CN115260232A - Method for improving phosphorus utilization rate in glyphosate production and glyphosate production device - Google Patents
Method for improving phosphorus utilization rate in glyphosate production and glyphosate production device Download PDFInfo
- Publication number
- CN115260232A CN115260232A CN202210511407.5A CN202210511407A CN115260232A CN 115260232 A CN115260232 A CN 115260232A CN 202210511407 A CN202210511407 A CN 202210511407A CN 115260232 A CN115260232 A CN 115260232A
- Authority
- CN
- China
- Prior art keywords
- water
- glyphosate
- tank
- stage
- filtrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 79
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 230000008979 phosphorus utilization Effects 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000706 filtrate Substances 0.000 claims abstract description 46
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 40
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000007062 hydrolysis Effects 0.000 claims abstract description 35
- 239000012452 mother liquor Substances 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 30
- 239000008235 industrial water Substances 0.000 claims abstract description 29
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 239000004471 Glycine Substances 0.000 claims abstract description 19
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 230000005494 condensation Effects 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- SGVDYFNFBJGOHB-UHFFFAOYSA-N 2-[methyl(phosphonomethyl)amino]acetic acid Chemical compound OC(=O)CN(C)CP(O)(O)=O SGVDYFNFBJGOHB-UHFFFAOYSA-N 0.000 description 1
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- AZIHIQIVLANVKD-UHFFFAOYSA-N N-(phosphonomethyl)iminodiacetic acid Chemical compound OC(=O)CN(CC(O)=O)CP(O)(O)=O AZIHIQIVLANVKD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid 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
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- -1 phosphate ester Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- 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)
Abstract
The invention relates to a method for improving the phosphorus utilization rate in glyphosate production in the process of producing glyphosate by a glycine method and a glyphosate production device. The method comprises the following steps: (1) Reacting a material methanol solution, paraformaldehyde, triethylamine, glycine and dimethyl phosphite step by step to obtain a condensation solution; (2) Adding low-concentration acid for hydrolysis and desolventizing to obtain a concentrated solution, and adding water into the system to obtain slurry; (3) Cooling the slurry and the added liquid alkali in a crystallization kettle, stirring and crystallizing to obtain a crystallization liquid; (4) Injecting the crystallization liquid into a solid-liquid separation device, adding washing water for multi-stage washing to obtain a glyphosate finished product, a mother liquid and a filtrate; the water part added into the system in the step (2) is from glyphosate mother liquor or filtrate, and the rest water is industrial water; part of the washing water in the step (4) comes from the filtrate, and the rest water is industrial water. The invention realizes the effects of high utilization rate of raw materials, low system loss, production energy consumption reduction and environmental protection treatment cost by improving the counter-current washing of the mother liquor and matching with equipment.
Description
Technical Field
The invention relates to a production technology of glyphosate pesticides, in particular to a method for improving the phosphorus utilization rate of glyphosate production in the process of producing glyphosate by a glycine method and a glyphosate production device.
Background
The glycine process is one of the mainstream processes for producing glyphosate, and the basic method comprises the following steps: preparing synthetic liquid by using glycine, dimethyl phosphite and paraformaldehyde as raw materials, alcohol as a solvent and triethylamine as a catalyst; adding low-concentration acid into the synthetic solution for hydrolysis and desolventizing, and adding industrial water after desolventizing to obtain slurry; and cooling, stirring and crystallizing the slurry and the liquid alkali in a crystallization kettle, and then carrying out solid-liquid separation, washing and drying to obtain the finished product of the glyphosate. The traditional production method has the defects of high solid powder yield, low phosphorus raw material selectivity, high waste liquid solid content, long hydrolysis time, high energy consumption and material consumption and the like due to high loss of the traditional production mother liquor. At present, the mother liquor treatment of most glyphosate production enterprises adopts the following method: oxidizing, concentrating and crystallizing to recover sodium chloride and phosphorus element. Has the disadvantages of large treatment capacity, complex process, high treatment cost, simultaneously generating a large amount of smoke, and losing nitrogen elements to enter an environment-friendly station. Through a large amount of in-situ tracking in the early stage, the glyphosate mother liquor is rich in phosphorus-containing substances such as glyphosine, phosphorous acid, PMIDA and the like and impurities such as sodium chloride and the like, and 1.87-2.68% of the glyphosate is still remained and is not utilized. The utilization rate of nitrogen and phosphorus elements in the glyphosate raw powder in the prior art is only 74 to 75 percent and 62 to 65 percent, about 1.5 percent of phosphorus is stored in the mother solution in a glyphosate form, and the rest is converted by side reaction to generate substances such as N- (phosphonomethyl) iminodiacetic acid, phosphorous acid, methyl glyphosate and the like, so that valuable elements are lost. Therefore, how to simply recover glyphosate from mother liquor at low cost is a need for improving the production process.
In addition, the hydrolysis process of the glycine method has obvious side reaction, takes 8-10 hours and has large steam consumption. How to save energy and reduce consumption is also the direction of improving the process.
CN 101830928A discloses a method for recovering glyphosate raw powder from glyphosate mother liquor, which is to apply alkali mother liquor after concentration, but has the disadvantages of large steam consumption, accumulation of salt and byproducts, and influence on glyphosate purity.
CN 113402549A provides a method for producing glyphosate technical, wherein a phosphate ester amphoteric surfactant is added outside a hydrolysis engineering to prevent local overheating and reduce side reactions. Because the active agent has complex components, the introduction of substance ions such as epichlorohydrin, ethanol, sodium dihydrogen phosphate, petroleum ether and the like increases the complexity of the system, influences the purity of glyphosate, increases the difficulty in processing glyphosate mother liquor, and has low practicability.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects and shortcomings of the existing glycine method glyphosate synthesis process, and providing the method for improving the phosphorus utilization rate in glyphosate production and the glyphosate production device, which have the advantages of high utilization rate of development raw materials, low system loss, obvious reduction of production energy consumption and environmental protection treatment cost, and obvious improvement of hydrolysis efficiency and economic benefit.
The invention relates to a method for improving the phosphorus utilization rate of glyphosate production, which is a basic method for producing glyphosate based on a glycine method, and comprises the following steps: (1) Mixing a methanol solution, paraformaldehyde and triethylamine, stirring, heating and fully reacting to obtain a depolymerization solution; adding glycine into the depolymerized clear liquid, and stirring and heating for reaction to obtain an ammoniation reaction liquid; adding dimethyl phosphite to react to obtain condensation liquid; (2) Adding 20% low-concentration acid for hydrolysis and desolventizing, and removing by-products by acidification and heating to obtain a concentrated solution; adding water into the system after desolventizing to obtain slurry; (3) Cooling the slurry and the added liquid caustic soda in a crystallization kettle, stirring and crystallizing to obtain a crystallization liquid; (4) Pumping water and the crystallization liquid into a solid-liquid separation device together to obtain glyphosate mother liquor and a solid product; adding washing water into the solid product, washing in multiple stages, and drying to obtain a glyphosate finished product and a filtrate;
the method is characterized in that: part of water added into the system in the step (2) is from the glyphosate mother liquor or the filtrate, and the rest water is industrial water; part of washing water in the step (4) comes from the filtrate, and the rest water is industrial water.
Preferably, the specific process of step (1) is: mixing the methanol solution, paraformaldehyde and triethylamine, stirring and heating to 32-42 ℃, and fully stirring for reaction to obtain a methanol solution which takes hemiacetal as a main component, namely depolymerization liquid; adding glycine into the depolymerized clear liquid, stirring and heating to 37-52 ℃, and fully stirring for reaction to obtain ammoniation reaction liquid completely dissolved in a methanol system; then adding dimethyl phosphite in batches, and stirring and fully reacting for 60-120 minutes at 47-60 ℃ to obtain condensation liquid; the mol ratio of the glycine to the paraformaldehyde to the methanol to the triethylamine to the dimethyl phosphite is 1 (1.5-2.4) to 8-14 to 0.8-1.6 to 1.15-1.17. Further, the dimethyl phosphite is intermittently/continuously fed, the condensation liquid is obtained after the feeding is finished and the reaction is carried out for 60-100 minutes, the optimal feeding batch of the condensation liquid-synthetic reaction liquid dimethyl phosphite is 6-10 batches/kettle or continuous feeding, and the reaction is carried out for 60-100 minutes after the feeding is finished. By controlling the dropping speed and the feeding ratio of the dimethyl phosphite, the hydrolysis of the dimethyl phosphite can be reduced, and the conversion rate is improved.
Preferably, the chloromethane, methylal, formaldehyde and methanol gas are released under the micro-negative pressure in the step (2) to obtain glyphosate concentrated solution; adding acid to hydrolyze at 30-40 deg.C, and mixing for 20-40min; the temperature rise process is two-stage temperature programming: the first stage material acidification and deep acidolysis desolventizing are carried out in a first-stage hydrolysis kettle, the reaction temperature range is controlled to be 30-100 ℃, and the material retention reaction time is 120-145 min; the second stage is transferred into a second stage hydrolysis kettle or is subjected to dehydration deacidification reaction in an original kettle at the temperature of 100-135 ℃ for the material retention time of 100-140 min. The temperature is raised in sections, so that the reaction rate is high, a large amount of solvent can be evaporated by utilizing reaction heat, the reaction is easier to control, the in-situ conversion rate of glyphosate can be improved, the waste heat is utilized hierarchically, and the energy consumption of hydrolysis is reduced.
Preferably, in the step (4), the solid product obtained after the solid-liquid separation device is dried after two-stage washing and filtering, and the filtrate generated by the two-stage washing is first-stage filtrate and second-stage filtrate in turn; the water added in the step (2) is glyphosate mother liquor and industrial water, and the dosage of the glyphosate mother liquor is 0.3-0.55 times of the mass of the glyphosate; or, the water added in the step (2) is primary filtrate and industrial water, and the dosage of the primary filtrate is 0.18-0.35 times of the mass of the glyphosate. The utilization rate of the glyphosate in the mother liquor is improved through effective combination, and the mother liquor amount and the treatment cost are reduced. Further preferably, the raw powder washing water in the step 4 comprises industrial water and the secondary filtrate, and the dosage of the secondary filtrate is 0.35-0.85 of the mass of the glyphosate respectively.
The glyphosate production device is based on the method and comprises a synthesis reaction kettle, a balance tank, a first-stage hydrolysis reaction kettle, a second-stage hydrolysis kettle and a crystallization reaction kettle which are connected in series; a feed inlet of the synthesis reaction kettle is respectively connected 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 branch pipe; the feed inlet of the first-stage hydrolysis reaction kettle is connected with a hydrochloric acid metering tank through a pipeline, and the feed inlet of the second-stage hydrolysis reaction kettle is communicated with an industrial water tank and a water reuse metering tank through a pipeline; the top gas outlet of the first-stage hydrolysis reaction kettle is respectively communicated with a byproduct recovery tower and a tail gas absorption tank; the top of the secondary hydrolysis reaction kettle is communicated with a hydrochloric acid absorption tank; the top of the crystallization reaction kettle is communicated with a liquid caustic soda metering tank through a pipeline, a discharge port at the bottom is connected with a solid-liquid separation device, and the bottom of the solid-liquid separation device is communicated with a drying device; the device also comprises a mother liquor primary filtrate collecting tank, a secondary filtrate collecting tank and a primary mother liquor large tank, wherein the feed inlets are respectively connected in parallel with the discharge hole of the solid-liquid separation device.
Further, the water outlet of the primary mother liquid large tank is communicated with a circulating reuse water tank and also can be communicated with the water inlet of an industrial washing water metering tank; the water outlets of the mother liquor first-stage filtrate collecting tank and the second-stage filtrate collecting tank are communicated with the water inlet of the industrial washing water metering tank, and the bottom of the industrial water metering tank is communicated with the feed inlet of the solid-liquid separation device.
Further, the outlet of the hydrochloric acid absorption tank is connected with the feed inlet of the hydrochloric acid metering tank.
Further, the device also comprises a plurality of flow meters and heat exchangers; the flow meters are respectively connected to the feeding branch pipe of the synthesis reaction kettle and between the balance tank and the first-stage hydrolysis kettle; the heat exchanger is connected in series between the first-stage hydrolysis kettle and the second-stage hydrolysis kettle.
Compared with the prior art, the invention has the following beneficial effects:
1. the consumption of DMP is properly reduced, the feeding mode of DMP is changed, and an optimized mother liquor recovery method is matched, so that the economy of phosphorus element is improved from the source and the tail end, the reaction direction is reasonably controlled, the conversion rate and the crystallization rate of glyphosate are greatly improved, the generation of byproducts is reduced, and the stability and the purity of the product are greatly improved;
2. the loss of the glyphosate in the mother liquor is reduced by reversely serially washing and mechanically applying the washing liquid.
3. The equipment is simply transformed in series to realize segmented continuous hydrolysis, the reaction heat is fully utilized through the optimization of the acid adding and acid hydrolysis processes, the treatment capacity of the device is improved, the treatment time is reduced, and the influence of formaldehyde dissolved in the solution in the acid hydrolysis process on the yield of glyphosate is reduced.
Drawings
FIG. 1 is a schematic view of the construction of a production apparatus in example 1 of an apparatus according to the present invention;
FIG. 2 is a schematic view showing the construction of a production apparatus in example 2 of the apparatus of the present invention;
wherein: 1-synthesis reaction kettle, 2-balance tank 3-first hydrolysis reaction kettle, 4-second hydrolysis reaction kettle, 5-crystallization reaction kettle, 6-solid-liquid separation system, 7-drying device, 8-raw material supply unit, 81-dimethyl carbinol metering tank, 82-triethylamine metering tank, 83-dimethyl phosphite metering tank, 84-paraformaldehyde metering tank, 85-glycine metering tank, 9-flowmeter, 10-heat exchanger, 11-byproduct recovery tower, 12-tail gas absorption tank, 13-hydrochloric acid metering tank, 14-hydrochloric acid absorption tank, 15-industrial water metering tank, 16-circulating water jacket water metering tank, 17-liquid alkali metering tank, 18-primary mother liquid large tank, 19-primary filtrate collection tank, 20-secondary filtrate collection tank, 21-washing industrial water metering tank and 22-mother liquid recovery system.
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 glyphosate production device in embodiment 1 of the invention is shown in figure 1, and comprises a synthesis reaction kettle 1, a balance groove 2, a first-stage hydrolysis reaction kettle 3, a second-stage hydrolysis reaction kettle 4 and a crystallization reaction kettle 5 which are connected in series in sequence; the feed inlet of the synthesis reaction kettle is respectively connected with a methanol metering tank 81, a triethylamine metering tank 82, a paraformaldehyde metering tank 84, a glycine metering tank 85 and a dimethyl phosphite metering tank 83 through feed branch pipes; the feed inlet of the first-stage hydrolysis reaction kettle 3 is connected with a hydrochloric acid metering tank 13 through a pipeline, and the feed inlet of the second-stage hydrolysis reaction kettle 4 is respectively communicated with an industrial water metering tank 15 and a circulating jacket water metering tank 16 through pipelines; a gas outlet at the top of the first hydrolysis reaction kettle 3 is respectively communicated with a byproduct recovery tank 11 such as methanol and a tail gas absorption tank 12; the top of the second hydrolysis reaction kettle is communicated with a hydrochloric acid absorption tank 14, and the outlet of the second hydrolysis reaction kettle is connected with the feed inlet of a hydrochloric acid metering tank 13; the top of the crystallization reaction kettle is connected with a liquid caustic soda metering tank 17, a bottom discharge hole is connected with a solid-liquid separation device 6, and the solid-liquid separation device 6 is communicated with a drying device 7.
In the embodiment of the device, the device also comprises a primary filtrate collecting tank 19, a secondary filtrate collecting tank 20 and a primary mother liquor vat 18, and the sample inlets are respectively connected in parallel with the discharge hole of the solid-liquid separation device 6. The water outlet pipe of the mother liquor large tank 18 is communicated with the water inlet of the circulating jacket water tank 16, the water outlets of the primary filtrate collecting tank 19 and the secondary filtrate collecting tank 20 are communicated with the water inlet of the washing industrial water metering tank 21, and the bottom of the industrial water metering tank 21 is connected with the feed inlet of the solid-liquid separation device 6.
The device further comprises a flow meter 9 and a heat exchanger 10. 3 series connections of flowmeter are in raw materials feed inlet branch road, and 1 feed inlet links to each other with the balance tank bottom, and the discharge gate links to each other with one-level hydrolysis kettle feed inlet. The heat exchanger is connected in series between the first-stage hydrolysis kettle and the second-stage hydrolysis kettle.
Example 2
The device of the embodiment 2 of the invention is different from the embodiment 1 in that a water outlet pipe 18 of a primary mother liquid large tank is not communicated with a water receiving tank 16 for a circulating sleeve; the water outlet of the primary filtrate collecting tank 19 is not communicated with the water inlet of the water washing industrial water metering tank 21, but is communicated with the circulating jacket water receiving tank 16.
Comparative example
The production is carried out in a conventional glyphosate synthesis device, and the synthesis device is different from the devices of the examples 1 and 2 in that the mother liquor and the filtrate of a solid-liquid separation system are not reused in the system, namely the mother liquor and the filtrate are not communicated with a water receiving tank 16 for circulating sleeve water and a water inlet of a water washing industrial water metering tank 21. The production steps are as follows: preparing materials of 57.6 kmol and 4.9 kmol in a methanol metering tank and a triethylamine metering tank respectively, feeding metered solvent methanol and catalyst triethylamine into a synthesis reaction kettle, and starting stirring; then putting 1.56 kmol paraformaldehyde prepared in a paraformaldehyde metering tank into a synthesis reaction kettle, controlling the temperature to be 32-42 ℃ and starting depolymerization reaction; after the paraformaldehyde completely dissolves the solution and is basically transparent, putting 4.86kmol glycine prepared by a glycine metering tank into a synthesis reaction kettle, and controlling the temperature to be 37-50 ℃ to react for 50 min; after the solution is basically transparent and reacts, quickly adding 5.96kmol dimethyl phosphite prepared by a dimethyl phosphite metering tank into a synthesis reaction kettle, controlling the temperature to be 47-60 ℃, maintaining the temperature for 8 min, then adding triethylamine and dimethyl phosphite, and reacting for 80min to obtain a synthetic liquid-esterified liquid A; the synthetic fluid is pumped into a first-stage hydrolysis reaction kettle in a balanced manner, and 33.8 kmol of 20% hydrochloric acid which is measured well is added to start acidification reaction; carrying out three-two-section temperature programming after the acidification reaction: the first stage is carried out in a first-stage hydrolysis kettle, the reaction end temperature is 85100 ℃, and the reaction time is 50140 min; the second and third stages are carried out in a second-stage hydrolysis kettle, the end temperature of the second-stage reaction is 10532 ℃, the reaction time is 50130 min, 192 kg of industrial water is added after the hydrolysis is finished, the obtained product is put into a crystallization kettle, liquid caustic soda is added, the obtained product is cooled, stirred and crystallized to obtain a crystallization liquid B, and 613.68 kg of glyphosate finished product is obtained after 490 kg of clean water is washed and dried.
Examples 3 to 5
Based on the glyphosate synthesis device (fig. 1) of example 1, the method of example 3 is different from the comparative example in that dimethyl phosphite is added in an amount of 5.85kmol during the esterification process, and the dimethyl phosphite is added into a synthesis reaction kettle in batches (6 times) according to the requirement, and 614.52 kg of glyphosate finished product is prepared after washing and drying.
Based on the glyphosate production device (figure 1) of the embodiment 1, the method of the embodiment 4 is different from the comparative example in that the adding amount of dimethyl phosphite is 5.85kmol in the esterification process, the dimethyl phosphite is added into a synthesis reaction kettle in batches (6 times) according to needs, mother liquor and filtrate are used indiscriminately, the mother liquor of a glyphosate large tank is added into a secondary hydrolysis kettle instead of partial industrial water after hydrolysis is finished, the mother liquor and the industrial water are 120 kg respectively, and the primary filtrate and the secondary filtrate are mixed for replacing partial industrial water and 180 kg of clear water to be washed and dried step by step to obtain 640.32 kg of glyphosate finished products.
The method of example 5 differs from the comparative example in that dimethyl phosphite is added in an amount of 5.85kmol during esterification and is fed into a synthesis reactor as required in batches, and the filtrate is used indiscriminately, based on the glyphosate production apparatus of example 2 (fig. 2). After hydrolysis, 300 kg of first-stage filtrate is added as water supplement and is pumped into a second-stage hydrolysis reaction kettle; the secondary filtrate and clear water are mixed to total 600 kg and enter a solid-liquid separation system to be used as washing water, and 628.1kg of glyphosate finished products are obtained after washing and drying.
The experimental analysis of the yield and purity of glyphosate prepared in each example is shown in table 1.
| Categories | Purity (%) | Yield of solid powder (%) | Total yield (%) |
| Comparative example | 95.82 | 74.68 | 80.7 |
| Example 3 | 96.24 | 74.79 | 81.1 |
| Example 4 | 95.61 | 77.92 | 84.6 |
| Example 5 | 96.02 | 76.44 | 82.5 |
TABLE 2
| Categories | Sodium ion (ppm) | In situ phosphorus utilization (%) |
| Comparative example | 550 | 67.25 |
| Example 2 | 415 | 68.72 |
| Example 3 | 502 | 71.69 |
| Example 4 | 436 | 69.91 |
As can be seen from the data in tables 1 and 2, the process of the present invention: 1. the unit consumption of dimethyl phosphite is reduced, the feeding mode is improved, the generation of byproducts is reduced, the solid glyphosate yield and the total yield are respectively improved by 0.11 percent and 0.4 percent compared with the prior level, and the acidolysis crystallization optimizes the synergistic effect and is matched with the directional cyclic utilization mode of the mother liquor, so that the total yield of the glyphosate is improved by 3.90 percent, and the solid powder yield is improved by 3.24 percent; 3. the content of sodium ions in the glyphosate raw powder produced by the new combined optimization process meets the export international standard (less than or equal to 500 ppm); 4. the experiment group reduces consumption, optimizes and cleanly produces glyphosate, greatly improves the utilization rate of phosphorus element by 1.4-4.5%, and simultaneously improves the hydrolysis efficiency by changing into a secondary device for hydrolysis.
Claims (9)
1. A method for improving the phosphorus utilization rate in glyphosate production comprises the following steps: (1) Mixing a methanol solution, paraformaldehyde and triethylamine, stirring, heating and fully reacting to obtain a depolymerization solution; adding glycine into the depolymerized clear liquid, and stirring and heating for reaction to obtain an ammoniation reaction liquid; adding dimethyl phosphite for reaction to obtain condensation liquid; (2) Adding 20% low-concentration acid for hydrolysis and desolventizing, and acidifying, heating to remove byproducts to obtain a concentrated solution; adding water into the system after desolventizing to obtain slurry; (3) Cooling the slurry and the added liquid alkali in a crystallization kettle, stirring and crystallizing to obtain a crystallization liquid; (4) The crystallization liquid is injected into a solid-liquid separation device to obtain glyphosate mother liquid and solid products; adding washing water into the solid product, washing and drying in multiple stages to obtain a glyphosate finished product and filtrate;
the method is characterized in that: the water part added into the system in the step (2) is from the glyphosate mother liquor or the filtrate, and the rest water is industrial water; part of washing water in the step (4) comes from the filtrate, and the rest water is industrial water.
2. The method for improving the phosphorus utilization rate in glyphosate production according to claim 1, which is characterized in that: the mol ratio of the glycine to the paraformaldehyde to the methanol to the triethylamine to the dimethyl phosphite is 1 (1.5-2.4) to 8-14 to 0.8-1.6 to 1.15-1.17; the dimethyl phosphite is fed intermittently/continuously, and after the feeding is finished, the condensation liquid-synthetic reaction liquid is obtained after the re-reaction is carried out for 60-100 minutes.
3. The method for improving the phosphorus utilization rate in glyphosate production according to claim 2, which is characterized in that: releasing chloromethane, methylal, formaldehyde and methanol gas under micro negative pressure to obtain glyphosate concentrated solution; adding acid for hydrolysis at 30-40 deg.C, and mixing for 20-40min; the temperature rise process is two-stage temperature programming: the first stage material acidification and deep acidolysis desolventizing are carried out in a first-stage hydrolysis kettle, the reaction temperature range is controlled to be 30-100 ℃, and the material retention reaction time is 120-145 min; the second stage is transferred to the second stage hydrolysis kettle or the original kettle for dehydration and deacidification reaction at 100-135 deg.C for 100-140 min.
4. The method for improving the phosphorus utilization rate in glyphosate production according to claim 2, which is characterized in that: in the step (4), the solid product obtained after the solid-liquid separation device is dried after two-stage washing and filtering, and the filtrate generated by the two-stage washing is first-stage filtrate and second-stage filtrate in turn; the water added in the step (2) is glyphosate mother liquor and industrial water, and the dosage of the glyphosate mother liquor is 0.3-0.55 times of the mass of the glyphosate; or, the water added in the step (2) is primary filtrate and industrial water, and the dosage of the primary filtrate is 0.18-0.35 time of the mass of the glyphosate.
5. The method for improving the phosphorus utilization rate in glyphosate production according to claim 5, which is characterized in that: and (5) washing the raw powder in the step (4) by using water comprising industrial water and the secondary filtrate, wherein the dosage of the secondary filtrate is 0.35-0.85 of the mass of the glyphosate respectively.
6. A glyphosate production plant based on the method of claim 1, characterized in that: comprises a synthesis reaction kettle, a balance groove, a first-stage hydrolysis reaction kettle, a second-stage hydrolysis kettle and a crystallization reaction kettle which are connected in series in sequence; a feed inlet of the synthesis reaction kettle is respectively connected 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 branch pipe; the feed inlet of the first-stage hydrolysis reaction kettle is connected with a hydrochloric acid metering tank through a pipeline, and the feed inlet of the second-stage hydrolysis reaction kettle is communicated with an industrial water tank and a water reuse metering tank through a pipeline; the top gas outlet of the first-stage hydrolysis reaction kettle is respectively communicated with a byproduct recovery tower and a tail gas absorption tank; the top of the secondary hydrolysis reaction kettle is communicated with a hydrochloric acid absorption tank; the top of the crystallization reaction kettle is communicated with a liquid caustic soda metering tank through a pipeline, a discharge port at the bottom is connected with a solid-liquid separation device, and the bottom of the solid-liquid separation device is communicated with a drying device; the device also comprises a primary filtrate collecting tank, a secondary filtrate collecting tank and a primary mother liquor large tank, wherein the feed inlets are respectively connected in parallel with the discharge outlet of the solid-liquid separation device.
7. The glyphosate production plant of claim 7, characterized in that: the water outlet of the primary mother liquor large tank is communicated with a circulating reuse water tank and also can be communicated with the water inlet of an industrial washing water metering tank; the water outlets of the mother liquor first-stage filtrate collecting tank and the second-stage filtrate collecting tank are communicated with the water inlet of the industrial water washing metering tank, and the bottom of the industrial water metering tank is communicated with the feed inlet of the solid-liquid separation device.
8. The glyphosate production apparatus of claim 7, wherein: and the outlet of the hydrochloric acid absorption tank is connected with the feed inlet of the hydrochloric acid metering tank.
9. The glyphosate production plant of claim 7, characterized in that: the apparatus also includes a plurality of flow meters and a heat exchanger; the flow meters are respectively connected on the feeding branch pipe of the synthesis reaction kettle and between the balance tank and the first-stage hydrolysis kettle; the heat exchanger is connected in series between the first-stage hydrolysis kettle and the second-stage hydrolysis kettle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210511407.5A CN115260232A (en) | 2022-05-11 | 2022-05-11 | Method for improving phosphorus utilization rate in glyphosate production and glyphosate production device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210511407.5A CN115260232A (en) | 2022-05-11 | 2022-05-11 | Method for improving phosphorus utilization rate in glyphosate production and glyphosate production device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115260232A true CN115260232A (en) | 2022-11-01 |
Family
ID=83759424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210511407.5A Pending CN115260232A (en) | 2022-05-11 | 2022-05-11 | Method for improving phosphorus utilization rate in glyphosate production and glyphosate production device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115260232A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117510539A (en) * | 2023-11-06 | 2024-02-06 | 镇江江南化工有限公司 | Method and device for preparing glyphosate through low-temperature hydrolysis |
-
2022
- 2022-05-11 CN CN202210511407.5A patent/CN115260232A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117510539A (en) * | 2023-11-06 | 2024-02-06 | 镇江江南化工有限公司 | Method and device for preparing glyphosate through low-temperature hydrolysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6931284B2 (en) | How to make taurine | |
| JP2019513688A5 (en) | ||
| CN104944398B (en) | Glyphosate mother solution recoverying and utilizing method | |
| CN102875594A (en) | Continuous synthesis technique of hydroxyethylidenediphosphonic acid | |
| CN115260232A (en) | Method for improving phosphorus utilization rate in glyphosate production and glyphosate production device | |
| CN102241601A (en) | Preparation technology for iminodiacetic acid | |
| CN101993384B (en) | Deamination new process by alkaline hydrolysis of nitrile compounds | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN111004162A (en) | Method and device for preparing L-selenocysteine by using sodium triacetoxyborohydride as reducing agent | |
| CN114920773A (en) | Method for synthesizing glyphosate by alkyl ester method and production device | |
| CN111659330B (en) | Process and equipment for continuously producing glufosinate-ammonium | |
| CN114853808A (en) | Method and device for producing glyphosate by glycine method | |
| CN101108839A (en) | System and method of manufacturing furol with pentose solution | |
| CN101070283A (en) | Fatty-acid methyl ester producing process and apparatus | |
| CN213141414U (en) | System for producing potassium dihydrogen phosphate by solvent method | |
| CN213924051U (en) | Potassium dihydrogen phosphate production system using wet-process phosphoric acid as raw material | |
| CN103554180A (en) | Preparation method of glyphosate | |
| CN106831321A (en) | Oxalic acid borneol acetate continuous saponification process stripping obtains the method and device of crude product borneol | |
| CN104447863A (en) | Method for preparing N-(Phosphonomethyl)iminodiacetic acid | |
| CN101519360A (en) | Method for preparing iminodiacetic acid | |
| CN103554182B (en) | Prepare the method for glyphosate | |
| CN104974054B (en) | The method and device of iminodiacetic acid is prepared using iminodiacetonitrile production mother liquor | |
| CN209810143U (en) | Low boiling point alcohol continuous esterification reaction rectification system | |
| CN102766160A (en) | Novel process for preparing glyphosate by utilizing glycine method | |
| CN101851253A (en) | Triethylamine-free method for preparing glyphosate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |