CN114835734A - Process for continuously producing Grignard reagent in kettle manner - Google Patents
Process for continuously producing Grignard reagent in kettle manner Download PDFInfo
- Publication number
- CN114835734A CN114835734A CN202210646844.8A CN202210646844A CN114835734A CN 114835734 A CN114835734 A CN 114835734A CN 202210646844 A CN202210646844 A CN 202210646844A CN 114835734 A CN114835734 A CN 114835734A
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- kettle
- temperature
- speed
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000004795 grignard reagents Chemical class 0.000 title claims abstract description 28
- 239000007818 Grignard reagent Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000008569 process Effects 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 95
- 239000000463 material Substances 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 18
- 239000000498 cooling water Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 150000008282 halocarbons Chemical class 0.000 claims description 13
- 150000004791 alkyl magnesium halides Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 7
- 229940073608 benzyl chloride Drugs 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 claims description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- CYSFUFRXDOAOMP-UHFFFAOYSA-M magnesium;prop-1-ene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C=C CYSFUFRXDOAOMP-UHFFFAOYSA-M 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- SCEZYJKGDJPHQO-UHFFFAOYSA-M magnesium;methanidylbenzene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C1=CC=CC=C1 SCEZYJKGDJPHQO-UHFFFAOYSA-M 0.000 description 7
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a continuous kettle type process for producing a Grignard reagent. The method adopts the continuous stirred tank type equipment which is connected in series in sequence, so that the batch yield of the product can be increased by at least one time, the total feeding molar ratio of the raw material magnesium to the allyl chloride is reduced to 1.2-1.8 times, the dosage of the raw material magnesium is greatly reduced, the post-treatment difficulty and time are greatly reduced, the operation cost is reduced, the raw material cost is saved, and the reaction time is saved by more than 2 times.
Description
Technical Field
The invention relates to the field of Grignard reagent production, in particular to a process for continuously producing a Grignard reagent in a kettle manner.
Background
The alkyl halide and magnesium metal react in anhydrous ether or tetrahydrofuran to form an organic magnesium reagent, which is called a Grignard reagent for short. The general formula of the Grignard reagent is R-Mg-X, wherein R is aliphatic hydrocarbon group or aromatic hydrocarbon group, X is halogen (Cl, Br or I), the nature of the Grignard reagent is very active, and the Grignard reagent can be reacted with a compound (such as H) with active hydrogen 2 O, ROH, RC ≡ CH) aldehyde, ketone, ester, acid halide, nitrile, ethylene oxide, or a mixture thereof,Alkyl halides, carbon dioxide, phosphorus trichloride, boron trichloride, silicon tetrachloride and the like are important organic synthesis reagents.
In the prior art, the Grignard reagent is produced in an intermittent kettle manner, and the synthesis of the Grignard reagent with high reaction activity at an allyl position needs to add a large excess of magnesium to inhibit the occurrence of coupling side reaction. For example, in the production process of allyl magnesium chloride, the feeding molar ratio of the raw material magnesium to the allyl chloride is more than 2.5 times, so that the concentration of the Grignard solution of the product can be ensured to be more than 1.0 to 1.5M, the production cost is greatly increased, a large amount of slurry-like solids are required to be settled or filtered in the product post-treatment, the operation difficulty is increased, and the production efficiency is reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a continuous kettle type process for producing a Grignard reagent.
In order to achieve the above purpose, the invention provides the following technical scheme:
a continuous kettle type process for producing Grignard reagent comprises the following steps:
respectively adding raw materials of magnesium and an organic solvent into a first reaction kettle, a second reaction kettle and a third reaction kettle which are connected in series in sequence, controlling the temperature of each reaction kettle to be-10-0 ℃, and replacing the reaction kettles with inert atmosphere;
continuously introducing a mixture of halogenated hydrocarbon and an organic solvent into a first reaction kettle, overflowing the material of the first reaction kettle to a second reaction kettle when the concentration of alkyl magnesium halide in the first reaction kettle reaches 1-1.2M, and overflowing the material of the second reaction kettle to a third reaction kettle when the concentration of alkyl magnesium halide in the second reaction kettle reaches 1.35-1.5M to obtain the Grignard reagent with the concentration of 1.5-1.7M.
In a specific embodiment, in the first reaction kettle, the mass volume ratio of the raw material magnesium to the organic solvent is (85-100) kg: 50L;
and/or in the second reaction kettle, the mass volume ratio of the raw material magnesium to the organic solvent is (50-65) kg: 30L;
and/or in the third reaction kettle, the mass volume ratio of the raw material magnesium to the organic solvent is (0.1-0.3) kg: 10L;
and/or the mass ratio of the raw material magnesium in the first reaction kettle, the second reaction kettle and the third reaction kettle is (85-100): (50-65): (0.1-0.3).
In a particular embodiment, the halogenated hydrocarbon is present in the mixture of halogenated hydrocarbon and organic solvent in a concentration of 2.5 to 3M;
and/or the molar ratio of the total consumption of the raw material magnesium to the halogenated hydrocarbon is 1.2-1.8: 1.
In a specific embodiment, continuously introducing a mixture of halogenated hydrocarbon and an organic solvent into a first reaction kettle at a speed of 0.8-1.2L/min, adjusting the speed of cooling water when the temperature of the first reaction kettle rises to 8-12 ℃, keeping the temperature of the first reaction kettle at 8-12 ℃, after 20-40min, raising the temperature of the first reaction kettle to 20-30 ℃, after 55-65min, continuously introducing the mixture of halogenated hydrocarbon and the organic solvent into the first reaction kettle at a speed of 1.8-2.2L/min, and continuously overflowing materials in the first reaction kettle into a second reaction kettle at a speed of 1.8-2.2L/min when the concentration of alkyl magnesium halide in the first reaction kettle reaches 1-1.2M.
In a specific embodiment, the first reaction kettle material overflows into the second reaction kettle, when the temperature of the second reaction kettle rises to 8-12 ℃, the cooling water speed is adjusted, the temperature of the second reaction kettle is kept at 8-12 ℃, after 8-12min, the temperature of the second reaction kettle rises to 20-30 ℃, when the concentration of the alkyl magnesium halide in the second reaction kettle reaches 1.35-1.5M, the second reaction kettle material continuously overflows into the third reaction kettle at the speed of 1.8-2.2L/min.
In a specific embodiment, the material of the second reaction kettle overflows into a third reaction kettle, when the temperature of the third reaction kettle rises to 8-12 ℃, the cooling water speed is adjusted, the temperature of the third reaction kettle is kept at 8-12 ℃, after 8-12min, the temperature of the third reaction kettle rises to 20-30 ℃, when the concentration of the alkyl magnesium halide in the third reaction kettle reaches 1.5-1.7M, the material is continuously discharged at the speed of 1.8-2.2L/min, and the Grignard reagent with the concentration of 1.5-1.7M is obtained.
In a particular embodiment, the halohydrocarbon comprises allyl chloride, allyl iodide, benzyl bromide, benzyl chloride, or benzyl iodide.
In a specific embodiment, the organic solvent is an ether solvent or a mixed solvent of an ether solvent and toluene. Wherein the ether solvent is common ether solvent for preparing Grignard reagent, such as tetrahydrofuran, diethyl ether, etc.
The invention has the following advantages:
the invention adopts the continuous stirred tank type equipment which is connected in series in sequence, can increase the batch yield of the product by at least one time, the total feeding molar ratio of the raw material magnesium and the allyl chloride is reduced to 1.2 to 1.8 times, the dosage of the raw material magnesium is greatly reduced, thereby greatly reducing the post-treatment difficulty and time, reducing the operation cost, saving the raw material cost, saving the reaction time by more than 2 times,
according to the invention, through carrying out a great deal of research on the feeding relation, the process parameters and the like of the materials, the process can not only obtain the Grignard reagent with the concentration of 1.5-1.7M, but also inhibit the occurrence of coupling side reaction, the concentration of coupling byproducts is not more than 5% at most, and the concentration and the yield of final products are ensured.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
FIG. 1 is a flow chart of a process for continuously producing Grignard reagent in a kettle manner according to an embodiment of the invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, the raw material magnesium includes magnesium powder, magnesium chips, or magnesium grains.
Example 1
This example provides a continuous kettle-type process for producing allyl magnesium chloride, which comprises the following steps:
the method comprises the following steps:
(1) the three kettles are connected in series in sequence through pipelines, 91.5kg of raw material magnesium and 50L of tetrahydrofuran are added into the first 1000L kettle, 54.9kg of raw material magnesium and 30L of tetrahydrofuran are added into the second 500L kettle, 0.16kg of raw material magnesium and 10L of tetrahydrofuran are added into the third 500L kettle, the temperature of each reaction kettle is reduced to-5 ℃ and is ensured to be more than 30min, and the three kettles are replaced by inert atmosphere for standby.
(2) Raw materials of allyl chloride and tetrahydrofuran are mixed into an allyl chloride solution with the concentration of 2.8M through a micro mixer, the allyl chloride solution is continuously introduced into a first kettle at the speed of 1L/min, the temperature and the pressure of the first kettle are obviously increased when the temperature of the first kettle is increased to 10 ℃, the speed of cooling water is adjusted, the temperature of the first kettle is kept at 10 ℃, after 30min, the temperature of the first kettle is increased to 30 ℃, after 1h, the allyl chloride solution with the concentration of 2.8M is continuously fed at the speed of 2L/min, after 7h, a sample is taken from a discharge port of the first kettle to detect that the concentration of allyl magnesium chloride is 1.2M, and reaction liquid in the first kettle continuously overflows to a second kettle at the speed of 2L/min.
(3) After the reaction of the second kettle is observed to be initiated, namely the temperature of the second kettle is increased to 10 ℃, the speed of cooling water is adjusted, the temperature of the second kettle is kept at 10 ℃, after 10min, the temperature of the second kettle is increased to 30 ℃, after 3h, a sample is taken from a discharge hole of the second kettle, the concentration of the allyl magnesium chloride is detected to be 1.4M, and the reaction liquid in the second kettle continuously overflows to a third kettle at the speed of 2L/min.
(4) After the reaction of the third kettle is observed to be initiated, namely the temperature of the third kettle is increased to 10 ℃, the speed of cooling water is adjusted, the temperature of the third kettle is kept at 10 ℃, after 10min, the temperature of the third kettle is increased to 30 ℃, after 1h, a material is sampled from a discharge hole of the third kettle, the concentration of the allyl magnesium chloride is detected to be 1.5M, and the material is continuously discharged at the speed of 2L/min.
(5) And discharging the materials into a settling tank for settling, and introducing the supernatant into a package.
The charging time of the first kettle lasts for 13 hours, 1700L of 1.5M tetrahydrofuran solution of allyl magnesium chloride is obtained in production, the reaction solution is extracted and quenched, then part of the organic solution is extracted for HNMR analysis, the extraction and quenching products of the allyl magnesium chloride are about 95%, the coupling product 1, 5-hexadiene is 3%, and the conversion rate of the raw material reaches more than 98%.
Example 2
The embodiment provides a continuous kettle type process for producing allyl magnesium chloride, which comprises the following steps:
(1) the three kettles are connected in series in sequence through pipelines, 98kg of raw material magnesium and 50L of tetrahydrofuran are added into the first 1000L kettle, 63.5kg of raw material magnesium and 30L of tetrahydrofuran are added into the second 500L kettle, 0.28kg of raw material magnesium and 10L of tetrahydrofuran are added into the third 500L kettle, the temperature of each reaction kettle is reduced to-10 ℃ and is ensured to be more than 30min, and the three kettles are replaced by inert atmosphere for standby.
(2) Mixing raw materials of allyl chloride and tetrahydrofuran into an allyl chloride solution with the concentration of 3M through a micro mixer, continuously introducing the allyl chloride solution into a first kettle at the speed of 1L/min, when the temperature and the pressure of the first kettle are obviously increased, raising the temperature of the first kettle to 12 ℃, adjusting the speed of cooling water, keeping the temperature of the first kettle at 12 ℃, raising the temperature of the first kettle to 30 ℃ after 30min, continuously feeding the allyl chloride solution with the concentration of 3M at the speed of 2L/min after 1h, sampling at a discharge port of the first kettle to detect that the concentration of allyl magnesium chloride is 1.3M after 7h, and continuously overflowing reaction liquid in the first kettle to a second kettle at the speed of 2L/min.
(3) After the reaction of the second kettle is observed to be initiated, namely the temperature of the second kettle is increased to 12 ℃, the cooling water speed is adjusted, the temperature of the second kettle is kept at 12 ℃, after 10min, the temperature of the second kettle is increased to 30 ℃, after 3h, a sample is taken from a discharge hole of the second kettle, the concentration of the allyl magnesium chloride is detected to be 1.5M, and the reaction liquid in the second kettle continuously overflows to a third kettle at the speed of 2L/min.
(4) After the reaction of the third kettle is observed to be initiated, namely the temperature of the third kettle is raised to 12 ℃, the cooling water speed is adjusted, the temperature of the third kettle is kept at 12 ℃, after 10min, the temperature of the third kettle is raised to 30 ℃, after 1h, a material is sampled from a discharge hole of the third kettle, the concentration of the allyl magnesium chloride is detected to be 1.55M, and the material is continuously discharged at the speed of 2L/min.
(5) And discharging the materials into a settling tank for settling, and introducing the supernatant into a package.
The charging time of the first kettle lasts for 12 hours, 1600L of 1.48M tetrahydrofuran solution of allyl magnesium chloride is obtained in production, the reaction solution is extracted from the organic part after extraction and extinction and then subjected to HNMR analysis, the extraction and extinction product of the allyl magnesium chloride is about 93 percent, the coupling product 1, 5-hexadiene is 4 percent, and the conversion rate of the raw material is higher than 97 percent.
Example 3
The embodiment provides a continuous kettle type process for producing benzyl magnesium chloride, which comprises the following steps:
(1) the three kettles are connected in series in sequence through pipelines, 90kg of raw material magnesium and 50L of tetrahydrofuran are added into the first 1000L kettle, 55kg of raw material magnesium and 30L of tetrahydrofuran are added into the second 500L kettle, 0.15kg of raw material magnesium and 10L of tetrahydrofuran are added into the third 500L kettle, the temperature of each reaction kettle is reduced to-10 ℃ and is ensured to be more than 30min, and the three kettles are replaced by inert atmosphere for standby.
(2) Dissolving raw material benzyl chloride in tetrahydrofuran to prepare a benzyl chloride solution with the concentration of 3M, continuously introducing the benzyl chloride solution into a first kettle at the speed of 1L/min, when the temperature and the pressure of the first kettle are obviously increased, increasing the temperature of the first kettle to 10 ℃, adjusting the speed of cooling water, keeping the temperature of the first kettle at 10 ℃, after 20min, increasing the temperature of the first kettle to 25 ℃, after 1h, continuously feeding the benzyl chloride solution with the concentration of 2.6M at the speed of 2L/min, after 7h, sampling at a discharge port of the first kettle to detect that the concentration of benzyl magnesium chloride is 1.2M, and continuously overflowing reaction liquid in the first kettle to a second kettle at the speed of 2L/min.
(3) After the reaction of the second kettle is observed to be initiated, namely when the temperature of the second kettle is increased to 10 ℃, adjusting the speed of cooling water, keeping the temperature of the second kettle at 10 ℃, after 10min, increasing the temperature of the second kettle to 25 ℃, after 3h, sampling at a discharge port of the second kettle, detecting the concentration of benzylmagnesium chloride to be 1.4M, and continuously overflowing the reaction liquid in the second kettle to a third kettle at the speed of 2L/min.
(4) After the reaction of the third kettle is observed to be initiated, namely the temperature of the third kettle is increased to 10 ℃, the cooling water speed is adjusted, the temperature of the third kettle is kept at 10 ℃, after 10min, the temperature of the third kettle is increased to 25 ℃, after 1h, the concentration of the benzylmagnesium chloride is sampled and detected at the discharge port of the third kettle to be 1.5M, and the benzylmagnesium chloride is continuously discharged at the speed of 2L/min.
(5) And discharging the materials into a settling tank for settling, and introducing the supernatant into a package.
The feeding time of the first kettle lasts 13 hours, 1700L of 1.5M tetrahydrofuran solution of benzyl magnesium chloride is obtained in production, gas chromatography analysis is carried out on the extracted organic part after the reaction liquid is extracted and extinguished, the content of the benzyl chloride of the raw material is only 0.4 percent, the coupling byproduct 1, 2-diphenylethane is 3.2 percent, the benzyl alcohol content of the extraction and extinction product of the benzyl magnesium chloride reaches 93.1 percent, and the conversion rate of the raw material exceeds 97 percent.
Although the invention has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A process for continuously producing Grignard reagents in a kettle manner, which is characterized by comprising the following steps:
respectively adding raw materials of magnesium and an organic solvent into a first reaction kettle, a second reaction kettle and a third reaction kettle which are connected in series in sequence, controlling the temperature of each reaction kettle to be-10-0 ℃, and replacing the reaction kettles with inert atmosphere;
continuously introducing a mixture of halogenated hydrocarbon and an organic solvent into a first reaction kettle, overflowing the material of the first reaction kettle to a second reaction kettle when the concentration of alkyl magnesium halide in the first reaction kettle reaches 1-1.2M, and overflowing the material of the second reaction kettle to a third reaction kettle when the concentration of alkyl magnesium halide in the second reaction kettle reaches 1.35-1.5M to obtain the Grignard reagent with the concentration of 1.5-1.7M.
2. The continuous kettle-type production process of Grignard reagent according to claim 1,
in the first reaction kettle, the mass volume ratio of the raw material magnesium to the organic solvent is (85-100) kg: 50L;
and/or in the second reaction kettle, the mass volume ratio of the raw material magnesium to the organic solvent is (50-65) kg: 30L;
and/or in the third reaction kettle, the mass volume ratio of the raw material magnesium to the organic solvent is (0.1-0.3) kg: 10L;
and/or the mass ratio of the raw material magnesium in the first reaction kettle, the second reaction kettle and the third reaction kettle is (85-100): (50-65): (0.1-0.3).
3. The continuous kettle-type production process of Grignard reagent according to claim 1,
the concentration of the halogenated hydrocarbon in the mixture of the halogenated hydrocarbon and the organic solvent is 2.5-3M;
and/or the molar ratio of the total consumption of the raw material magnesium to the halogenated hydrocarbon is 1.2-1.8: 1.
4. The continuous autoclave production process of Grignard reagents according to any of claims 1 to 3,
continuously introducing a mixture of halogenated hydrocarbon and an organic solvent into a first reaction kettle at a speed of 0.8-1.2L/min, adjusting the speed of cooling water when the temperature of the first reaction kettle rises to 8-12 ℃, keeping the temperature of the first reaction kettle at 8-12 ℃, after 20-40min, raising the temperature of the first reaction kettle to 20-30 ℃, after 55-65min, continuously introducing the mixture of the halogenated hydrocarbon and the organic solvent into the first reaction kettle at a speed of 1.8-2.2L/min, and continuously overflowing materials in the first reaction kettle into a second reaction kettle at a speed of 1.8-2.2L/min when the concentration of alkyl magnesium halide in the first reaction kettle reaches 1-1.2M.
5. The continuous kettle-type production process of Grignard reagent according to claim 1,
overflowing the first reaction kettle material into a second reaction kettle, adjusting the cooling water speed when the temperature of the second reaction kettle rises to 8-12 ℃, keeping the temperature of the second reaction kettle at 8-12 ℃, after 8-12min, rising the temperature of the second reaction kettle to 20-30 ℃, and continuously overflowing the second reaction kettle material into a third reaction kettle at the speed of 1.8-2.2L/min when the concentration of the alkyl magnesium halide in the second reaction kettle reaches 1.35-1.5M.
6. The continuous kettle-type production process of Grignard reagent according to claim 1,
and overflowing the material of the second reaction kettle into a third reaction kettle, adjusting the speed of cooling water when the temperature of the third reaction kettle rises to 8-12 ℃, keeping the temperature of the third reaction kettle at 8-12 ℃, after 8-12min, rising the temperature of the third reaction kettle to 20-30 ℃, and continuously discharging at the speed of 1.8-2.2L/min when the concentration of the alkyl magnesium halide in the third reaction kettle reaches 1.5-1.7M to obtain the Grignard reagent with the concentration of 1.5-1.7M.
7. The continuous kettle-type production process of Grignard reagent according to claim 1,
the halogenated hydrocarbon includes allyl chloride, allyl iodide, benzyl bromide, benzyl chloride or benzyl iodide.
8. The continuous kettle-type production process of Grignard reagent according to claim 1,
the organic solvent is an ether solvent or a mixed solvent of the ether solvent and toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210646844.8A CN114835734A (en) | 2022-06-09 | 2022-06-09 | Process for continuously producing Grignard reagent in kettle manner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210646844.8A CN114835734A (en) | 2022-06-09 | 2022-06-09 | Process for continuously producing Grignard reagent in kettle manner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114835734A true CN114835734A (en) | 2022-08-02 |
Family
ID=82574321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210646844.8A Pending CN114835734A (en) | 2022-06-09 | 2022-06-09 | Process for continuously producing Grignard reagent in kettle manner |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114835734A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3381017A (en) * | 1965-06-04 | 1968-04-30 | Syntex Corp | Production of carbinols employing cyclopentadienyl or lower alkyl substituted cyclopentadienyl grignard reagents and hydrogenation |
| CN104497026A (en) * | 2014-11-25 | 2015-04-08 | 上虞华伦化工有限公司 | Production equipment and preparation technology for o-chlorotoluene Grignard reagent |
| CN106674257A (en) * | 2016-12-30 | 2017-05-17 | 江苏创拓新材料有限公司 | Continuous production method of Grignard reagent |
| CN107383073A (en) * | 2017-07-11 | 2017-11-24 | 江苏新淮河医药科技有限公司 | The preparation method of vinylimidazolium chloride magnesium |
| CN111138461A (en) * | 2019-12-05 | 2020-05-12 | 海利尔药业集团股份有限公司 | Continuous preparation method of o-chlorobenzyl chloride Grignard reagent |
-
2022
- 2022-06-09 CN CN202210646844.8A patent/CN114835734A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3381017A (en) * | 1965-06-04 | 1968-04-30 | Syntex Corp | Production of carbinols employing cyclopentadienyl or lower alkyl substituted cyclopentadienyl grignard reagents and hydrogenation |
| CN104497026A (en) * | 2014-11-25 | 2015-04-08 | 上虞华伦化工有限公司 | Production equipment and preparation technology for o-chlorotoluene Grignard reagent |
| CN106674257A (en) * | 2016-12-30 | 2017-05-17 | 江苏创拓新材料有限公司 | Continuous production method of Grignard reagent |
| CN107383073A (en) * | 2017-07-11 | 2017-11-24 | 江苏新淮河医药科技有限公司 | The preparation method of vinylimidazolium chloride magnesium |
| CN111138461A (en) * | 2019-12-05 | 2020-05-12 | 海利尔药业集团股份有限公司 | Continuous preparation method of o-chlorobenzyl chloride Grignard reagent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113956141A (en) | Method for producing difluorobenzophenone | |
| CN103333137B (en) | The synthetic method of glycidyl allyl ether | |
| CN101289368A (en) | Technological process for continuously producing sec-butyl alcohol by direct hydration of n-butene | |
| CN114835734A (en) | Process for continuously producing Grignard reagent in kettle manner | |
| CN112592261A (en) | Preparation method of trimethylolpropane diallyl ether | |
| CN107011151B (en) | Method for improving benzaldehyde selectivity in toluene liquid-phase catalytic oxidation process | |
| CN115784181B (en) | Continuous reactive distillation preparation system and preparation method of phosphorus pentafluoride | |
| CN114685253A (en) | Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone | |
| CN104744211A (en) | An alkynol preparing method | |
| CN109369354B (en) | Synthesis method of 4,4, 4-trifluorobutanol | |
| CN108164393B (en) | Preparation method of deuterated tert-butyl alcohol | |
| CN108863717B (en) | Method for efficiently preparing alkynol | |
| CN110255632B (en) | Method for preparing ruthenium trichloride from ruthenium-containing waste | |
| CN110452094B (en) | Method for preparing 2,4-dichlorophenol by catalytic chlorination of phenol | |
| US3038922A (en) | Process for preparation of triethylaluminum | |
| CN109265392B (en) | Method for continuously synthesizing pyridinium hydroxy propane sulfonate | |
| CN112375091A (en) | Green synthesis process of alkynol double Grignard reagent | |
| CN206359242U (en) | A kind of utilization chlorosilane raffinate produces the device of gas phase chlorination hydrogen | |
| CN110724041B (en) | Separation method of glycerol monomethyl ether reaction mixed liquid | |
| CN116023257B (en) | Continuous production method of high-purity propionyl chloride | |
| CN104592101A (en) | New synthesis method of sodium 3,5,6-trichloropyridyl-2-alkoxide | |
| US20240174628A1 (en) | Method for continuously preparing crude ethylene sulfate | |
| CN114195675B (en) | Method for preparing ethyl hydrazine by continuous flow of microreactor | |
| CN108409776B (en) | Synthetic method of 2- (trimethylsilyl) ethoxymethyl chloride | |
| EP4032873B1 (en) | Method for performing addition reaction between acetylene and ketone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |