 7 and discharged after reaching the adsorption standard. In some embodiments of the present invention, the adsorber 7 is an activated carbon adsorber, i.e. the adsorbent filled in the adsorber is activated carbon.
The feed inlet of the chloromethane rectifying tower 8 is communicated with the discharge outlet at the bottom of the chloromethane absorption tower 5 and is used for rectifying the chloromethane methylal solution discharged from the chloromethane absorption tower 5. In the rectification process, the gas phase containing the chloromethane is discharged from the top of the tower, the methylal flows to the bottom of the tower, the methylal and the gas phase are separated, and the chloromethane gas discharged from the top of the tower is collected to obtain a chloromethane product.
In some embodiments of the invention, the continuous recovery apparatus further comprises: and a chloromethane absorption tower transfer pump 5a, wherein the feed inlet of the chloromethane rectifying tower 8 is communicated with the discharge outlet at the bottom of the chloromethane absorption tower 5 through the chloromethane absorption tower transfer pump 5a, namely, the liquid at the bottom of the chloromethane absorption tower 5 is transferred into the chloromethane rectifying tower 8 through the chloromethane absorption tower transfer pump 5 a.
In some embodiments of the invention, the number of theoretical plates of the methyl chloride rectifying tower 8 is 15-20; in one embodiment, the number of theoretical plates of methyl chloride rectification column 8 is 18. In the invention, the feed inlet of the methyl chloride rectifying tower 8 is preferably arranged in the middle of the rectifying tower, and particularly can be arranged at the 7 th-10 th tower plate of the methyl chloride rectifying tower 8.
The air inlet of the third condensing device 9 is communicated with the top exhaust port of the chloromethane rectifying tower 8, and the liquid outlet is communicated with the chloromethane receiving tank 10. Used for condensing the methyl chloride gas discharged from the top of the methyl chloride rectifying tower 8 and collecting the condensed methyl chloride liquid into a methyl chloride receiving tank.
In the invention, the liquid outlet of the third condensing device 9 is also communicated with the liquid return port of the methyl chloride rectifying tower 8, one part of the condensed methyl chloride liquid flows back to the methyl chloride rectifying tower 8, and the other part of the condensed methyl chloride liquid is collected in the methyl chloride receiving tank 10. In the present invention, the liquid return port is preferably provided at the upper part or the top of the methyl chloride rectification column 8.
In the invention, the non-condensable gas exhaust port of the third condensing device 9 is communicated with the gas inlet of the adsorber 7, and the condensed non-condensable gas is subjected to adsorption treatment by the adsorber 7 and is exhausted after reaching the adsorption standard.
In some embodiments of the invention, the third condensation device 9 is a two-stage condenser, i.e. two condensers connected in series. In some embodiments of the invention, the condenser is a vertical condenser.
The feed inlet of the methylal receiving tank 11 is communicated with the liquid outlet at the bottom of the methyl chloride rectifying tower 8 and is used for receiving the methylal liquid discharged from the bottom of the methyl chloride rectifying tower 8.
In some embodiments of the present invention, the liquid outlet at the bottom of the chloromethane rectification tower 8 is also communicated with the liquid inlet of the cooler 6; namely, the methylal liquid discharged from the bottom of the methyl chloride rectifying tower 8 is partially collected in the methylal receiving tank 11, and the other part is sent back to the cooler 6 again and is sent to the methyl chloride absorbing tower 6 as an absorbent again after being cooled.
In some embodiments of the invention, the continuous recovery apparatus further comprises: a chloromethane rectifying tower material transfer pump 12; and a tower bottom liquid outlet of the methyl chloride rectifying tower 8 is communicated with a feeding hole of a methylal receiving tank 11 through the methyl chloride rectifying tower material transferring pump 12. Namely, the bottom liquid of the methyl chloride rectifying tower 8 is extracted by a methyl chloride rectifying tower material transfer pump 12 and respectively sent to a methylal receiving tank 11 and a cooler 6.
The invention is provided with the methyl chloride absorption tower 5 and the methyl chloride rectifying tower 8, and recovers the methyl chloride in the glyphosate hydrolysis gas in the modes of absorption and rectification, thereby avoiding hazardous waste generated by drying concentrated sulfuric acid in the prior art and improving the product yield.
The continuous recovery device for the glyphosate hydrolyzed gas phase provided by the invention has the following beneficial effects:
(1) according to the invention, the deacidification tower and the first condensing device are arranged, and hydrogen chloride and water in the glyphosate hydrolysis gas can be removed by using a water washing rectification mode through the matching of the deacidification tower and the first condensing device, compared with the structure arrangement (namely deacidification by adding alkali) in the prior art, on one hand, the hydrolysis of methyl chloride in a high-temperature alkaline environment in the alkali adding neutralization process is avoided, the methyl chloride loss is reduced, the recovery rate of methyl chloride is improved, and salt-containing wastewater cannot be generated; on the other hand, the deacidification and the dehydration can be completed in one step, the operation is simple, and the obtained dilute acid can be recovered.
(2) The invention combines the methyl chloride absorption tower 5 and the methyl chloride rectifying tower 8, can recover the methyl chloride in the glyphosate hydrolysis gas in the modes of absorption and rectification, can avoid hazardous waste generated by drying concentrated sulfuric acid in the prior art, and improves the product yield.
(3) According to the invention, the liquid outlet of the second condensing device 4 is communicated with the liquid inlet of the chloromethane absorption tower 5, namely, a condensate liquid conveying pipeline leading the second condensing device 4 to the chloromethane absorption tower 5 is arranged, so that a methylal component separated from glyphosate hydrolysis gas is used as an absorbent to separate chloromethane, on one hand, the absorbent is not required to be additionally introduced, and the cost is reduced; on the other hand, substances in the glyphosate hydrolysis gas system are used as an absorbent, and materials with other new components are not introduced for absorption, so that impurities can be prevented from being introduced, and the purity of the methyl chloride product is improved.
The invention also provides a continuous recovery process of the glyphosate hydrolyzed gas phase, which is carried out on the continuous recovery device of the glyphosate hydrolyzed gas phase in the technical scheme; the continuous recovery process comprises:
a) feeding the glyphosate hydrolysis gas into a deacidification tower, discharging part of gas phase through the tower top of the deacidification tower, condensing the gas phase through a first condensing device, refluxing condensate to the deacidification tower, and feeding non-condensable gas into a methanol removing tower; acid water is produced at the bottom of the deacidification tower and is extracted;
the tower top temperature of the deacidification tower is 60-64 ℃, and the tower bottom temperature is 100-105 ℃;
b) the non-condensable gas entering the methanol removing tower in the step a) is rectified by the methanol removing tower; in the rectification process, gas phase discharged from the top of the tower is condensed by a second condensing device, one part of condensate liquid reflows, the other part of condensate liquid is used as an absorbent and is sent into a methyl chloride absorption tower, and non-condensable gas is also sent into the methyl chloride absorption tower; methanol liquid is generated at the bottom of the methanol removing tower and is extracted;
c) the absorbent fed into the methyl chloride absorption tower is contacted with the non-condensable gas to absorb the methyl chloride in the non-condensable gas; in the absorption process, gas phase discharged from the tower top is sent to an adsorber for adsorption treatment, and tower bottom liquid generated at the tower bottom is extracted;
d) feeding the tower bottom liquid obtained in the step c) into a methyl chloride rectifying tower for rectification treatment, condensing gas phase discharged from the tower top in the rectification process through a third condensing device, refluxing one part of condensate, feeding the other part of condensate into a methyl chloride receiving tank, and feeding non-condensable gas into an absorber for adsorption treatment; and (4) extracting a methylal liquid generated at the bottom of the tower.
According to the invention, the glyphosate hydrolysis gas is sent into a deacidification tower, part of gas phase is discharged from the tower top of the deacidification tower and condensed by a first condensing device, condensate liquid flows back to the deacidification tower, and non-condensable gas enters a methanol removing tower; acid water is generated at the bottom of the deacidification tower and is extracted.
In the invention, the glyphosate hydrolysis gas refers to a byproduct gas generated in a glyphosate acidification hydrolysis process. In the invention, the tower top temperature of the deacidification tower is 60-64 ℃; in some embodiments of the invention is 63 ℃. The temperature of the tower bottom of the deacidification tower is 100-105 ℃; in some embodiments of the invention is 101 deg.c.
In the operation process of the deacidification tower, water and methanol in the hydrolysis gas form self-reflux in the tower, so that the processes of acid washing and dehydration are realized. Specifically, in operation, the chloromethane, methylal and methanol in the hydrolysis gas are discharged from the tower top in a gas state (namely, no hydrogen chloride and water exist at the tower top), the hydrogen chloride and the water flow to the tower bottom to form a tower bottom liquid, and deacidification and dehydration are completed. Wherein, the gas phase discharged from the top of the tower is condensed by a first condensing device, the condensate liquid flows back to the deacidification tower, and the non-condensable gas enters the methanol removing tower. And sending low-concentration acid water formed at the bottom of the deacidification tower to an acid liquid absorber for absorbing hydrochloric acid. In the invention, the temperature of the refrigerant in the first condensing device 2 is 7-30 ℃.
According to the invention, the non-condensable gas entering the methanol removing tower in the steps is rectified by the methanol removing tower; in the rectification process, gas phase discharged from the top of the tower is condensed by a second condensing device, one part of condensate liquid reflows, the other part of condensate liquid is used as an absorbent and is sent into a methyl chloride absorption tower, and non-condensable gas is also sent into the methyl chloride absorption tower; methanol liquid is produced at the bottom of the methanol removing tower and is extracted.
In the invention, the tower top temperature of the methanol removing tower is 36-42 ℃; in some embodiments 36 ℃ or 38 ℃. The temperature of the bottom of the methanol removing tower is 63-66 ℃; in some embodiments 63 ℃ or 65 ℃. The reflux ratio of the condensate reflux is 2-5; in some embodiments the reflux ratio is 3. In the invention, the reflux ratio refers to the ratio of tower return amount to produced amount, wherein the sum of the tower return amount and the produced amount is the condensation amount of the condensation device. During the rectification, the methylal and methyl chloride are converted into gas and discharged from the top of the methanol removal column 3, and methanol flows in liquid form to the bottom of the column to be removed. Wherein, after the gas discharged from the top is condensed by the second condensing device, the methylal condensate is discharged, one part of the methylal condensate refluxes, the other part of the methylal condensate is used as an absorbent and is sent into a methyl chloride absorption tower, and the non-condensable gas methyl chloride is also sent into the methyl chloride absorption tower. In the invention, the temperature of the refrigerant in the second condensing device 4 is 7-28 ℃.
According to the invention, the absorbent fed into the methyl chloride absorption tower is contacted with the non-condensable gas to absorb the methyl chloride in the non-condensable gas; in the absorption process, gas phase discharged from the tower top is sent to an adsorber for adsorption treatment, and tower bottom liquid generated at the tower bottom is extracted.
In the present invention, preferably, the condensate from the second condensing device is cooled by the cooler and then sent to the methyl chloride absorption tower. In the invention, the temperature is preferably cooled to below 10 ℃ by a cooler, and more preferably 0-10 ℃; in some embodiments of the invention, cooling is to 5 ℃.
In the invention, methylal condensate is used as an absorbent to absorb the non-condensable gas containing chloromethane, and the absorbent is in reverse contact with the non-condensable gas in a chloromethane absorption tower to fully absorb the chloromethane in the non-condensable gas to form methylal solution of the chloromethane, which flows to the bottom of the tower and is extracted; meanwhile, the non-absorbed condensable gas is discharged through the top of the methyl chloride absorption tower.
In the invention, the gas discharged from the top of the chloromethane absorption tower is absorbed by the absorber and discharged after the absorption reaches the standard.
According to the invention, the tower bottom liquid extracted in the steps is sent into a chloromethane rectifying tower for rectification treatment, in the rectification process, gas phase discharged from the tower top is condensed by a third condensing device, one part of condensate liquid reflows, the other part of condensate liquid enters a chloromethane receiving tank, and noncondensable gas is sent into an absorber for adsorption treatment; and (4) extracting a methylal liquid generated at the bottom of the tower.
In the invention, the operation pressure of the methyl chloride rectifying tower is preferably 10-15 bar; in some embodiments, the operating pressure is 10bar or 15 bar. In the invention, the chloromethane rectifying tower is a pressurizing tower, and through the better operation pressure, low-cost circulating water can be used as a refrigerant in the tower top condensing device, so that the energy consumption can be greatly reduced compared with a cold brine refrigerant.
In the invention, the tower top temperature of the chloromethane rectifying tower is preferably 45-64 ℃; in some embodiments, the overhead temperature is 45 ℃ or 63 ℃. The bottom temperature of the chloromethane rectifying tower is preferably 125-148 ℃; in some embodiments, the bottom temperature is 125 ℃ or 148 ℃. In the rectification process, the methyl chloride is converted into gas and discharged from the top of the tower, and the methylal liquid flows to the bottom of the tower. And condensing the methyl chloride gas discharged from the top of the tower through a third condensing device, refluxing one part of condensate, and collecting the other part of condensate to a methyl chloride receiving tank to obtain a methyl chloride product. In the present invention, the reflux ratio of the reflux is preferably 1.5 to 4.5.
In the invention, the methylal liquid obtained from the bottom of the methyl chloride rectifying tower is extracted, one part of the methylal liquid is collected into the methylal receiving tank, and the other part of the methylal liquid is sent back to the system to be reused as the absorbent of the methyl chloride absorption tower.
The continuous recovery process of the glyphosate hydrolyzed gas phase provided by the invention has the following beneficial effects:
(1) according to the invention, hydrogen chloride and water in the glyphosate hydrolysis gas are removed in a water washing and rectifying manner, compared with the prior art that an alkali-adding and alkali-adding neutralization deacidification manner is adopted, on one hand, the hydrolysis of methyl chloride in a high-temperature alkaline environment in the alkali-adding neutralization process is avoided, the methyl chloride loss is reduced, the methyl chloride recovery rate is favorably improved, and salt-containing wastewater is not generated; on the other hand, the deacidification and the dehydration can be completed in one step, the operation is simple, and the obtained dilute acid can be recovered.
(2) The method recovers the methyl chloride in the glyphosate hydrolysis gas by an absorption and rectification mode, can avoid hazardous waste generated by drying concentrated sulfuric acid in the prior art, and improves the product yield.
(3) The methylal component separated from the glyphosate hydrolysis gas is used as an absorbent and is put into a methyl chloride absorption tower to absorb and separate methyl chloride, on one hand, the absorbent does not need to be additionally introduced, and the cost is reduced; on the other hand, substances in the glyphosate hydrolysis gas system are used as an absorbent, and materials with other new components are not introduced for absorption, so that impurities can be prevented from being introduced, and the purity of the methyl chloride product is improved.
(4) The invention controls the operation condition of the chloromethane rectifying tower, can adopt low-cost circulating water as the refrigerant in the tower top condensing device, and can greatly reduce the energy consumption compared with cold brine refrigerant.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. In the following examples, the continuous recovery apparatus shown in FIG. 1 was used.
Example 1
S1, allowing the glyphosate hydrolysis gas to enter a deacidification tower, wherein the tower top temperature is 63 ℃, the tower bottom temperature is 102 ℃, and the refrigerant temperature of a first condensing device at the tower top is 28 ℃. And part of gas components are discharged from the top of the deacidification tower, condensed methanol completely refluxes after condensation, non-condensable gas enters the methanol removing tower, water and methanol in the hydrolyzed gas form self-reflux, and hydrogen chloride and water flow to the bottom of the tower and are extracted and sent to an acid liquid absorber for absorption.
Wherein, the number of theoretical plates of the deacidification tower is 18, and the air inlet of the glyphosate hydrolysis gas is arranged at the 10 th plate.
And S2, feeding the non-condensable gas of the deacidification tower into a methanol removing tower, wherein the tower top temperature is 38 ℃, the tower bottom temperature is 65 ℃, and the refrigerant temperature of a second condensing device at the tower top is 28 ℃. In the rectification process, gas phase is discharged from the top of the tower, after condensation, one part of condensate (methylal) reflows (the reflux ratio is 3), and the other part of condensate is sent into a cooler for further cooling and then is sent into an absorption tower as an absorbent from the upper part of a methyl chloride absorption tower; the non-condensable gas is sent into the absorption tower from the lower part of the methyl chloride absorption tower.
Wherein the theoretical plate number of the methanol removing tower is 24, and the feed inlet is positioned in the middle part at the 12 th plate. The cooling temperature of the cooler was 5 ℃.
S3, reversely contacting the absorbent fed from the upper part with the non-condensable gas fed from the lower part in a methyl chloride absorption tower to absorb the methyl chloride in the non-condensable gas to form a methyl chloride methylal solution, flowing to the bottom of the tower and extracting; the unabsorbed gas is discharged from the top and is discharged after reaching the standard through the adsorption of active carbon;
wherein, the number of theoretical plates of the chloromethane absorption tower is 15, the upper liquid inlet is positioned at the 1 st plate, and the lower gas inlet is positioned at the 15 th plate.
S4, sending the produced liquid at the bottom of the methyl chloride absorption tower into a methyl chloride rectifying tower, wherein the pressure in the tower is 10bar, the temperature at the top of the tower is 45 ℃, and the temperature at the bottom of the tower is 125 ℃. In the rectification process, the chloromethane is converted into gas which is discharged from the top of the rectification tower and condensed by a cold third condensing device, part of the condensate liquid flows back (the reflux ratio is 3), and the other part of the condensate liquid is sent to a chloromethane receiving tank; the noncondensable gas is sent to an activated carbon adsorption absorber to be adsorbed and discharged after reaching the standard. And obtaining a high-content methylal liquid at the bottom of the tower, wherein one part of the high-content methylal liquid is used as an absorbent for recycling, and the other part of the high-content methylal liquid is collected to a methylal receiving tank as a product.
Wherein, the theoretical plate number of the chloromethane rectifying tower is 18, and the liquid inlet is arranged at the 7 th plate. The refrigerant in the third condensing device is circulating water.
The amount of methyl chloride in the initial hydrolysis gas and the amount of methyl chloride obtained in the final methyl chloride receiving tank were measured, and the result of measuring the recovery rate of methyl chloride showed that the recovery rate of methyl chloride was 99%.
Example 2
S1, allowing the glyphosate hydrolysis gas to enter a deacidification tower, wherein the tower top temperature is 60 ℃, the tower bottom temperature is 100 ℃, and the refrigerant temperature of a first condensing device at the tower top is 30 ℃. And part of gas components are discharged from the top of the deacidification tower, condensed methanol completely refluxes after condensation, non-condensable gas enters the methanol removing tower, water and methanol in the hydrolyzed gas form self-reflux, and hydrogen chloride and water flow to the bottom of the tower and are extracted and sent to an acid liquid absorber for absorption.
Wherein, the theoretical plate number of the deacidification tower is 18, and the air inlet of the glyphosate hydrolysis gas is arranged at the 12 th plate.
S2, feeding the non-condensable gas of the deacidification tower into a methanol removing tower, wherein the tower top temperature is 36 ℃, the tower bottom temperature is 63 ℃, and the refrigerant temperature of a second condensing device at the tower top is 12 ℃. In the rectification process, gas phase is discharged from the top of the tower, after condensation, one part of condensate (methylal) reflows (the reflux ratio is 3), and the other part of condensate is sent into a cooler for further cooling and then is sent into an absorption tower as an absorbent from the upper part of a methyl chloride absorption tower; the non-condensable gas is sent into the absorption tower from the lower part of the methyl chloride absorption tower.
Wherein the theoretical plate number of the methanol removing tower is 24, and the feed inlet is positioned in the middle part at the 10 th plate. The cooling temperature of the cooler was 5 ℃.
S3, reversely contacting the absorbent fed from the upper part with the non-condensable gas fed from the lower part in a methyl chloride absorption tower to absorb the methyl chloride in the non-condensable gas to form a methyl chloride methylal solution, flowing to the bottom of the tower and extracting; the unabsorbed gas is discharged from the top and is discharged after reaching the standard through the adsorption of active carbon;
wherein, the number of theoretical plates of the chloromethane absorption tower is 15, the upper liquid inlet is positioned at the 1 st plate, and the lower gas inlet is positioned at the 15 th plate.
S4, sending the produced liquid at the bottom of the methyl chloride absorption tower into a methyl chloride rectifying tower, wherein the pressure in the tower is 15bar, the temperature at the top of the tower is 63 ℃, and the temperature at the bottom of the tower is 148 ℃. In the rectification process, the chloromethane is converted into gas which is discharged from the top of the rectification tower and condensed by a cold third condensing device, part of the condensate liquid flows back (the reflux ratio is 2.7), and the other part of the condensate liquid is sent to a chloromethane receiving tank; the noncondensable gas is sent to an activated carbon adsorption absorber to be adsorbed and discharged after reaching the standard. And obtaining a high-content methylal liquid at the bottom of the tower, wherein one part of the high-content methylal liquid is used as an absorbent for recycling, and the other part of the high-content methylal liquid is collected to a methylal receiving tank as a product.
Wherein, the theoretical plate number of the chloromethane rectifying tower is 18, and the liquid inlet is arranged at the 8 th plate. The refrigerant in the third condensing device is circulating water.
The amount of methyl chloride in the initial hydrolysis gas and the amount of methyl chloride obtained in the final methyl chloride receiving tank were measured, and the result of measuring the recovery rate of methyl chloride showed that the recovery rate of methyl chloride was 99.2%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A continuous recovery device of glyphosate hydrolyzed gas phase is characterized by comprising:
a deacidification tower;
the gas inlet of the first condensing device is communicated with the gas outlet at the top of the deacidification tower; the liquid outlet of the first condensing device is communicated with the liquid return port of the deacidification tower;
the gas inlet of the methanol removing tower is communicated with the non-condensable gas exhaust port of the first condensing device;
the gas inlet of the second condensing device is communicated with the gas outlet at the top of the methanol removing tower; the liquid outlet of the second condensing device is communicated with the liquid return port of the methanol removing tower;
a gas inlet of the chloromethane absorption tower is communicated with a non-condensable gas exhaust port of the second condensing device; and the liquid inlet of the absorbent of the chloromethane absorption tower is communicated with the liquid outlet of the second condensing device;
the gas inlet is communicated with the top gas outlet of the chloromethane absorption tower;
the feed inlet of the methyl chloride rectifying tower is communicated with the discharge outlet at the bottom of the methyl chloride absorption tower;
the air inlet of the third condensing device is communicated with the tower top air outlet of the chloromethane rectifying tower; a liquid outlet of the third condensing device is respectively communicated with a liquid inlet of the chloromethane receiving tank and a liquid return port of the chloromethane rectifying tank; and the non-condensable gas exhaust port of the third condensing unit is communicated with the gas inlet of the adsorber;
and the feeding port of the methylal receiving tank is communicated with the liquid outlet at the bottom of the chloromethane rectifying tower.
2. The continuous recovery apparatus of claim 1, further comprising:
a cooler;
and the liquid inlet of the cooler is communicated with the liquid outlet of the second condensing device, and the liquid outlet of the cooler is communicated with the liquid inlet of the absorbent of the chloromethane absorption tower.
3. The continuous recycling device according to claim 2, wherein the liquid outlet of the methyl chloride rectifying tower is further communicated with the liquid inlet of the cooler.
4. The continuous recovery apparatus of claim 1, further comprising:
an acid liquid absorber; a feed inlet of the acid liquid absorber is communicated with a tower bottom liquid outlet of the deacidification tower;
a methanol receiving tank; and a feed inlet of the methanol receiving tank is communicated with a liquid outlet at the bottom of the methanol removing tower.
5. The continuous recovery apparatus of claim 4, further comprising:
a material transfer pump of the deacidification tower; communicating a feed inlet of the acid liquid absorber with a tower bottom liquid outlet of the deacidification tower through a material transferring pump of the deacidification tower;
a material transfer pump of the methanol removing tower; a feed inlet of the methanol receiving tank is communicated with a tower bottom liquid outlet of the methanol removing tower through the material transferring pump of the methanol removing tower;
a chloromethane rectifying tower material transfer pump; and a tower bottom liquid outlet of the methyl chloride rectifying tower is communicated with a feed inlet of a methylal receiving tank through the methyl chloride rectifying tower material transferring pump.
6. The continuous recovery device according to claim 1, wherein the number of theoretical plates of the deacidification tower is 15-20;
the number of theoretical plates of the methanol removing tower is 20-25;
the number of theoretical plates of the chloromethane absorption tower is 15-20;
the number of theoretical plates of the chloromethane rectifying tower is 15-20.
7. A continuous recovery process of a glyphosate hydrolyzed gas phase, which is characterized by being carried out on a continuous recovery device of the glyphosate hydrolyzed gas phase as claimed in any one of claims 1 to 6; the continuous recovery process comprises:
a) feeding the glyphosate hydrolysis gas into a deacidification tower, discharging part of gas phase through the tower top of the deacidification tower, condensing the gas phase through a first condensing device, refluxing condensate to the deacidification tower, and feeding non-condensable gas into a methanol removing tower; acid water is produced at the bottom of the deacidification tower and is extracted;
the tower top temperature of the deacidification tower is 60-64 ℃, and the tower bottom temperature is 100-105 ℃;
b) the non-condensable gas entering the methanol removing tower in the step a) is rectified by the methanol removing tower; in the rectification process, gas phase discharged from the top of the tower is condensed by a second condensing device, one part of condensate liquid reflows, the other part of condensate liquid is used as an absorbent and is sent into a methyl chloride absorption tower, and non-condensable gas is also sent into the methyl chloride absorption tower; methanol liquid is generated at the bottom of the methanol removing tower and is extracted;
c) the absorbent fed into the methyl chloride absorption tower is contacted with the non-condensable gas to absorb the methyl chloride in the non-condensable gas; in the absorption process, gas phase discharged from the tower top is sent to an adsorber for adsorption treatment, and tower bottom liquid generated at the tower bottom is extracted;
d) feeding the tower bottom liquid obtained in the step c) into a methyl chloride rectifying tower for rectification treatment, condensing gas phase discharged from the tower top in the rectification process through a third condensing device, refluxing one part of condensate, feeding the other part of condensate into a methyl chloride receiving tank, and feeding non-condensable gas into an absorber for adsorption treatment; and (4) extracting a methylal liquid generated at the bottom of the tower.
8. The continuous recovery process of claim 7, wherein in step b): the temperature of the top of the methanol removing tower is 36-42 ℃, and the temperature of the bottom of the methanol removing tower is 63-66 ℃; the reflux ratio of the reflux is 2-5.
9. The continuous recovery process of claim 7, wherein in step b): cooling the condensate serving as an absorbent before feeding the condensate into a methyl chloride absorption tower, and then feeding the condensate into the methyl chloride absorption tower after cooling;
the cooling temperature is below 10 ℃;
the absorbent is fed from the upper part or the top of the methyl chloride absorption tower, the non-condensable gas is fed from the lower part or the bottom of the methyl chloride absorption tower, and the absorbent is in reverse mass transfer contact with the non-condensable gas to absorb the methyl chloride in the non-condensable gas.
10. The continuous recovery process of claim 7, wherein in step d):
the operating pressure of the chloromethane rectifying tower is 10-15 bar;
the temperature of the top of the chloromethane rectifying tower is 45-64 ℃, and the temperature of the bottom of the chloromethane rectifying tower is 125-148 ℃;
the reflux ratio of the reflux is 1.5-4.5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170826A (en) * | 2020-03-16 | 2020-05-19 | 浙江新安化工集团股份有限公司 | Clean recovery system and clean recovery process for chloromethane in glyphosate production tail gas |
| CN111269089A (en) * | 2020-03-16 | 2020-06-12 | 浙江新安化工集团股份有限公司 | Method and system for recovering hydrolysis tail gas of glyphosate synthetic liquid |
| CN113582811A (en) * | 2020-04-30 | 2021-11-02 | 蓝星（北京）技术中心有限公司 | Deacidification method of methane chloride |
| CN113929555A (en) * | 2021-11-02 | 2022-01-14 | 浙江新安化工集团股份有限公司 | Method and device for recovering byproduct chloromethane for preparing glyphosate or dimethyl phosphite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070269467A1 (en) * | 2006-05-22 | 2007-11-22 | Leatherman Mark D | Use of hydrolysis resistant organomodified silylated surfactants |
| CN103736384A (en) * | 2014-01-27 | 2014-04-23 | 山东潍坊润丰化工股份有限公司 | Treatment process of glyphosate hydrolyzing tail gas |
| CN103752158A (en) * | 2014-01-27 | 2014-04-30 | 山东潍坊润丰化工股份有限公司 | Method for treating glyphosate hydrolyzing tail gas |
| CN105753901A (en) * | 2016-03-19 | 2016-07-13 | 安徽东至广信农化有限公司 | Technology for recovering chloromethane washing wastewater in glyphosate production |
| CN108586190A (en) * | 2018-07-31 | 2018-09-28 | 山东海昆化工技术有限公司 | A method of recycling chloromethanes from chloromethanes exhaust gas |
-
2019
- 2019-11-05 CN CN201911070121.2A patent/CN110698320B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070269467A1 (en) * | 2006-05-22 | 2007-11-22 | Leatherman Mark D | Use of hydrolysis resistant organomodified silylated surfactants |
| CN103736384A (en) * | 2014-01-27 | 2014-04-23 | 山东潍坊润丰化工股份有限公司 | Treatment process of glyphosate hydrolyzing tail gas |
| CN103752158A (en) * | 2014-01-27 | 2014-04-30 | 山东潍坊润丰化工股份有限公司 | Method for treating glyphosate hydrolyzing tail gas |
| CN105753901A (en) * | 2016-03-19 | 2016-07-13 | 安徽东至广信农化有限公司 | Technology for recovering chloromethane washing wastewater in glyphosate production |
| CN108586190A (en) * | 2018-07-31 | 2018-09-28 | 山东海昆化工技术有限公司 | A method of recycling chloromethanes from chloromethanes exhaust gas |
Non-Patent Citations (2)
| Title |
|---|
| 肖颖: "草甘膦水解尾气的节能回收工艺", 《现代化工》 * |
| 郝振兴等: "国内草甘膦尾气处理技术的专利分析", 《河南科技》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170826A (en) * | 2020-03-16 | 2020-05-19 | 浙江新安化工集团股份有限公司 | Clean recovery system and clean recovery process for chloromethane in glyphosate production tail gas |
| CN111269089A (en) * | 2020-03-16 | 2020-06-12 | 浙江新安化工集团股份有限公司 | Method and system for recovering hydrolysis tail gas of glyphosate synthetic liquid |
| CN111170826B (en) * | 2020-03-16 | 2023-08-22 | 浙江新安化工集团股份有限公司 | Clean recovery system and clean recovery process for chloromethane in tail gas from glyphosate production |
| CN113582811A (en) * | 2020-04-30 | 2021-11-02 | 蓝星（北京）技术中心有限公司 | Deacidification method of methane chloride |
| CN113929555A (en) * | 2021-11-02 | 2022-01-14 | 浙江新安化工集团股份有限公司 | Method and device for recovering byproduct chloromethane for preparing glyphosate or dimethyl phosphite |
| CN113929555B (en) * | 2021-11-02 | 2023-01-03 | 浙江新安化工集团股份有限公司 | Method and device for recovering byproduct chloromethane for preparing glyphosate or dimethyl phosphite |
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