CN112194677A - Novel process and synthesis device for preparing glyphosate by hydrolyzing by-product acid instead of hydrochloric acid - Google Patents
Novel process and synthesis device for preparing glyphosate by hydrolyzing by-product acid instead of hydrochloric acid Download PDFInfo
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- CN112194677A CN112194677A CN202010960332.XA CN202010960332A CN112194677A CN 112194677 A CN112194677 A CN 112194677A CN 202010960332 A CN202010960332 A CN 202010960332A CN 112194677 A CN112194677 A CN 112194677A
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- hydrochloric acid
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 161
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 49
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 49
- 239000006227 byproduct Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 23
- 230000003301 hydrolyzing effect Effects 0.000 title claims description 11
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 61
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 43
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 230000007062 hydrolysis Effects 0.000 claims abstract description 27
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 19
- 239000004471 Glycine Substances 0.000 claims abstract description 18
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 15
- 239000011552 falling film Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000011718 vitamin C Substances 0.000 claims description 7
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 6
- 229930003268 Vitamin C Natural products 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 235000019154 vitamin C Nutrition 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 230000001502 supplementing effect Effects 0.000 claims description 5
- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 238000004134 energy conservation Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000012691 depolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZHSKUOZOLHMKEA-UHFFFAOYSA-N 4-[5-[bis(2-chloroethyl)amino]-1-methylbenzimidazol-2-yl]butanoic acid;hydron;chloride Chemical compound Cl.ClCCN(CCCl)C1=CC=C2N(C)C(CCCC(O)=O)=NC2=C1 ZHSKUOZOLHMKEA-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RMQGPHXSMAEDQK-UHFFFAOYSA-N OCOP(OC)(OC)=O Chemical compound OCOP(OC)(OC)=O RMQGPHXSMAEDQK-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FCEYBZHADGDCNN-UHFFFAOYSA-N dimethyl hydrogen phosphite hydrochloride Chemical compound Cl.P(OC)(OC)O FCEYBZHADGDCNN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- OXHDYFKENBXUEM-UHFFFAOYSA-N glyphosine Chemical compound OC(=O)CN(CP(O)(O)=O)CP(O)(O)=O OXHDYFKENBXUEM-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- VFNOXQPPJXXRNB-UHFFFAOYSA-N hydroxymethyl dihydrogen phosphate Chemical compound OCOP(O)(O)=O VFNOXQPPJXXRNB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 known as "Zhenning" Chemical compound 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002420 orchard Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3813—N-Phosphonomethylglycine; Salts or complexes thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a novel process and a synthesis device for preparing glyphosate by replacing hydrochloric acid with a by-product acid through hydrolysis, which comprises the following steps: (1) preparing a synthetic solution L1 by using glycine, dimethyl phosphite and paraformaldehyde as raw materials, methanol as a solvent and triethylamine as a catalyst; (2) adding post-treatment hydrochloric acid into the synthetic liquid L1 for hydrolysis and desolventizing, and adding alkali to adjust the pH value after the hydrolysis and desolventizing are finished; (3) adding deionized water, cooling, stirring and crystallizing to obtain a crystal liquid L2, and washing and drying to obtain a glyphosate finished product; the method is improved on the basis of producing glyphosate by a glycine-alkyl ester method, and the byproduct hydrochloric acid for preparing phosphorus trichloride is subjected to aftertreatment to replace hydrochloric acid to hydrolyze the synthetic solution, so that key process index parameters are optimized, the utilization rate of the byproduct acid in a chemical industrial park is improved, and the yield and the purity of the glyphosate raw powder are greatly improved. Meanwhile, a large amount of moisture carried by the introduction of hydrochloric acid is avoided, and the energy consumption for recovering byproducts such as methanol and the like and the discharge amount of wastewater are reduced.
Description
Technical Field
The invention relates to the technical field of glyphosate pesticide production, in particular to a novel process and a synthesis device for preparing glyphosate by replacing hydrochloric acid with a by-product acid.
Background
Glyphosate, also known as glyphosate, is also known as glyphosate, known as "glyphosate", a known name of N- (phosphonomethyl) glycine, known as "Zhenning", Benda, and the like, is an agrochemical which is a low-toxic systemic, conductive, broad-spectrum, biocidal herbicide. Is mainly used in economic crop gardens such as orchards and the like, and has obvious effect of preventing and controlling perennial malignant weeds. At present, two mainstream production routes at home and abroad are available, one is iminodiacetic acid (IDA) as a raw material, the process is simple, the process conditions are mild, the product yield is high, but due to high requirements on equipment and limitation of the raw material, the domestic application is less, and the process is mostly adopted by large companies at home and abroad at present; one method is to take dialkyl phosphite and glycine as raw materials, the method is started at the end of the last century, the purity of the produced glyphosate is high, the process is stable, industrialization is realized quickly in China, however, the yield is only about 81%, and a plurality of byproducts are generated; in view of this, numerous scholars and institutions deeply research the technology, continuously improve the production process conditions, and the Chinese patent application No. 201210266617.9 discloses a continuous production method of glyphosate crystals, which provides continuous production of glyphosate, saves energy and reduces consumption; the yield and productivity of the one-step condensation method provided by Beijing Qinghua purple light England Limited company are greatly improved.
However, the traditional hydrolysis process is complex in process, and the reaction between byproducts or between byproducts and raw materials seriously restricts the further optimization of the glyphosate synthesis process. And the hydrochloric acid is mainly from recycling of the byproduct hydrogen chloride of dimethyl phosphite, and needs to be subjected to condensation, water washing and alkali washing, so that the refining process is complex. Chinese patent application No. 201910453082.8 discloses a method and apparatus for applying dimethyl phosphite hydrogen chloride tail gas to glyphosate synthesis, which proposes to directly use hydrogen chloride to replace hydrochloric acid for hydrolysis, thereby reducing the discharge amount of waste water, but the utilization rate of hydrogen chloride is only 20%, and in addition, hydrogen chloride as gas is not easy to measure, and is difficult to transport to a reaction system, and the energy consumption is large.
In addition, the target glyphosate is separated in the last step, and the influence factors are many. The time required by the acidification and desolventization stage as an important step before crystallization is long, and the subsequent crystallization process is seriously influenced, so that the quality of the glyphosate is influenced. At a lower temperature, the glyphosate precursor is difficult to hydrolyze to generate glyphosate, more part of other intermediates are hydrolyzed to generate byproducts such as hydroxymethyl phosphoric acid, and the glyphosate precursor needs to be generated at a higher temperature. Therefore, how to regulate and control the temperature in the desolventizing stage effectively avoids hydrolysis of other methoxy-containing byproducts in the esterification stage, and accurately promotes the directional generation of glyphosate is a great problem in the glyphosate industry; in addition, the paraformaldehyde and the dimethyl phosphite are usually added in excess in the production, so that the intermediate reaction is more complicated; it is generally believed that the side reaction is in positive correlation with temperature, and other reported processes neglect this, for example, the charging temperature of dimethyl phosphite, if it is too high, will result in the formation of intermediates such as dimethyl hydroxymethyl phosphate, etc., which seriously affects the yield, which is also a disadvantage of previous researches.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the existing defects, and provide a novel process for preparing glyphosate by replacing hydrochloric acid with a by-product acid, which comprises the following steps:
(1) mixing methanol, paraformaldehyde and catalyst triethylamine, stirring, heating to 32-42 ℃, and stirring for reaction for 30-55min to obtain depolymerization liquid; adding glycine into the depolymerization solution, stirring and heating to 37-52 ℃, and stirring and reacting for 30-55min to obtain a reaction addition solution; adding dimethyl phosphite into the addition reaction liquid at the charging temperature of 34-40 ℃, then stirring and heating to 47-60 ℃, supplementing triethylamine and dimethyl phosphite, and stirring and reacting for 50-100min to obtain synthetic liquid L1; wherein, the mol ratio of the glycine, the paraformaldehyde, the methanol, the triethylamine and the dimethyl phosphite is 1 (1.5-2.4) to (5-12) to (0.7-1.5) to (0.8-1.6);
(2) adding post-treatment hydrochloric acid into the synthetic liquid L1 for hydrolysis and desolventizing, wherein the hydrolysis and desolventizing process is a process of hydrolyzing under the action of the post-treatment hydrochloric acid, then heating by a program to remove by-products of methylal, methanol and acid, and adding alkali to adjust the pH value after the hydrolysis and desolventizing are finished; wherein the molar ratio of the post-treatment hydrochloric acid to the glycine is (2.2-3.3) to 1;
(3) adding deionized water, cooling, stirring and crystallizing to obtain a crystal liquid L2, and washing and drying to obtain a glyphosate finished product.
Preferably, the post-treatment hydrochloric acid is the post-treatment hydrochloric acid with the concentration of 30-32% which is prepared by the byproduct hydrochloric acid in the phosphorus trichloride preparation process through a packed tower filled with a reducing agent and activated carbon and then through a falling film type absorption tower under the micro-negative pressure.
Preferably, the reducing agent is vitamin C.
Preferably, the hydrolysis temperature in the hydrolysis desolventizing process in the step (2) is less than 38 ℃.
Preferably, the temperature rise in the hydrolysis and desolventizing procedure in the step (2) adopts three-stage temperature rise, the reaction temperature in the first stage is 30-50 ℃, and the reaction time is 20-38 min; the second-stage reaction temperature is 90-110 ℃, the reaction time is 20-40min, the third-stage reaction temperature is 110-130 ℃, and the reaction time is 100-120 min.
Preferably, the crystallization temperature in the step (3) is below 35 ℃, and the crystallization time is 3-7 h.
A synthesizer for preparing glyphosate by replacing hydrochloric acid with a byproduct acid through hydrolysis comprises a first synthesis reaction kettle, a balance tank, a hydrolysis reaction kettle and a crystallization reaction kettle which are sequentially connected in series; the feed inlet of the first synthesis reaction kettle is respectively communicated with a methanol metering tank, a triethylamine metering tank, a paraformaldehyde metering tank, a glycine metering tank and a dimethyl phosphite metering tank through a feed pipe; the feed inlet of the hydrolysis reaction kettle is respectively communicated with the hydrochloric acid metering tank, the liquid alkali metering tank and the water metering tank through pipelines; the bottom discharge hole and the top gas outlet of the hydrolysis reaction kettle are respectively communicated with a byproduct recovery tank and a tail gas absorption tank; a discharge port at the bottom of the crystallization reaction kettle is respectively connected with a mother liquor vat and a material washing machine through pipelines, a liquid outlet of the material washing machine is communicated with the mother liquor vat, and a solid outlet of the material washing machine is communicated with a dryer; the hydrochloric acid metering tank is connected in series with a post-treatment system, the post-treatment system comprises a packed tower, a falling film absorption tower and a hydrochloric acid storage tank which are sequentially communicated according to a hydrochloric acid loop, and the hydrochloric acid storage tank is communicated with a liquid inlet of the hydrochloric acid metering tank.
The device comprises a packed tower, a hydrochloric acid storage tank, a vitamin C packing layer, an activated carbon adsorption layer, a falling film absorption tower and a hydrochloric acid storage tank, wherein the packed tower is internally provided with the vitamin C packing layer and the activated carbon adsorption layer from bottom to top in sequence, the hydrochloric acid as a byproduct is purified and then enters the falling film absorption tower, and the falling film absorption tower is communicated with the hydrochloric acid storage tank through a hydrochloric acid discharge port at the bottom.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the process of preparing phosphorus trichloride, a large amount of hydrochloric acid which is by-produced is generated, and the hydrochloric acid by-produced may have various concentrations when sold out, and usually contains a part of hypochlorous acid due to the dissolved chlorine gas, the invention reduces hypochlorous acid into hydrochloric acid by arranging the packed tower and the falling film type absorption tower and utilizing the reducing agent packing layer and the active carbon adsorption layer arranged in the packed tower, the active carbon adsorption layer can adsorb fine impurities in the hydrochloric acid, the falling film type absorption tower can adjust the hydrochloric acid to the required concentration, thereby improving the productivity and the purity of the hydrochloric acid to a certain extent, the corresponding raw material and equipment investment cost is reduced, the requirements of energy conservation and consumption reduction in a new era are met, the recycling of waste acid and elements in a chemical industrial park is effectively improved, and the guide effect on promoting the element flow in the fine chemical industry is achieved;
(2) the condensation reaction time of the addition reaction liquid and dimethyl phosphite and the reaction time of a desolventizing stage are greatly shortened by regulating and controlling the temperature, the reaction time and the pH value, wherein the desolventizing reaction time is reduced to 60% of the time reported in the prior art, meanwhile, the generation of unnecessary byproducts is reduced, particularly, the conversion of the glyphosine to the glyphosate is further promoted by improving the terminal temperature of the desolventizing reaction, the yield of the glyphosate is ensured, according to a determination method specified by GB/T12686-2017, the yield of glyphosate raw powder reaches 77.45%, the total yield of mother liquor and the raw powder reaches 80.41%, and the method has guiding significance in energy conservation and consumption reduction in the glyphosate industry.
Drawings
FIG. 1 is a schematic structural diagram of a synthesizer for preparing glyphosate by hydrolyzing a byproduct acid instead of hydrochloric acid according to the present invention;
wherein: 1-a first synthesis reaction kettle, 11-methanol metering tank, 12-triethylamine metering tank, 13-paraformaldehyde metering tank, 14-glycine metering tank, 15-dimethyl phosphite metering tank, 2-equilibrium tank, 3-hydrolysis reaction kettle, 31-hydrochloric acid metering tank, 32-liquid alkali metering tank, 33-water metering tank, 34-byproduct recovery tank, 35-tail gas absorption tank, 4-crystallization reaction kettle, 41-mother liquor large tank, 42-material washing machine, 43-drying machine, 5-packed tower, 51-vitamin C packing layer, 52-active carbon adsorption layer, 6-falling film absorption tower, 61-hydrochloric acid discharge port and 7-hydrochloric acid storage tank.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A synthesizer for preparing glyphosate by replacing hydrochloric acid with a byproduct acid through hydrolysis comprises a first synthesis reaction kettle 1, a balance groove 2, a hydrolysis reaction kettle 3 and a crystallization reaction kettle 4 which are sequentially connected in series; the feed inlet of the first synthesis reaction kettle 1 is respectively communicated with a methanol metering tank 11, a triethylamine metering tank 12, a paraformaldehyde metering tank 13, a glycine metering tank 14 and a dimethyl phosphite metering tank 15 through a feed pipe; the feed inlet of the hydrolysis reaction kettle 3 is respectively communicated with a hydrochloric acid metering tank 31, a liquid alkali metering tank 32 and a water metering tank 33 through pipelines; the bottom discharge hole and the top gas outlet of the hydrolysis reaction kettle 3 are respectively communicated with a byproduct recovery tank 34 and a tail gas absorption tank 35; a discharge port at the bottom of the crystallization reaction kettle 4 is respectively connected with a mother liquor large groove 41 and a material washing machine 42 through pipelines, a liquid outlet of the material washing machine 42 is communicated with the mother liquor large groove 41, and a solid outlet of the material washing machine 42 is communicated with a dryer 43; the hydrochloric acid metering tank 31 is connected in series with a post-treatment system, the post-treatment system comprises a packed tower 5, a falling film absorption tower 6 and a hydrochloric acid storage tank 7 which are sequentially communicated according to a hydrochloric acid loop, and the hydrochloric acid storage tank 7 is communicated with a liquid inlet of the hydrochloric acid metering tank 31.
The vitamin C packing layer 51 and the activated carbon adsorption layer 52 are sequentially arranged in the packed tower 5 from bottom to top, the hydrochloric acid produced by the production by-products is purified and then enters the falling film type absorption tower 6, and the falling film type absorption tower 6 is communicated with the hydrochloric acid storage tank 7 through a hydrochloric acid discharge port 61 positioned at the bottom.
Example 2
Preparing 4.5mol and 0.41mol of raw materials in a methanol metering tank and a triethylamine metering tank respectively, pumping the metered solvent methanol and catalyst triethylamine into a first synthesis reaction kettle, and starting stirring; then 0.12mol of paraformaldehyde prepared in a paraformaldehyde metering tank is fed into a first synthesis reaction kettle, and the temperature is controlled to be 32-42 ℃ to start depolymerization reaction. After paraformaldehyde is completely dissolved, feeding 0.43mol of glycine prepared in a glycine metering tank into a first synthesis reaction kettle, and controlling the temperature to be 37-52 ℃ to react for 30-55 min; after the reaction is finished, quickly adding 0.5mol of dimethyl phosphite prepared by a dimethyl phosphite metering tank into a first synthesis reaction kettle in batches, controlling the temperature to 47-60 ℃, preserving the heat for 8-10min, supplementing triethylamine and dimethyl phosphite, adjusting the pH value of a system to 7.5-7.8, reacting for 50-100min, and obtaining a synthetic liquid L1 after the reaction is finished; and then pumping the synthetic liquid L1 into a balance tank for balancing, then pumping into a hydrolysis reaction kettle, adding 2.5-3.1mol of metered hydrochloric acid to start hydrolysis reaction, carrying out temperature programming to remove by-products of methylal, methanol and acid after hydrolysis is finished, finally adding 0.1-0.15mol of metered liquid alkali for neutralization, pumping into a crystallization reaction kettle after adding deionized water, cooling, stirring and crystallizing to obtain a crystal liquid L2, and washing and drying to obtain a glyphosate finished product.
Example 3
Preparing 4.5mol and 0.41mol of raw materials in a methanol metering tank and a triethylamine metering tank respectively, pumping the metered solvent methanol and catalyst triethylamine into a first synthesis reaction kettle, and starting stirring; then 0.12mol of paraformaldehyde prepared in a paraformaldehyde metering tank is fed into a first synthesis reaction kettle, and the temperature is controlled to be 36-40 ℃ to start depolymerization reaction. After paraformaldehyde is completely dissolved, feeding 0.43mol of glycine prepared in a glycine metering tank into a first synthesis reaction kettle, and controlling the temperature to be 37-52 ℃ to react for 30-55 min; after the reaction is finished, quickly adding 0.5mol of dimethyl phosphite prepared by a dimethyl phosphite metering tank into a first synthesis reaction kettle in batches, controlling the temperature to 47-60 ℃, preserving the heat for 8-10min, supplementing triethylamine and dimethyl phosphite, adjusting the pH value of a system to 7.5-7.8, reacting for 50-100min, and obtaining a synthetic liquid L1 after the reaction is finished; and then pumping the synthetic liquid L1 into a balance tank for balancing, then pumping into a hydrolysis reaction kettle, adding 3.0-3.6mol of metered post-treatment hydrochloric acid to start hydrolysis reaction, carrying out temperature programming to remove by-products of methylal, methanol and acid after hydrolysis is finished, finally adding 0.1-0.15mol of metered liquid alkali for neutralization, pumping into a crystallization reaction kettle after deionized water is added, cooling, stirring and crystallizing to obtain a crystalline liquid L2, washing and drying to obtain a glyphosate finished product.
Example 4
Preparing 5mol and 0.5mol of raw materials in a methanol metering tank and a triethylamine metering tank respectively, pumping the metered solvent methanol and catalyst triethylamine into a first synthesis reaction kettle, and starting stirring; then 0.14mol of paraformaldehyde prepared in a paraformaldehyde metering tank is fed into a first synthesis reaction kettle, and the temperature is controlled to be 32-42 ℃ to start depolymerization reaction. After paraformaldehyde is completely dissolved, feeding 0.48mol of glycine prepared in a glycine metering tank into a first synthesis reaction kettle, and controlling the temperature to be 37-52 ℃ to react for 30-55 min; after the reaction is finished, quickly adding 0.62mol of dimethyl phosphite prepared by a dimethyl phosphite metering tank into a first synthesis reaction kettle in batches, controlling the temperature to 47-60 ℃, preserving the heat for 8-10min, supplementing triethylamine and dimethyl phosphite, adjusting the pH value of a system to 7.5-7.8, reacting for 50-100min, and obtaining a synthetic liquid L1 after the reaction is finished; and then pumping the synthetic liquid L1 into a balance tank for balancing, then pumping into a hydrolysis reaction kettle, adding 3.5-3.8mol of metered post-treatment hydrochloric acid to start hydrolysis reaction, carrying out temperature programming to remove by-products of methylal, methanol and acid after hydrolysis is finished, finally adding 0.15-0.2mol of metered liquid alkali for neutralization, pumping into a crystallization reaction kettle after deionized water is added, cooling, stirring and crystallizing to obtain a crystalline liquid L2, washing and drying to obtain a glyphosate finished product.
Performance verification
Table 1 shows the yield and purity of glyphosate prepared in examples 3-6;
TABLE 1
| Categories | Purity (%) | Yield of raw powder (%) | Total yield (%) |
| Example 2 | 96.74 | 76.81 | 79.20 |
| Example 3 | 96.77 | 77.01 | 79.82 |
| Example 4 | 97.21 | 77.45 | 80.41 |
The embodiment 2 adopts hydrochloric acid for hydrolysis, and the embodiments 3 and 4 adopt post-treatment hydrochloric acid for hydrolysis, and the data in table 1 show that the improvement is carried out on the basis of producing glyphosate by a glycine-alkyl ester method, and the by-product hydrochloric acid for preparing phosphorus trichloride is adopted for hydrolysis of synthetic solution instead of hydrochloric acid after post-treatment, so that the hydrochloric acid cost can be saved, the discharge amount of waste liquid and corresponding waste liquid treatment cost and solvent recovery cost can be reduced, and meanwhile, the more ideal purity and yield of glyphosate can be ensured; in addition, the reaction time is greatly shortened by regulating and controlling the temperature, the pH value and the time, and the method has demonstration significance for promoting energy conservation and consumption reduction of an enterprise park; the reaction time required by the process implemented by adopting the device is about 8.5 hours, and compared with the report time of the same type of industry, the reaction time is saved by 3-5 hours; in conclusion, the production process and the synthesis device have positive leading effects in the field of energy conservation and consumption reduction of the glyphosate industry.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A novel process for preparing glyphosate by replacing hydrochloric acid with a by-product acid through hydrolysis is characterized by comprising the following steps:
(1) mixing methanol, paraformaldehyde and catalyst triethylamine, stirring, heating to 32-42 ℃, and stirring for reaction for 30-55min to obtain depolymerization liquid; adding glycine into the depolymerization solution, stirring and heating to 37-52 ℃, and stirring and reacting for 30-55min to obtain a reaction addition solution; adding dimethyl phosphite into the addition reaction liquid at the charging temperature of 34-40 ℃, then stirring and heating to 47-60 ℃, supplementing triethylamine and dimethyl phosphite, and stirring and reacting for 50-100min to obtain synthetic liquid L1; wherein, the mol ratio of the glycine, the paraformaldehyde, the methanol, the triethylamine and the dimethyl phosphite is 1 (1.5-2.4) to (5-12) to (0.7-1.5) to (0.8-1.6);
(2) adding post-treatment hydrochloric acid into the synthetic liquid L1 for hydrolysis and desolventizing, wherein the hydrolysis and desolventizing process is a process of hydrolyzing under the action of the post-treatment hydrochloric acid, then heating by a program to remove by-products of methylal, methanol and acid, and adding alkali to adjust the pH value after the hydrolysis and desolventizing are finished; wherein the molar ratio of the post-treatment hydrochloric acid to the glycine is (2.2-3.3) to 1;
(3) adding deionized water, cooling, stirring and crystallizing to obtain a crystal liquid L2, and washing and drying to obtain a glyphosate finished product.
2. The novel process for preparing glyphosate by hydrolyzing a byproduct acid instead of hydrochloric acid according to claim 1, which is characterized in that: the post-treatment hydrochloric acid is the post-treatment hydrochloric acid with the concentration of 30-32% which is prepared by the byproduct hydrochloric acid in the phosphorus trichloride preparation process through a packed tower filled with a reducing agent and active carbon and then through a falling film type absorption tower under the micro-negative pressure.
3. The novel process for preparing glyphosate by hydrolyzing a byproduct acid instead of hydrochloric acid according to claim 1, which is characterized in that: the reducing agent is vitamin C.
4. The novel process for preparing glyphosate by hydrolyzing a byproduct acid instead of hydrochloric acid according to claim 1, which is characterized in that: the hydrolysis temperature in the hydrolysis desolventizing process in the step (2) is less than 38 ℃.
5. The novel process for preparing glyphosate by hydrolyzing a byproduct acid instead of hydrochloric acid according to claim 1, which is characterized in that: in the hydrolysis desolventizing procedure in the step (2), three-stage temperature programming is adopted for temperature programming, the first stage reaction temperature is 30-50 ℃, and the reaction time is 20-38 min; the second-stage reaction temperature is 90-110 ℃, the reaction time is 20-40min, the third-stage reaction temperature is 110-130 ℃, and the reaction time is 100-120 min.
6. The novel process for preparing glyphosate by hydrolyzing a byproduct acid instead of hydrochloric acid according to claim 1, which is characterized in that: the crystallization temperature in the step (3) is below 35 ℃, and the crystallization time is 3-7 h.
7. A synthesizer for preparing glyphosate by replacing hydrochloric acid with a byproduct acid is characterized in that: comprises a first synthesis reaction kettle, a balance tank, a hydrolysis reaction kettle and a crystallization reaction kettle which are connected in series in sequence; the feed inlet of the first synthesis reaction kettle is respectively communicated with a methanol metering tank, a triethylamine metering tank, a paraformaldehyde metering tank, a glycine metering tank and a dimethyl phosphite metering tank through a feed pipe; the feed inlet of the hydrolysis reaction kettle is respectively communicated with the hydrochloric acid metering tank, the liquid alkali metering tank and the water metering tank through pipelines; the bottom discharge hole and the top gas outlet of the hydrolysis reaction kettle are respectively communicated with a byproduct recovery tank and a tail gas absorption tank; a discharge port at the bottom of the crystallization reaction kettle is respectively connected with a mother liquor vat and a material washing machine through pipelines, a liquid outlet of the material washing machine is communicated with the mother liquor vat, and a solid outlet of the material washing machine is communicated with a dryer; the hydrochloric acid metering tank is connected in series with a post-treatment system, the post-treatment system comprises a packed tower, a falling film absorption tower and a hydrochloric acid storage tank which are sequentially communicated according to a hydrochloric acid loop, and the hydrochloric acid storage tank is communicated with a liquid inlet of the hydrochloric acid metering tank.
8. The synthesizer for preparing glyphosate by hydrolyzing a byproduct acid instead of hydrochloric acid according to claim 2, 3 or 7, characterized in that: the device is characterized in that a vitamin C packing layer and an active carbon adsorption layer are sequentially arranged in the packed tower from bottom to top, the by-product hydrochloric acid is purified and then enters the falling film type absorption tower, and the falling film type absorption tower is communicated with the hydrochloric acid storage tank through a hydrochloric acid discharge port at the bottom.
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