CN110759944B - Heterogeneous continuous acidolysis device and process for producing glyphosate by using glycine method - Google Patents
Heterogeneous continuous acidolysis device and process for producing glyphosate by using glycine method Download PDFInfo
- Publication number
- CN110759944B CN110759944B CN201911039402.1A CN201911039402A CN110759944B CN 110759944 B CN110759944 B CN 110759944B CN 201911039402 A CN201911039402 A CN 201911039402A CN 110759944 B CN110759944 B CN 110759944B
- Authority
- CN
- China
- Prior art keywords
- acidolysis
- circulating
- gas
- reactor
- glyphosate
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 131
- 239000005562 Glyphosate Substances 0.000 title claims abstract description 108
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229940097068 glyphosate Drugs 0.000 title claims abstract description 108
- 230000008569 process Effects 0.000 title claims abstract description 93
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000004471 Glycine Substances 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 210
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 90
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 41
- 230000005494 condensation Effects 0.000 claims abstract description 23
- 238000009833 condensation Methods 0.000 claims abstract description 22
- 239000006227 byproduct Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 77
- 239000012071 phase Substances 0.000 claims description 57
- 239000000463 material Substances 0.000 claims description 48
- 238000000926 separation method Methods 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000010791 quenching Methods 0.000 claims description 19
- 230000000171 quenching effect Effects 0.000 claims description 19
- 239000007790 solid phase Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000005907 alkyl ester group Chemical group 0.000 claims description 10
- 108010077895 Sarcosine Proteins 0.000 claims description 9
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 150000002373 hemiacetals Chemical class 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 3
- 239000002351 wastewater Substances 0.000 abstract description 23
- 239000000243 solution Substances 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 14
- 239000012452 mother liquor Substances 0.000 abstract description 13
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 229940050176 methyl chloride Drugs 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- -1 alkyl phosphite Chemical compound 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 125000001477 organic nitrogen group Chemical group 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000004063 acid-resistant material Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a heterogeneous continuous acidolysis process and a device for producing glyphosate by a glycine method. The specific expression is that a horizontal heterogeneous reactor is adopted for acidolysis reaction, the synthesis solution is atomized and sprayed into the reactor, and reacts with fresh hydrogen chloride gas and circulating gas introduced into the reactor, and the fluidized glyphosate seed crystal surface in the reactor is subjected to heterogeneous acidolysis reaction to directly generate glyphosate powder, and the reaction temperature is controlled by controlling the condensation and recirculation of the mixed circulating gas to evaporate in the reactor. Compared with the traditional process, the method has the advantages that no aqueous solution is introduced into an acidolysis system, the generation of glyphosate mother liquor wastewater and methanol wastewater is directly avoided in the acidolysis process, the environmental-friendly treatment cost of glyphosate is reduced, various losses and consumption are reduced, the yield of a byproduct of chloromethane, which has high economic value, is increased, and the environmental-friendly and economic benefits are very obvious.
Description
Technical Field
The invention belongs to the technical field of glyphosate production by a glycine method, and particularly relates to a process and a device for applying a heterogeneous continuous acidolysis method to an acidolysis procedure in a glyphosate synthesis process.
Background
Glyphosate is also called nongda, and is a non-selective systemic conductive stem leaf herbicide. At present, two main production methods of glyphosate exist, one is a production method taking iminodiacetic acid (IDA) as a raw material, and the other is a production method taking glycine and alkyl phosphite as raw materials. In China, a process for synthesizing glyphosate by a glycine-alkyl ester method occupies a dominant position, and the specific flow is as follows: taking triethylamine as a catalyst, depolymerizing paraformaldehyde in a solvent methanol to generate hemiacetal, further reacting with glycine, esterifying with dimethyl phosphite to generate an organic phosphine intermediate, and then mixing the synthetic solution with hydrochloric acid, carrying out acidolysis (hydrolysis), desolventizing, deacidifying, crystallizing, separating and drying to obtain the solid glyphosate. Therefore, the continuous perfection of the alkyl ester method glyphosate production process has strong practical significance for China. The invention is also the result of experimental development under the background of energy conservation, consumption reduction, emission reduction and ecological green development.
The traditional hydrochloric acid hydrolysis method applied to glyphosate synthesis comprises the following process flows: the synthetic liquid generated by the reaction of dimethyl phosphite, glycine, paraformaldehyde, triethylamine (liquid catalyst) and methanol (liquid solvent) is stirred and mixed with 25 to 35 percent hydrochloric acid (aqueous solution of hydrogen chloride) to carry out acidolysis reaction. Because a large amount of water is brought into the reaction in the hydrochloric acid, the methoxy group of the organic phosphine intermediate in the synthetic solution is subjected to acidolysis reaction with hydrogen chloride, and simultaneously the water is also subjected to hydrolysis reaction with the methoxy group of the organic phosphine intermediate, so the acidolysis process is also a hydrolysis process, and the main reaction is as follows:
the method has the advantages that: firstly, the used industrial hydrochloric acid (25-35%) is easy to obtain and low in price. Secondly, a liquid-phase batch kettle type reaction is adopted, and the process control is simple.
However, the problems associated with this approach are also quite significant: as 25% -35% hydrochloric acid solution is introduced, 65% -75% of water is passively introduced into a synthesis reaction system. A part of the passively introduced water is evaporated along with the methanol in the solvent removal process, enters a solvent recovery system and finally enters a dirty station in the form of methanol wastewater; the other part enters a crystallization procedure along with the liquid phase and finally enters glyphosate mother liquor. In the process, the water brought by the hydrochloric acid is about 2.1t/t (namely, about 2.1 tons of water in the wastewater generated by each ton of glyphosate is brought into the system by the hydrochloric acid), and accounts for about 20 percent of the total amount of the waste liquid (the methanol recovery wastewater and the mother liquid) and about 40 percent of the total water amount in the waste liquid.
These waste waters produced during the acidolysis process, in turn, cause the following problems. Firstly, because the acidolysis process is performed at a lower pH value, in the subsequent crystallization process, an equivalent amount of alkali liquor is required to be added to neutralize excessive hydrochloric acid to ensure that glyphosate is precipitated from the solution as much as possible, so that the salt content of the glyphosate mother liquor finally generated is high, and meanwhile, the glyphosate mother liquor also contains dissolved organic matters with biological toxicity such as glyphosate, glyphosine, triethylamine salt and the like, so that biochemical treatment cannot be directly performed, and high-cost and complex treatment methods such as advanced oxidation, evaporative crystallization, rectification, incineration and the like are required. Therefore, how to treat the glyphosate mother liquor wastewater with large discharge amount, high salt content, high biological toxicity organic matter content and high organic nitrogen content at low cost becomes the bottleneck of the environmental protection technology of enterprises producing glyphosate by a glycine method. Secondly, because a large amount of water is introduced, a large amount of high-methanol-content wastewater is generated in the subsequent desolventizing process, methanol recovery is needed, and because the specific heat capacity and the phase-change enthalpy of the water are high, the energy consumption is high in the treatment processes of heating, evaporation, cooling condensation, rectification separation, incineration and the like. Thirdly, the process waste water such as methanol waste water, mother liquor waste water and the like generated in the synthesis process has large amount, so that the material carrying and product dissolving loss is large. Fourthly, due to the introduction of water, hydrolysis reaction is carried out between water and methoxy groups of the organic phosphine intermediate, about half of the methoxy groups are converted into methanol, only about half of the methoxy groups are reacted with hydrogen chloride to be converted into methyl chloride, the methyl chloride can be used as an industrial important chemical raw material such as organic silicon, and the like, and the methanol is a common organic solvent, so the atom economic benefit of the methyl oxide group is greatly reduced. Fifthly, as alkali liquor is needed for neutralization, the content of sodium ions in the product is relatively high, when glyphosate with low sodium and high purity grade is needed to be produced, the product can be repeatedly washed by high-purity soft water, the dissolution loss is increased, and therefore the total yield of glyphosate is reduced, the water consumption is increased, and the wastewater amount is increased.
From the engineering perspective, because the acidolysis process introduces high-concentration hydrochloric acid, the acidolysis system needs to consider acid corrosion resistance and needs some equipment made of acid-resistant materials. Meanwhile, due to the introduction of a large amount of chloride ions, the problem of corrosion of high-concentration chloride ions needs to be considered in a subsequent treatment device, and dual-phase steel, titanium materials, even zirconium materials and other special alloy equipment need to be considered when equipment of devices such as wet glyphosate mother liquor oxidation, evaporative crystallization and the like are selected, so that the equipment investment of the whole system is very large. In addition, the traditional acidolysis process adopts a batch kettle type process, the utilization rate of a reactor is low, the back mixing is serious, the side reaction products are more, the single-batch yield is limited by the size of the reaction kettle, and the large-scale amplification is difficult.
In conclusion, in the acidolysis process for synthesizing glyphosate by the traditional glycine method, the addition of hydrochloric acid brings environmental protection problems of glyphosate mother liquor, methanol wastewater and the like, and increases the material consumption and energy consumption in the production process. Therefore, the production of glyphosate mother liquor and methanol recovery waste liquor is reduced from the source of the glyphosate synthesis production process by an innovative production process, the method is the first research direction of pollution treatment subjects in the glyphosate industry, and the process scheme is also optimization and innovation carried out in the direction.
Disclosure of Invention
Aiming at the technical problems, the invention provides a heterogeneous continuous acidolysis process and a device for producing glyphosate by a glycine method. The method aims to adopt a brand-new heterogeneous continuous acidolysis process to replace a hydrochloric acid batch-type liquid phase acidolysis (hydrolysis) process adopted in the traditional process; the new process does not introduce aqueous liquid phase solution, does not generate wastewater, does not have the environmental protection problem of subsequent treatment of wastewater with high salt content, high content of biotoxic organic matters and high content of organic nitrogen, and simultaneously improves the yield of the glyphosate; water is not introduced, hydrolysis reaction of methoxyl groups is not generated, the yield of methyl chloride is increased, and the atom economic benefit is improved; in the acidolysis reaction process, the acidolysis reaction heat is directly utilized to directly separate the organic solvent from the glyphosate powder, so that the energy consumption of solvent recovery in the production process is reduced, and simultaneously methanol wastewater is not generated; the utilization rate of equipment is improved, the capacity of a single set of system is improved, and the scale benefit of the device is improved; the requirement of equipment material is reduced, and the investment of fixed assets is reduced. The purposes of high-efficiency synthesis, emission reduction, environmental protection, consumption reduction, energy conservation, cost reduction and benefit improvement are achieved on the whole.
The heterogeneous continuous acidolysis process for producing glyphosate by using a glycine method provided by the invention comprises the following specific implementation steps:
a device for heterogeneous continuous acidolysis in production of glyphosate by a glycine method specifically comprises: the device comprises a synthetic liquid buffer tank, a synthetic liquid feeding pump, a hydrogen chloride gas cabinet, a hydrogen chloride gas inlet compressor, an acidolysis reactor, a circulating gas cyclone separator, a fine powder recycling ejector, a primary circulating condenser, a primary circulating tank, a secondary circulating condenser, a secondary circulating tank, a quenching circulating pump, a circulating gas compressor and the like.
The synthetic liquid pipeline from the upstream synthetic process is connected with a synthetic liquid buffer tank, then connected with a synthetic liquid feeding pump and then connected with a synthetic liquid feeding port at the upper part of the acidolysis reactor, and the synthetic liquid is sprayed into the acidolysis reactor for acidolysis reaction.
The hydrogen chloride gas pipeline from the outside is connected with a hydrogen chloride gas cabinet, then connected with a hydrogen chloride gas inlet compressor and then connected with a circulating gas distribution pipe at the bottom of the acidolysis reactor, and the hydrogen chloride gas is sent into the acidolysis reactor for reaction.
The mixed circulating gas produced in the acidolysis reactor is discharged from the acidolysis reactor from a pipeline at the top of the acidolysis reactor, and the mixed circulating gas pipeline is connected with the cyclone separator. The fine powder in the mixed gas is settled and separated to the bottom of the cyclone separator in the cyclone separator, a fine powder outlet at the bottom of the cyclone separator is connected with a fine powder recirculation ejector, and the separated fine powder is ejected by the circulating gas to return to the top of the acidolysis reactor to participate in the reaction process.
The mixed recycle gas after the fine powder is separated is discharged from a pipeline at the top of the cyclone separator and is divided into two branch pipelines.
One of the mixed circulating gas pipelines is connected with a first circulating condenser, is partially condensed and then is connected with a first circulating tank, and gas-liquid phases are separated. The gas phase of the first circulating tank is discharged from the top, then is connected with the second circulating condenser, is partially condensed, and then is connected with the second circulating tank, and gas-liquid two phases are separated. The liquid phase pipeline of the first circulating tank is connected with the lower part of the second circulating tank, and the liquid phases in the two tanks are mixed and then sent back to the acidolysis reactor by the quenching circulating pump for atomization, and are attached to the surface of glyphosate seed crystal to participate in the reaction process.
The other mixed circulating gas pipeline is connected to the downstream circulating gas separation process for purifying the mixed circulating gas. And a purified circulating gas pipeline generated in the downstream circulating gas separation process is connected to the lower part of the second circulating tank, is mixed with a gas phase generated by two-stage condensation separation to form circulating gas, and is discharged from the top of the second circulating tank, and the circulating gas pipeline is connected with a circulating gas compressor. The outlet pipeline of the recycle gas compressor is divided into two branches, one branch is connected to the fine powder recycling ejector, and the other branch is connected with a recycle gas distribution header pipe at the bottom of the acidolysis reactor, returns to the acidolysis reactor, is uniformly distributed as a gas phase and participates in the reaction process.
And the glyphosate powder generated by the reaction is discharged from the bottom of the acidolysis reactor and is conveyed to the downstream desolventizing process by the circulating nitrogen from the downstream desolventizing process in a wind conveying mode.
A heterogeneous continuous acidolysis process for producing glyphosate by a glycine method specifically comprises the following steps:
the heterogeneous continuous acidolysis process is a continuous gas-liquid-solid three-phase chemical reaction process.
The continuous reaction means that reaction raw materials and circulating materials are uninterruptedly, proportionally and stably conveyed into the acidolysis reactor by corresponding pumps to participate in chemical reaction; the glyphosate powder produced by the reaction is uninterruptedly and stably discharged out of the acidolysis reactor, and is conveyed to the desolventizing procedure by circulating nitrogen in a pneumatic conveying mode, wherein the conveying gas is the circulating nitrogen from the desolventizing procedure, and the volume percentage content of the nitrogen is more than 85 percent.
The heterogeneous phase refers to the simultaneous occurrence of gas, liquid and solid phases in the reaction process, and the acidolysis reaction occurs between phase interfaces.
The main raw materials of the reaction are hydrogen chloride gas from the outside and synthetic liquid from an upstream process, and the hydrogen chloride gas is respectively conveyed into the acidolysis reactor by a hydrogen chloride gas inlet compressor and a synthetic liquid feed pump in proportion for reaction.
The purity of the hydrogen chloride gas coming from the outside requires that the mass percentage of the hydrogen chloride is more than 95 percent; the adding ratio (molar ratio) of the hydrogen chloride gas from the outside (converted into pure hydrogen chloride) to the synthetic liquid from the upstream process (converted into the amount of the N-methoxy alkyl ester methyl glycine organic phosphorus intermediate in the synthetic liquid) is 2-4.5: 1.
The circulating materials in the reaction process comprise gas, liquid and solid, and gas, liquid and solid circulating materials are respectively separated from a gas-phase mixture discharged from the acidolysis reactor through the processes of purification, two-stage condensation, separation and the like and then are recycled and returned to the acidolysis reactor.
The gas phase circulating material is partly gas separated by cyclone separation and two-stage condensation of the gas phase mixture from the acidolysis reactor, and partly circulating purified gas purified by the gas phase mixture from the acidolysis reactor through a downstream circulating gas separation process. After the two circulation gases are mixed in the second circulation tank, the circulation gas compressor is used for pressurizing, one part of the circulation gas is directly conveyed back to the acidolysis reactor, and the other part of the circulation gas is used as conveying power of solid phase circulation materials.
The liquid phase circulating material is liquid obtained by two-stage condensation and separation of a gas phase mixture from the acidolysis reactor, and is conveyed back to the acidolysis reactor by a quenching circulating pump.
The solid phase circulating material is a solid separated from a gas phase mixture from the acidolysis reactor through a circulating gas cyclone separator, and is conveyed back to the acidolysis reactor by a part of gas phase circulating material.
The acidolysis reactor is filled with glyphosate powder as reaction seed crystal and is also a solid phase carrier for acidolysis reaction semifluidization.
The glyphosate seed crystal is glyphosate powder with the purity of more than 95 percent (mass percentage), the average grain diameter is between 0.05 and 900 microns, and the filling amount of the glyphosate seed crystal is 55 to 80 percent of the total volume of the acidolysis reactor.
The acidolysis reaction is carried out in an acidolysis reactor, the acidolysis reactor is a horizontal fluidized bed reactor, the horizontal mechanical stirring of the horizontal type is arranged in the reactor and is used for stirring and distributing glyphosate seed crystals in the reactor, the upper part of the reactor is provided with a vertical settling section for preliminarily separating coarse powder in the mixed circulating gas discharged out of the reactor, and the lower part of the reactor is provided with a group of gas phase distribution pipes for uniformly distributing the circulating gas and the fresh hydrogen chloride gas.
The ratio of the total horizontal length to the internal diameter of the acidolysis reactor is 5-30: 1; the built-in horizontal mechanical stirring is of a paddle type; the vertical settling section is in a circular truncated cone shape, the cone angle is between 5 degrees and 30 degrees, and the ratio of the inner diameter of the lower circular truncated cone to the inner diameter of the horizontal section of the reactor main body is 0.1 to 0.8: 1, and the total height of the vertical settling section is between 2.5 and 10 m.
Under the double stirring action of the mechanical stirring of the acidolysis reactor and the gas phase stirring of the recycle gas, the glyphosate seed crystal is fluidized in the reactor by controlling the speed of the mechanical stirring and the flow rate of the recycle gas in the reactor.
The mechanical stirring speed of the acidolysis reactor is controlled to be 10 rpm-50 rpm, and the gas flow speed in the acidolysis reactor is controlled to be 0.05 m/s-0.5 m/s.
Continuously spraying the synthetic liquid containing the organic phosphorus intermediate into an acidolysis reactor in an atomized form, uniformly attaching the synthetic liquid to the surface of semi-fluidized glyphosate seed crystal, carrying out gas-solid-liquid heterogeneous acidolysis reaction on the surface of the glyphosate seed crystal, attaching the newly generated glyphosate to the surface of the seed crystal, discharging the seed crystal out of the reactor in a solid phase form, and entering a subsequent desolventizing process. The main reactions taking place in the acidolysis reactor are as follows:
the pressure in the acidolysis reactor is controlled to be 30kPa (absolute pressure) to 210kPa (absolute pressure), and the temperature is controlled to be 30 ℃ to 120 ℃.
The acidolysis process is an exothermic process, so that reaction heat needs to be removed in time in the reaction process, and the forward reaction is ensured. The synthetic liquid and the liquid-phase circulating material are sprayed into the acidolysis reactor through the atomizing nozzle and are uniformly attached to the surface of the glyphosate seed crystal, the solvent and the catalyst in the synthetic liquid, the solvent, the catalyst, the low-boiling by-products and the like in the circulating material are evaporated into gaseous state by the heat released by the reaction while the acidolysis reaction is carried out on the surface of the seed crystal, and the gaseous state and the excessive hydrogen chloride gas form mixed circulating gas to be discharged out of the reactor. And (3) introducing part of the mixed recycle gas into a subsequent recycle gas separation process to separate out methanol, chloromethane, triethylamine and the like, returning to the acidolysis process, and continuing to react. The other part of the mixed circulating gas is separated into a liquid phase by two-stage condensation, the liquid phase is circulated and returned to the acidolysis reactor to be evaporated and absorbed again, and the gas phase is mixed with the purified circulating gas from the downstream circulating gas separation process and then conveyed back to the acidolysis reactor by a circulating gas compressor to continue the reaction.
The heat transfer in the reaction process is realized by adopting a mode of direct endothermic evaporation of a liquid phase. And one part of reaction heat is taken away by synthesis liquid feeding heat absorption evaporation, the other part of reaction heat is taken away by liquid phase circulating material feeding heat absorption evaporation, mixed circulating gas is finally formed in the acidolysis reactor together with the circulating gas and is discharged out of the acidolysis reactor, and meanwhile, the reaction heat is taken out of the acidolysis reactor along with the mixed circulating gas.
Preferably, in the above, the volume ratio of the mixed recycle gas to be subjected to the downstream recycle gas separation step to the mixed recycle gas to be subjected to the two-stage condensation is controlled to be 0.5 to 3: 1.
the volume ratio of the gas-phase mixture subjected to cyclone separation and two-stage condensation to the gas-phase mixture purified in the downstream circulating gas separation process is 1: 0.5 to 3; 60 to 85 percent of the recycle gas in the recycle gas from the outlet of the recycle gas compressor returns to the acidolysis reactor; 15-40% of the circulating gas is used as the conveying power of the solid phase circulating material. The flow rate of the gas phase returned to the interior of the acidolysis reactor after the two circulation gases are mixed in the secondary circulation tank is 0.05-0.5 m/s.
The synthetic solution in the invention and the technical scheme is a mixed solution of organophosphorus intermediates (glyphosate precursors) with main components of N-methoxy alkyl ester methyl glycine and the like through depolymerization, condensation and esterification reactions by taking materials such as methanol, paraformaldehyde (or other formaldehyde sources), glycine (or other raw materials/intermediates taking chloroacetic acid as a starting material), dimethyl phosphite (or other alkyl phosphates) as raw materials and triethylamine as a catalyst.
Advantageous effects
Compared with the traditional hydrochloric acid liquid intermittent acidolysis (hydrolysis) process, the invention adopts a non-aqueous heterogeneous continuous acidolysis method, and has the following beneficial effects:
1. compared with the highly difficult-to-treat glyphosate crystallization mother liquor with high salt content, high content of biological toxic organic matters and high content of organic nitrogen, which can be generated in the traditional process, in the novel process, glyphosate powder is directly crystallized and generated in the heterogeneous acidolysis process, and the processes of acid solution crystallization and alkali liquor neutralization are not needed, so that the generation of highly difficult-to-treat glyphosate crystallization mother liquor wastewater is directly avoided at the source of the reaction process, and the environmental protection pressure is greatly reduced.
2. Compared with the traditional process, in the new process, methanol used in the upstream process is directly evaporated in the heterogeneous acidolysis reaction process and is directly separated from glyphosate powder by gas-solid phase, and the heterogeneous reaction process has no water participation, so that the methanol can be directly recovered in the form of methanol in the subsequent process, the generation of methanol wastewater is directly avoided at the source of the reaction process, and the environmental protection pressure is further reduced.
3. Compared with the traditional process, the novel process can reduce the emission of the glyphosate mother liquor by more than 1.7 tons/ton of glyphosate, reduce the emission of the methanol wastewater by more than 2.5 tons/ton of glyphosate, directly reduce the emission of the wastewater by more than 4.2 tons/ton of glyphosate in total, and reduce the cost of reducing the emission of the wastewater in each ton of glyphosate into 1100-1775 yuan/ton of glyphosate (the treatment cost of the glyphosate mother liquor is 200-300 yuan/ton and the treatment cost of the methanol wastewater is 100-200 yuan/ton). The production cost of the glyphosate is greatly reduced, and the market competitiveness of the product is improved.
4. Compared with the traditional process, the new process has no dissolution loss of the glyphosate due to no introduction of water, and can improve the yield of the glyphosate by more than 0.4 percent. The methanol loss along with the methanol recovery wastewater is also reduced, the methanol consumption is reduced by more than 3.5 kg/ton glyphosate, and the production cost is further reduced.
5. Compared with the traditional process, the new process has no water participation in the reaction process, the hydrolysis reaction of methoxyl does not occur, the yield of methyl chloride is increased, the yield of the byproduct methyl chloride is increased by about 0.4 ton/ton glyphosate (from about 0.55 ton/ton glyphosate to about 0.95 ton/ton glyphosate), the byproduct resources are utilized more reasonably and efficiently, and the economic benefit of the byproduct is further improved.
6. Compared with the traditional batch kettle type process, the novel process is a continuous process, the capacity of the reactor with unit volume is larger, and the scale benefit is more obvious.
7. Compared with the traditional process, the new process is an anhydrous environment, the problem of corrosion of an acid solution does not exist, the requirement can be reduced by selecting materials for equipment, and the investment of fixed assets is reduced, so that the depreciation cost of the fixed assets of the glyphosate is reduced, and the market competitiveness of the product is improved.
The Heterogeneous Continuous reaction (also called "Heterogeneous Continuous reaction") used in the present invention is a general term for two-phase or more components (solid and gas, solid and liquid, two immiscible liquids), or a chemical reaction of one or more reactants at an interface (such as a solid catalyst surface, a seed crystal surface, etc.). The main characteristic of this reaction mode is that the chemical reaction takes place at the interface of two phases, the product is produced directly at the interface of the phases and appears in one phase, while the reactant and by-product remain in the other phase, the reaction process is also the separation process of the product from the reactant and by-product. The product is discharged out of the reaction system in a single phase, and simultaneously, the other phase containing the reactant and the byproduct is subjected to secondary separation, the unreacted raw material returns to the reactor to circularly continue to participate in the reaction, and the byproduct is discharged out of the system in a separated manner, so that the reaction driving force is improved, and the continuous and efficient reaction is facilitated. Meanwhile, due to the adoption of the continuous reactor, the back mixing degree of the reactor is lower than that of a batch kettle reactor, the forward reaction is facilitated, the side reaction is less, and the product purity is higher. In addition, the airspeed of the continuous reactor is higher than that of an intermittent kettle type reactor, the capacity of the continuous reactor with the same volume is larger, the scale is easier to enlarge, and the scale benefit is more obvious.
Drawings
FIG. 1 is a structural diagram of a heterogeneous continuous acidolysis device for producing glyphosate by a glycine method, wherein the heterogeneous continuous acidolysis device comprises a synthesis solution buffer tank 1, a synthesis solution feed pump 2, an acidolysis reactor 3, a hydrogen chloride gas holder 4, a hydrogen chloride gas inlet compressor 5, a recycle gas cyclone separator 6, a fine powder recycling ejector 7, a primary recycle condenser 8, a primary recycle tank 9, a secondary recycle condenser 10, a secondary recycle tank 11, a quenching recycle pump 12, a recycle gas compressor 13 and a recycle nitrogen pipeline 14.
Detailed Description
Example 1
A heterogeneous continuous acidolysis device for producing glyphosate by using a glycine method comprises a synthetic liquid buffer tank 1 connected with an acidolysis reactor 3 through a synthetic liquid feed pump 2, and a hydrogen chloride gas holder 4 connected with the acidolysis reactor 3 through a hydrogen chloride gas inlet compressor 5;
the acidolysis reactor 3 is connected with a circulating gas cyclone separator 6, the circulating gas cyclone separator 6 is connected with a primary circulating condenser 8, the primary circulating condenser 8 is connected with a primary circulating tank 9, the primary circulating tank 9 is connected with a secondary circulating condenser 10, the secondary circulating condenser 10 is connected with a secondary circulating tank 11, and the secondary circulating tank 11 is connected with the acidolysis reactor 3 through a circulating gas holder compressor 13;
the acidolysis reactor 3 is connected to a downstream desolventizing device after being merged with a circulating nitrogen gas pipeline 14.
The circulating gas cyclone separator 6 is connected to a downstream circulating separation device through a pipeline, the downstream circulating separation device is connected with a secondary circulating tank 11, and the secondary circulating tank 11 is connected with the acidolysis reactor 3 through a quenching circulating pump 12.
The first-stage circulating tank 9 is connected with the second-stage circulating tank 11, and the second-stage circulating tank 11 is connected with the acidolysis reactor 3 through a quenching circulating pump 12.
The acidolysis reactor 3 is connected with a recycle gas cyclone 6, the recycle gas cyclone 6 is connected with a fine powder recirculation ejector 7, and the fine powder recirculation ejector 7 is connected with the acidolysis reactor 3.
The secondary circulation tank 11 is connected with a fine powder recirculation ejector 7 through a circulation gas holder compressor 13, and the fine powder recirculation ejector 7 is connected with the acidolysis reactor 3.
Example 2
The method adopts a heterogeneous continuous acidolysis process in the acidolysis process of a glyphosate powder production device with the capacity of 5000 tons/year, the diameter of an acidolysis reactor is 1 meter, the length of a horizontal straight edge section is 10 meters, the cone angle of a vertical settling section is 26 degrees, the diameter of a lower round table is 0.6 meter, and the height of the vertical settling section is 2.5 meters. 9.5 tons of glyphosate powder (the purity is not lower than 95 percent and the average grain diameter is 50 microns) is filled into the acidolysis reactor. The stirring of the reactor was turned on and the stirring speed was controlled at 25 rpm.
Starting a circulating gas compressor, returning a part of gas phase mixture discharged from an acidolysis reactor to the acidolysis reactor through a solid phase separated by cyclone, feeding a liquid phase obtained by condensing the gas phase through two stages to a secondary circulating tank, pumping the liquid phase into the acidolysis reactor through a quenching liquid circulating pump, mixing the gas phase separated by condensation and purified circulating gas coming from the downstream in the secondary circulating tank, directly returning 80% vol of circulating gas to the acidolysis reactor through the circulating gas compressor, using 20% vol of circulating gas as conveying power of solid phase circulating material separated from the bottom of the cyclone, and controlling the total outlet flow of the circulating gas compressor at 2800Nm3H is used as the reference value. And directly sending the other part of gas-phase mixture discharged from the acidolysis reactor to a downstream circulating gas separation process, and adjusting the volume ratio of the mixed circulating gas sent to the downstream circulating gas separation process to the mixed circulating gas sent to cyclone separation and two-stage condensation to be 2.35: 1.
the synthetic liquid is sprayed into the acidolysis reactor by a synthetic liquid feeding pump to form a composition: the dosage of the synthetic liquid is controlled to be 1.55t/h, wherein the synthetic liquid comprises 48 wt% of N-methoxy alkyl ester methyl glycine organophosphorus intermediate, 31 wt% of methanol, 13 wt% of hemiacetal and 8 wt% of other impurities. Meanwhile, a hydrogen chloride gas inlet compressor is started to feed hydrogen chloride gas into the acidolysis reactor, and the adding proportion (molar ratio) of hydrogen chloride (calculated by pure hydrogen chloride) to the synthetic liquid (calculated by an organic phosphorus intermediate) is controlled to be 2.04: 1. the liquid level of the quenching circulating pump and the liquid level of the secondary circulating tank are interlocked, the liquid level of the secondary circulating tank is controlled at 50 percent, the temperature in the reactor is controlled at 70-80 ℃, and the pressure in the acidolysis reactor is stabilized at about 120kPa (absolute pressure).
And (4) observing the material level height in the acidolysis reactor, opening a discharge port of the acidolysis reactor when the material level height in the reactor reaches 85% of the material level height of the reactor, and conveying the glyphosate powder to a downstream desolventizing process by circulating nitrogen. The material level in the reactor is maintained at 85% by adjusting the air input of the hydrogen chloride, the feeding amount of the synthetic solution and the discharging speed of the discharge of the acidolysis reactor, so that the continuous heterogeneous acidolysis process is started.
The yield of the glyphosate finally obtained by adopting the heterogeneous continuous acidolysis process is 74.5-75.5%, and the purity of the glyphosate is not lower than 97.5%.
Example 3
The method adopts a heterogeneous continuous acidolysis process in the acidolysis process of the glyphosate powder production device with the capacity of 1 ten thousand tons/year, the diameter of the acidolysis reactor is 1.2 meters, the length of a horizontal straight edge section is 12 meters, the cone angle of a vertical settling section is 24 degrees, the diameter of a lower round table is 0.75 meter, and the height of the vertical settling section is 2.8 meters. 16.5 tons of glyphosate powder (the purity is not lower than 95 percent and the average grain diameter is 100 micrometers) is filled in the acidolysis reactor. The stirring of the reactor was turned on and the stirring speed was controlled at 22 rpm.
And starting a circulating gas compressor, returning a part of gas phase mixture discharged from the acidolysis reactor to the acidolysis reactor through a solid phase separated by cyclone, feeding a liquid phase obtained by two-stage condensation of the gas phase into a secondary circulating tank, and returning the gas phase into the acidolysis reactor by a quenching liquid circulating pump, mixing the condensed and separated gas phase with purified circulating gas coming from downstream in the secondary circulating tank, directly returning 77% vol of circulating gas to the acidolysis reactor by the circulating gas compressor, using 23% vol of circulating gas as conveying power of solid phase circulating material separated from the bottom of the cyclone separator, and controlling the total outlet flow of the circulating gas compressor at 5000Nm 3/h. And directly sending the other part of gas-phase mixture discharged from the acidolysis reactor to a downstream circulating gas separation process, and adjusting the volume ratio of the mixed circulating gas sent to the downstream circulating gas separation process to the mixed circulating gas sent to cyclone separation and two-stage condensation to be 2.05: 1.
the synthetic liquid is sprayed into the acidolysis reactor by a synthetic liquid feeding pump to form a composition: the dosage of the synthetic liquid is controlled to be between 4.25t/h, wherein the synthetic liquid comprises 42 wt% of N-methoxy alkyl ester methyl glycine organophosphorus intermediate, 35 wt% of methanol, 17 wt% of hemiacetal and 6 wt% of other impurities. Meanwhile, a hydrogen chloride gas inlet compressor is started to feed hydrogen chloride gas into the acidolysis reactor, and the adding proportion (molar ratio) of hydrogen chloride (calculated by pure hydrogen chloride) to the synthetic liquid (calculated by an organic phosphorus intermediate) is controlled to be 2.06: 1. the liquid level of the quenching circulating pump and the liquid level of the secondary circulating tank are interlocked, the liquid level of the secondary circulating tank is controlled at 50 percent, the temperature in the reactor is controlled at 75-85 ℃, and the pressure in the acidolysis reactor is stabilized at about 109kPa (absolute pressure).
And (4) observing the material level height in the acidolysis reactor, opening a discharge port of the acidolysis reactor when the material level height in the reactor reaches 85% of the material level height of the reactor, and conveying the glyphosate powder to a downstream desolventizing process by circulating nitrogen. The material level in the reactor is maintained at 85% by adjusting the air input of the hydrogen chloride, the feeding amount of the synthetic solution and the discharging speed of the discharge of the acidolysis reactor, so that the continuous heterogeneous acidolysis process is started.
The yield of the glyphosate finally obtained by adopting the heterogeneous continuous acidolysis process is 75.5-76.5%, and the purity of the glyphosate is not lower than 97.2%.
Example 4
The method adopts a heterogeneous continuous acidolysis process in the acidolysis process of the glyphosate powder production device with the capacity of 5 ten thousand tons per year, the diameter of the acidolysis reactor is 1.6 meters, the length of a horizontal straight edge section is 14 meters, the cone angle of a vertical settling section is 22 degrees, the diameter of a lower round table is 0.9 meter, and the height of the vertical settling section is 3.5 meters. 34.5 tons of glyphosate powder (the purity is not lower than 95 percent and the average grain diameter is 200 microns) is filled into the acidolysis reactor. The stirring of the reactor was turned on and the stirring speed was controlled at 21 rpm.
And starting a circulating gas compressor, returning a part of gas-phase mixture discharged from the acidolysis reactor to the acidolysis reactor through a solid phase separated by cyclone, feeding a liquid phase obtained by two-stage condensation of the gas phase into a secondary circulating tank, and then returning the gas phase into the acidolysis reactor by a quenching liquid circulating pump, mixing the condensed and separated gas phase with purified circulating gas coming from downstream in the secondary circulating tank, directly returning 75% vol of circulating gas to the acidolysis reactor by the circulating gas compressor, using 25% vol of circulating gas as conveying power of solid-phase circulating material separated from the bottom of the cyclone separator, and controlling the total outlet flow of the circulating gas compressor at 8500Nm 3/h. And directly sending the other part of gas-phase mixture discharged from the acidolysis reactor to a downstream circulating gas separation process, and adjusting the volume ratio of the mixed circulating gas sent to the downstream circulating gas separation process to the mixed circulating gas sent to cyclone separation and two-stage condensation to be 1.85: 1.
the synthetic liquid is sprayed into the acidolysis reactor by a synthetic liquid feeding pump to form a composition: 39 wt% of N-methoxy alkyl ester methyl glycine organophosphorus intermediate, 29 wt% of methanol, 25 wt% of hemiacetal and 7 wt% of other impurities, and the adding amount of the synthetic liquid is controlled between 18.05 t/h. Meanwhile, a hydrogen chloride gas inlet compressor is started to feed hydrogen chloride gas into the acidolysis reactor, and the adding proportion (molar ratio) of hydrogen chloride (calculated by pure hydrogen chloride) to the synthetic liquid (calculated by an organic phosphorus intermediate) is controlled to be 2.02: 1. the liquid level of the quenching circulating pump and the liquid level of the secondary circulating tank are interlocked, the liquid level of the secondary circulating tank is controlled at 50 percent, the temperature in the reactor is controlled at 78-84 ℃, and the pressure in the acidolysis reactor is stabilized at about 105kPa (absolute pressure).
And (4) observing the material level height in the acidolysis reactor, opening a discharge port of the acidolysis reactor when the material level height in the reactor reaches 85% of the material level height of the reactor, and conveying the glyphosate powder to a downstream desolventizing process by circulating nitrogen. The material level in the reactor is maintained at 85% by adjusting the air input of the hydrogen chloride, the feeding amount of the synthetic solution and the discharging speed of the discharge of the acidolysis reactor, so that the continuous heterogeneous acidolysis process is started.
The yield of the glyphosate finally obtained by adopting the heterogeneous continuous acidolysis process is 75.5-76.5%, and the purity of the glyphosate is not lower than 96.3%.
Example 5
The method adopts a heterogeneous continuous acidolysis process in the acidolysis process of a glyphosate powder production device with the capacity of 10 ten thousand tons/year, the diameter of an acidolysis reactor is 2 meters, the length of a horizontal straight edge section is 16 meters, the cone angle of a vertical settling section is 20 degrees, the diameter of a lower round table is 1.2 meters, and the height of the vertical settling section is 4.3 meters. 60.5 tons of glyphosate powder (the purity is not lower than 95 percent and the average grain diameter is 250 micrometers) is filled into the acidolysis reactor. The stirring of the reactor was turned on and the stirring speed was controlled at 18 rpm.
And starting a circulating gas compressor, returning a part of gas phase mixture discharged from the acidolysis reactor to the acidolysis reactor through a solid phase separated by cyclone, feeding a liquid phase obtained by two-stage condensation of the gas phase into a secondary circulating tank, and returning the gas phase into the acidolysis reactor by a quenching liquid circulating pump, mixing the condensed and separated gas phase with purified circulating gas coming from downstream in the secondary circulating tank, directly returning 70% vol of circulating gas to the acidolysis reactor by the circulating gas compressor, using 30% vol of circulating gas as conveying power of solid phase circulating material separated from the bottom of the cyclone separator, and controlling the total outlet flow of the circulating gas compressor at 11500Nm 3/h. And directly sending the other part of gas-phase mixture discharged from the acidolysis reactor to a downstream circulating gas separation process, and adjusting the volume ratio of the mixed circulating gas sent to the downstream circulating gas separation process to the mixed circulating gas sent to the cyclone separation process and subjected to two-stage condensation to be 1.68: 1.
the synthetic liquid is sprayed into the acidolysis reactor by a synthetic liquid feeding pump to form a composition: the dosage of the synthetic liquid is controlled between 40.55t/h, wherein the synthetic liquid comprises 44 wt% of N-methoxy alkyl ester methyl glycine organophosphorus intermediate, 31 wt% of methanol, 21 wt% of hemiacetal and 4 wt% of other impurities. Meanwhile, a hydrogen chloride gas inlet compressor is started to feed hydrogen chloride gas into the acidolysis reactor, and the adding proportion (molar ratio) of hydrogen chloride (calculated by pure hydrogen chloride) to the synthetic liquid (calculated by an organic phosphorus intermediate) is controlled to be 2.09: 1. the liquid level of the quenching circulating pump and the liquid level of the secondary circulating tank are interlocked, the liquid level of the secondary circulating tank is controlled at 50 percent, the temperature in the reactor is controlled at 79-85 ℃, and the pressure in the acidolysis reactor is stabilized at about 115kPa (absolute pressure).
And (4) observing the material level height in the acidolysis reactor, opening a discharge port of the acidolysis reactor when the material level height in the reactor reaches 85% of the material level height of the reactor, and conveying the glyphosate powder to a downstream desolventizing process by circulating nitrogen. The material level in the reactor is maintained at 85% by adjusting the air input of the hydrogen chloride, the feeding amount of the synthetic solution and the discharging speed of the discharge of the acidolysis reactor, so that the continuous heterogeneous acidolysis process is started.
The yield of the glyphosate finally obtained by adopting a heterogeneous continuous acidolysis process is 75-76%, and the purity of the glyphosate is not lower than 97.6%.
Example 6
The method adopts a heterogeneous continuous acidolysis process in the acidolysis process of a production device for glyphosate powder with the capacity of 30 ten thousand tons/year, the diameter of an acidolysis reactor is 3 meters, the length of a horizontal straight edge section is 22 meters, the cone angle of a vertical sedimentation section is 18 degrees, the diameter of a lower circular truncated cone is 1.55 meters, and the height of the vertical sedimentation section is 5 meters. 185 tons of glyphosate powder (the purity is not lower than 95 percent and the average particle size is 100 microns) are filled into the acidolysis reactor. The stirring of the reactor was turned on and the stirring speed was controlled at 14 rpm.
And starting a circulating gas compressor, returning a part of gas phase mixture discharged from the acidolysis reactor to the acidolysis reactor through a solid phase separated by cyclone, feeding a liquid phase obtained by two-stage condensation of the gas phase into a secondary circulating tank, and returning the gas phase into the acidolysis reactor by a quenching liquid circulating pump, mixing the condensed and separated gas phase with purified circulating gas coming from downstream in the secondary circulating tank, directly returning 70% vol of circulating gas to the acidolysis reactor by the circulating gas compressor, using 30% vol of circulating gas as conveying power of solid phase circulating material separated from the bottom of the cyclone separator, and controlling the total outlet flow of the circulating gas compressor at 11500Nm 3/h. And directly sending the other part of gas-phase mixture discharged from the acidolysis reactor to a downstream circulating gas separation process, and adjusting the volume ratio of the mixed circulating gas sent to the downstream circulating gas separation process to the mixed circulating gas sent to cyclone separation and two-stage condensation to be 1: 1.
the synthetic liquid is sprayed into the acidolysis reactor by a synthetic liquid feeding pump to form a composition: the synthetic liquid comprises 40 wt% of N-methoxy alkyl ester methyl glycine organophosphorus intermediate, 30 wt% of methanol, 25 wt% of hemiacetal and 5 wt% of other impurities, and the adding amount of the synthetic liquid is controlled between 125 t/h. Meanwhile, a hydrogen chloride gas inlet compressor is started to feed hydrogen chloride gas into the acidolysis reactor, and the adding proportion (molar ratio) of hydrogen chloride (calculated by pure hydrogen chloride) to the synthetic liquid (calculated by an organic phosphorus intermediate) is controlled to be 3.15: 1. the liquid level of the quenching circulating pump and the liquid level of the secondary circulating tank are interlocked, the liquid level of the secondary circulating tank is controlled at 50 percent, the temperature in the reactor is controlled at 75-80 ℃, and the pressure in the acidolysis reactor is stabilized at about 105kPa (absolute pressure).
And (4) observing the material level height in the acidolysis reactor, opening a discharge port of the acidolysis reactor when the material level height in the reactor reaches 85% of the material level height of the reactor, and conveying the glyphosate powder to a downstream desolventizing process by circulating nitrogen. The material level in the reactor is maintained at 85% by adjusting the air input of the hydrogen chloride, the feeding amount of the synthetic solution and the discharging speed of the discharge of the acidolysis reactor, so that the continuous heterogeneous acidolysis process is started.
The yield of the glyphosate finally obtained by adopting the heterogeneous continuous acidolysis process is 76.5-77.5%, and the purity of the glyphosate is not lower than 97.3%.
Claims (8)
1. The heterogeneous continuous acidolysis device for producing glyphosate by using the glycine method is characterized in that a synthetic solution buffer tank (1) is connected with an acidolysis reactor (3) through a synthetic solution feed pump (2), and a hydrogen chloride gas holder (4) is connected with the acidolysis reactor (3) through a hydrogen chloride gas inlet compressor (5);
the acidolysis reactor (3) is connected with a circulating gas cyclone separator (6), the circulating gas cyclone separator (6) is connected with a first-stage circulating condenser (8), the first-stage circulating condenser (8) is connected with a first-stage circulating tank (9), the first-stage circulating tank (9) is connected with a second-stage circulating condenser (10), the second-stage circulating condenser (10) is connected with a second-stage circulating tank (11), the second-stage circulating tank (11) is connected with the acidolysis reactor (3) through a circulating gas compressor (13), the circulating gas cyclone separator (6) is connected to a downstream circulating separator through a pipeline, the downstream circulating separator is connected with the second-stage circulating tank (11), the second-stage circulating tank (11) is connected with the acidolysis reactor (3) through a quenching circulating pump (12), the acidolysis reactor (3) is connected with the circulating gas cyclone separator (6), the circulating gas cyclone separator (6) is connected with a fine powder recirculation ejector (7), the fine powder recycling ejector (7) is connected with the acidolysis reactor (3);
the acidolysis reactor (3) is connected to a downstream desolventizing device after being converged with a circulating nitrogen pipeline (14).
2. The heterogeneous continuous acidolysis device for producing glyphosate by using the glycine method as claimed in claim 1, wherein the primary circulation tank (9) is connected with the secondary circulation tank (11), and the secondary circulation tank (11) is connected with the acidolysis reactor (3) through a quenching circulation pump (12).
3. The heterogeneous continuous acidolysis device for the glycine process to produce glyphosate according to claim 1, wherein the secondary recycle tank (11) is connected to the fines recycle ejector (7) via a recycle gas compressor (13), and the fines recycle ejector (7) is connected to the acidolysis reactor (3).
4. A heterogeneous continuous acidolysis process for the glycine process for the production of glyphosate using the apparatus of any one of claims 1 to 3, comprising the steps of:
(1) filling glyphosate powder into an acidolysis reactor, and mechanically stirring at 10-50 rpm;
(2) conveying the hydrogen chloride gas coming from the outside into the acidolysis reactor by a hydrogen chloride gas inlet compressor, and controlling the pressure in the acidolysis reactor to be 80-200 KPa;
(3) starting a circulating gas compressor, spraying synthetic liquid into the acidolysis reactor, and allowing a part of gas-phase mixture discharged from the acidolysis reactor to enter a secondary circulating tank after cyclone separation and two-stage condensation; a part of gas phase mixture is purified by a downstream circulating gas separation process to obtain circulating purified gas, the circulating purified gas enters a secondary circulating tank, two parts of circulating gas are mixed in the secondary circulating tank and then are pressurized by a circulating gas compressor, one part of circulating gas is directly conveyed back to an acidolysis reactor, the other part of circulating gas is used as conveying power of solid phase circulating materials, and the temperature in an acidolysis reaction kettle is controlled to be 30-120 ℃ and the pressure is controlled to be 30-210 KPa in the process;
(4) a part of gas phase mixture discharged from the acidolysis reactor enters a secondary circulation tank after cyclone separation and two-stage condensation, and is conveyed back to the acidolysis reactor by a quenching circulation pump;
(5) the gas phase from the acidolysis reactor returns to the acidolysis reactor through the solid separated from the cyclone separator;
(6) when the material level height in the acidolysis reactor reaches 85 percent of the material level height of the reactor, a discharge port of the acidolysis reactor is opened, and the glyphosate powder is conveyed to a downstream desolventizing procedure by circulating nitrogen, so that the heterogeneous continuous acidolysis process can be completed.
5. The heterogeneous continuous acidolysis process for producing glyphosate by using the glycine method as claimed in claim 4, wherein the addition amount of the glyphosate powder is 55-80% of the volume of the acidolysis reaction kettle.
6. The heterogeneous continuous acidolysis process for producing glyphosate by using the glycine method as claimed in claim 4, wherein in the steps (2) and (3), the adding molar ratio of the hydrogen chloride gas from the outside to the synthetic fluid from the upstream process is 2-4.5: 1, the purity of the hydrogen chloride gas coming from the outside is more than 95 percent; the hydrogen chloride gas is calculated by the amount of pure hydrogen chloride, and the synthetic fluid from the upstream process is calculated by the amount of an N-methoxy alkyl ester methyl glycine organophosphorus intermediate; the synthetic fluid comprises 30-50 wt% of N-methoxy alkyl ester methyl glycine organophosphorus intermediate, 20-40 wt% of methanol and hemiacetal CH3OCH2OH 10-30 wt%, and other impurities of upstream reaction byproducts, unreacted glycine and dimethyl phosphite 5-15 wt%.
7. The heterogeneous continuous acidolysis process for producing glyphosate by using the glycine method as claimed in claim 4, wherein in the step (3), the volume ratio of the gas phase mixture subjected to cyclone separation and two-stage condensation to the gas phase mixture purified by the downstream circulating gas separation process is 1: 0.5 to 3; 60 to 85 percent of the recycle gas in the recycle gas from the outlet of the recycle gas compressor returns to the acidolysis reactor; 15-40% of the circulating gas is used as the conveying power of the solid phase circulating material.
8. The heterogeneous continuous acidolysis process for producing glyphosate by using the glycine method as claimed in claim 4, wherein the gas phase flow rate of the two recycle gases which are mixed in the secondary recycle tank and then sent back to the interior of the acidolysis reactor is 0.05m/s to 0.5 m/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911039402.1A CN110759944B (en) | 2019-10-29 | 2019-10-29 | Heterogeneous continuous acidolysis device and process for producing glyphosate by using glycine method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911039402.1A CN110759944B (en) | 2019-10-29 | 2019-10-29 | Heterogeneous continuous acidolysis device and process for producing glyphosate by using glycine method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110759944A CN110759944A (en) | 2020-02-07 |
| CN110759944B true CN110759944B (en) | 2022-03-08 |
Family
ID=69334753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911039402.1A Active CN110759944B (en) | 2019-10-29 | 2019-10-29 | Heterogeneous continuous acidolysis device and process for producing glyphosate by using glycine method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110759944B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674273A (en) * | 2016-12-02 | 2017-05-17 | 湖北泰盛化工有限公司 | Hydrolysis device for producing glyphosate employing glycine method |
| CN106699808A (en) * | 2016-12-02 | 2017-05-24 | 湖北泰盛化工有限公司 | Acidolysis and solvent recycling process and device for producing glyphosate by using glycine method |
| CN110128469A (en) * | 2019-05-28 | 2019-08-16 | 内蒙古兴发科技有限公司 | A kind of dimethylphosphite by-product hydrogen chloride is applied to the device and technique of glyphosate synthesis |
| CN210765084U (en) * | 2019-10-29 | 2020-06-16 | 湖北泰盛化工有限公司 | Heterogeneous continuous acidolysis device for glyphosate |
-
2019
- 2019-10-29 CN CN201911039402.1A patent/CN110759944B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674273A (en) * | 2016-12-02 | 2017-05-17 | 湖北泰盛化工有限公司 | Hydrolysis device for producing glyphosate employing glycine method |
| CN106699808A (en) * | 2016-12-02 | 2017-05-24 | 湖北泰盛化工有限公司 | Acidolysis and solvent recycling process and device for producing glyphosate by using glycine method |
| CN110128469A (en) * | 2019-05-28 | 2019-08-16 | 内蒙古兴发科技有限公司 | A kind of dimethylphosphite by-product hydrogen chloride is applied to the device and technique of glyphosate synthesis |
| CN210765084U (en) * | 2019-10-29 | 2020-06-16 | 湖北泰盛化工有限公司 | Heterogeneous continuous acidolysis device for glyphosate |
Non-Patent Citations (1)
| Title |
|---|
| "氯化氢用于甘氨酸法草甘膦水解工艺的研究";朱正江 等;《上海化工》;20130331;第38卷(第3期);第4-6页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110759944A (en) | 2020-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102755759B (en) | Continuous reaction rectification process and rectification equipment for synthesizing isopropyl alcohol | |
| EP4049748A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| CN109070043B (en) | Urea production with controlled biuret | |
| CN102875594A (en) | Continuous synthesis technique of hydroxyethylidenediphosphonic acid | |
| CN107074751A (en) | The manufacture method of the high purity urea aqueous solution in urea manufacturing process | |
| CN104910031B (en) | The combine production method and device of glycine and hydantoins | |
| CN210765084U (en) | Heterogeneous continuous acidolysis device for glyphosate | |
| CN1176901C (en) | Production method of isopropanolamine | |
| CN102659650B (en) | Device and method for preparing DL-methionine salt | |
| CN110759944B (en) | Heterogeneous continuous acidolysis device and process for producing glyphosate by using glycine method | |
| CN111153823B (en) | Method for preparing oxamide from dimethyl oxalate | |
| CN105367439A (en) | Process method of co-production of oxamide and carbamic acid ester through ammonia ester exchange method | |
| CN112552197A (en) | Kettle type continuous glycine production method | |
| CN101070283A (en) | Fatty-acid methyl ester producing process and apparatus | |
| CN112321462B (en) | Method for synthesizing chlorosulfonyl isocyanate by continuous method | |
| CN101544574A (en) | Environment-friendly clean process method for continuously synthesizing iminodiacetic acid (salt) | |
| CN102050751A (en) | Synthesis as well as tail gas treatment technology and device of iminodiacetate | |
| CN101747177A (en) | Device and method for preparing butane diacid by continuously hydrolyzing dialkyl succinate ester | |
| CN114181115A (en) | Salifying system, salifying process and preparation process of trimethyl orthoacetate | |
| CN209352804U (en) | A kind of ethamine production system of saline solution extraction-hydrolysis | |
| CN103641797B (en) | Preparation method for N-acetyl morpholine | |
| CN111362819A (en) | Process and device for producing glycine by alcohol phase method | |
| EP4058436A1 (en) | Process and plant for the production of epsilon-caprolactam and ammonium sulfate on industrial scale | |
| CN111205319A (en) | Continuous synthesis method and system of glyphosate | |
| CN212102646U (en) | Device for producing glycine by adopting alcohol phase method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |