CN116196868A - Continuous production device and continuous preparation method of diaryl chlorophosphate - Google Patents
Continuous production device and continuous preparation method of diaryl chlorophosphate Download PDFInfo
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- -1 diaryl chlorophosphate Chemical compound 0.000 title claims abstract description 84
- 238000010924 continuous production Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 288
- 238000005886 esterification reaction Methods 0.000 claims abstract description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 76
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 74
- 239000000376 reactant Substances 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 44
- 239000011968 lewis acid catalyst Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 4
- 229940117389 dichlorobenzene Drugs 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000010408 film Substances 0.000 claims 5
- 239000010409 thin film Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 abstract description 10
- 239000010452 phosphate Substances 0.000 abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract 1
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000004321 preservation Methods 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 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 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
- B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1887—Stationary reactors having moving elements inside forming a thin film
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (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 belongs to the technical field of organic synthesis, and particularly relates to a continuous production device and a continuous preparation method of diaryl chlorophosphate. The device provided by the invention comprises a two-stage reaction system, and the esterification reaction for synthesizing the aryl dichlorophosphate and the esterification reaction for synthesizing the diaryl chlorophosphate are carried out at different temperatures by arranging the two-stage reaction system, so that the conditions of different synchronous reactions can be accurately controlled, the generation of triaryl phosphate byproducts is reduced, and the purity of the diaryl chlorophosphate is improved. Meanwhile, the device provided by the invention comprises a plurality of stages of reaction units which are connected in series, so that the residence time of reaction materials in a reactor can be prolonged, and the conversion rate of the materials can be ensured; in the synthesis process, the generated hydrogen chloride can be timely removed through a scraper film reactor, so that the reaction is further promoted, and the yield and purity of diaryl chlorophosphate are improved.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a continuous production device and a continuous preparation method of diaryl chlorophosphate.
Background
Diaryl chlorophosphate with lower volatility and good thermal stability is an intermediate for synthesizing flame retardant, and has a structure shown as (I), wherein R is 1 And R is 2 Respectively alkyl with 1-5 carbon atoms, R 3 Is an alkyl group having 1 to 5 carbon atoms.
Aromatic bisphosphates are intermediates for the synthesis of diaryl chlorophosphates, having the structure shown in (II), wherein R 1 And R is 2 Respectively alkyl with 1-5 carbon atoms, R 3 And R is 4 Respectively alkyl with 1-5 carbon atoms, Y is-CH 2 -、-C(CH 3 ) 2 -、-S-、-SO 2 -, -O-, -CO-or-n=n-, k is 0 or 1, and m is an integer of 0 to 4.
Currently, diaryl chlorophosphate is mainly prepared by a batch synthesis method, for example, phosphorus oxychloride is dropwise added into a mixed solution of an aromatic monohydroxy compound, a solvent and a catalyst to undergo batch reaction to synthesize the diaryl chlorophosphate in China patent CN 102985430A; the reaction process is specifically as follows: the phosphoryl chloride and the aromatic monohydroxy compound firstly generate aryl dichloro phosphate, and the generated aryl dichloro phosphate is continuously dehalogenated to generate diaryl chloro phosphate. However, diaryl chlorophosphates and aromatic monohydroxy compounds can further form triarylphosphate byproducts during the production process. When the phosphorus oxychloride is excessive, the output ratio of aryl dichloro phosphate in the system can be improved; when the phosphorus oxychloride is too small, the yield of the by-product triaryl phosphate ester in the system is increased. To increase the content of diaryl chlorophosphate in the product, the patent adds phosphorus oxychloride at a ratio of 0.5 mole relative to 1 mole of aromatic monohydroxy compound. Although the content of diaryl chlorophosphate in the product can be improved by controlling the addition amount of the reactants, the intermittent synthesis dripping mode can cause the system proportion to be in an unbalanced state for a long time, and the purity of the diaryl chlorophosphate can not be well ensured. Meanwhile, in the intermittent synthesis mode, HCl generated by dechlorination is difficult to timely discharge, the reaction speed is slow, the production efficiency is reduced, the side reaction proportion is increased, and the purity of diaryl chlorophosphate is further reduced.
Disclosure of Invention
In view of the above, the invention provides a continuous production device and a continuous preparation method of diaryl chlorophosphate, and the yield and purity of the diaryl chlorophosphate can be obviously improved by utilizing the continuous production device to prepare the diaryl chlorophosphate.
In order to solve the technical problems, the invention provides a continuous production device, which comprises a first reactant container 1;
a second reactant reservoir 3;
a first reaction system 2 with an inlet connected with the outlet of the first reactant container 1 and the outlet of the second reactant container 3 respectively; the first reaction system 2 comprises first reaction units connected in series, wherein any one of the first reaction units comprises a mixer 5, a scraper film reactor 6-1, a condenser 10-1 and a gas-liquid separator 11-1 which are connected in sequence;
the inlet is respectively connected with the outlet of the first reactant container 1 and the outlet of the first reaction system 2; the second reaction system 4 comprises second reaction units connected in series, wherein any one of the second reaction units comprises a mixer 9-1, a scraper film reactor 7-1, a condenser 12-1 and a gas-liquid separator 13-1 which are connected in sequence; the first stage second reaction unit in the second reaction system 4 also comprises a heater 14 with an inlet connected with the outlet of the mixer 9-1;
a tail gas absorbing unit 15 communicated with the gas outlets of the first reaction system 2 and the second reaction system 4;
and a product collection unit 16 in fluid communication with the second reaction system 4 outlet.
Preferably, the number of stages of the first reaction unit is 2 to 15; the number of stages of the second reaction unit is 2-20.
Preferably, the liquid outlet of the gas-liquid separator 11-1 in the first reaction system 2 is connected with the inlet of the scraper film reactor 6-1;
the liquid outlet of the gas-liquid separator 13-1 in the second reaction system 4 is connected with the inlet of the scraper film reactor 7-1.
The invention also provides a method for preparing diaryl chlorophosphate by using the device in the technical scheme, which comprises the following steps:
mixing an aromatic monohydroxy compound and a Lewis acid catalyst in a first reactant vessel 1 to obtain a premix; the aromatic monohydroxy compound has a structure represented by formula III:
wherein R is 1 、R 2 And R is 3 Independently is-H or alkyl with 1-5 carbon atoms;
delivering part of the premixed solution and phosphorus oxychloride in the second reactant container 3 to a first reaction system 2, mixing the premixed solution and phosphorus oxychloride in the first reaction system by a mixer 5, and performing a first esterification reaction in a scraper film reactor 6-1 to obtain aryl dichloro phosphate; the hydrogen chloride gas generated by the first esterification reaction is removed by a condenser 10-1 and a gas-liquid separator 11-1;
delivering the aryl dichlorophosphate and the rest of the premix to a second reaction system 4, mixing the mixture by a mixer 9-1, and then carrying out a second esterification reaction in a scraper film reactor 7-1 to obtain diaryl chlorophosphate; the hydrogen chloride gas generated in the second esterification reaction is removed by a condenser 12-1 and a gas-liquid separator 13-1.
Preferably, the molar ratio of the aromatic monohydroxy compound to the Lewis acid catalyst is 40-1500:1;
the molar ratio of the aromatic monohydroxy compound to the phosphoryl chloride in the partial premix is 1-1.5:1.
Preferably, the pre-mixed liquid is divided into a plurality of strands, and enters the first reaction system 2 from one or more stages of first reaction units in the first reaction system 2;
the rest of the premixed solution is divided into a plurality of strands, and enters the second reaction system 4 from one or more stages of second reaction units in the second reaction system 4.
Preferably, the temperature of the first esterification reaction is 80 to 150 ℃.
Preferably, the temperature of the second esterification reaction is 100 to 200 ℃.
Preferably, the mixing of the aromatic monohydroxy compound and the lewis acid catalyst in the first reactant vessel 1 further comprises: adding an organic solvent to the first reactant vessel 1;
the organic solvent comprises one or more of toluene, xylene, trimethylbenzene, chlorobenzene and dichlorobenzene.
Preferably, the lewis acid catalyst comprises one or more of aluminum chloride, magnesium chloride, titanium tetrachloride, antimony pentachloride, zinc chloride, and tin chloride.
The invention provides a continuous production device, which comprises a first reactant container 1; a second reactant reservoir 3; a first reaction system 2 with an inlet connected with the outlet of the first reactant container 1 and the outlet of the second reactant container 3 respectively; the first reaction system 2 comprises first reaction units connected in series, wherein any one of the first reaction units comprises a mixer 5, a scraper film reactor 6-1, a condenser 10-1 and a gas-liquid separator 11-1 which are connected in sequence; the inlet is respectively connected with the outlet of the first reactant container 1 and the outlet of the first reaction system 2; the second reaction system 4 comprises second reaction units connected in series, wherein any one of the second reaction units comprises a mixer 9-1, a scraper film reactor 7-1, a condenser 12-1 and a gas-liquid separator 13-1 which are connected in sequence; the first stage second reaction unit in the second reaction system 4 also comprises a heater 14 with an inlet connected with the outlet of the mixer 9-1; a tail gas absorbing unit 15 communicated with the gas outlets of the first reaction system 2 and the second reaction system 4; and a product collection unit 16 in fluid communication with the second reaction system 4 outlet. The device provided by the invention comprises a two-stage reaction system, and the first esterification reaction and the second esterification reaction are carried out at different temperatures by arranging the two-stage reaction system, so that the conditions of different steps of reaction can be accurately controlled, thereby reducing the generation of triaryl phosphate byproducts and improving the purity of diaryl chlorophosphate. Meanwhile, the device provided by the invention comprises a plurality of stages of reaction units which are connected in series, so that the residence time of reaction materials in a reactor can be prolonged, and the conversion rate of the materials can be ensured; in the synthesis process, the generated hydrogen chloride can be removed through a gas-liquid separator, so that the reaction is further promoted, and the yield and purity of diaryl chlorophosphate are improved.
Drawings
FIG. 1 is a schematic structural view of a continuous production apparatus, wherein 1 is a first reactant container, 1-1 is a first inlet, 1-2 is a second inlet, 1-3 is a heating system, 1-4 is a first transfer pump, 1-5 is a stirring device, 2 is a first reaction system, 5 is a mixer in the first reaction system, 6-1 is a scraper film reactor in the first reaction system, 10-1 is a condenser in the first reaction system, 11-1 is a gas-liquid separator in the first reaction system, 3 is a second reactant container, 3-1 is a feed inlet, 3-2 is a second transfer pump, 4 is a second reaction system, 9-1 is a mixer in the second reaction system, 7-1 is a scraper film reactor in the second reaction system, 12-1 is a condenser in the second reaction system, 13-1 is a gas-liquid separator in the second reaction system, 14 is a heater, 15 is a tail gas absorption unit, and 16 is a product collection unit;
FIG. 2 is a schematic structural view of a continuous production apparatus in which a first reaction system is a 2-stage first reaction unit, a second reaction system is a 3-stage second reaction unit, wherein 1 is a first reactant reservoir, 1-1 is a first inlet, 1-2 is a second inlet, 1-3 is a heating system, 1-4 is a first transfer pump, 1-5 is a stirring device, 5 is a mixer in the first-stage first reaction unit, 6-1 is a scraper film reactor in the first-stage first reaction unit, 10-1 is a condenser in the first-stage first reaction unit, 11-1 is a gas-liquid separator in the first-stage first reaction unit, 8 is a mixer in the second-stage first reaction unit, 6-2 is a scraper film reactor in the second-stage first reaction unit, 10-2 is a condenser in the second-stage first reaction unit, 11-2 is a gas-liquid separator in a second-stage first reaction unit, 3 is a second reactant container, 3-1 is a feed inlet, 3-2 is a second transfer pump, 9-1 is a scratch film reactor in the first-stage second reaction unit, 7-1 is a scratch film reactor in the first-stage second reaction unit, 12-1 is a condenser in the first-stage second reaction unit, 13-1 is a gas-liquid separator in the first-stage second reaction unit, 14 is a heater, 9-2 is a mixer in the second-stage second reaction unit, 7-2 is a scratch film reactor in the second-stage second reaction unit, 12-2 is a condenser in the second-stage second reaction unit, 13-2 is a gas-liquid separator in the second-stage second reaction unit, 9-3 is a mixer in a third-stage second reaction unit, 7-3 is a scraper film reactor in a third-stage second reaction unit, 12-3 is a condenser in the third-stage second reaction unit, 13-3 is a gas-liquid separator in the third-stage second reaction unit, 15 is a tail gas absorption unit, and 16 is a product collection unit.
Detailed Description
The invention provides a continuous production device comprising a first reactant container 1. In the present invention, the outer wall surface of the first reactant reservoir 1 is preferably provided with a heating system 1-3. In the present invention, the heating system 1-3 is preferably steam heating, and the present invention preferably uses the heating system 1-3 to heat the material in the first reactant container 1 to ensure the temperature required for the subsequent chemical reaction in the first reaction system 2.
As an embodiment of the present invention, the top end of the first reactant container 1 is provided with a first inlet 1-1 and a second inlet 1-2. In the present invention, an aromatic monohydroxy compound and a Lewis acid catalyst are introduced into a first reactant vessel 1 through a first inlet 1-1; the organic solvent is introduced into the first reactant reservoir 1 through the second inlet 1-2. As an embodiment of the invention, the first reactant reservoir is provided with stirring means 1-5; the stirring device 1-5 can uniformly mix the reaction materials. The outlet of the first reactant reservoir 1 is connected to a first transfer pump 1-4 as an embodiment of the present invention.
The present invention provides a continuous production apparatus comprising a second reactant reservoir 3. As an embodiment of the invention, a feed port 3-1 is arranged at the top end of the second reactant container 3, and a second delivery pump 3-2 is connected to the outlet of the second reactant container 3.
The continuous production device provided by the invention comprises a first reaction system 2, wherein the inlet of the first reaction system is respectively connected with the outlet of a first reactant container 1 and the outlet of a second reactant container 3; the first reaction system 2 comprises first reaction units connected in series, and any one of the first reaction units comprises a mixer 5, a scraper film reactor 6-1, a condenser 10-1 and a gas-liquid separator 11-1 which are connected in sequence. As an embodiment of the present invention, the number of stages of the first reaction unit is preferably 2 to 15 stages, more preferably 2 to 8 stages, still more preferably 2 to 5 stages. The invention has the advantages that the multistage series-connected first reaction units are arranged, so that enough residence time can be ensured to finish the reaction, and the yield of the product is improved. As one embodiment of the invention, the liquid outlet of the gas-liquid separator 11-1 in the first reaction system 2 is connected with the inlet of the scraper film reactor 6-1; the liquid separated in the gas-liquid separator is returned to the scraper film reactor 6-1 to continue the first esterification reaction.
In the present invention, the outlet of the first reaction unit of the upper stage is communicated with the inlet of the first reaction unit of the lower stage. As an embodiment of the present invention, the reaction material in the first reactant vessel 1 is divided into a plurality of strands and enters different first reaction units to perform a first esterification reaction; condensing the gas generated in the reaction process through a condenser 10-1, separating hydrogen chloride, and removing the separated hydrogen chloride through a gas-liquid separator 11-1; the removal of hydrogen chloride during the reaction facilitates the forward progress of the reaction.
In the present invention, the reaction materials in the first reactant reservoir 1 and the second reactant reservoir 3 are mixed in the mixer 5 in the first reaction unit of each stage.
The invention carries out chemical reaction in the scraper film reactor 6-1 of each stage of the first reaction unit, increases the contact probability of reaction materials, can timely remove generated gas, and is beneficial to the reaction. As one embodiment of the invention, the outer wall of the scraper film reactor is provided with a heat preservation system, and the heat preservation system is a steam heat preservation system. The invention uses a heat preservation system to ensure the required reaction temperature in the scraper film reactor.
The continuous production device provided by the invention comprises a second reaction system 4, wherein the inlet of the second reaction system 4 is respectively connected with the outlet of a first reactant container 1 and the outlet of a first reaction system 2; the second reaction system 4 comprises second reaction units connected in series, and any one of the second reaction units comprises a mixer 9-1, a scraper film reactor 7-1, a condenser 12-1 and a gas-liquid separator 13-1 which are connected in sequence. As an embodiment of the present invention, the first stage second reaction unit in the second reaction system 4 further comprises a heater 14 having an inlet connected to the outlet of the mixer 9-1. The present invention heats the material entering the second reaction system 4 by the heater 14 to ensure the temperature required for the chemical reaction in the second reaction system. As one embodiment of the invention, the liquid outlet of the gas-liquid separator 13-1 in the second reaction system 4 is connected with the inlet of the scraper film reactor 7-1; the liquid separated in the gas-liquid separator 13-1 is returned to the scraper film reactor 7-1 to continue the second esterification reaction.
As an embodiment of the present invention, the number of stages of the second reaction unit is preferably 2 to 20 stages, more preferably 2 to 15 stages, still more preferably 2 to 8 stages. The multistage serial second reaction units are arranged, so that enough residence time can be ensured to finish the reaction, and the yield of the product is improved.
In the present invention, the outlet of the upper stage second reaction unit is communicated with the inlet of the lower stage second reaction unit. As an embodiment of the present invention, the reaction material in the first reactant vessel 1 is divided into a plurality of strands and enters into a different second reaction unit to carry out a second esterification reaction; condensing the gas generated in the reaction process by a condenser, separating hydrogen chloride, and removing the separated hydrogen chloride by a gas-liquid separator; the removal of hydrogen chloride during the reaction facilitates the forward progress of the reaction.
The continuous production device provided by the invention comprises a tail gas absorption unit 15 which is communicated with the gas outlets of the first reaction system 2 and the second reaction system 4. In the present invention, the tail gas absorbing unit 15 functions to absorb hydrogen chloride separated and removed by the gas-liquid separator.
The continuous production apparatus provided by the invention comprises a product collection unit 16 in fluid communication with the liquid outlet of the second reaction system 4. The present invention preferably allows the product produced by the continuous production apparatus to be collected and stored in the product collection unit 16.
The invention also provides a method for preparing diaryl chlorophosphate by using the device in the technical scheme, which comprises the following steps:
mixing an aromatic monohydroxy compound and a Lewis acid catalyst in a first reactant vessel 1 to obtain a premix; the aromatic monohydroxy compound has a structure represented by formula III:
wherein R is 1 、R 2 And R is 3 Independently is-H or alkyl with 1-5 carbon atoms;
delivering part of the premixed solution and phosphorus oxychloride in the second reactant container 3 to a first reaction system 2, mixing the premixed solution and phosphorus oxychloride in the first reaction system by a mixer 5, and performing a first esterification reaction in a scraper film reactor 6-1 to obtain aryl dichloro phosphate; the hydrogen chloride gas generated by the first esterification reaction is removed by a condenser 10-1 and a gas-liquid separator 11-1;
delivering the aryl dichlorophosphate and the residual pre-mixed solution to a second reaction system 4, mixing the mixture by a mixer 9-1, and performing a second esterification reaction in a scraper film reactor 7-1 to obtain diaryl chlorophosphate; the hydrogen chloride gas generated in the second esterification reaction is removed by a condenser 12-1 and a gas-liquid separator 13-1.
The present invention mixes an aromatic monohydroxy compound and a lewis acid catalyst in a first reactant vessel 1 to obtain a premix. In the present invention, the aromatic monohydroxy compound has a structure represented by formula III:
wherein R is 1 、R 2 And R is 3 independently-H or an alkyl group having 1 to 5 carbon atoms, preferably independently an alkyl group having 2 to 4 carbon atoms; in the present invention, the alkyl group preferably includes a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group, more preferably a methyl group or an ethyl group. In the present invention, the aromatic monohydroxy compound is preferably 2, 6-dimethylphenol.
In the present invention, the lewis acid catalyst preferably includes one or more of aluminum chloride, magnesium chloride, titanium tetrachloride, antimony pentachloride, zinc chloride, and tin chloride, more preferably aluminum chloride or magnesium chloride. In the invention, when the Lewis acid catalyst comprises more than two specific substances, the invention has no special requirement on the proportion of the specific substances, and the Lewis acid catalyst can be prepared by adopting any proportion.
In the present invention, the molar ratio of the aromatic monohydroxy compound to the Lewis acid catalyst is preferably 40 to 1500:1, more preferably 50 to 300:1.
The aromatic monohydroxy compound and the lewis acid catalyst are preferably introduced into the first reactant reservoir from the first inlet 1-1.
In the present invention, the aromatic monohydroxy compound is preferably a molten liquid when the aromatic monohydroxy compound and the lewis acid catalyst are mixed in the first reactant vessel 1. When the aromatic monohydroxy compound is described, the present invention preferably adds an organic solvent to the first reactant vessel 1. In the present invention, the organic solvent preferably includes one or more of toluene, xylene, trimethylbenzene, chlorobenzene and dichlorobenzene, more preferably toluene or dichlorobenzene. In the invention, when the organic solvent is more than two specific substances, the invention has no special requirement on the proportion of the specific substances, and the invention can be used by adopting any proportion.
In the present invention, the mass ratio of the aromatic monohydroxy compound to the organic solvent is preferably 1 to 20:1, more preferably 5 to 15:1.
The present invention preferably introduces the organic solvent into the first reactant reservoir through the second inlet 1-2.
The invention preferably utilizes the stirring device 1-5 to uniformly mix the aromatic monohydroxy compound, the Lewis acid catalyst and the organic solvent; the invention preferably uses a heating system 1-3 to heat the premix.
After the premixed solution is obtained, part of the premixed solution and phosphoryl chloride in a second reactant container 3 are conveyed to a first reaction system 2, mixed by a mixer 5, and subjected to a first esterification reaction in a scraper film reactor 6-1 to obtain aryl dichloro phosphate; the hydrogen chloride gas generated in the first esterification reaction is removed by a condenser 10-1 and a gas-liquid separator 11-1. The present invention preferably uses a first transfer pump 1-4 to transfer a portion of the premix and a second transfer pump 3-2 to transfer phosphorus oxychloride. In the present invention, the molar ratio of the aromatic monohydroxy compound to the phosphorus oxychloride in the partial premix is preferably 1 to 1.5:1, more preferably 1 to 1.2:1.
Because only aryl dichloro phosphate can be generated at the first esterification reaction temperature, more aromatic monohydroxy compounds have little significance in feeding, and the amount of the aromatic monohydroxy compounds carried out by HCl gas can be increased; the present invention defines that the molar ratio of the aromatic monohydroxy compound and the phosphorus oxychloride in the portion of the premix is within the above-mentioned range.
In the present invention, the pre-mixture is divided into a plurality of strands, and the multi-stage pre-mixture is introduced into the first reaction system 2 from one or more stages of the first reaction units in the first reaction system 2. In the invention, part of the premixed solution is preferably divided into a plurality of strands and is conveyed to a first reaction system 2 to carry out first esterification reaction in different first reaction units; the number of strands of the plurality of strands is less than or equal to the number of stages of the first reaction unit.
In the present invention, the temperature of the first esterification reaction is preferably 80 to 150 ℃, more preferably 100 to 130 ℃. The invention preferably heats the premix to ensure the reaction temperature of the first esterification reaction. In the present invention, the pressure of the first esterification reaction is preferably-30 to +20kPaG, more preferably-30 to 0kPaG.
After the aryl dichlorophosphate is obtained, the aryl dichlorophosphate and the residual premixed solution are conveyed to a second reaction system 4, mixed by a mixer 9-1, and subjected to a second esterification reaction in a scraper film reactor 7-1 to obtain the diaryl dichlorophosphate; the hydrogen chloride gas generated in the second esterification reaction is removed by a condenser 12-1 and a gas-liquid separator 13-1.
The present invention preferably divides the remaining portion of the premix into a plurality of strands, and enters the second reaction system 4 from one or more stages of the second reaction units in the second reaction system 4. The invention preferably divides the rest of the premix into a plurality of strands and conveys the strands to a second reaction system 4 to carry out a second esterification reaction in a different second reaction unit; the number of strands of the plurality of strands is less than or equal to the number of stages of the second reaction unit. The invention divides the rest of the premixed solution into a plurality of strands of transportation to gradually promote the conversion of the phosphoryl chloride and the aryl dichloro phosphate into the diaryl chloro phosphate, and keeps the quantity of the phosphoryl chloride and the aryl dichloro phosphate in the system to be superior to that of the aromatic monohydroxy compound so as to avoid the generation of the impurity triaryl phosphate.
In the present invention, the temperature of the second esterification reaction is preferably 100 to 200 ℃, more preferably 130 to 180 ℃. The present invention preferably uses the heater 14 to heat the mixed solution of the aryl dichlorophosphate and the rest of the premix to ensure the reaction temperature of the second esterification reaction.
In the present invention, the pressure of the second esterification reaction is preferably-30 to +20kPaG, more preferably-30 to 0kPaG.
In the present invention, the total amount of phosphorus oxychloride and aryl dichlorophosphate introduced into the final stage second reaction unit in the second reaction system 4 is excessive compared with the residual aromatic monohydroxy compound; the molar excess is preferably 0.5 to 10%, more preferably 1 to 6%. In the present invention, the aryl dichlorophosphate has a structure represented by formula IV:
wherein R is 1 、R 2 And R is 3 independently-H or an alkyl group having 1 to 5 carbon atoms, preferably independently an alkyl group having 2 to 4 carbon atoms; in the present invention, the alkyl group preferably includes a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group, more preferably a methyl group or an ethyl group.
In the present invention, the triaryl phosphate has a structure represented by formula V:
wherein R is 1 、R 2 And R is 3 independently-H or an alkyl group having 1 to 5 carbon atoms, preferably independently an alkyl group having 2 to 4 carbon atoms; in the present invention, the alkyl group preferably includes a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group, more preferably a methyl group or an ethyl group.
In the invention, both phosphorus oxychloride and aryl dichlorophosphate can react with an aromatic monohydroxy compound to synthesize a main product diaryl chlorophosphate, and the triaryl phosphate cannot be converted into the main product diaryl chlorophosphate. The final reactor is required to adjust the proportion of the supplementary feeding of the aromatic monohydroxy compound according to the excessive condition of the phosphoryl chloride and the aryl dichloro phosphate relative to the aromatic monohydroxy compound in the previous-stage discharging, so that the residual phosphoryl chloride and the aryl dichloro phosphate are converted into the diaryl chloro phosphate as much as possible, and the generation of the impurity triaryl phosphate is avoided.
According to the invention, the temperature of the second esterification reaction is precisely controlled, the proportion of the supplemental feeding of the aromatic monohydroxy compound to the system residual phosphoryl chloride and the aryl dichlorophosphate is regulated according to the conversion condition, the phosphoryl chloride, the diaryl chlorophosphate and the aromatic monohydroxy compound are promoted to react to the greatest extent to generate the diaryl chlorophosphate, and the generation of the impurity triaryl phosphate is inhibited, so that the yield and the purity of the diaryl chlorophosphate are improved.
In the invention, a first reaction system 2 and a second reaction system 4 are composed of a plurality of stages of scraper film reactors connected in series, hydrogen chloride gas generated by the reaction is discharged from the upper part of each stage of scraper film reactor, synthetic liquid flows out from the bottom of each stage of scraper film reactor and enters the next stage of reactors connected in series until flowing out from the last stage of scraper film reactor of the second reaction system 4, and diaryl chlorophosphate is obtained.
In the invention, the gas discharged from the upper part of each stage of the scraper film reactor is condensed by a condenser to recover the phosphoryl chloride and the aromatic monohydroxy compound carried out by the gas, and the phosphoryl chloride and the aromatic monohydroxy compound are returned to the inlet end of the corresponding scraper film reactor to reenter the reaction system.
In the invention, the organic solvent is preferably added into the condenser in the condensation process to wash the gas and the condenser, and the washing liquid returns to the inlet end of the corresponding scraper film reactor along with the washed and condensed phosphoryl chloride and aromatic monohydroxy compound to reenter the reaction system.
The device for continuously preparing diaryl chlorophosphate has the following beneficial effects:
1) The invention greatly improves the production efficiency by continuously synthesizing diaryl chlorophosphate, shortens the synthesis process of kettle type intermittent reaction for more than 20 hours to be completed within a few minutes, greatly improves the production efficiency of the device and greatly saves the investment.
2) The invention adopts the scraper film reactor for each stage in the two-stage series reactor, and the reaction feed liquid flows from top to bottom by utilizing gravity, so that back mixing can be well controlled, and the reaction can be completed as soon as possible; the reaction feed liquid is in a film shape, and under the combined action of the reaction higher temperature, the micro negative pressure and the reactor scraping plate, generated hydrogen chloride can rapidly escape from the reaction feed liquid, the flow direction of the feed liquid film layer is opposite to the discharge direction of hydrogen chloride gas, the closer to the end point material is, the lower the concentration of the hydrogen chloride in the gas-liquid two phases is, the influence of the hydrogen chloride on the reaction is avoided to the greatest extent, the forward reaction is promoted, and the production time is shortened.
3) According to the reaction process, the reaction of the aryl dichlorophosphate is easier to carry out than that of the diaryl chlorophosphate, the continuous reactor adopts a two-stage series gradient heating mode in combination with the reaction mechanism, the aryl dichlorophosphate is firstly generated at a lower temperature in a first-stage reactor, then the aromatic monohydroxy compound is added in a second-stage reactor step by step or by selecting a proper stage for supplementing, and the aromatic monohydroxy compound reacts with the aryl dichlorophosphate at a higher temperature to generate the diaryl chlorophosphate, so that the problems of quick and easy material flushing, slow heating side reaction increase and the like of kettle type reaction heating are avoided.
4) The invention does not need a huge vacuumizing system, does not need to be introduced with dry air or nitrogen to assist the discharge of HCl gas, reduces the exhaust emission, can well complete the reaction under micro negative pressure, normal pressure or micro positive pressure, and has good energy-saving and environment-friendly effects.
5) The invention realizes continuous production, the process parameters are easy to realize stable control, the excessive phosphorus oxychloride is controlled to react in advance, the addition of the aromatic monohydroxy compound is very convenient to flexibly adjust in a second-stage final-stage reactor according to actual conditions, the high-yield and accurate synthesis of diaryl chlorophosphate is realized, and the existence of byproduct aryl dichlorophosphate and triaryl phosphate in the produced liquid is inhibited to the greatest extent.
6) The invention has the advantages of continuous production process, high equipment utilization rate, high production capacity, easy realization of automatic operation, stable process parameters, low difficulty in amplification of the reactor, high operation elasticity and good guarantee of product yield and quality.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
2, 6-dimethylphenol and magnesium chloride are introduced into the first reactant container 1 from the first inlet 1-1 according to a molar ratio of 150:1, and dimethylbenzene is introduced into the second reactant container 3 from the second inlet 1-2, wherein the mass ratio of the dimethylbenzene to the 2, 6-dimethylphenol is 1:15; stirring uniformly by using a stirring device 1-5, and heating the mixed solution to 90 ℃ by using a steam heating system 1-3 to obtain a premix;
the first reaction system 2 is a first reaction unit with 3 stages connected in series, the phosphoryl chloride is conveyed to the first stage first reaction unit in the first reaction system 2 by using a second conveying pump 3-2, and the premixed liquid is respectively conveyed to the 3 stage first reaction units in the first reaction system 2 by using a first conveying pump 1-4; the mole ratio of the phosphoryl chloride to the 2, 6-dimethylphenol is 1:1.2; the premixed solution and phosphoryl chloride enter a scraping plate film reactor of a first-stage first reaction unit after being mixed by a mixer 5 to carry out a first esterification reaction under the condition that the pressure is-3 kPaG and the temperature is 115 ℃; the generated gas is condensed by a condenser 10-1 and then hydrogen chloride is removed by a gas-liquid separator 11-1; the liquid and the premix generated by the first-stage first reaction unit enter a subsequent two-stage first reaction unit to obtain aryl dichloro phosphate; the flow ratio of the premix in the first stage first reaction unit, the premix in the second stage first reaction unit and the premix in the third stage first reaction unit is 0.5:0.4:0.1.
The second reaction system is a 6-level series second reaction unit, aryl dichlorophosphate and the premix are mixed by a mixer 9-1, then heated to 140 ℃ by a heater 14, and enter a scraper film reactor of the first-level second reaction unit to carry out a second esterification reaction under the conditions of the pressure of-3 kPaG and the temperature of 165 ℃; the generated gas is condensed by a condenser 12-1 and then hydrogen chloride is removed by a gas-liquid separator 13-1; the liquid and the premix generated by the first-stage second reaction unit enter the second-stage second reaction unit, the steps are repeated to respectively carry out second esterification reaction in the 6-stage second reaction unit, and the obtained diaryl chlorophosphate is collected and stored in a product collection unit 16; the flow ratio of the premix in the first-stage second reaction unit, the premix in the second-stage second reaction unit, the premix in the third-stage second reaction unit, the premix in the fourth-stage second reaction unit, the premix in the fifth-stage second reaction unit and the premix in the sixth-stage second reaction unit is 0.3:0.2:0.2:0.2:0.07:0.03;
HCl gas discharged from a gas phase outlet at the upper part of each stage of reactor enters a tail gas absorption unit 15; the outlet temperature of the condenser is controlled at 55 ℃, and the liquid trapped by the gas-liquid separator returns to the inlet of the corresponding scraper film reactor to return to the reaction system.
Example 2
2, 6-dimethylphenol and magnesium chloride are introduced into the first reactant container 1 from the first inlet 1-1 according to the mol ratio of 100:1, and dimethylbenzene is introduced into the second reactant container 3 from the second inlet 1-2, wherein the mass ratio of the dimethylbenzene to the 2, 6-dimethylphenol is 1:15; stirring uniformly by using a stirring device 1-5, and heating the mixed solution to 100 ℃ by using a steam heating system 1-3 to obtain a premix;
the first reaction system 2 is a first reaction unit with 4 stages connected in series, the phosphoryl chloride is conveyed to the first stage first reaction unit in the first reaction system 2 by using a second conveying pump 3-2, and the premixed liquid is respectively conveyed to the 4 stage first reaction units in the first reaction system 2 by using a first conveying pump 1-4; the mole ratio of the phosphoryl chloride to the 2, 6-dimethylphenol is 1:1.3; the premixed solution and phosphoryl chloride enter a scraping plate film reactor of a first-stage first reaction unit after being mixed by a mixer 5 to carry out first esterification reaction under the conditions of the pressure of-2 kPaG and the temperature of 120 ℃; the generated gas is condensed by a condenser 10-1 and then hydrogen chloride is removed by a gas-liquid separator 11-1; the liquid and the premix generated by the first-stage first reaction unit enter a second-stage second reaction unit, and the steps are repeated to react in the 4-stage first reaction unit respectively to obtain aryl dichloro phosphate; the flow ratio of the premix in the first stage first reaction unit, the premix in the second stage first reaction unit, the premix in the third stage first reaction unit and the premix in the fourth stage first reaction unit is 0.4:0.3:0.2:0.1.
The second reaction system is a 7-stage series connection of second reaction units, aryl dichlorophosphate and the premix are mixed by a mixer 9-1, then heated to 150 ℃ by a heater 14, and enter a scraper film reactor of the first-stage second reaction unit to carry out a second esterification reaction under the conditions of the pressure of-2 kPaG and the temperature of 175 ℃; the generated gas is condensed by a condenser 12-1 and then hydrogen chloride is removed by a gas-liquid separator 13-1; the liquid and the premix generated by the first-stage second reaction unit enter the second-stage second reaction unit, the steps are repeated to respectively carry out second esterification reaction in the 7-stage second reaction unit, and the obtained diaryl chlorophosphate is collected and stored in a product collection unit 16; the flow ratio of the premix in the first-stage second reaction unit, the premix in the second-stage second reaction unit, the premix in the third-stage second reaction unit, the premix in the fourth-stage second reaction unit, the premix in the fifth-stage second reaction unit, the premix in the sixth-stage second reaction unit and the premix in the seventh-stage second reaction unit is 0.25:0.2:0.15:0.15:0.13:0.1:0.02;
HCl gas discharged from a gas phase outlet at the upper part of each stage of reactor enters a tail gas absorption unit 15; the outlet temperature of the condenser is controlled at 55 ℃, and the liquid trapped by the gas-liquid separator returns to the inlet of the corresponding scraper film reactor to return to the reaction system.
Example 3
2, 6-dimethylphenol and magnesium chloride are introduced into the first reactant container 1 from the first inlet 1-1 according to the mol ratio of 300:1, dimethylbenzene is introduced into the second reactant container 3 from the second inlet 1-2, and the mass ratio of the dimethylbenzene to the 2, 6-dimethylphenol is 1:12; stirring uniformly by using a stirring device 1-5, and heating the mixed solution to 120 ℃ by using a steam heating system 1-3 to obtain a premix;
the first reaction system 2 is a first reaction unit with 4 stages connected in series, the phosphoryl chloride is conveyed to the first stage first reaction unit in the first reaction system 2 by using a second conveying pump 3-2, and the premixed liquid is respectively conveyed to the 4 stage first reaction units in the first reaction system 2 by using a first conveying pump 1-4; the mole ratio of the phosphoryl chloride to the 2, 6-dimethylphenol is 1:1.2; the premixed solution and phosphoryl chloride enter a scraping plate film reactor of a first-stage first reaction unit after being mixed by a mixer 5 to carry out first esterification reaction under the conditions of the pressure of-9 kPaG and the temperature of 125 ℃; the generated gas is condensed by a condenser 10-1 and then hydrogen chloride is removed by a gas-liquid separator 11-1; the liquid and the premix liquid generated by the first-stage first reaction unit enter a second-stage second reaction unit, and the steps are repeated to respectively perform first esterification in the 4-stage first reaction unit to obtain aryl dichloro phosphate; the flow ratio of the premix in the first stage first reaction unit, the premix in the second stage first reaction unit, the premix in the third stage first reaction unit and the premix in the fourth stage first reaction unit is 0.4:0.3:0.2:0.1.
The second reaction system is a 5-stage series connection of second reaction units, aryl dichlorophosphate and the premix are mixed by a mixer 9-1, then heated to 140 ℃ by a heater 14, and enter a scraper film reactor of the first-stage second reaction unit to carry out a second esterification reaction under the conditions of the pressure of-9 kPaG and the temperature of 150 ℃; the generated gas is condensed by a condenser 12-1 and then hydrogen chloride is removed by a gas-liquid separator 13-1; the liquid and the premix generated by the first-stage second reaction unit enter the second-stage second reaction unit, the steps are repeated to respectively carry out second esterification reaction in the 5-stage second reaction unit, and the obtained diaryl chlorophosphate is collected and stored in a product collection unit 16; the flow ratio of the premix in the first-stage second reaction unit, the premix in the second-stage second reaction unit, the premix in the third-stage second reaction unit, the premix in the fourth-stage second reaction unit and the premix in the fifth-stage second reaction unit is 0.3:0.2:0.2:0.2:0.08:0.02;
HCl gas discharged from a gas phase outlet at the upper part of each stage of reactor enters a tail gas absorption unit 15; the outlet temperature of the condenser is controlled at 55 ℃, and the liquid trapped by the gas-liquid separator returns to the inlet of the corresponding scraper film reactor to return to the reaction system.
The obtained product was analyzed by nuclear magnetism and liquid chromatography, and the conversion of 2, 6-dimethylphenol, the yield of diaryl chlorophosphate and the ratio of diaryl chlorophosphate to aryl dichlorophosphate and triaryl phosphate were calculated, the results of which are shown in Table 1.
TABLE 1 conversion of 2, 6-dimethylphenol and yield of diaryl chlorophosphate in examples 1-3
As can be seen from Table 1, the diaryl chlorophosphate continuously prepared by the device provided by the invention has higher yield and purity.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. A continuous production apparatus comprising a first reactant reservoir (1);
a second reactant reservoir (3);
a first reaction system (2) with an inlet connected with the outlet of the first reactant container (1) and the outlet of the second reactant container (3) respectively; the first reaction system (2) comprises first reaction units connected in series, wherein any one of the first reaction units comprises a mixer (5), a scraper film reactor (6-1), a condenser (10-1) and a gas-liquid separator (11-1) which are connected in sequence;
the inlet is respectively connected with the outlet of the first reactant container (1) and the outlet of the first reaction system (2); the second reaction system (4) comprises second reaction units connected in series, wherein any one of the second reaction units comprises a mixer (9-1), a scraper film reactor (7-1), a condenser (12-1) and a gas-liquid separator (13-1) which are connected in sequence; the first stage second reaction unit in the second reaction system (4) also comprises a heater (14) with an inlet connected with the outlet of the mixer (9-1);
a tail gas absorption unit (15) communicated with the gas outlet of the first reaction system (2) and the gas outlet of the second reaction system (4);
and a product collection unit (16) in fluid communication with the second reaction system (4) outlet.
2. The apparatus according to claim 1, wherein the number of stages of the first reaction unit is 2 to 15 stages; the number of stages of the second reaction unit is 2-20.
3. The apparatus according to claim 1, wherein the liquid outlet of the gas-liquid separator (11-1) in the first reaction system (2) is connected to the inlet of the scraped-surface thin-film reactor (6-1);
the liquid outlet of the gas-liquid separator (13-1) in the second reaction system (4) is connected with the inlet of the scraper film reactor (7-1).
4. A process for preparing diaryl chlorophosphate using the apparatus of any of claims 1 to 3, comprising the steps of:
mixing an aromatic monohydroxy compound and a Lewis acid catalyst in a first reactant vessel (1) to obtain a premix; the aromatic monohydroxy compound has a structure represented by formula III:
wherein R is 1 、R 2 And R is 3 Independently is-H or alkyl with 1-5 carbon atoms;
delivering part of the pre-mixed solution and phosphorus oxychloride in the second reactant container (3) to a first reaction system (2), mixing the mixture by a mixer (5), and carrying out a first esterification reaction in a scraper film reactor (6-1) to obtain aryl dichloro phosphate; the hydrogen chloride gas generated by the first esterification reaction is removed by a condenser (10-1) and a gas-liquid separator (11-1);
delivering the aryl dichlorophosphate and the rest of the premix to a second reaction system (4), mixing the mixture by a mixer (9-1), and then carrying out a second esterification reaction in a scraper film reactor (7-1) to obtain the diaryl chlorophosphate; the hydrogen chloride gas generated by the second esterification reaction is removed by a condenser (12-1) and a gas-liquid separator (13-1).
5. The process according to claim 4, wherein the molar ratio of the aromatic monohydroxy compound to the Lewis acid catalyst is from 40 to 1500:1;
the molar ratio of the aromatic monohydroxy compound to the phosphoryl chloride in the partial premix is 1-1.5:1.
6. The method according to claim 4, wherein the pre-mixture is divided into a plurality of strands, and the pre-mixture is introduced into the first reaction system (2) from one or more stages of the first reaction units in the first reaction system (2);
the rest of the premixed solution is divided into a plurality of strands, and enters the second reaction system (4) from one or more stages of second reaction units in the second reaction system (4).
7. The process according to any one of claims 4 to 6, wherein the temperature of the first esterification reaction is 80 to 150 ℃.
8. The process according to any one of claims 4 to 6, wherein the temperature of the second esterification reaction is 100 to 200 ℃.
9. The process of claim 4, wherein mixing the aromatic monohydroxy compound and the lewis acid catalyst in the first reactant vessel (1) further comprises: adding an organic solvent to the first reactant reservoir (1);
the organic solvent comprises one or more of toluene, xylene, trimethylbenzene, chlorobenzene and dichlorobenzene.
10. The method of claim 4, wherein the lewis acid catalyst comprises one or more of aluminum chloride, magnesium chloride, titanium tetrachloride, antimony pentachloride, zinc chloride, and tin chloride.
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| CN115845758B (en) * | 2021-09-24 | 2024-10-08 | 浙江医药股份有限公司新昌制药厂 | Continuous reaction device and method for preparing phosphoric acid diester compound by continuous reaction |
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