CN114163473B - Method for preparing diisobutylphosphine from liquid hydrogen phosphide - Google Patents
Method for preparing diisobutylphosphine from liquid hydrogen phosphide Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- LREAZWJEBORMTB-UHFFFAOYSA-N bis(2-methylpropyl)phosphane Chemical compound CC(C)CPCC(C)C LREAZWJEBORMTB-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 81
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 73
- 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 13
- 239000000463 material Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 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 5
- 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 1
- 239000000047 product Substances 0.000 abstract description 21
- 239000006227 byproduct Substances 0.000 abstract description 13
- 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 10
- 239000002994 raw material Substances 0.000 abstract description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract description 10
- 239000007791 liquid phase Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000926 separation method 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
- 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 17
- 238000004817 gas chromatography Methods 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 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
- 238000005406 washing Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- -1 alkyl phosphine Chemical compound 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
- OJNSBQOHIIYIQN-UHFFFAOYSA-M sodium;bis(2-methylpropyl)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CC(C)CP([S-])(=S)CC(C)C OJNSBQOHIIYIQN-UHFFFAOYSA-M 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 3
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-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
- 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
- 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
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 2
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 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
- 229940121710 HMGCoA reductase inhibitor Drugs 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
- 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
- 230000000977 initiatory effect Effects 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
- 229910000510 noble metal Inorganic materials 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
- 238000002360 preparation method 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
- 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
- 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: sequentially adding low-temperature liquid phosphine and liquid isobutene into a reaction kettle, uniformly mixing, then 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 rectifying and separating the reaction product after the reaction is finished 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 phosphine and isobutene is realized, a large amount of organic reaction solvents such as toluene and the like are 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 is an addition reaction byproduct, and a new solvent substance is not introduced into the system, so that separation and recovery of the initiator solvent are avoided.
Description
Technical Field
The invention relates to a method for preparing diisobutylphosphine by liquid phosphine of byproducts in the sodium hypophosphite production process.
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 in the production raw material is converted into phosphine. The main components of the byproduct phosphine are (V/V%): PH 3=35-45%,H2=50-60%,N2=5-10%,CO2 =0.01 to 0.1%. At present, the treatment mode of the sodium hypophosphite byproduct phosphine mainly comprises the following steps:
1. The phosphine tail gas is used as raw material to synthesize quaternary phosphonium salt series fire retardant and bactericide. If the phosphine tail gas is directly used as a raw material, the phosphine tail gas is subjected to water washing or alkali washing treatment and then reacts with formaldehyde and sulfuric acid to obtain the tetrakis (hydroxymethyl) phosphonium sulfate (THPS) or reacts with formaldehyde and hydrochloric acid to obtain the tetrakis (hydroxymethyl) phosphonium chloride (THPC). The treatment method has simple process and low investment, can directly utilize phosphine tail gas as a raw material, only removes yellow phosphorus entrained in the tail gas through water washing and alkali washing, and can obtain quaternary phosphonium salt series products with high added value, thereby obtaining the adoption of most sodium hypophosphite manufacturers.
2. The phosphine is burnt and oxidized into 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 hydrogen phosphide absorption and utilization rate of the quaternary phosphonium salt series products of the method 1 is about 75-85%, the phosphine tail gas which is not completely reacted adopts a burning treatment mode, the process is simple, and the investment is low.
The method has good treatment effect on the phosphine tail gas generated in the sodium hypophosphite production process, realizes the recycling of the highly toxic gas byproducts, and has lower added value.
On the other hand, phosphine is an important raw material for industrially synthesizing alkyl phosphine, and the alkyl phosphine has wide industrial application, such as trialkyl phosphine for synthesizing quaternary phosphonium salt, and is used as bactericide and surfactant; dialkylphosphines are used in the synthesis of dialkyldithiophosphinates, as sulfide flotation collectors, flame retardants, and the like.
Diisobutylphosphine is an important raw material for preparing sodium diisobutyldithiophosphinate, and the sodium diisobutyldithiophosphinate is used as a sulphide ore flotation collector, has excellent flotation effect, and is applied to flotation of copper and lead sulphide ores and copper and lead sulphide ores accompanied with rare noble metals. The preparation method of diisobutylphosphine mainly comprises a phosphine method, a diethyl phosphite method or a phosphorus trichloride method.
Among these synthetic routes, the most promising industrial prospect is that phosphine is obtained by reacting phosphine with olefin, and the process route for preparing alkyl phosphine by the addition reaction of phosphine and olefin under the action of initiator is shortest, the cost is lowest, the yield is highest, and the byproducts are least. Bi (2, 4-trimethylpentyl) phosphine was synthesized using phosphine and diisobutylene and phosphine as Zhou Yuehui et al (CN 201410019641.1), yu Weifa et al (CN 200810117469.8) and Peter's, black statin et al (CN 201110057830.4) was synthesized using phosphine and alpha-olefin to trialkylphosphine, she Zhisong. Synthesis of sodium diisobutyldithiophosphinate [ J ]. Scientific & financial 2016, (7) diisobutylphosphine was prepared using phosphine and isobutylene.
The process for synthesizing the organic phosphorus product by reacting phosphine with olefin has been developed in the last 50 th century, but the source of phosphine is always the key of the process, wherein the yellow phosphoric acid process and the phosphorous acid pyrolysis process are mainly used, in addition, the byproduct phosphine of the sodium hypophosphite process is another important source, but the tail gas of the byproduct phosphine contains hydrogen with the volume ratio of up to 60% and a small amount of nitrogen, the phosphine with the purity can only be synthesized into the organic phosphorus product in low yield and uneconomically, and the reaction pressure is up to 9-10 MPa. Therefore, how to improve the purity of the byproduct phosphine of sodium hypophosphite, reduce the reaction pressure, improve the reaction safety and realize the efficient and economical synthesis of the organic phosphine product is the problem to be solved by the invention.
Disclosure of Invention
The invention aims to solve the problems and provide a method for preparing diisobutylphosphine by utilizing purified sodium hypophosphite byproduct phosphine.
The invention provides a method for preparing diisobutylphosphine by taking liquid phosphine as a raw material, which comprises the following steps:
(1) The purified low-temperature liquid phosphine is conveyed to an addition reaction kettle after precooling treatment by a pump, after the liquid phosphine is fed, stirring is started, liquid isobutene is conveyed to the addition reaction kettle, after the phosphine and isobutene are fed, heating is continued, stirring is carried out, and an initiator solution is added under the condition of target reaction temperature for addition reaction;
(2) Discharging the gaseous phosphine and isobutene which are not completely reacted after the addition reaction is finished, and discharging a reaction completion 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, discharging after the pressure of the addition reaction kettle is discharged to 0.1-0.2 MPa; in addition, the pressure relief buffer tank can also be used as an emergency pressure relief buffer tank for emergently discharging phosphine and isobutene in the reaction kettle when the reaction pressure or temperature exceeds a set value during abnormal addition reaction, and is discharged to a tail gas incineration system through the pressure relief buffer tank.
(3) The rectification system is used for collecting light-component monoisobutyl phosphine through normal pressure distillation, and then the rest materials are subjected to reduced pressure distillation to collect the product diisobutyl phosphine.
The addition reaction kettle in the step (1) is pre-cooled by a low-temperature conduction oil system before feeding, so that the temperature in the reaction kettle reaches minus 30 to minus 40 ℃;
the temperature of the low-temperature liquid phosphine is-60 to-80 ℃, and the feeding pressure is 0.1 to 0.8MPa; after the liquid phosphine is fed, the temperature in the reaction kettle is 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 isobutene is fed.
After phosphine and isobutene are fed, heating and continuously stirring, and adding an initiator solution under the condition of target reaction temperature to carry out addition reaction; under the above 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 azodiisobutyronitrile, azodiisovaleronitrile and azodiisoheptonitrile.
The solvent used as the initiator in the initiator solution is one or a mixture of a plurality of triisobutyl phosphine, diisobutyl phosphine and monoisobutyl phosphine, and the concentration of the initiator solution is 3-5%; the solvent triisobutylphosphine, diisobutylphosphine or monoisobutylphosphine is derived from the separation of the product in the rectification system.
The atmospheric distillation pressure is 0-2 KPa, and the temperature is 70-75 ℃; the vacuum degree of reduced pressure distillation is-95 to-97 KPa, and the temperature is 80 to 85 ℃.
After the feeding of the liquid phosphine and the liquid isobutene in the step (1) is finished, the main reaction raw materials phosphine and isobutene in the reaction kettle are uniformly mixed in a liquid phase, the gas phase material ratio is extremely small, the pressure condition required by the reaction is 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 phosphine and isobutene are fed in the step (1), controlling the temperature in a reaction kettle according to the half-life period of an initiator, wherein the temperature in the reaction kettle is 82-87 ℃ when azodiisobutyronitrile or azodiisovaleronitrile is used as the initiator, and the pressure in the reaction kettle is the saturated vapor pressure of liquid phosphine and liquid isobutene mixed liquid at the temperature, and is specifically 4.0-5.0 MPa; when azodiisoheptonitrile 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 liquid phosphine and liquid isobutene at the temperature, specifically 3.0-4.0 MPa. After the reaction temperature is reached, initiating an addition reaction by dripping an initiator solution, and reacting for 2-4 hours under the condition.
The technical scheme of the invention has the following beneficial effects: the purity of the sodium hypophosphite byproduct phosphine is improved through a low-temperature liquefaction method, the phosphine adopts a low-temperature liquid feeding mode, the feeding pressure of the phosphine and isobutene is reduced, the liquid phase mixing reaction of the phosphine and isobutene is realized, a large amount of reaction solvents are 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 is an addition reaction byproduct, and a new solvent substance is not introduced into the system, so that separation and recovery of the initiator solvent are avoided.
Detailed Description
Example 1
The synthesis of diisobutylphosphine includes 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 at-70 to-80 ℃ and the feeding pressure at 0.2-0.5 MPa; stirring is started, 15.6kg of isobutene is added by using a diaphragm metering pump, and the feeding pressure is controlled to be 0.5-0.8 MPa; after the feeding is finished, the temperature in the reaction kettle is-30 to-35 ℃; after phosphine and isobutene are fed, the temperature of the reaction kettle is controlled to be 82-85 ℃ and the pressure is controlled to be 4.4-4.6 MPa through a heat conduction oil system; after the temperature and the pressure are stable, adding 3.0kg of triisobutyl phosphine solution of azodiisobutyronitrile through a diaphragm metering pump, wherein the concentration of an initiator solution is 4%, the dropwise adding time is 3h, continuing to carry out heat preservation reaction for 1h after the initiator solution is added, reducing the temperature in a reaction kettle to 20-25 ℃ after the heat preservation reaction is finished, discharging after the pressure is discharged to 0.1-0.2 MPa through a pressure relief buffer tank, and obtaining 22.5kg of addition reaction completion material containing monoisobutyl phosphine, diisobutyl phosphine and triisobutyl phosphine; the composition was analyzed by gas chromatography as follows: 30.3% of mono-isobutyl phosphine, 38.2% of diisobutyl phosphine and 31.5% of triisobutyl phosphine.
In the addition reaction process, after phosphine and isobutene complete feeding and are heated to a target reaction temperature through a heat conducting oil system, the pressure in the reaction kettle is up to 3-5MPa, and meanwhile, the addition reaction is exothermic, if the heat released by the reaction cannot be timely removed through a circulating cooling system, or the dropping speed of an initiator solution is too fast, the temperature of a reaction system is possibly out of control, so that the addition reaction is accelerated to be initiated, and the reaction system is out of control, and the temperature and the pressure are abnormally increased. In the present patent, if the above situation occurs, the following emergency interlocking measures are adopted: (1) immediately stopping the initiator solution feed; (2) activating the emergency cooling system; (3) Starting a safety relief system, gradually releasing the pressure in the reaction kettle to a safe and controllable range through an automatic safety relief valve, and arranging a 5000L pressure relief buffer tank and a tail gas incineration system in a matched mode, wherein the pressure relief buffer tank can buffer the relief pressure to be within 20KPa and then slowly release the relief pressure to the tail gas incineration system.
(2) Rectifying
After transferring the liquid material obtained in the step (1) into a rectifying kettle, rectifying at normal pressure, slowly heating to 73-75 ℃ at the tower top pressure of 0-2 KPa, and collecting light-component monoisobutyl phosphine; and (3) carrying out reduced pressure rectification on the rest materials, controlling the vacuum degree to be-95 to-97 KPa, increasing the temperature to 80-82 ℃, firstly collecting part of the front cut fraction, starting to collect the target product diisobutylphosphine after the target product content is qualified, and stopping collecting after the product content is reduced to be unqualified.
8.6Kg of diisobutylphosphine is collected in the step (2), and the composition of the diisobutylphosphine is analyzed by gas chromatography as follows: 97.5% of diisobutylphosphine, 1.7% of monoisobutylphosphine and 0.8% 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 at-70 to-80 ℃ and the feeding pressure at 0.2-0.5 MPa; stirring is started, 15.2kg of isobutene is added by using a diaphragm metering pump, and the feeding pressure is controlled to be 0.5-0.8 MPa; after the feeding is finished, the temperature in the reaction kettle is minus 35 to minus 40 ℃; after phosphine and isobutene are fed, the temperature of the reaction kettle is controlled to be 64-67 ℃ and the pressure is controlled to be 3.5-3.8 MPa through a heat conduction oil system; after the temperature and the pressure temperature are reached, adding 2.8kg of initiator solution through a diaphragm metering pump, wherein the concentration of the initiator azodiisoheptanenitrile is 3%, the solvent is mixed solution of mono-isobutyl phosphine and diisobutyl phosphine (the proportion is 8:2), the dropwise adding time of the initiator solution is 2h, continuing to carry out heat preservation reaction for 1h after the adding of the initiator solution is finished, reducing the temperature in the reaction kettle to 20-25 ℃ after the heat preservation reaction is finished, discharging after the pressure is discharged to 0.1-0.2 MPa through a pressure relief buffer tank, and obtaining 22.3kg of addition reaction finished material containing mono-isobutyl phosphine, diisobutyl phosphine and triisobutyl phosphine; the composition was analyzed by gas chromatography as follows: 35.3% of mono-isobutyl phosphine, 46.2% of diisobutyl phosphine and 18.5% of triisobutyl phosphine.
In the addition reaction process, after phosphine and isobutene complete feeding and are heated to a target reaction temperature through a heat conducting oil system, the pressure in the reaction kettle is up to 3-5MPa, and meanwhile, the addition reaction is exothermic, if the heat released by the reaction cannot be timely removed through a circulating cooling system, or the dropping speed of an initiator solution is too fast, the temperature of a reaction system is possibly out of control, so that the addition reaction is accelerated to be initiated, and the reaction system is out of control, and the temperature and the pressure are abnormally increased. In the present patent, if the above situation occurs, the following emergency interlocking measures are adopted: (1) immediately stopping the initiator solution feed; (2) activating the emergency cooling system; (3) Starting a safety relief system, gradually releasing the pressure in the reaction kettle to a safe and controllable range through an automatic safety relief valve, and arranging a 5000L pressure relief buffer tank and a tail gas incineration system in a matched mode, wherein the pressure relief buffer tank can buffer the relief pressure to be within 20KPa and then slowly release the relief pressure to the tail gas incineration system.
(2) Rectifying
After transferring the liquid material obtained in the step (1) into a rectifying kettle, rectifying at normal pressure, slowly heating to 73-75 ℃ at the tower top pressure of 0-2 KPa, and collecting light-component monoisobutyl phosphine; and (3) carrying out reduced pressure rectification on the rest materials, controlling the vacuum degree to be-95 to-97 KPa, increasing the temperature to 80-82 ℃, firstly collecting part of the front cut fraction, starting to collect the target product diisobutylphosphine after the target product content is qualified, and stopping collecting after the product content is reduced to be unqualified.
Step (2) 10.3kg of diisobutylphosphine was collected and analyzed by gas chromatography for its composition as follows: 98.1% of diisobutylphosphine, 1.4% of monoisobutylphosphine and 0.5% 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 at-60 to-70 ℃ and the feeding pressure at 0.3-0.6 MPa; stirring is started, 15.2kg of isobutene is added by using a diaphragm metering pump, the feeding pressure is controlled to be 0.6-1.0 MPa, and after feeding is finished, the temperature in a reaction kettle is minus 30-minus 32 ℃; after phosphine and isobutene are fed, the temperature of the reaction kettle is controlled to be 83-86 ℃ and the pressure is controlled to be 4.5-4.8 MPa through a heat conduction oil system; after the temperature and the pressure temperature, adding 2.5kg of monoisobutyl phosphine solution of azodiisovaleronitrile through a diaphragm metering pump, wherein the concentration of an initiator solution is 3.5%, the dropwise adding time is 2 hours, continuing to carry out heat preservation reaction for 1 hour after the initiator solution is added, reducing the temperature in a reaction kettle to 20-25 ℃ after the heat preservation reaction is finished, discharging after the pressure is discharged to 0.1-0.2 MPa through a pressure relief buffer tank, and obtaining 22.1kg of addition reaction completion material containing monoisobutyl phosphine, diisobutyl phosphine and triisobutyl phosphine; the composition was analyzed by gas chromatography as follows: 36.8% of mono-isobutyl phosphine, 47.1% of diisobutyl phosphine and 16.1% of triisobutyl phosphine.
In the addition reaction process, after phosphine and isobutene complete feeding and are heated to the target reaction temperature by a heat conducting oil system, the pressure in the reaction kettle is up to 3-5MPa, and the reaction kettle is simultaneously
The addition reaction is exothermic, if the heat released by the reaction cannot be removed in time through a circulating cooling system, or the dropping speed of the initiator solution is too high, the temperature of the reaction system is possibly out of control, so that the addition reaction is accelerated to be initiated, the reaction system is out of control, and the temperature and the pressure are abnormally increased. In the present patent, if the above situation occurs, the following emergency interlocking measures are adopted: (1) immediately stopping the initiator solution feed; (2) activating the emergency cooling system; (3) Starting a safety relief system, gradually releasing the pressure in the reaction kettle to a safe and controllable range through an automatic safety relief valve, and arranging a 5000L pressure relief buffer tank and a tail gas incineration system in a matched mode, wherein the pressure relief buffer tank can buffer the relief pressure to be within 20KPa and then slowly release the relief pressure to the tail gas incineration system.
(2) Rectifying
After transferring the liquid material obtained in the step (1) into a rectifying kettle, rectifying at normal pressure, slowly heating to 73-75 ℃ at the tower top pressure of 0-2 KPa, and collecting light-component monoisobutyl phosphine; and (3) carrying out reduced pressure rectification on the rest materials, controlling the vacuum degree to be-95 to-97 KPa, increasing the temperature to 80-82 ℃, firstly collecting part of the front cut fraction, starting to collect the target product diisobutylphosphine after the target product content is qualified, and stopping collecting after the product content is reduced to be unqualified.
Step (2) 10.4kg of diisobutylphosphine was collected and analyzed by gas chromatography for its composition as follows: 98.2% of diisobutylphosphine, 1.2% of monoisobutylphosphine and 0.6% of triisobutylphosphine.
Example 4
The method steps are the same as in example 3, and only the concentration of the initiator solution is 2.5%, so that 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 mono-isobutyl phosphine, 44.6% of diisobutyl phosphine and 14.3% of triisobutyl phosphine; the initiator solution concentration is less than 3%, so that the single batch yield of the addition reaction and the yield of the target product diisobutylphosphine are obviously lower than those of the example 3.
Example 5
The method steps are the same as in example 3, and the concentration of the initiator solution is 4.5%, so that 22.1kg of reaction finished material is obtained after the addition reaction is finished; the composition was analyzed by gas chromatography as follows: 36.7% of mono-isobutyl phosphine, 47.3% of diisobutyl phosphine and 16.0% of triisobutyl phosphine. The single batch yield of the addition reaction and the yield of the target product diisobutylphosphine were at the same level as in example 3.
Example 6
The method steps are the same as in example 3, and only the concentration of the initiator solution is 5.5%, so that 22.2kg of reaction finished material is obtained after the addition reaction is finished; the composition was analyzed by gas chromatography as follows: 36.9% of mono-isobutyl phosphine, 47.2% of diisobutyl phosphine and 15.9% of triisobutyl phosphine. The concentration of the initiator solution is more than 5%, 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 embodiment 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 leads to the increase of the production cost.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but any modifications, equivalents, improvements, etc. made without departing from the technical scope of the present invention as set forth in the claims below are included in the scope of the present invention.
Claims (5)
1. A method for preparing diisobutylphosphine by liquid phosphine, which is characterized by comprising the following steps:
(1) The low-temperature liquid phosphine is conveyed to an addition reaction kettle after precooling treatment through a pump, the addition reaction kettle is precooled through a low-temperature conduction oil system before feeding, the temperature in the reaction kettle reaches-30 to-40 ℃, after the liquid phosphine is fed, stirring is started, liquid isobutene is conveyed to the addition reaction kettle, after the phosphine and isobutene are fed, the temperature in the reaction kettle is-30 to-40 ℃, heating is continued, stirring is continued, initiator solution is added under the condition of target reaction temperature for addition reaction, the temperature of the low-temperature liquid phosphine is-60 to-80 ℃, and the feeding pressure is 0.1 to 0.8MPa; the feeding pressure of the liquid isobutene is 0.5-1.0 MPa; the solvent used as the initiator in the initiator solution is one or a mixture of a plurality of triisobutyl phosphine, diisobutyl phosphine and monoisobutyl phosphine, the temperature in the reaction kettle is controlled to be 82-87 ℃ after phosphine and isobutene are fed, the pressure in the reaction kettle is controlled to be 4.0-5.0 MPa, and the reaction is carried out for 2-4 hours under the condition;
(2) Discharging the gaseous phosphine and isobutene which are not completely reacted after the addition reaction is finished, and discharging a reaction completion mixture containing diisobutylphosphine to a rectification system;
(3) The rectification system is used for collecting light-component monoisobutyl phosphine through normal pressure distillation, and then the rest materials are subjected to reduced pressure distillation to collect the product diisobutyl phosphine.
2. The method according to claim 1, wherein the initiator in step (1) is any one of azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile.
3. The process of claim 1, wherein the initiator solution concentration in step (1) is 3-5%.
4. 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.
5. The method according to claim 1, wherein the pressure at the top of the atmospheric distillation in the step (3) is 0-2 kpa and the temperature is 70-75 ℃; the vacuum degree of reduced pressure distillation is-95 to-97 KPa, and the temperature is 80 to 85 ℃.
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| US2803597A (en) * | 1949-04-30 | 1957-08-20 | Shell Dev | Process for producing organic phosphines |
| 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 |
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| JP4271455B2 (en) * | 2002-02-19 | 2009-06-03 | 北興化学工業株式会社 | Method for producing tertiary phosphine bonded with bulky hydrocarbon group |
| 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 |
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| CN102304149B (en) * | 2011-06-28 | 2013-12-25 | 中国原子能科学研究院 | Synthesis method of triisobutyl phosphine sulfide |
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| US2803597A (en) * | 1949-04-30 | 1957-08-20 | Shell Dev | Process for producing organic phosphines |
| 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 |
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