CN1075507C - Hydrolysis subsequent procedure in synthesis of glyphosphonic acid - Google Patents
Hydrolysis subsequent procedure in synthesis of glyphosphonic acid Download PDFInfo
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- CN1075507C CN1075507C CN99119970A CN99119970A CN1075507C CN 1075507 C CN1075507 C CN 1075507C CN 99119970 A CN99119970 A CN 99119970A CN 99119970 A CN99119970 A CN 99119970A CN 1075507 C CN1075507 C CN 1075507C
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Abstract
The present invention relates to a hydrolysis subsequent procedure in the synthesis of glyphosphonate acid. The hydrolysis subsequent procedure has the steps that (1), the hydrolytic tail gas is led to a water scrubber to be washed, methylal and methanol in the tail gas are removed, and thus, the first-stage processed gas is prepared; (2) the first-stage processed gas is led to an alkali liquor absorption tower to be washed, acidic materials in the gas are removed, and thus, the second-stage processed gas is prepared; the second-stage processed gas is led to a concentrated sulfuric acid drying tower to be dried, the tertiary processing gas is prepared, and methyl chloride gas with the purity greater than or equal to 99.95% is prepared. Then, the methyl chloride gas is pressurized, liquefied and collected into a liquid storage tank. The present invention can decrease the synthesis cost of glyphosate acid, eliminate the waste, and overcome the environment pollution.
Description
The present invention relates to the synthetic of glyphosphonic acid, particularly the recovery technology of the synthetic middle hydrolysis tail gas of glyphosphonic acid.
The N-(phosphonomethyl) glycine [(OH)
2POCH
2NHCH
2COOH], be commonly referred to as glyphosphonic acid or be called for short glyphosate, it is one of pesticide species of strong sales, and its output and sales volume were increasing progressively always in recent years.At present, the output of domestic employing dialkyl group method synthesizing glyphosate acid has exceeded 30,000 tons/year.Hydrolysis was at HCl, H during glyphosphonic acid was synthetic
2O, CH
3Carry out in the OH system.According to traditional reaction mechanism, hydrolysis reaction does not consume methyl alcohol, does not produce methyl chloride yet.So traditional way is to reclaim methyl alcohol after the hydrolysis, does not consider the generation and the collection of tail gas.But find in the practice that the consumption of methyl alcohol is very big after the hydrolysis, the former powder of the nearly 600kg/T of its consumption.Trace it to its cause, have two kinds may, the one, the methanol recovery system imperfection causes the rate of recovery low, the 2nd, consumed methyl alcohol in the hydrolytic process and generated new material.The present invention has determined to generate in the hydrolysis fact of methyl chloride on the basis of doing in-depth analysis research.And traditional way is not know to produce methyl chloride gas and this methyl chloride exhaust emissions in the hydrolysis is fallen, and has both wasted, again contaminate environment.
The objective of the invention is to provides a kind of and both can eliminate waste for solving the problem of above-mentioned existence, can eliminate the synthetic middle hydrolysis subsequent procedure of glyphosphonic acid of environmental pollution again, and this is the tail gas recycle operation of appending on traditional hydrolyzing process.
Hydrolysis subsequent procedure during glyphosphonic acid of the present invention is synthetic, described synthetic be to be raw material with Paraformaldehyde 96, glycine, triethylamine, phosphonous acid dimethyl ester, be that the alkyl esterification method of solvent is synthetic with the lower alcohol, the special character of this operation is:
(1) one-level is handled the water wash column washing of stimulating the menstrual flow of described hydrolysis tail gas, removes methylal, methyl alcohol in the tail gas, one-level is handled back gas;
(2) second-stage treatment is handled the alkali lye absorption tower washing of stimulating the menstrual flow of back gas with described one-level, removes acidic substance, gas after the second-stage treatment;
(3) tertiary treatment with described second-stage treatment after the gas vitriol oil drying tower drying of stimulating the menstrual flow, gas after the tertiary treatment.
For ease of accumulating, will be collected in container for storing liquid after the gas pressurization liquefaction after the described tertiary treatment.
Hydrolyzing process during glyphosphonic acid is synthetic, traditional reaction mechanism is:
The present invention proposes new hydrolysis reaction mechanism on the basis of research that performs an analysis:
Enforcement of the present invention is based on qualitative, quantitative test.The glyphosphonic acid synthetic technological condition is all simulated big production and is carried out, divide tertiary treatment with hydrolysis tail gas, one-level is for washing to remove methylal, the methyl alcohol of carrying secretly in the gas, secondary is that alkali lye absorbs, remove HCl gas, use vitriol oil drying for three grades, at last gas is inhaled collection, whether carry out gas spectrum analysis, combustion method mensuration respectively, react with piperidines absorption reaction, sodium iodide, be methyl chloride gas with checking.The result is shown in table 1-table 4.
The pH value test of table 1 tail gas
| Title | Testing method | Phenomenon |
| Tail gas | Test with the wide pH value test paper | Nondiscoloration |
| Exhaust combustion | Test with the wide pH value test paper | The test paper look (pH＜1) that reddens |
| Use AgNO 3、HNO 3The test combustion tail gas | (proof has Cl to become muddiness -) |
Table 2 gas spectrum analysis
| Title | Appearance time (min) | Content % (normalization method) |
| Pure methyl chloride (standard specimen) | 1.54 | 99.96 |
| Dimethyl ester+hydrochloric acid produces tail gas | 1.54 | 99.10 |
| Glyphosphonic acid hydrolysis tail gas | 1.54 | 99.56 |
Table 3 and sodium iodide, piperidines reaction test
| Title | IodineSodium Solution | React with piperidines |
| Glyphosate hydrolysis tail gas in big the production | Muddy and separate out solid by transparent change | Separate out solid by homogeneous liquid |
| Glyphosate hydrolysis tail gas in the lab scale | Analyse and go out solid by transparent change muddiness | Separate out solid by homogeneous liquid |
Table 4 is measured the quantitative of methyl chloride for three times
Annotate: 1. these table data are methyl chloride with sodium iodide react infer and obtain.
| Title | Once | Secondary | Three times |
| Methyl chloride (kg/T) | 510.5 | 520.0 | 517.6 |
2. the amount of methyl chloride is the amount that the former powder of every production 1 ton of folding, hundred glyphosates can produce methyl chloride.
During quantitative test is produced in the production as to press the method for lab scale quantitative, expensive raw material price not only, facility investment is big, complex operation, and also the test period is long.Suitable manner is to adopt the under meter of quantitative gas, with hydrolysis tail gas through directly receiving on the gas meter after the tertiary treatment, note the gas gross of hydrolysis whole process, draw the amount of methyl chloride by PV=NRT, under meter is proofreaied and correct with pure methyl chloride gas, draw the amount that the former powder of 1 ton of folding of every production, hundred glyphosates produces methyl chloride, as shown in the table:
| Title | The amount of methyl chloride (the former powder of kg/T) | ||
| Hydrolysis tail gas | 515.0 | 521.5 | 526.0 |
| Average 520.8 | |||
Year produces 10000 tons of glyphosate devices and can produce～5208 tons of methyl chloride, supposes that it is 75% that methyl chloride reclaims yield, and 3906 tons of then recyclable methyl chloride had both been eliminated waste, had overcome problem of environmental pollution again.Hydrolysis tail gas compresses through three grades of washings, and the quality of product has reached the specification of quality of producing organosilane monomer.So economic benefit of the present invention and social benefit are all very remarkable, have beyond thought technique effect.
The exhaust flow that produces in the hydrolytic process during glyphosphonic acid is synthetic is unbalanced, is normal distribution from 40 ℃～130 ℃ airsheds, reaches maximum value 100 ℃～110 ℃ airsheds.The present invention introduces surge tank to guarantee assimilated efficiency with hydrolysis tail gas earlier, adopts more piece water spray washing again, to remove the water-soluble fatty compounds of low-carbon (LC) class such as methyl alcohol, methylal effectively.Washing equipment is a polypropylene filler tower, controls the quality that absorbs back gas by regulating quantity of circulating water.Gas after the washing contains HCl, H
2Impurity such as O are that 30% the NaOH aqueous solution absorbs to remove the acidic substance in the gas through over-richness again, and soda-wash tower also is a packing tower.At last by pickling tower drying, adopt the vitriol oil, three tower cascade connected, through the drying washing of three different gradients methyl chloride purity is reached more than 99.95%.Methyl chloride gas after refining is delivered to gas holder through roots blower, adopts ammonia compressor to be compressed to 7～8atm again, through interchanger it is condensed into liquid input storage tank then.
Claims (4)
1, glyphosphonic acid synthetic in hydrolysis subsequent procedure, described synthetic be to be raw material with Paraformaldehyde 96, glycine, triethylamine, phosphonous acid dimethyl ester, be that the alkyl esterification method of solvent is synthetic with the lower alcohol, it is characterized in that:
(1) one-level is handled the water wash column washing of stimulating the menstrual flow of tail gas with described hydrolysis, removes methylal, methyl alcohol in the tail gas, one-level is handled back gas;
(2) second-stage treatment is handled the alkali lye absorption tower washing of stimulating the menstrual flow of back gas with described one-level, removes the acidic substance in the gas, gas after the second-stage treatment;
(3) tertiary treatment with described second-stage treatment after the gas vitriol oil drying tower drying of stimulating the menstrual flow, gas after the tertiary treatment.
2, the synthetic middle hydrolysis subsequent procedure of glyphosphonic acid as claimed in claim 1 is characterized in that and will be collected in container for storing liquid after the gas pressurization liquefaction after the described tertiary treatment.
3, glyphosphonic acid as claimed in claim 1 synthetic in hydrolysis subsequent procedure, it is characterized in that with gas after the described tertiary treatment after blower fan is delivered to gas holder again with compressor compresses to 7～8atm, through interchanger it is condensed into liquid collecting in container for storing liquid then.
4, as claim 1,2 or 3 described glyphosphonic acids synthetic in hydrolysis subsequent procedure, it is characterized in that it is described tail gas to be introduced the water wash column that stimulates the menstrual flow again behind the surge tank earlier wash that described one-level is handled, described water wash column is a polypropylene filler tower; Described alkali lye absorption tower is a packing tower, and described alkali lye is the NaOH aqueous solution of weight concentration 30%; Described vitriol oil drying tower is three tower cascade connected formula drying tower, and gas is the methyl chloride gas of purity 〉=99.95% after the described tertiary treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119970A CN1075507C (en) | 1999-11-08 | 1999-11-08 | Hydrolysis subsequent procedure in synthesis of glyphosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119970A CN1075507C (en) | 1999-11-08 | 1999-11-08 | Hydrolysis subsequent procedure in synthesis of glyphosphonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1260348A CN1260348A (en) | 2000-07-19 |
| CN1075507C true CN1075507C (en) | 2001-11-28 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99119970A Expired - Lifetime CN1075507C (en) | 1999-11-08 | 1999-11-08 | Hydrolysis subsequent procedure in synthesis of glyphosphonic acid |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100421769C (en) * | 2005-08-02 | 2008-10-01 | 黄立维 | Method for unwanted exhaust gas purification and dedicated apparatus |
| CN101225030B (en) * | 2007-01-15 | 2011-07-20 | 浙江新安化工集团股份有限公司 | Method for utilizing thermal energy during continuous synthesis of glyphosate |
| CN100509786C (en) * | 2008-04-18 | 2009-07-08 | 浙江金帆达生化股份有限公司 | Comprehensive process for tail gas in glyphosate production |
| CN106748637A (en) * | 2016-11-09 | 2017-05-31 | 四川福思达生物技术开发有限责任公司 | A kind of glyphosate hydrolyzing tail gas recovery method |
| CN110860194B (en) * | 2018-08-27 | 2021-09-07 | 湖北泰盛化工有限公司 | Device and method for treating paraformaldehyde dust in glyphosate production feeding process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050542A (en) * | 1989-08-17 | 1991-04-10 | 孟山都公司 | The method of purifying N-phosphonomethylglycine |
| EP0474955A1 (en) * | 1988-11-07 | 1992-03-18 | Monsanto Company | Process for the preparation of N-phosphonomethylglycine by means of an oxidation/dealkylation process |
| EP0717046A1 (en) * | 1994-07-01 | 1996-06-19 | Showa Denko Kabushiki Kaisha | Process for producing phosphonic acid derivative |
-
1999
- 1999-11-08 CN CN99119970A patent/CN1075507C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0474955A1 (en) * | 1988-11-07 | 1992-03-18 | Monsanto Company | Process for the preparation of N-phosphonomethylglycine by means of an oxidation/dealkylation process |
| CN1050542A (en) * | 1989-08-17 | 1991-04-10 | 孟山都公司 | The method of purifying N-phosphonomethylglycine |
| EP0717046A1 (en) * | 1994-07-01 | 1996-06-19 | Showa Denko Kabushiki Kaisha | Process for producing phosphonic acid derivative |
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| CN1260348A (en) | 2000-07-19 |
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