CN114163473A - Method for preparing diisobutylphosphine from liquid phosphine - Google Patents
Method for preparing diisobutylphosphine from liquid phosphine Download PDFInfo
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- CN114163473A CN114163473A CN202111313731.8A CN202111313731A CN114163473A CN 114163473 A CN114163473 A CN 114163473A CN 202111313731 A CN202111313731 A CN 202111313731A CN 114163473 A CN114163473 A CN 114163473A
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 44
- LREAZWJEBORMTB-UHFFFAOYSA-N bis(2-methylpropyl)phosphane Chemical compound CC(C)CPCC(C)C LREAZWJEBORMTB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000007788 liquid Substances 0.000 title claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000007259 addition reaction Methods 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 43
- 239000002904 solvent Substances 0.000 claims abstract description 10
- TXBIZRLVIDXDGB-UHFFFAOYSA-N 2-methylpropylphosphane Chemical compound CC(C)CP TXBIZRLVIDXDGB-UHFFFAOYSA-N 0.000 claims description 22
- DAGQYUCAQQEEJD-UHFFFAOYSA-N tris(2-methylpropyl)phosphane Chemical compound CC(C)CP(CC(C)C)CC(C)C DAGQYUCAQQEEJD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 21
- 239000006227 byproduct Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 10
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 2
- 230000006835 compression Effects 0.000 abstract description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000006053 organic reaction Methods 0.000 abstract 1
- 238000007342 radical addition reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- -1 alkyl phosphine Chemical compound 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000005188 flotation Methods 0.000 description 4
- 150000004714 phosphonium salts Chemical group 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZGTNBBQKHJMUBI-UHFFFAOYSA-N bis[tetrakis(hydroxymethyl)-lambda5-phosphanyl] sulfate Chemical compound OCP(CO)(CO)(CO)OS(=O)(=O)OP(CO)(CO)(CO)CO ZGTNBBQKHJMUBI-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229940056932 lead sulfide Drugs 0.000 description 2
- 229910052981 lead sulfide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- OFGFUPAXBMLHGP-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphane Chemical compound CC(C)(C)CC(C)CPCC(C)CC(C)(C)C OFGFUPAXBMLHGP-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- AIRPJJGSWHWBKS-UHFFFAOYSA-N hydroxymethylphosphanium;chloride Chemical compound [Cl-].OC[PH3+] AIRPJJGSWHWBKS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- KVNGCRKOAIBVRI-UHFFFAOYSA-M sodium;2-methylpropoxy-(2-methylpropylsulfanyl)-oxido-sulfanylidene-$l^{5}-phosphane Chemical compound [Na+].CC(C)COP([O-])(=S)SCC(C)C KVNGCRKOAIBVRI-UHFFFAOYSA-M 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 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 1
- 239000002341 toxic gas Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
-
- 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
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5059—Preparation; Separation; Purification; Stabilisation by addition of phosphorus compounds to alkenes or alkynes
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 preparing diisobutylphosphine by liquid phosphine, which comprises the following steps: adding low-temperature liquid phosphine and liquid isobutene into a reaction kettle in sequence, uniformly mixing, raising the temperature to a target reaction temperature, and slowly dropwise adding an initiator solution into the reaction kettle through a diaphragm metering pump to initiate a free radical addition reaction; and after the reaction is finished, rectifying and separating the obtained reaction product to obtain the target product diisobutylphosphine. The invention not only improves the purity of the sodium hypophosphite byproduct phosphine as a raw material, but also creates conditions for low-pressure feeding of liquid phosphine and isobutene; the purified liquid phosphine is used as a raw material, so that the liquid-phase uniform mixing reaction of the phosphine and isobutene is realized, the use of a large amount of organic reaction solvents such as toluene and the like is avoided, and the reaction efficiency is improved; meanwhile, compared with a phosphine gas compression method, the method reduces the reaction pressure of the system and improves the reaction safety. In addition, the initiator solvent adopts the addition reaction by-product, and a new solvent substance is not introduced into the system, so that the separation and recovery of the initiator solvent are avoided.
Description
Technical Field
The invention relates to a method for preparing diisobutylphosphine from liquid phosphine serving as a byproduct in the production process of sodium hypophosphite.
Background
Sodium hypophosphite is an important variety in inorganic phosphorus chemical products, a large amount of phosphine tail gas is inevitably generated in the production process, and about 20-25% of yellow phosphorus consumption of production raw materials is converted into phosphine. The main components of the phosphine byproduct are (V/V%): PH value3=35-45%，H2=50-60%，N2=5-10%，CO2And = 0.01-0.1%. At present, the treatment mode of the phosphine serving as a by-product of sodium hypophosphite mainly comprises the following steps:
1. the phosphine tail gas is used as a raw material to synthesize the quaternary phosphonium salt series flame retardant and bactericide. For example, the phosphine tail gas is directly used as a raw material, and is subjected to water washing or alkali washing treatment, and then reacts with formaldehyde and sulfuric acid to obtain Tetrakis Hydroxymethyl Phosphonium Sulfate (THPS), or reacts with formaldehyde and hydrochloric acid to obtain Tetrakis Hydroxymethyl Phosphonium Chloride (THPC). The treatment method has simple process and lower investment, can directly utilize phosphine tail gas as a raw material, only needs water washing and alkali washing to remove the tail gas carrying yellow phosphorus, and can obtain quaternary phosphonium salt series products with higher added values, thereby being adopted by most sodium hypophosphite manufacturers.
2. The phosphine is combusted and oxidized to phosphoric acid. The method reduces the added value of yellow phosphorus, but can be used as a beneficial supplement of the method 1, because the absorption utilization rate of the phosphine of the quaternary phosphonium salt series product of the method 1 is about 75-85%, the incompletely reacted phosphine tail gas adopts an incineration treatment mode, the process is simple, and the investment is low.
The method has good treatment effect on phosphine tail gas generated in the production process of sodium hypophosphite, realizes the recycling of highly toxic gas by-products, and has lower generated added value.
On the other hand, phosphine is an important raw material for industrially synthesizing alkyl phosphine, and the alkyl phosphine has wide application in industry, such as trialkyl phosphine for synthesizing quaternary phosphonium salt and is used as a bactericide and a surfactant; the dialkyl phosphine is used for synthesizing dialkyl dithio phosphinate and is used as a sulfide flotation collector, a flame retardant and the like.
The diisobutylphosphine is an important raw material for preparing the diisobutyldithiophosphine sodium, and the diisobutyldithiophosphine sodium is used as a sulfide flotation collector, has excellent flotation effect, and is applied to the flotation of copper and lead sulfide ores and copper and lead sulfide ores associated with rare and precious metals. The preparation method of diisobutylphosphine mainly comprises a hydrogen phosphide method, a diethyl phosphite method or a phosphorus trichloride method.
Among these synthetic routes, the most promising is the reaction of phosphine and olefin to obtain alkyl phosphine, and the addition reaction of phosphine and olefin under the action of initiator has the shortest process route, lowest cost, highest yield and least byproducts to prepare alkyl phosphine. Such as the synthesis of bis (2, 4, 4-trimethylpentyl) phosphine by using phosphine and diisobutylene and phosphine, by using Zhonghui et al (CN 201410019641.1), the synthesis of trialkylphosphine by using phosphine and alpha-olefin by using Emerichsin et al (CN 200810117469.8) and Pedervistin et al (CN 201110057830.4), the synthesis of sodium bisisobutyldithiophosphate by using shimasa [ J ]. science and wealth.2016, (7).
The process for synthesizing the organic phosphorus product by reacting phosphine with olefin has been developed in the past 50 years, but the source of the phosphine is always the key of the process, wherein the yellow phosphoric acid method process and the phosphorous acid pyrolysis method process are mainly used, the byproduct phosphine of the sodium hypophosphite process is another important source, but the byproduct phosphine tail gas contains hydrogen and a small amount of nitrogen with the volume ratio of 60 percent, the phosphine with the purity can only synthesize the organic phosphorus product with low yield and uneconomic property, and the reaction pressure is up to 9-10 MPa. Therefore, the invention aims to solve the problems of improving the purity of the phosphine byproduct of sodium phosphate, reducing the reaction pressure, improving the reaction safety and realizing the high-efficiency and economic synthesis of the organic phosphine product.
Disclosure of Invention
The invention aims to solve the problems and provides a method for preparing diisobutylphosphine by using phosphine serving as a purified sodium hypophosphite byproduct.
The invention provides a method for preparing diisobutylphosphine by taking liquid phosphine as a raw material, which comprises the following steps:
(1) conveying the purified low-temperature liquid phosphine to the precooled addition reaction kettle by a pump, starting stirring and conveying liquid isobutene to the addition reaction kettle after the liquid phosphine is fed, heating and continuously stirring after the hydrogen phosphide and isobutene are fed, and adding an initiator solution under the condition of a target reaction temperature to perform addition reaction;
(2) after the addition reaction is finished, discharging the incompletely reacted gaseous phosphine and isobutene, and discharging the reaction-finished mixture containing diisobutylphosphine to a rectification system;
after the addition reaction is finished, discharging unreacted gaseous phosphine and isobutene through a pressure relief buffer tank, and discharging after the pressure of an addition reaction kettle is discharged to 0.1-0.2 MPa; in addition, the pressure relief buffer tank can be used for emergently releasing phosphine and isobutene in the reaction kettle when the addition reaction is abnormal and the reaction pressure or temperature exceeds a set value, and the phosphine and isobutene are discharged to a tail gas incineration system through the pressure relief buffer tank.
(3) The rectification system firstly carries out normal pressure distillation to collect light component monoisobutylphosphine, and then carries out reduced pressure distillation on the residual material to collect the product diisobutylphosphine.
Precooling the addition reaction kettle in the step (1) through a low-temperature heat conduction oil system before feeding, so that the temperature in the reaction kettle is controlled to be-30 to-40 ℃;
the temperature of the low-temperature liquid phosphine is-60 to-80 ℃, and the feeding pressure is 0.1 to 0.8 MPa; after the feeding of the liquid phosphine is finished, the temperature in the reaction kettle is within minus 30 to minus 40 ℃.
The feeding pressure of the isobutene is 0.5-1.0 MPa, and the temperature in the reaction kettle is-30 to-40 ℃ after the feeding of the isobutene is finished.
After the feeding of phosphine and isobutene is finished, heating and stirring continuously, and adding an initiator solution under the condition of a target reaction temperature to perform addition reaction; under the conditions, phosphine and isobutene mainly exist in a liquid phase, so that the reaction is easier to carry out, and the reaction efficiency is higher.
The initiator is any one of azobisisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile.
The solvent used as the initiator in the initiator solution is one or a mixture of more of triisobutylphosphine, diisobutylphosphine and monoisobutylphosphine, and the concentration of the initiator solution is 3-5%; the solvent triisobutylphosphine, diisobutylphosphine or monoisobutylphosphine comes from the product separated by rectification system.
The atmospheric distillation pressure is 0-2 KPa, and the temperature is 70-75 ℃; the vacuum degree of the reduced pressure distillation is-95 to-97 KPa, and the temperature is 80 to 85 ℃.
After the liquid phosphine and the liquid isobutene are fed in the step (1), the main reaction raw materials, namely the phosphine and the isobutene, in the reaction kettle belong to liquid phase uniform mixing, the gas phase material ratio is very small, pressure conditions required by the reaction are mainly provided for a reaction system, and the pressure of the reaction system is the saturated vapor pressure of the mixed liquid of the liquid phosphine and the liquid isobutene at the reaction temperature.
After the feeding of phosphine and isobutene in the step (1) is finished, controlling the temperature in the reaction kettle according to the half-life period of an initiator, specifically, when azodiisobutyronitrile or azodiisovaleronitrile is used as the initiator, the temperature in the reaction kettle is 82-87 ℃, and the pressure in the reaction kettle is the saturated vapor pressure of a mixed liquid of liquid phosphine and liquid isobutene at the temperature, specifically 4.0-5.0 MPa; when the azodiisoheptanonitrile is used as an initiator, the temperature in the reaction kettle is 63-68 ℃, and the pressure in the reaction kettle is the saturated vapor pressure of the mixed liquid of the liquid phosphine and the liquid isobutene at the temperature, and is specifically 3.0-4.0 MPa. And after the reaction temperature is reached, dropwise adding an initiator solution to initiate an addition reaction, and reacting for 2-4 hours under the conditions.
The technical scheme of the invention has the following beneficial effects: the purity of the phosphine serving as a sodium hypophosphite byproduct is improved by a low-temperature liquefaction method, the phosphine is fed in a low-temperature liquid state manner, the feeding pressure of the phosphine and isobutene is reduced, the liquid-phase mixed reaction of the phosphine and isobutene is realized, the use of a large amount of reaction solvent is avoided, and the reaction efficiency is improved; meanwhile, compared with a phosphine compression method, the method reduces the reaction pressure of the system and improves the reaction safety. In addition, the initiator solvent adopts the addition reaction by-product, and a new solvent substance is not introduced into the system, so that the separation and recovery of the initiator solvent are avoided.
Detailed Description
Example 1
The synthesis of diisobutylphosphine comprises the following steps
(1) Addition reaction
Adding 9.2kg of phosphine into a 50L addition reaction kettle by using a diaphragm metering pump, controlling the feeding temperature to be-70 to-80 ℃ and the feeding pressure to be 0.2 to 0.5 MPa; starting stirring, adding 15.6kg of isobutene by using a diaphragm metering pump, and controlling the feeding pressure to be 0.5-0.8 MPa; after feeding is finished, the temperature in the reaction kettle is between-30 ℃ and-35 ℃; after the feeding of phosphine and isobutene is finished, controlling the temperature of the reaction kettle to be 82-85 ℃ and the pressure to be 4.4-4.6 MPa through a heat conducting oil system; after the temperature and the pressure are stable, adding 3.0kg of triisobutylphosphine solution of azobisisobutyronitrile through a diaphragm metering pump, wherein the concentration of the initiator solution is 4%, the dripping time is 3h, keeping the temperature for reaction for 1h after the initiator solution is added, reducing the temperature in the reaction kettle to 20-25 ℃ after the heat-preservation reaction is finished, discharging after the pressure is released to 0.1-0.2 MPa through a pressure-releasing buffer tank, and obtaining 22.5kg of addition reaction finished material containing monoisobutylphosphine, diisobutylphosphine and triisobutylphosphine; the composition was analyzed by gas chromatography as follows: 30.3 percent of monoisobutylphosphine, 38.2 percent of diisobutylphosphine and 31.5 percent of triisobutylphosphine.
In the addition reaction process, after the phosphine and the isobutene are fed and heated to the target reaction temperature through the heat conduction oil system, the pressure in the reaction kettle is up to 3-5MPa, and meanwhile, the addition reaction is an exothermic reaction, if the heat released by the reaction cannot be timely removed through the circulating cooling system, or the dropping speed of the initiator solution is too high, the temperature of the reaction system is out of control, so that the addition reaction is accelerated, the reaction system is out of control, and the temperature and the pressure are abnormally increased. If the above situation occurs in the patent of the invention, the following emergency interlocking measures are taken: (1) immediately stopping the feeding of the initiator solution; (2) starting the emergency cooling system; (3) the safe discharge system is started, the pressure in the reaction kettle is gradually discharged to a safe controllable range through the automatic safe discharge valve, the safe discharge system is matched with a 5000L pressure release buffer tank and a tail gas incineration system, the pressure release buffer tank can buffer the discharge pressure to within 20KPa, and then the pressure is slowly released to the tail gas incineration system.
(2) Rectification
Transferring the liquid material obtained in the step (1) into a rectifying still, then carrying out normal pressure rectification, slowly heating the pressure at the top of the rectifying still to 73-75 ℃ at the pressure of 0-2 KPa, and collecting light component of mono-isobutyl phosphine; and carrying out reduced pressure rectification on the residual materials, controlling the vacuum degree to be-95 to-97 KPa, raising the temperature to be 80 to 82 ℃, collecting partial front cut, collecting the target product diisobutylphosphine after the content of the target product is qualified, and stopping collecting after the content of the product is reduced to be unqualified.
Step (2) 8.6kg of diisobutylphosphine was collected and analyzed by gas chromatography for the following composition: 97.5 percent of diisobutylphosphine, 1.7 percent of monoisobutylphosphine and 0.8 percent of triisobutylphosphine.
EXAMPLE 2 Synthesis of diisobutylphosphine
(1) Addition reaction
Adding 9.5kg of phosphine into a 50L addition reaction kettle by using a diaphragm metering pump, controlling the feeding temperature to be-70 to-80 ℃ and the feeding pressure to be 0.2 to 0.5 MPa; starting stirring, adding 15.2kg of isobutene by using a diaphragm metering pump, and controlling the feeding pressure to be 0.5-0.8 MPa; after feeding is finished, the temperature in the reaction kettle is-35 to-40 ℃; after the feeding of phosphine and isobutene is finished, controlling the temperature of the reaction kettle to be 64-67 ℃ and the pressure to be 3.5-3.8 MPa through a heat-conducting oil system; after the temperature and the pressure temperature are reached, 2.8kg of initiator solution is added through a diaphragm metering pump, the concentration of the initiator azodiisoheptanonitrile is 3%, the solvent is a mixed solution of monoisobutylphosphine and diisobutylphosphine (the ratio is 8: 2), the dropping time of the initiator solution is 2 hours, the temperature of the reaction kettle is reduced to 20-25 ℃ after the initiator solution is added, the reaction kettle is discharged to 0.1-0.2 MPa through a pressure-releasing buffer tank, and 22.3kg of addition reaction completion material containing monoisobutylphosphine, diisobutylphosphine and triisobutylphosphine is obtained; the composition was analyzed by gas chromatography as follows: 35.3 percent of monoisobutylphosphine, 46.2 percent of diisobutylphosphine and 18.5 percent of triisobutylphosphine.
In the addition reaction process, after the phosphine and the isobutene are fed and heated to the target reaction temperature through the heat conduction oil system, the pressure in the reaction kettle is up to 3-5MPa, and meanwhile, the addition reaction is an exothermic reaction, if the heat released by the reaction cannot be timely removed through the circulating cooling system, or the dropping speed of the initiator solution is too high, the temperature of the reaction system is out of control, so that the addition reaction is accelerated, the reaction system is out of control, and the temperature and the pressure are abnormally increased. If the above situation occurs in the patent of the invention, the following emergency interlocking measures are taken: (1) immediately stopping the feeding of the initiator solution; (2) starting the emergency cooling system; (3) the safe discharge system is started, the pressure in the reaction kettle is gradually discharged to a safe controllable range through the automatic safe discharge valve, the safe discharge system is matched with a 5000L pressure release buffer tank and a tail gas incineration system, the pressure release buffer tank can buffer the discharge pressure to within 20KPa, and then the pressure is slowly released to the tail gas incineration system.
(2) Rectification
Transferring the liquid material obtained in the step (1) into a rectifying still, then carrying out normal pressure rectification, slowly heating the pressure at the top of the rectifying still to 73-75 ℃ at the pressure of 0-2 KPa, and collecting light component of mono-isobutyl phosphine; and carrying out reduced pressure rectification on the residual materials, controlling the vacuum degree to be-95 to-97 KPa, raising the temperature to be 80 to 82 ℃, collecting partial front cut, collecting the target product diisobutylphosphine after the content of the target product is qualified, and stopping collecting after the content of the product is reduced to be unqualified.
Step (2) 10.3kg of diisobutylphosphine was collected and analyzed by gas chromatography for the following composition: 98.1 percent of diisobutylphosphine, 1.4 percent of monoisobutylphosphine and 0.5 percent of triisobutylphosphine.
EXAMPLE 3 Synthesis of diisobutylphosphine
(1) Addition reaction
Adding 9.5kg of phosphine into a 50L addition reaction kettle by using a diaphragm metering pump, controlling the feeding temperature to be-60 to-70 ℃ and the feeding pressure to be 0.3 to 0.6 MPa; starting stirring, adding 15.2kg of isobutene by using a diaphragm metering pump, controlling the feeding pressure to be 0.6-1.0 MPa, and controlling the temperature in the reaction kettle to be-30 to-32 ℃ after the feeding is finished; after the feeding of phosphine and isobutene is finished, controlling the temperature of the reaction kettle to be 83-86 ℃ and the pressure to be 4.5-4.8 MPa through a heat conducting oil system; after the temperature and the pressure temperature, 2.5kg of the monoisobutylphosphine solution of azodiisovaleronitrile is added through a diaphragm metering pump, the concentration of the initiator solution is 3.5 percent, the dripping time is 2 hours, the temperature is kept for reaction for 1 hour after the initiator solution is added, the temperature in the reaction kettle is reduced to 20-25 ℃ after the temperature keeping reaction is finished, the pressure is released to 0.1-0.2 MPa through a pressure release buffer tank, and then the mixture is discharged, so that 22.1kg of addition reaction finished materials containing monoisobutylphosphine, diisobutylphosphine and triisobutylphosphine are obtained; the composition was analyzed by gas chromatography as follows: 36.8 percent of monoisobutylphosphine, 47.1 percent of diisobutylphosphine and 16.1 percent of triisobutylphosphine.
In the addition reaction process, after the phosphine and the isobutene are fed and heated to the target reaction temperature through a heat conduction oil system, the pressure in the reaction kettle is up to 3-5MPa, and meanwhile, the pressure in the reaction kettle is increased
The addition reaction is an exothermic reaction, and if the heat released by the reaction cannot be timely removed through a circulating cooling system or the dropping speed of the initiator solution is too high, the temperature of the reaction system is out of control, so that the addition reaction is accelerated, the reaction system is out of control, and the temperature and the pressure are abnormally increased. If the above situation occurs in the patent of the invention, the following emergency interlocking measures are taken: (1) immediately stopping the feeding of the initiator solution; (2) starting the emergency cooling system; (3) the safe discharge system is started, the pressure in the reaction kettle is gradually discharged to a safe controllable range through the automatic safe discharge valve, the safe discharge system is matched with a 5000L pressure release buffer tank and a tail gas incineration system, the pressure release buffer tank can buffer the discharge pressure to within 20KPa, and then the pressure is slowly released to the tail gas incineration system.
(2) Rectification
Transferring the liquid material obtained in the step (1) into a rectifying still, then carrying out normal pressure rectification, slowly heating the pressure at the top of the rectifying still to 73-75 ℃ at the pressure of 0-2 KPa, and collecting light component of mono-isobutyl phosphine; and carrying out reduced pressure rectification on the residual materials, controlling the vacuum degree to be-95 to-97 KPa, raising the temperature to be 80 to 82 ℃, collecting partial front cut, collecting the target product diisobutylphosphine after the content of the target product is qualified, and stopping collecting after the content of the product is reduced to be unqualified.
Step (2) 10.4kg of diisobutylphosphine was collected and analyzed by gas chromatography for the following composition: 98.2 percent of diisobutylphosphine, 1.2 percent of monoisobutylphosphine and 0.6 percent of triisobutylphosphine.
Example 4
The steps of the method are the same as those of the example 3, and only when the concentration of the initiator solution is 2.5 percent, 20.5kg of reaction finished material is obtained after the addition reaction is finished; the composition was analyzed by gas chromatography as follows: 41.1% of monoisobutylphosphine, 44.6% of diisobutylphosphine and 14.3% of triisobutylphosphine; if the concentration of the initiator solution is less than 3%, the yield of the addition reaction in one batch and the yield of the target product, namely diisobutylphosphine, are both significantly lower than those of example 3.
Example 5
The steps of the method are the same as those of the example 3, and 22.1kg of reaction finished material is obtained after the addition reaction is finished only if the concentration of the initiator solution is 4.5 percent; the composition was analyzed by gas chromatography as follows: 36.7 percent of monoisobutylphosphine, 47.3 percent of diisobutylphosphine and 16.0 percent of triisobutylphosphine. The yield of the addition reaction in one batch and the yield of the target product, diisobutylphosphine, were at the same level as in example 3.
Example 6
The steps of the method are the same as those of the example 3, and 22.2kg of reaction finished material is obtained after the addition reaction is finished only if the concentration of the initiator solution is 5.5 percent; the composition was analyzed by gas chromatography as follows: 36.9 percent of monoisobutylphosphine, 47.2 percent of diisobutylphosphine and 15.9 percent of triisobutylphosphine. The concentration of the initiator solution is more than 5 percent, the single-batch yield of the addition reaction and the yield of the target product diisobutylphosphine are at the same level as those of the example 3, but the addition reaction speed is increased along with the increase of the concentration of the initiator, the reaction control difficulty is increased, and the increase of the consumption of the initiator also brings about the increase of the production cost.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the present invention, and any modifications, equivalents, improvements and the like made without departing from the technical scope of the present invention as set forth in the claims should be included in the scope of the present invention.
Claims (9)
1. The method for preparing diisobutylphosphine from liquid phosphine is characterized by comprising the following steps:
(1) conveying low-temperature liquid phosphine to the precooled addition reaction kettle by a pump, starting stirring and conveying liquid isobutene to the addition reaction kettle after the liquid phosphine is fed, heating and continuously stirring after the hydrogen phosphide and isobutene are fed, and adding an initiator solution under the condition of a target reaction temperature to perform addition reaction;
(2) after the addition reaction is finished, discharging the incompletely reacted gaseous phosphine and isobutene, and discharging the reaction-finished mixture containing diisobutylphosphine to a rectification system;
(3) the rectification system firstly carries out normal pressure distillation to collect light component monoisobutylphosphine, and then carries out reduced pressure distillation on the residual material to collect the product diisobutylphosphine.
2. The method according to claim 1, wherein the addition reaction kettle in the step (1) is precooled by a low-temperature heat conduction oil system before feeding, so that the temperature in the reaction kettle reaches-30 to-40 ℃.
3. The method according to claim 1, wherein the temperature of the low-temperature liquid phosphine in the step (1) is-60 to-80 ℃, and the feeding pressure is 0.1 to 0.8 MPa; after the feeding of the liquid phosphine is finished, the temperature in the reaction kettle is within minus 30 to minus 40 ℃.
4. The method according to claim 1, wherein the feeding pressure of the liquid isobutene in the step (1) is 0.5-1.0 MPa, and the temperature in the reaction kettle is-30 to-40 ℃ after the feeding of the liquid isobutene is finished.
5. The method according to claim 1, wherein the temperature in the reaction kettle is controlled to be 82-87 ℃ after the feeding of the phosphine and the isobutene in the step (1) is finished, the pressure in the reaction kettle is controlled to be 4.0-5.0 MPa, and the reaction is carried out for 2-4 h under the condition.
6. The method of claim 1, wherein the initiator in step (1) is any one of azobisisobutyronitrile, azobisisovaleronitrile and azobisisoheptonitrile.
7. The method according to claim 1, wherein the solvent used as the initiator in the initiator solution in step (1) is one or a mixture of triisobutylphosphine, diisobutylphosphine and monoisobutylphosphine, and the concentration of the initiator solution is 3-5%.
8. The method according to claim 1, wherein the mass ratio of the liquid phosphine to the isobutene in the step (1) is 1: 1.6-1: 1.7, and the addition amount of the initiator solution is 10-12% of the total mass of the phosphine and the isobutene.
9. The method according to claim 1, wherein the atmospheric distillation pressure in the step (3) is 0-2 KPa, and the temperature is 70-75 ℃; the vacuum degree of the reduced pressure distillation is-95 to-97 KPa, and the temperature is 80 to 85 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116002639A (en) * | 2023-01-09 | 2023-04-25 | 杭州磷源技术研发有限公司 | Purification of sodium hypophosphite byproduct phosphine and application of sodium hypophosphite byproduct phosphine in synthesis of alkyl phosphine |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2803597A (en) * | 1949-04-30 | 1957-08-20 | Shell Dev | Process for producing organic phosphines |
| US4324919A (en) * | 1979-09-07 | 1982-04-13 | Hoechst Aktiengesellschaft | Production of tertiary phosphines |
| JP2003313194A (en) * | 2002-02-19 | 2003-11-06 | Hokko Chem Ind Co Ltd | Method for producing tertiary phosphine bonded with bulky hydrocarbon group |
| CN102180902A (en) * | 2011-03-10 | 2011-09-14 | 常熟新特化工有限公司 | Preparation method of tributylphosphane |
| CN102180900A (en) * | 2011-03-10 | 2011-09-14 | 常熟新特化工有限公司 | Method for preparing bis(2,4,4-trimethylpentyl)phosphonic acid |
| CN102304149A (en) * | 2011-06-28 | 2012-01-04 | 中国原子能科学研究院 | Synthesis method of triisobutyl phosphine sulfide |
| CN103772429A (en) * | 2014-01-16 | 2014-05-07 | 常熟新特化工有限公司 | Method for preparing bis(2,4,4-trimethylpentyl) phosphinic acid from hydrogen phosphide as byproduct in sodium hypophosphite production process |
| CN112142782A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of dialkyl phosphinic acid |
-
2021
- 2021-11-08 CN CN202111313731.8A patent/CN114163473A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2803597A (en) * | 1949-04-30 | 1957-08-20 | Shell Dev | Process for producing organic phosphines |
| US4324919A (en) * | 1979-09-07 | 1982-04-13 | Hoechst Aktiengesellschaft | Production of tertiary phosphines |
| JP2003313194A (en) * | 2002-02-19 | 2003-11-06 | Hokko Chem Ind Co Ltd | Method for producing tertiary phosphine bonded with bulky hydrocarbon group |
| CN102180902A (en) * | 2011-03-10 | 2011-09-14 | 常熟新特化工有限公司 | Preparation method of tributylphosphane |
| CN102180900A (en) * | 2011-03-10 | 2011-09-14 | 常熟新特化工有限公司 | Method for preparing bis(2,4,4-trimethylpentyl)phosphonic acid |
| CN102304149A (en) * | 2011-06-28 | 2012-01-04 | 中国原子能科学研究院 | Synthesis method of triisobutyl phosphine sulfide |
| CN103772429A (en) * | 2014-01-16 | 2014-05-07 | 常熟新特化工有限公司 | Method for preparing bis(2,4,4-trimethylpentyl) phosphinic acid from hydrogen phosphide as byproduct in sodium hypophosphite production process |
| CN112142782A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of dialkyl phosphinic acid |
Non-Patent Citations (2)
| Title |
|---|
| A. R. STILE，等: "The preparation of organo-phosphines by the addition of phosphine to unsaturated compounds", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》, pages 3282 - 3284 * |
| 张骥红，等: "三正丁基膦的合成和表征", 《精细化工中间体》, pages 39 - 41 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116002639A (en) * | 2023-01-09 | 2023-04-25 | 杭州磷源技术研发有限公司 | Purification of sodium hypophosphite byproduct phosphine and application of sodium hypophosphite byproduct phosphine in synthesis of alkyl phosphine |
| CN116002639B (en) * | 2023-01-09 | 2023-09-19 | 杭州磷源技术研发有限公司 | Purification of sodium hypophosphite byproduct phosphine and application of sodium hypophosphite byproduct phosphine in synthesis of alkyl phosphine |
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