CN108727160A - A kind of alkyl esterification method production glyphosate hydrolyzing tail gas pressure control reclaimer and technique - Google Patents
A kind of alkyl esterification method production glyphosate hydrolyzing tail gas pressure control reclaimer and technique Download PDFInfo
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- CN108727160A CN108727160A CN201810362619.5A CN201810362619A CN108727160A CN 108727160 A CN108727160 A CN 108727160A CN 201810362619 A CN201810362619 A CN 201810362619A CN 108727160 A CN108727160 A CN 108727160A
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- tail gas
- methanol
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- dimethoxym ethane
- tower
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- 239000005562 Glyphosate Substances 0.000 title claims abstract description 60
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 60
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 43
- 230000032050 esterification Effects 0.000 title claims abstract description 32
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 432
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 18
- 238000009833 condensation Methods 0.000 claims abstract description 17
- 230000005494 condensation Effects 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 22
- 230000003472 neutralizing effect Effects 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 17
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000004064 recycling Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001241 acetals Chemical class 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910002804 graphite Inorganic materials 0.000 abstract description 9
- 239000010439 graphite Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 230000006837 decompression Effects 0.000 abstract description 5
- 238000002309 gasification Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- -1 alkyl phosphates Chemical class 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- RRUHHJFQZXSOTJ-UHFFFAOYSA-N P(OC)(OC)OC.NCC(=O)O Chemical compound P(OC)(OC)OC.NCC(=O)O RRUHHJFQZXSOTJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- 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
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment 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
- C07C29/94—Use of additives, e.g. for stabilisation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the glyphosate hydrolyzing tail gas pressure control reclaimers and technique of alkyl esterification method production, the glyphosate hydrolyzing tail gas pretreatment system of alkyl esterification method production is connect with dilute methanol solution collecting tank, dilute methanol solution collecting tank is connect through pipeline with dimethoxym ethane rectifier, condensed device one is connect with dimethoxym ethane rectifier column reflux tank at the top of dimethoxym ethane rectifying column, and dimethoxym ethane rectifier column reflux tank is connected to dimethoxym ethane finished pot；Dimethoxym ethane rectifier bottoms are connect through pipeline with methanol aqueous solution pans；Methanol aqueous solution pans are connect through pipeline with methanol rectifying tower, and the condensed device of methanol rectification top of tower three is connect with methanol rectifying tower return tank, and methanol rectifying tower return tank is connected to methanol finished pot.Also disclose specific processing step.The energy consumption that solvent recovery is reduced by pressure control condensation, decompression gasification measure, improves the stability of hydrolysis tail gas recycle, does not use the delicate graphite condenser highly relied in stoste phase recovery process.
Description
Technical field
The invention belongs to alkyl esterification method production glyphosate solvent recovery new equipment and its techniques.
Background technology
Glyphosate technology profile
Glyphosate is efficient one kind, low toxicity, wide spectrum, natural disposition of going out, nonselective herbicide, has excellent biological nature.At present
Domestic glyphosate mainstream production technology has two lines：Alkyl esterification method and iminodiacetic acid (salt) acid system.External production technology is then led
If the iminodiacetic acid (salt) acid system of Monsanto Chemicals, the prevailing technology that China produces glyphosate is alkyl esterification method.Arrcostab
Method and predominantly glycine-dialkyl phosphite method separately have monoxone-alkane that glyphosate is produced using monoxone as starting material
Base ester method and glycine-Trimethyl phosphite method etc. minority's route.
Glyphosate hydrolyzing tail gas recovery process brief introduction
It is water, dimethoxym ethane, methanol, hydrogen chloride and chloromethanes mixing that alkyl esterification method glyphosate synthesis solution, which hydrolyzes tail gas main component,
The removal process of object, the tail gas is referred to as solvent recovery in glyphosate industry.
The Synthesis liquid refers to by methanol, paraformaldehyde（Or other formaldehyde sources）, glycine（Or using monoxone as starting point
Other raw materials of raw material）, dimethylphosphite（Or other alkyl phosphates）Equal raw material are obtained through depolymerization, condensation, esterification
The main component arrived is the organophosphors intermediates such as N- methoxyalkyl ester methyl glycine（Glyphosate precursor）Mixed solution.
It hydrolyzes there are two types of tail gas recycle tradition recycling routes：
First, liquid phase recycles route, i.e.,：Main component is water, dimethoxym ethane, methanol, hydrogen chloride and chloromethanes glyphosate hydrolyzing tail gas
It is condensed through Multistage graphite condenser, fixed gas goes to the recycling of chloromethanes device, water, dimethoxym ethane, methanol, hydrogen chloride warp in tail gas
Condensation liquefaction obtains acid dilute methanol, neutralized except after de-chlorine hydride, neutral dilute methanol is obtained, for by dimethoxym ethane（A）Methanol
（B）Water（C）The ternary mixes liquid mixed system of composition.The volatility of wherein A, B, C reduce successively, and three components use two-stage
Tower is detached, and specially isolates A, B, detailed process from tower top successively according to the sequence of component relative volatility size
For：First order column overhead distillates component A, and bottom of tower mixed liquor is B+C, and B+C enters second level tower and is further separated into B（Tower top evaporates
Go out liquid）And C（Tower bottoms）.
This method is easy to operate but there is the shortcomings that height relies on graphite condenser, intrinsic safety difference and high energy consumption：
It is the sour gas containing a large amount of hydrogen chloride that the process route, which hydrolyzes tail gas, so height relies on graphite condenser.And graphite condenses
Device not temperature variation resistant, not pressure-resistant, leaks it so being endured to the fullest extent in graphite condenser using the glyphosate gas-liquid of this glyphosate process route
Hardship, equipment investment is big, maintenance cost is high；Leakage causes acidic materials and organic matter to enter chilled water and circulating water in condenser
System, corrodes chilled water and circulation, chilled water fire risk, causes essential safety degree low, environmental protection pressure is big；Condensation
Leakage also results in chilled water and seals in dilute methanol system in device, increases dilute methanol treating capacity and operating cost.In addition, this method process
In, material is by " condensation, condenses gasification again " multiple phase transformation, so energy consumption is very high, it is uneconomical.
Second is that gas phase recycles route, i.e.,：Main component is water, dimethoxym ethane, methanol, hydrogen chloride and the hydrolysis of chloromethanes glyphosate
Tail gas is through, with removing hydrogen chloride gas, residual exhaust is by dimethoxym ethane in gas phase（A）Methanol（B）Water（C）Chloromethanes（D）Group
At quaternary mixed gaseous mixed system, detached through two stage rectification tower and condenser, specially according to component boiling point height
Sequence isolate C, B from bottom of tower successively, detailed process is：C is isolated in first order tower bottom of tower, and tower top isolates component A+B+
D；A+B+D enters second level tower and is further separated into B（Tower bottoms）With A+D（Overhead distillate）, the condensed device condensations of A+D
It is separated into A（Condensate liquid）And D（Fixed gas）.
This method mutually tails off, low energy consumption, but haves the shortcomings that operation stability is poor：First, hydrolysis tail gas removes de-chlorine hydride
Remaining tail gas is by dimethoxym ethane after gas（A）Methanol（B）Water（C）Chloromethanes（D）The quaternary mixes liquid system of composition,
Opposite liquid phase route, material total amount is big, and logistics load is big（It is 1.5 times of liquid phase）, chloromethanes component ratio is big（Account for tail gas total amount
30%）, lead to recovery system fluctuation of service.In the case of especially shutting off power in emergency, a large amount of dimethoxym ethanes（A）, methanol（B）, chloromethane
Alkane（D）Material system is from urgent pressure relief system discharging decompressing, and therefore, there are larger safe and environment-friendly hidden danger for operation stability difference.
Invention content
The purpose of invention
In view of the above problems and defect, the present invention provides a kind of alkyl esterification method glyphosate hydrolyzing tail gas to recycle new equipment
And technique, the delicate graphite condenser highly relied in stoste phase recovery process can be eliminated, while improving hydrolysis tail gas and returning
The stability of receipts；And the energy consumption in production process is reduced by pressure control condensation, decompression gasification technology, glyphosate solvent is improved and returns
The essential safety and economy of receipts.
For achieving the above object, the present invention uses following technical scheme：
A kind of glyphosate hydrolyzing tail gas pressure control reclaimer of alkyl esterification method production, including dilute methanol solution collecting tank, dimethoxym ethane
Rectifying column, methanol aqueous solution pans, methanol rectifying tower,
The glyphosate hydrolyzing tail gas pretreatment system of alkyl esterification method production is connect with dilute methanol solution collecting tank,
Dilute methanol solution collecting tank is connect through pipeline with dimethoxym ethane rectifier, at the top of dimethoxym ethane rectifying column condensed device one with
Dimethoxym ethane rectifier column reflux tank connects, and dimethoxym ethane rectifier column reflux tank is connected to dimethoxym ethane finished pot；
Dimethoxym ethane rectifier bottoms are connect through pipeline with methanol aqueous solution pans；
Methanol aqueous solution pans are connect through pipeline with methanol rectifying tower, the condensed device three of methanol rectification top of tower and methanol rectification
Tower return tank connects, and methanol rectifying tower return tank is connected to methanol finished pot.
The glyphosate hydrolyzing tail gas pretreatment system of the alkyl esterification method production includes glyphosate hydrolyzing tail gas tank, liquid caustic soda
Tank, dilute alkali liquid tank；
The glyphosate hydrolyzing tail gas tank couples through feeding pipe with tail gas neutralizing tower lower part, and liquid caustic soda tank is through conveying pipeline and thin liquid
It is connect again with tail gas neutralizing tower top after the connection of alkali tank；
It is connect with tail gas condenser through compressor one at the top of tail gas neutralizing tower, tail gas condenser connects with dilute methanol solution collecting tank
It connects；
Dilute alkali liquid tank is connect through pipeline with dilute methanol solution collecting tank.
The dimethoxym ethane rectifier column reflux tank is connect through pipeline with dimethoxym ethane rectifier；Methanol rectifying tower return tank
It is connect with methanol rectifying tower top through pipeline.
The dimethoxym ethane rectifier bottoms are connect with dimethoxym ethane rectifying column lower part again after pipeline is connect with reboiler one.
The methanol rectification tower bottom is connect with methanol rectifying tower lower part again after pipeline is connect with reboiler two；
Methanol rectification tower bottom is connected to sewage plant through pipeline.
Another object of the present invention is to provide a kind of alkyl esterification method production glyphosate hydrolyzing tail gas pressure control recovery process,
Glyphosate hydrolyzing tail gas of the present invention is to hydrolyze contracting including hydrogen chloride, chloromethanes, methanol, first for post from glyphosate
The mixture of aldehyde, vapor, wherein predominantly water 40-45%, methanol 25-35%, also contain a small amount of dimethoxym ethane 10-15%, chloromethanes
10-15% and micro hydrogen chloride 0.1-2%；In the technique of the present invention, after testing 43%, methanol 30%, also contain a small amount of dimethoxym ethane
13%, chloromethanes 13% and micro hydrogen chloride 1%.Include the following steps：
Neutralization and pressure control step：Glyphosate hydrolyzing tail gas is neutralized, pressure control, condensation, condensate liquid goes to dilute methanol solution recovery tank；
Auxiliary agent is added, mixing -30 minutes 10 seconds is placed, so that the organic impurities in dilute methanol is decomposed or is overflowed and realize removing, removing
Dilute methanol after organic impurities goes to solvent recovery unit, and recycling obtains methanol, dimethoxym ethane product.The auxiliary agent includes alkalinity
Any one of substance or oxidant, the alkaline matter include but not limited to sodium hydroxide, potassium hydroxide solid or solution,
The oxidant includes but not limited to sodium hypochlorite, hydrogen peroxide；The addition of auxiliary agent is that dilute methanol collection buffering pot liquid is total
The 0.01 ‰ -10% of weight.
Dimethoxym ethane recycling step：Condensate liquid in dilute methanol solution collecting tank, after expenditure and pressure on pump to dimethoxym ethane rectifying column
Portion, the condensed device condensation of dimethoxym ethane rectifying column tower top gas return to dimethoxym ethane rectifier column reflux tank all the way, and another way is pumped through extraction
It is sent to dimethoxym ethane finished pot, dimethoxym ethane rectifying column bottom liquid goes to methanol aqueous solution pans；
Methanol Recovery step：Material in methanol aqueous solution pans is squeezed into through pump into methanol rectifying tower top, methanol rectifying tower
The condensed device condensation of overhead gas returns to methanol rectifying tower return tank all the way, and another way is pumped through extraction toward methanol finished pot, first
Alcohol rectifying column bottom liquid is adopted toward station at dirt.
In the neutralization and pressure control step, it is 7-14 that glyphosate hydrolyzing tail gas is neutralized to pH through liquid caustic soda；The alkalinity
Substance includes but not limited to sodium hydroxide, potassium hydroxide solid or solution, while controlling tail gas neutralizing tower, the collection of dilute methanol solution
Pressure inside the tank is 0.1-0.4MPa ranges, system temperature in 10-88 DEG C of range.
The temperature control of the dimethoxym ethane rectifier bottoms is 65 ± 10 DEG C, and the temperature control on top is 42 ± 3 DEG C.
The temperature control of the methanol rectification tower bottom is 100 ± 10 DEG C, and the temperature control on top is 65 ± 5 DEG C.
The present invention provides a kind of alkyl esterification method glyphosate hydrolyzing tail gas recycling new equipment and techniques, have eliminated stoste phase and have returned
The delicate graphite condenser highly relied in skill of knocking off, avoid the interior leakage of condenser causes this grass of chilled water COD high sweet
Phosphine professional problem, while the stability for reducing system pressure, improving hydrolysis tail gas recycle pass through pressure control condensation, decompression
Gasification measure reduces the energy consumption of solvent recovery, improves essential safety, stability and the economy of glyphosate hydrolyzing tail gas operation
Property.
Description of the drawings
Fig. 1 is alkyl esterification method glyphosate hydrolyzing tail gas reclaimer figure of the present invention, wherein 1. glyphosate hydrolyzing tail gas tanks,
2. liquid caustic soda tank, 3. dilute alkali liquid tanks, 4. compressors one, 5. compressors two, 6. tail gas condensers, 7. dilute alkali liquid tanks, 8. dilute first
Alcoholic solution collecting tank, 9. dimethoxym ethane rectifying columns, 10. reboilers one, 11 condensers one, 12. dimethoxym ethane rectifier column reflux tanks,
13. methanol aqueous solution pans, 14. methanol rectifying towers, 15. condensers three, 16. reboilers two, 17. methanol rectifying towers
Return tank, 18. dimethoxym ethane finished pots, 19. methanol finished pots, 20. sewage plants.
Specific implementation mode
Embodiment 1
A kind of glyphosate hydrolyzing tail gas pressure control reclaimer of alkyl esterification method production, including dilute methanol solution collecting tank 8, dimethoxym ethane
Rectifying column 9, methanol aqueous solution pans 13, methanol rectifying tower 14,
The glyphosate hydrolyzing tail gas pretreatment system of alkyl esterification method production is connect with dilute methanol solution collecting tank 8,
Dilute methanol solution collecting tank 8 is connect through pipeline with 9 top of dimethoxym ethane rectifying column, the 9 condensed device in top of dimethoxym ethane rectifying column
One 11 connect with dimethoxym ethane rectifier column reflux tank 12, and dimethoxym ethane rectifier column reflux tank 12 is connected to dimethoxym ethane finished pot 18, first contracting
The bottom of aldehyde rectifying column 9 is equipped with reboiler；
9 bottom of dimethoxym ethane rectifying column is connect through pipeline with methanol aqueous solution pans 13；
Methanol aqueous solution pans 13 are connect through pipeline with methanol rectifying tower 14, the condensed device in the top of methanol rectifying tower 14 3 15 with
Methanol rectifying tower return tank 17 connects, and methanol rectifying tower return tank 17 is connected to methanol finished pot 19, the bottom of methanol rectifying tower 14
Portion is equipped with reboiler.
The glyphosate hydrolyzing tail gas pretreatment system of the alkyl esterification method production includes glyphosate hydrolyzing tail gas tank 1, liquid
Alkali tank 2, dilute alkali liquid tank 3；
The glyphosate hydrolyzing tail gas tank 1 couples through feeding pipe with 3 lower part of tail gas neutralizing tower, liquid caustic soda tank 2 through conveying pipeline with
Dilute alkali liquid tank 7 is connect with 3 top of tail gas neutralizing tower again after connecting；
Glyphosate hydrolyzing tail gas feeding pipe couples with tail gas neutralizing tower lower part.It is also mended by liquid caustic soda on tail gas neutralizing tower top
It fills pipeline to connect with liquid caustic soda tank, tail gas neutralizing tower lower part also produces pipeline by dilute alkali liquid and with dilute alkali liquid tank couples.Dilute alkali liquid tank
It is connect with tail gas neutralizing tower top by feeding pipe, and cycle is formed by pumping.
3 top of tail gas neutralizing tower is connect through compressor 1 with tail gas condenser 6, and tail gas condenser 6 is received with dilute methanol solution
Collect tank 8 to connect；
Tail gas neutralizing tower top is coupled by feeding pipe with tail gas condenser；The tail gas neutralizing tower and tail gas condenser
Between and tail gas condenser after be respectively arranged with compressor 1, compressor 2.
It should be appreciated that the tail gas condenser at least condenser in the condenser system, but it is not limited to only one
Condenser.When tail gas condenser there are more, can couple in parallel or series or by way of connection in series-parallel combination.
The liquid phase blanking of the tail gas condenser goes to dilute methanol solution collecting tank by the feeding pipe.The dilute methanol
Solution collecting tank top is provided with pressure-equalizing pipe, and both ends join with dilute methanol solution collecting tank and tail gas condenser outlet respectively
It connects.
The tail gas passes through tail gas neutralizing tower, 1# compressors, condenser, 2# compressors successively, from tail gas condenser
Incoagulability tail gas and the tail gas from dilute methanol solution collecting tank through 2# compressors go to Chloromethane recovery device after converging.
Dilute alkali liquid tank 7 is connect through pipeline with dilute methanol solution collecting tank 8.
The dimethoxym ethane rectifier column reflux tank 12 is connect through pipeline with 9 top of dimethoxym ethane rectifying column；Methanol rectifying tower returns
Stream tank 17 is connect through pipeline with 14 top of methanol rectifying tower.
9 bottom of dimethoxym ethane rectifying column after pipeline is connect with reboiler 1 again with 9 lower part of dimethoxym ethane rectifying column
Connection.
14 bottom of methanol rectifying tower connects with 14 lower part of methanol rectifying tower again after pipeline is connect with reboiler 2 16
It connects；
14 bottom of methanol rectifying tower is connected to sewage plant 20 through pipeline.
Embodiment 2
A kind of glyphosate hydrolyzing tail gas pressure control recovery process of alkyl esterification method production, includes the following steps：
Neutralization and pressure control step：What it is from glyphosate hydrolysis post includes hydrogen chloride, chloromethanes, methanol, dimethoxym ethane, vapor
It is 7-11 that mixture is neutralized to pH together with liquid caustic soda into tail gas neutralizing tower, the acid ingredient in tail gas is removed, then again through control
Enter tail gas condenser after pressure and carry out condensation separation, condensate liquid goes to dilute methanol solution collecting tank respectively, and incoagulable gas is gone to
Chloromethane recovery device.
By being where 1#, 2# compressor control tail gas condenser, dilute methanol solution collecting tank and its pressure-equalizing pipe
Pressure of uniting is denoted as P in 0.1-0.4MPa.The specific boundary of the system is 1# compressor outlets, 2# compressor inlets, valve 1.
By water, methanol, dimethoxym ethane, chloromethanes physical property it is found that under a certain pressure, saturation temperature size order
For：Water > methanol > dimethoxym ethane > chloromethanes.Under a certain pressure, it controls exhaust temperature T by condenser to gradually reduce, works as tail
When temperature degree is down under the respective saturation temperature of water, methanol, dimethoxym ethane, water, methanol, dimethoxym ethane are condensed, are detached respectively.
As system pressure increases, the saturation temperature of material also increases therewith in water, methanol, dimethoxym ethane, chloromethanes 4, i.e.,
They can condense at higher temperatures.Through looking into, above-mentioned substance saturation temperature data are as follows：
Specific pressure control condenses scheme：
When the control pressure of tail gas condenser is P above-mentioned, water under corresponding pressure, methanol, dimethoxym ethane saturation temperature be denoted as T
（Water saturation）,T（Methanol is saturated）,T（Dimethoxym ethane is saturated）, it is known that T（Dimethoxym ethane is saturated）< T（Methanol is saturated）< T（Water saturation）.
When control system temperature T meets：T < T1（Dimethoxym ethane is saturated）When, water, methanol, dimethoxym ethane in tail gas condense, and chloromethane
Alkane does not condense, and realizes that the separation of the water, methanol, dimethoxym ethane and chloromethanes in tail gas, condensate liquid enter dilute methanol solution receipts
Collect tank, uncooled chloromethanes tail gas continues to go to Chloromethane recovery device processing.In embodiment, control system pressure P1 exists
0.1-0.4MPa ranges, system temperature T1 lift specific example in 13-88 DEG C of range:1. control system pressure P=0.4MPa, control
80-88 DEG C of system temperature processed, can reach separation requirement;2. control system pressure P=0.2MPa, 10-62 DEG C of control system temperature,
It can reach separation requirement.It should be appreciated that as P=0.1MPa, as normal pressure condenses this special operation condition.
Dimethoxym ethane recycling step：Dilute methanol in dilute methanol solution collecting tank, goes to dimethoxym ethane rectifying after expenditure and pressure
Tower top, its boiling point reduces after material decompression, gasifies in tower.The condensed device condensation of dimethoxym ethane rectifying column tower top gas returns to first
Acetal rectifier column reflux tank, the liquid in dimethoxym ethane rectifier column reflux tank is formed through reflux pump to flow back, and another way is pumped through extraction
Toward dimethoxym ethane finished pot.Dimethoxym ethane rectifying column bottom liquid goes to methanol aqueous solution pans.The temperature of dimethoxym ethane rectifier bottoms
Degree control is 65 ± 10 DEG C, and the temperature control on top is 42 ± 3 DEG C.
Methanol Recovery step：Material in methanol aqueous solution pans is squeezed into through pump into methanol rectifying tower top.Methanol essence
It evaporating the condensed device condensation of column overhead gas and returns to methanol rectifying tower return tank, the liquid in return tank is formed through reflux pump and is flowed back,
Another way is pumped through extraction toward methanol finished pot.Methanol rectifying tower bottom liquid is adopted toward station at dirt.The temperature of two-stage rectification tower bottom
Degree control is 100 ± 10 DEG C, and the temperature control on top is 65 ± 5 DEG C DEG C.
It should be appreciated that material boiling point after decompression reduces in dimethoxym ethane rectifying column, only self heat is leaned on to realize ebullition, gasification
It is detached with rectifying, in addition when normal operation need not supplement steam, energy saving to realize.The reboiler only drive first or
Raw steam is supplemented when system temperature is too low on a small quantity.Compared to traditional handicraft, control system is under 1 temperature of examples detailed above, pressure condition
（System pressure P=0.4MPa, 80-88 DEG C of control system temperature）, on methanol, dimethoxym ethane moisture, content quality index basis up to standard
On, ton glyphosate solvent recovery steam mono-consumption significantly declines, and declines about 1.8t/t.Control system is in 2 temperature of examples detailed above, pressure
Under the conditions of power（System pressure 0.2MPa, 10-62 DEG C of control system temperature）, in methanol, dimethoxym ethane moisture, content quality index
On the basis of up to standard, ton glyphosate solvent recovery steam mono-consumption significantly declines, and declines about 1.4t/t.This Processes and apparatus is also eliminated
The delicate graphite condenser highly relied in stoste phase recovery process, avoid leaked in condenser leads to chilled water COD
This high problem, intrinsic safety are improved.
Claims (10)
1. a kind of glyphosate hydrolyzing tail gas pressure control reclaimer of alkyl esterification method production, including dilute methanol solution collecting tank（8）, first
Acetal rectifying column（9）, methanol aqueous solution pans（13）, methanol rectifying tower（14）, which is characterized in that
The glyphosate hydrolyzing tail gas pretreatment system and dilute methanol solution collecting tank of alkyl esterification method production（8）Connection,
Dilute methanol solution collecting tank（8）Through pipeline and dimethoxym ethane rectifying column（9）Top connects, dimethoxym ethane rectifying column（9）Top passes through
Condenser one（11）With dimethoxym ethane rectifier column reflux tank one（12）Connection, dimethoxym ethane rectifier column reflux tank one（12）It is connected to first contracting
Aldehyde finished pot（18）；
Dimethoxym ethane rectifying column（9）Bottom is through pipeline and methanol aqueous solution pans（13）Connection；
Methanol aqueous solution pans（13）Through pipeline and methanol rectifying tower（14）Connection, methanol rectifying tower（14）The condensed device in top
Three（15）With methanol rectifying tower return tank two（17）Connection, methanol rectifying tower return tank two（17）It is connected to methanol finished pot
（19）.
2. the glyphosate hydrolyzing tail gas pressure control reclaimer of alkyl esterification method production described in claim 1, which is characterized in that described
Alkyl esterification method production glyphosate hydrolyzing tail gas pretreatment system include glyphosate hydrolyzing tail gas tank（1）, liquid caustic soda tank（2）, tail
Gas neutralizing tower（3）, dilute alkali liquid tank（7）；
The glyphosate hydrolyzing tail gas tank（1）Through pipeline and tail gas neutralizing tower（3）Lower part couples, liquid caustic soda tank（2）Through pipeline with
Dilute alkali liquid tank（7）After connection again with tail gas neutralizing tower（3）Top connects, tail gas neutralizing tower（3）Bottom and dilute alkali liquid tank（7）Connection
Form circulation loop；
Dilute alkali liquid tank（7）Through pipeline and dilute methanol solution collecting tank（8）Connection.
3. the glyphosate hydrolyzing tail gas pressure control reclaimer of the alkyl esterification method production described in claim 2, which is characterized in that tail gas
Neutralizing tower（3）Top is through compressor one（4）With tail gas condenser（6）Connection, tail gas condenser（6）With dilute methanol solution collecting tank
（8）Connection；
Tail gas condenser（6）With dilute methanol solution collecting tank（8）Through balancing pressure pipe connection balance pressure, tail gas condenser is not
The tail gas of solidifying property gas and dilute methanol solution collecting tank is connected to compressor two after converging（5）Connection, compressor two（5）It is connected to
Chloromethanes collecting tank；
The tail gas condenser（6）At least one, including when multiple condensers, multiple condensers connect in parallel or series.
4. the glyphosate hydrolyzing tail gas pressure control reclaimer of alkyl esterification method production described in claim 1, which is characterized in that first contracts
Aldehyde rectifier column reflux tank one（12）Through pipeline and dimethoxym ethane rectifying column（9）Top connects；Methanol rectifying tower return tank two（17）Through
Pipeline and methanol rectifying tower（14）Top connects.
5. the glyphosate hydrolyzing tail gas pressure control reclaimer of alkyl esterification method production described in claim 1, which is characterized in that first contracts
Aldehyde rectifying column（9）Bottom is through pipeline and reboiler one（10）After connection again with dimethoxym ethane rectifying column（9）Lower part connects.
6. the glyphosate hydrolyzing tail gas pressure control reclaimer of alkyl esterification method production described in claim 1, which is characterized in that methanol
Rectifying column（14）Bottom is through pipeline and reboiler two（16）After connection again with methanol rectifying tower（14）Lower part connects；
Methanol rectifying tower（14）Bottom is connected to sewage plant through pipeline（20）.
7. a kind of glyphosate hydrolyzing tail gas pressure control recovery process of alkyl esterification method production, which is characterized in that include the following steps：
Neutralization and pressure control step：Glyphosate hydrolyzing tail gas is neutralized, pressure control, condensation, condensate liquid goes to dilute methanol solution recovery tank；
Dimethoxym ethane recycling step：Condensate liquid in dilute methanol solution collecting tank enters dimethoxym ethane essence after throttling is decompressed to normal pressure
Tower top is evaporated, the condensed device condensation of dimethoxym ethane rectifying column tower top gas returns to dimethoxym ethane rectifier column reflux tank, another way warp all the way
Toward dimethoxym ethane finished pot, dimethoxym ethane rectifying column bottom liquid goes to methanol aqueous solution pans for extraction pumping；
Methanol Recovery step：Material in methanol aqueous solution pans is squeezed into through pump into methanol rectifying tower top, methanol rectifying tower
The condensed device condensation of overhead gas returns to methanol rectifying tower return tank all the way, and another way is pumped through extraction toward methanol finished pot, first
Alcohol rectifying column bottom liquid is adopted toward station at dirt.
8. the glyphosate hydrolyzing tail gas pressure control recovery process of the alkyl esterification method production described in claim 7, which is characterized in that neutralize
And in pressure control step, glyphosate hydrolyzing tail gas is 7-14 through alkali neutralization to pH；, while controlling tail gas neutralizing tower, dilute methanol solution
Collecting tank system pressure is denoted as P in 0.1-0.4MPa, which is denoted as T, and T controls are:TChloromethanes saturation temperature< T <
TDimethoxym ethane saturation temperature。
9. the glyphosate hydrolyzing tail gas pressure control recovery process of the alkyl esterification method production described in claim 7, which is characterized in that first contracts
The temperature control of aldehyde rectifier bottoms is 65 ± 10 DEG C, and the temperature control on top is 42 ± 3 DEG C.
10. the glyphosate hydrolyzing tail gas pressure control recovery process of the alkyl esterification method production described in claim 7, which is characterized in that first
The temperature control of alcohol rectifier bottoms is 100 ± 10 DEG C, and the temperature control on top is 65 ± 5 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128469A (en) * | 2019-05-28 | 2019-08-16 | 内蒙古兴发科技有限公司 | A kind of dimethylphosphite by-product hydrogen chloride is applied to the device and technique of glyphosate synthesis |
| CN111068497A (en) * | 2019-12-13 | 2020-04-28 | 湖北泰盛化工有限公司 | Device and method for recovering solvent methanol in glyphosate production |
| CN111203090A (en) * | 2020-03-16 | 2020-05-29 | 浙江新安化工集团股份有限公司 | System and process for treating hydrolysis tail gas of glyphosate and phosphonated synthetic liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288606A (en) * | 2013-06-09 | 2013-09-11 | 湖北泰盛化工有限公司 | Method for recycling methylal in glyphosate wastewater |
| 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 |
| CN104353339A (en) * | 2014-10-30 | 2015-02-18 | 江西金龙化工有限公司 | Method for continuously recovering by-products from tail gas obtained by hydrolyzing glyphosate |
| CN104959002A (en) * | 2015-06-29 | 2015-10-07 | 江西金龙化工有限公司 | Method for removing hydrogen chloride by continuously recycling glyphosate hydrolyzed tail gas |
-
2018
- 2018-04-20 CN CN201810362619.5A patent/CN108727160B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288606A (en) * | 2013-06-09 | 2013-09-11 | 湖北泰盛化工有限公司 | Method for recycling methylal in glyphosate wastewater |
| 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 |
| CN104353339A (en) * | 2014-10-30 | 2015-02-18 | 江西金龙化工有限公司 | Method for continuously recovering by-products from tail gas obtained by hydrolyzing glyphosate |
| CN104959002A (en) * | 2015-06-29 | 2015-10-07 | 江西金龙化工有限公司 | Method for removing hydrogen chloride by continuously recycling glyphosate hydrolyzed tail gas |
Non-Patent Citations (2)
| Title |
|---|
| 胡跃华,周海扬,周曙光,陈晓祥: "烷基酯法草甘膦尾气的连续回收工艺" * |
| 黄伟果;陆宗盛;何明金;黄剑敏;潘力勇;: "草甘膦水解尾气回收的新型工艺设计" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128469A (en) * | 2019-05-28 | 2019-08-16 | 内蒙古兴发科技有限公司 | A kind of dimethylphosphite by-product hydrogen chloride is applied to the device and technique of glyphosate synthesis |
| CN110128469B (en) * | 2019-05-28 | 2021-07-13 | 内蒙古兴发科技有限公司 | Device and process for applying dimethyl phosphite byproduct hydrogen chloride to glyphosate synthesis |
| CN111068497A (en) * | 2019-12-13 | 2020-04-28 | 湖北泰盛化工有限公司 | Device and method for recovering solvent methanol in glyphosate production |
| CN111203090A (en) * | 2020-03-16 | 2020-05-29 | 浙江新安化工集团股份有限公司 | System and process for treating hydrolysis tail gas of glyphosate and phosphonated synthetic liquid |
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