CN101270077A - Comprehensive process for tail gas in glyphosate production - Google Patents
Comprehensive process for tail gas in glyphosate production Download PDFInfo
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- CN101270077A CN101270077A CNA200810060763XA CN200810060763A CN101270077A CN 101270077 A CN101270077 A CN 101270077A CN A200810060763X A CNA200810060763X A CN A200810060763XA CN 200810060763 A CN200810060763 A CN 200810060763A CN 101270077 A CN101270077 A CN 101270077A
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- tail gas
- pyridine
- glyphosate
- reaction
- methyl alcohol
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- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 43
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 43
- 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 132
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000002585 base Substances 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 35
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- 229940050176 methyl chloride Drugs 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 78
- 239000002253 acid Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- HZONRRHNQILCNO-UHFFFAOYSA-N 1-methyl-2h-pyridine Chemical class CN1CC=CC=C1 HZONRRHNQILCNO-UHFFFAOYSA-N 0.000 abstract 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000007670 refining Methods 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 methoxyl groups Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Abstract
The present invention relates to an integrated disposal method of exhaust gas in the production of glyphosate, and belongs to the technological field of the disposals of the exhaust gas. The exhaust gas in the production of glyphosate is washed by lye to remove hydrogen chloride; then the exhaust gas is transmitted into the mixed solution of pyridine, methanol and a catalyst for quaternary alkaline reaction; the prepared N-methyl-pyridine salt solution is used as an intermediate for the production of paraquat; the excessive exhaust gas after the quaternary alkaline reaction is purified and separated by the lye and then washed by concentrated sulfuric acid so as to prepare methane chloride with the content of higher than 99.9 percent; pyridine is separated, recycled and reused in the quaternary alkaline reaction; the lye containing the methanol can be used for neutralizing the methanol with acid in the recovery technology of the solvent of the glyphosate; the low-concentration sulfuric acid washed by acid can be recycled and reused after concentration; thus the cost of separation and purification is reduced. The integrated disposal method solves the problem of the secondary pollution in the disposal of the exhaust gas, realizes the integrated utilization of resources, and reduces the production cost of the glyphosate.
Description
Technical field
The invention belongs to the exhaust gas treating method technical field, be specially the integrated conduct method of tail gas in glyphosate production.
Background technology
Glyphosate is the maximum and the fastest weedicide kind of rate of growth of global sales, and domestic present preparation glyphosate adopts alkyl esterification method mostly.This technology is raw material with Paraformaldehyde 96, Padil, dimethylphosphite, methyl alcohol, triethylamine, through depolymerization, addition, condensation reaction, adds the reaction that is hydrolyzed of 30% hydrochloric acid soln then.Two methoxyl groups in the hydrolysis reaction intensification precipitation process on the phosphono are in the presence of hydrochloric acid; methyl and the fracture of oxygen base; produce methyl chloride gas; this gas contains impurity such as methyl alcohol, methylal, hydrogenchloride, moisture content, adopts washing, alkali cleaning, sulfuric acid drying to reach the purification purpose in relevant patent and obtains methyl chloride gas.At present on the industrial production, adopt synthetic methyl chloride of methyl alcohol hydrochlorinate method and similar organic chemistry to produce that the methyl chloride open source literature describes in synthetic, all make wash with water, methods such as alkali cleaning, sulfuric acid drying handle the methyl chloride gas that is produced.
The method of conventional process methyl chloride tail gas can only obtain purer methyl chloride gas merely in treating processes, and water washing process produces the waste water that contains methyl chloride again to be difficult to administer by biochemical method; The waste water that alkaline cleaning procedure produces not only contains methyl chloride gas, produces sodium-chlor owing to absorbed hydrogen chloride in gas, and this waste water not only is difficult to biochemistry, and can't utilize.The low-concentration sulfuric acid that acid cleaning process produces is worth cheap, can't recycle, increase the production cost of enterprise.
Summary of the invention
The problems referred to above at the prior art existence, the objective of the invention is to design the technical scheme of the integrated conduct method that the tail gas in glyphosate production that a kind of tail gas can fully utilize is provided, solved secondary pollution problem in the vent gas treatment process, realize the comprehensive utilization of resource, reduce the glyphosate production cost.
The integrated conduct method of described tail gas in glyphosate production is characterized in that may further comprise the steps:
1) the tail gas alkali liquid washing that produces in the glyphosate hydrolyzing process is removed hydrogenchloride;
2) tail gas after alkali cleaning feeds in pyridine, methyl alcohol, the catalyst mixed liquid and carries out the quaternary base reaction, makes N-picoline salts solution, and reaction formula is:
3) with step 2) tail gas that produces in the unnecessary tail gas in reaction back and the dimethylphosphite synthesis procedure mixes, feed together and carry out the quaternary base reaction in pyridine, methyl alcohol, the catalyst mixed liquid once more, the intermediate that the N-picoline salts solution that makes for twice is produced as Paraquat;
4) unnecessary tail gas adopts the alkali lye purification to separate after the quaternary base reaction, and the tail gas that reclaims of purifying enters down step process; The pyridine that is suspended in the alkali lye upper strata circulates after Separation and Recovery and is used for the quaternary base reaction; The remaining alkali lye that contains methyl alcohol is used for the neutralization that the glyphosate solvent recovery process contains sour dilute methanol;
5) organic impurity and moisture content are removed in the tail gas employing vitriol oil washing of purifying and reclaiming through step 4), and the methyl chloride gas pressurization condensation liquefaction that makes is collected in the storage tank; Low-concentration sulfuric acid after the pickling concentrates the back recycle.
The integrated conduct method of described tail gas in glyphosate production, it is characterized in that step 2), 3) merge and to carry out step quaternary base reaction, promptly the tail gas that produces in the tail gas after alkali cleaning and the dimethylphosphite synthesis procedure mixes, and feeds together and carries out the quaternary base reaction in pyridine, methyl alcohol, the catalyst mixed liquid.
The integrated conduct method of described tail gas in glyphosate production is characterized in that the alkali lye described in the step 1) is sodium hydroxide or potassium hydroxide solution, and concentration is 20-40%, preferred 20-32%.
The integrated conduct method of described tail gas in glyphosate production is characterized in that step 2), 3) in the mass ratio of pyridine, methyl alcohol, catalyzer be 1: 0.5-2: 0.001, preferred 1: 0.5-1: 0.001, described catalyzer is DMAP or KI.
The integrated conduct method of described tail gas in glyphosate production, it is characterized in that described quaternary base temperature of reaction is 10-80 ℃, preferred 30-60 ℃, reaction pressure is 0-0.1MPa, preferred 0.05-0.1MPa, reaction control terminal point is PH=3.5～7.5, preferred PH=3.5-5, or with the content of pyridine in the gas Chromatographic Determination mixed solution less than 0.5%.
The integrated conduct method of described tail gas in glyphosate production is characterized in that the alkali lye described in the step 4) is sodium hydroxide, potassium hydroxide, yellow soda ash or solution of potassium carbonate, and concentration is 3-20%, preferred 3-10%.
The integrated conduct method of described tail gas in glyphosate production is characterized in that vitriol oil concentration is 95-98%.
The integrated conduct method of above-mentioned tail gas in glyphosate production is removed hydrogenchloride with tail gas in glyphosate production after with alkali liquid washing, and the tail gas after alkali cleaning carries out the quaternary base reaction, the intermediate that the N-picoline salts solution that makes is produced as Paraquat; Obtain content after unnecessary tail gas adopts the alkali lye purification separation and the vitriol oil to wash after the quaternary base reaction and be higher than 99.9% methyl chloride, pyridine circulates after Separation and Recovery and is used for the quaternary base reaction, the alkali lye that contains methyl alcohol is used for the neutralization that the glyphosate solvent recovery process contains sour dilute methanol, low-concentration sulfuric acid after the pickling concentrates the back recycle, reduces the purification separation cost.This integrated conduct method has solved secondary pollution problem in the vent gas treatment process, realizes the comprehensive utilization of resource, reduces the glyphosate production cost.
In the present patent application related percentage composition unless otherwise indicated outside, other be weight percentage.
Embodiment
Now with the following Examples, the invention will be further described.
The integrated conduct method of tail gas in glyphosate production comprises following processing step:
1) the tail gas alkali liquid washing that produces in the glyphosate hydrolyzing process is removed hydrogenchloride, and described alkali lye is sodium hydroxide or potassium hydroxide solution, and concentration is 20-40%, preferred 20-32%;
2) tail gas after alkali cleaning feeds in pyridine, methyl alcohol, the catalyst mixed liquid and carries out the quaternary base reaction, makes N-picoline salts solution, and reaction formula is:
3) with step 2) tail gas that produces in the unnecessary tail gas in reaction back and the dimethylphosphite synthesis procedure mixes, feed together and carry out the quaternary base reaction in pyridine, methyl alcohol, the catalyst mixed liquid once more, the intermediate that the N-picoline salts solution that makes for twice is produced as Paraquat;
Above-mentioned steps 2), 3) in the mass ratio of pyridine, methyl alcohol, catalyzer be 1: 0.5-2: 0.001, preferred 1: 0.5-1: 0.001, described catalyzer is DMAP or KI; The quaternary base temperature of reaction is 10-80 ℃, and preferred 30-60 ℃, reaction pressure is 0-0.1MPa, preferred 0.05-0.1MPa, reaction control terminal point is PH=3.5～7.5, preferred PH=3.5-5, or with the content of pyridine in the gas Chromatographic Determination mixed solution less than 0.5%;
4) unnecessary tail gas adopts the alkali lye purification to separate after the quaternary base reaction, and the tail gas that reclaims of purifying enters down step process; The pyridine that is suspended in the alkali lye upper strata circulates after Separation and Recovery and is used for the quaternary base reaction; The remaining alkali lye that contains methyl alcohol is used for the neutralization that the glyphosate solvent recovery process contains sour dilute methanol; Described alkali lye is sodium hydroxide, potassium hydroxide, yellow soda ash or solution of potassium carbonate, and concentration is 3-20%, preferred 3-10%;
5) organic impurity and moisture content are removed in the tail gas employing 95-98% vitriol oil washing of purifying and reclaiming through step 4), and the methyl chloride gas pressurization condensation liquefaction that makes is collected in the storage tank; Low-concentration sulfuric acid after the pickling concentrates the back recycle.
Step 2 wherein), 3) can merge and carry out step quaternary base reaction, promptly the tail gas that produces in the tail gas after alkali cleaning and the dimethylphosphite synthesis procedure mixes, and feeds together and carries out the quaternary base reaction in pyridine, methyl alcohol, the catalyst mixed liquid.
Embodiment 1: glyphosate tail gas is after 32% sodium hydroxide solution absorbs, send into 5000L quaternary base reactor, add 1500kg pyridine, methyl alcohol, catalyst mixed liquid in the still, pyridine: methyl alcohol: the mass ratio of catalyzer is 1: 1: 0.001, and catalyzer is DMAP, 60 ℃ of still temperature controls, still is pressed 0MPa (gauge pressure), when in the still during mixed solution PH=3.5, react completely, obtain the N-picoline salts solution 1970kg of content 60%; The tail gas merging that produces in reaction end gas and the dimethylphosphite synthesis procedure enters the quaternary base packed absorber that diameter is 800mm, the absorption tower connects the circulation groove of 3000L, 1500kg pyridine, methyl alcohol, catalyst mixed liquid are housed in the circulation groove, pyridine: methyl alcohol: the catalyst quality ratio is 1: 1: 0.001, and catalyzer is KI, and the tower temperature is 40 ℃, tower is pressed 0MPa (gauge pressure), when in the circulation groove during mixed solution PH=4.0, react completely, obtain the N-picoline salts solution 1970kg of content 60%; The reacted unnecessary tail gas of quaternary baseization separates in the soda-wash tower absorption refining with 10% sodium hydroxide solution, the pyridine on circulation groove alkali lye upper strata circulates after Separation and Recovery and is used for the quaternary base reaction, and the alkali lye that contains methyl alcohol is used for the neutralization that the glyphosate solvent recovery process contains sour dilute methanol; Tail gas after the purification is removed organic impurity and moisture content with 95% vitriol oil washing absorption, and the methyl chloride gas that obtains content 99.98% is collected in the storage tank through the pressurization condensation liquefaction; Low-concentration sulfuric acid after the pickling concentrates the back recycle.
Embodiment 2: glyphosate tail gas is after 20% potassium hydroxide solution absorbs, send into 5000L quaternary base reactor, add 1500kg pyridine, methyl alcohol, catalyst mixed liquid in the still, pyridine: methyl alcohol: the mass ratio of catalyzer is 1: 2: 0.001, catalyzer is DMAP, 75 ℃ of still temperature controls, and still is pressed 0.05MPa (gauge pressure), when in the still during mixed solution PH=7.0, obtain the N-picoline salts solution 1790kg of content 40%; The tail gas merging that produces in reaction end gas and the dimethylphosphite synthesis procedure enters the quaternary base packed absorber that diameter is 800mm, the absorption tower connects the circulation groove of 3000L, 1500kg pyridine, methyl alcohol, catalyst mixed liquid are housed in the circulation groove, pyridine: methyl alcohol: the catalyst quality ratio is 1: 1.5: 0.001, catalyzer is KI, the tower temperature is 45 ℃, tower is pressed 0.02MPa (gauge pressure), when in the circulation groove during mixed solution PH=5.0, react completely, obtain the N-picoline salts solution 1870kg of content 51%; The reacted unnecessary tail gas of quaternary baseization separates in the soda-wash tower absorption refining with 15% potassium hydroxide solution, the pyridine on circulation groove alkali lye upper strata circulates after Separation and Recovery and is used for the quaternary base reaction, and the alkali lye that contains methyl alcohol is used for the neutralization that the glyphosate solvent recovery process contains sour dilute methanol; Tail gas after the purification is removed organic impurity and moisture content with 97% vitriol oil washing absorption, and the methyl chloride gas that obtains content 99.95% is collected in the storage tank through the pressurization condensation liquefaction; Low-concentration sulfuric acid after the pickling concentrates the back recycle.
Embodiment 3: glyphosate tail gas is after 25% potassium hydroxide solution absorbs, send into 5000L quaternary base reactor, add 1500kg pyridine, methyl alcohol, catalyst mixed liquid in the still, pyridine: methyl alcohol: the mass ratio of catalyzer is 1: 0.5: 0.001, and catalyzer is DMAP, 20 ℃ of still temperature controls, still is pressed 0.06MPa (gauge pressure), when in the still during mixed solution PH=3.5, react completely, obtain the N-picoline salts solution 2120kg of content 75%; The tail gas merging that produces in reaction end gas and the dimethylphosphite synthesis procedure enters the quaternary base packed absorber that diameter is 800mm, the absorption tower connects the circulation groove of 3000L, 1500kg pyridine, methyl alcohol, catalyst mixed liquid are housed in the circulation groove, pyridine: methyl alcohol: the catalyst quality ratio is 1: 0.8: 0.001, catalyzer is KI, the tower temperature is 50 ℃, tower is pressed 0.1MPa (gauge pressure), when in the circulation groove during mixed solution PH=6.0, react completely, obtain the N-picoline salts solution 2000kg of content 65%; The reacted unnecessary tail gas of quaternary baseization separates in the soda-wash tower absorption refining with 3.5% solution of potassium carbonate, and next the processing of each step is identical with embodiment 2.
Embodiment 4: glyphosate tail gas is after 28% sodium hydroxide solution absorbs, enter the quaternary base packed absorber that diameter is 800mm with the tail gas merging that produces in the dimethylphosphite synthesis procedure, the absorption tower connects the circulation groove of 3000L, 1500kg pyridine, methyl alcohol, catalyst mixed liquid are housed in the circulation groove, pyridine: methyl alcohol: the catalyst quality ratio is 1: 0.6: 0.001, catalyzer is DMAP, the tower temperature is 55 ℃, tower is pressed 0.03MPa (gauge pressure), when in the circulation groove during mixed solution PH=4.5, react completely, obtain the N-picoline salts solution 2080kg of content 72%; The reacted unnecessary tail gas of quaternary baseization separates in the soda-wash tower absorption refining with 4% sodium carbonate solution, and next the processing of each step is identical with embodiment 1.
Embodiment 5: glyphosate tail gas carries out the quaternary base reaction with the tail gas merging that produces in the dimethylphosphite synthesis procedure after 40% sodium hydroxide solution absorbs, obtain the N-picoline salts solution 2080kg of content 72%; The reacted unnecessary tail gas of quaternary baseization separates in the soda-wash tower absorption refining with 3% sodium carbonate solution, and other processing is identical with embodiment 4.
Embodiment 6: record with gas-chromatography that the content of pyridine was less than 0.5% o'clock in the mixed solution in quaternary base reactor, the circulation groove, quaternary baseization reacts completely; The reacted unnecessary tail gas of quaternary baseization is with 20% solution of potassium carbonate alkali cleaning, and other processing is identical with embodiment 2.
Claims (7)
1, the integrated conduct method of tail gas in glyphosate production is characterized in that may further comprise the steps:
1) the tail gas alkali liquid washing that produces in the glyphosate hydrolyzing process is removed hydrogenchloride;
2) tail gas after alkali cleaning feeds in pyridine, methyl alcohol, the catalyst mixed liquid and carries out the quaternary base reaction, makes N-picoline salts solution, and reaction formula is:
3) with step 2) tail gas that produces in the unnecessary tail gas in reaction back and the dimethylphosphite synthesis procedure mixes, feed together and carry out the quaternary base reaction in pyridine, methyl alcohol, the catalyst mixed liquid once more, the intermediate that the N-picoline salts solution that makes for twice is produced as Paraquat;
4) unnecessary tail gas adopts the alkali lye purification to separate after the quaternary base reaction, and the tail gas that reclaims of purifying enters down step process; The pyridine that is suspended in the alkali lye upper strata circulates after Separation and Recovery and is used for the quaternary base reaction; The remaining alkali lye that contains methyl alcohol is used for the neutralization that the glyphosate solvent recovery process contains sour dilute methanol;
5) organic impurity and moisture content are removed in the tail gas employing vitriol oil washing of purifying and reclaiming through step 4), and the methyl chloride gas pressurization condensation liquefaction that makes is collected in the storage tank; Low-concentration sulfuric acid after the pickling concentrates the back recycle.
2, the integrated conduct method of tail gas in glyphosate production as claimed in claim 1, it is characterized in that step 2), 3) merge and to carry out step quaternary base reaction, promptly the tail gas that produces in the tail gas after alkali cleaning and the dimethylphosphite synthesis procedure mixes, and feeds together and carries out the quaternary base reaction in pyridine, methyl alcohol, the catalyst mixed liquid.
3, the integrated conduct method of tail gas in glyphosate production as claimed in claim 1 or 2 is characterized in that the alkali lye described in the step 1) is sodium hydroxide or potassium hydroxide solution, and concentration is 20-40%, preferred 20-32%.
4, the integrated conduct method of tail gas in glyphosate production as claimed in claim 1 or 2, it is characterized in that step 2), 3) in the mass ratio of pyridine, methyl alcohol, catalyzer be 1: 0.5-2: 0.001, preferred 1: 0.5-1: 0.001, described catalyzer is DMAP or KI.
5, the integrated conduct method of tail gas in glyphosate production as claimed in claim 1 or 2, it is characterized in that described quaternary base temperature of reaction is 10-80 ℃, preferred 30-60 ℃, reaction pressure is 0-0.1MPa, preferred 0.05-0.1MPa, reaction control terminal point is PH=3.5～7.5, preferred PH=3.5-5, or with the content of pyridine in the gas Chromatographic Determination mixed solution less than 0.5%.
6, the integrated conduct method of tail gas in glyphosate production as claimed in claim 1 or 2 is characterized in that the alkali lye described in the step 4) is sodium hydroxide, potassium hydroxide, yellow soda ash or solution of potassium carbonate, and concentration is 3-20%, preferred 3-10%.
7, the integrated conduct method of tail gas in glyphosate production as claimed in claim 1 or 2 is characterized in that vitriol oil concentration is 95-98%.
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| CN104190104A (en) * | 2014-08-27 | 2014-12-10 | 江苏凯茂石化科技有限公司 | Process equipment and method for refining dimethoxymethane in byproducts produced in production of glyphosate by glycine method |
| CN107456843A (en) * | 2017-09-11 | 2017-12-12 | 安徽智博新材料科技有限公司 | A kind of pharmaceutical factory's waste gas dedicated treating liquid |
| CN114159934A (en) * | 2021-11-12 | 2022-03-11 | 浙江省天正设计工程有限公司 | A recovery device for chlorothalonil chlorinated tail gas and its treatment process |
| CN115490634A (en) * | 2022-10-26 | 2022-12-20 | 安徽国星生物化学有限公司 | Synthesis process of 1,1-dimethyl-4,4-bipyridine cation |
| CN117138574A (en) * | 2023-08-18 | 2023-12-01 | 南通利华农化有限公司 | A device for controlling tail gas odor in the production of glyphosate isopropylamine salt solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075507C (en) * | 1999-11-08 | 2001-11-28 | 浙江新安化工集团股份有限公司 | Hydrolysis subsequent procedure in synthesis of glyphosphonic acid |
| CN100540535C (en) * | 2007-07-27 | 2009-09-16 | 浙江金帆达生化股份有限公司 | Production method with the glyphosate cogeneration Paraquat |
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2008
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| CN114159934A (en) * | 2021-11-12 | 2022-03-11 | 浙江省天正设计工程有限公司 | A recovery device for chlorothalonil chlorinated tail gas and its treatment process |
| CN115490634A (en) * | 2022-10-26 | 2022-12-20 | 安徽国星生物化学有限公司 | Synthesis process of 1,1-dimethyl-4,4-bipyridine cation |
| CN117138574A (en) * | 2023-08-18 | 2023-12-01 | 南通利华农化有限公司 | A device for controlling tail gas odor in the production of glyphosate isopropylamine salt solution |
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