CN104592012A - Continuous production method and device for chloroformyl substituted benzenes - Google Patents
Continuous production method and device for chloroformyl substituted benzenes Download PDFInfo
- Publication number
- CN104592012A CN104592012A CN201510073134.0A CN201510073134A CN104592012A CN 104592012 A CN104592012 A CN 104592012A CN 201510073134 A CN201510073134 A CN 201510073134A CN 104592012 A CN104592012 A CN 104592012A
- Authority
- CN
- China
- Prior art keywords
- reaction
- substituted benzene
- trichloromethyl
- benzene
- chloroformyl
- 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
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a continuous production method for chloroformyl substituted benzenes. According to the method, uniformly mixed reaction materials are continuously added in a reaction system composed of multiple stages of reactors which are connected in series, and the reaction materials have reaction under certain temperature conditions, and after the materials continuously flow out of the reactors, a chloroformyl substituted benzene crude product is obtained; and gas produced in the reaction is subjected to condensation treatment, a chloroformyl substituted benzene condensed fluid flows back to the reaction system, and non-condensable gas is optionally further subjected to tail gas treatment. The invention also discloses a continuous production device for chloroformyl substituted benzenes; the device comprises a proportioning system, a reaction system and a condensing system, wherein the reaction system comprises more than two stages of reactors which are connected in series, and the device also can further comprise a purification system and a tail gas treatment system. According to the invention, the continuous production of chloroformyl substituted benzenes is realized by using the continuous production of trichloromethyl substituted benzenes, the quality of prepared products is good, the yield is high, and tail gas is easily treated.
Description
Technical field
The present invention relates to the method and apparatus producing chloroformyl substituted benzene in a kind of chemical industry, be specifically related to continuous production method and the device of chloroformyl substituted benzene.
Background technology
Chloroformyl substituted benzene is a kind of organic industry raw material of outbalance; can be used as the monomers such as polymeric amide, polyester, polyarylester, polyaramide, polyacrylic ester, fire resistant resin, liquid crystal polymer, insulating material, dyestuff, pigment, aramid fiber; can be used as the properties-correcting agent of superpolymer, the intermediate of agricultural chemicals, medicine industry simultaneously.For two (chloroformyl) benzene; according to the position of substitution difference of chloroformyl on phenyl ring can be divided into neighbour, p-two (chloroformyl) benzene; wherein adjacent two (chloroformyl) benzene is the important starting raw material preparing softening agent and synthetic resins, is also the composite structure unit of synthetic drugs and pesticide activity component.Between position and contraposition two (chloroformyl) benzene have been widely used in Industrial materials, protective clothing, electrical apparatus insulation material etc.Two (chloroformyl) benzene of polymerization-grade can as the raw materials for production of high-quality aramid fiber.
The preparation method of chloroformyl substituted benzene in prior art, mainly react with carboxylic acid and different chlorizating agents, mainly contain sulfur oxychloride method (such as, see CN104230612A, CN 102516060A, CN 102344362A), phosgenation (such as, see US5200560, WO/2000/026171), phosphorus trichloride method (such as, see CN1054062A) etc., but above production method also can produce other non-ambient friendly by products except byproduct hydrogen chloride, such as sulfur oxychloride method can produce sulfurous gas, phosgenation can produce carbonic acid gas, phosphorus trichloride method can produce phosphorous acid etc., these by products are made troubles to the subsequent disposal of product, and very easily cause environmental pollution.
Chloroformyl substituted benzene also has a kind of preparation method, is to adopt trichloromethyl substituted benzene and carboxylic acid or water to react obtained chloroformyl substituted benzene.It is external that about the sixties in 20th century, prepare the research of chloroformyl substituted benzene to the method more; such as US2525723, GB949574 and US3835187 all mention the carboxylic acid that employing two (trichloromethyl) benzene is corresponding with it or water reaction preparation two (chloroformyl) benzene.Domestic also have some to study to this method, such as Wang Shen, Song Caisheng, Wu Shenghua. the synthesis of p-phthaloyl chloride and the gas chromatographic analysis [J] of product thereof. the pedagogical journal in Jiangxi: natural science edition, 1981 (2): 43-49., phthalic acid and Light chlorimation prepare 1,4-chlordene dimethylbenzene is placed in three-necked bottle, adds the catalyst Fe Cl of reactant consumption 2 ~ 3%
3, add tetracol phenixin during preparation contraposition phthalyl chloride, react completely when being finally warming up to 140 DEG C, react and can complete at 1 ~ 1.5 hour, productive rate is 89%; Between preparation during the phthalyl chloride of position, react and carry out at 70-80 DEG C, react and completed at 0.5 ~ 1 hour, productive rate reaches 95%.The synthesis [J] of Shi Daqing, Zhou Longhu p-phthaloyl chloride. chemistry world, 1994 (10): 518-519. add Isosorbide-5-Nitrae-two (trichloromethyl) benzene, terephthalic acid, tetrachloroethane and catalyst Fe Cl in round-bottomed flask
3reaction, p-phthaloyl chloride productive rate is 80%.Wang Lumin, Cui Bingcun etc., the study on the synthesis of chlorination reaction, institute of Tonghua Teachers College reports, 2005,26 (4): 46-47, in three mouthfuls of round bottom reaction flasks, m-xylene two (trichloromethyl) benzene between Light chlorimation preparation under the existence of benzoyl peroxide, product directly adds the catalyst Fe Cl of 1% weight ratio without being separated
3, add water in batches, react after 7 hours, through underpressure distillation, productive rate is 82%, and purity is 99%.
To sum up; although with trichloromethyl substituted benzene, for raw material, to prepare chloroformyl substituted benzene by product compared with traditional preparation method few; but what usually adopt at present is batch production mode; if it is large to there is energy consumption in suitability for industrialized production; unstable product quality, the problem such as output is little, yield is low, environmental pollution, byproduct hydrogen chloride not easily process.
Summary of the invention
An object of the present invention is for the problems referred to above, provide a kind of with trichloromethyl substituted benzene for the continuous production method of chloroformyl substituted benzene prepared by raw material.
A continuous production method for chloroformyl substituted benzene, comprises the following steps:
1) prepare burden: each reaction mass is added in batching kettle, under being at trichloromethyl substituted benzene the state melted completely, to water or corresponding aromatic acid and catalyst mix, stir;
2) reacting: by step 1) the reaction mass continuous print that mixes delivers in the reactive system that is made up of more than 2 grades reactors in series and reacts; and reacting by heating system to certain temperature is carried out to maintain reaction; reaction mass enters adjacent next stage reactor successively from first step reactor; from last step reactor continuous discharge, obtain chloroformyl substituted benzene crude product.
Further, if needed, the chloroformyl substituted benzene crude product of gained, also can according to optional purification step, and such as rectifying, distillation, molecular distillation or recrystallization etc. are further purified, the preferred rectifying of the present invention.
Production method of the present invention; preferably in the process of batching, as solvent, trichloromethyl substituted benzene is melted by raised temperature and/or the target product chloroformyl substituted benzene that adds reaction, and mix completely to chloroformyl substituted benzene, corresponding aromatic acid or water and catalyzer.Such as Isosorbide-5-Nitrae-two (trichloromethyl) benzene and phthalic acid react prepares Isosorbide-5-Nitrae-two (chloroformyl) benzene, preferably in the process of batching, adds target product Isosorbide-5-Nitrae-two (chloroformyl) benzene of reaction as solvent.The add-on of the described chloroformyl substituted benzene as solvent is preferably 20% ~ 30% of trichloromethyl substituted benzene weight.
Preferably, the molar ratio of trichloromethyl substituted benzene of the present invention and corresponding aromatic acid is 1:1 ~ 1:1.1, excessive a little on the basis of the variable that the molar ratio of preferred fragrance acid carries out completely at chemical reaction, such as preferably the molar ratio of trichloromethyl substituted benzene and corresponding aromatic acid is 1:1.01 ~ 1:1.03; Preferred 1:2 ~ the 1:2.2 of molar ratio of described trichloromethyl substituted benzene and water, more preferably 1:2.03 ~ 1:2.05.
Step 1 of the present invention) described in reaction catalyzer be Lewis acid, such as aluminum chloride, zinc chloride, iron trichloride etc., preferred iron trichloride; Especially, for preferably also there is a small amount of corresponding construction formula when trichloromethyl substituted benzene and water react for (X)
ac
6h
6-a-b(COOH)
bcorresponding aromatic acid.Step 1) in catalyst charge be 0.01% ~ 10% of trichloromethyl substituted benzene weight, be preferably trichloromethyl substituted benzene weight 0.2% ~ 0.3%.
Production method of the present invention, step 2) described in reactive system, preferably include 2 ~ 10 stage reactors, more preferably comprise 2 ~ 5 stage reactors.
Described is trichloromethyl substituted benzene, when aromatic acid corresponding to it reacts in the presence of a catalyst, in general, step 2) in temperature of reaction be 40 ~ 300 DEG C, preferably 85 ~ 120 DEG C; Step 2) in reaction times be 0.5 ~ 4h, preferably 0.8 ~ 2.5h; Described is trichloromethyl substituted benzene, when reacting in the presence of a catalyst with water, in general, step 2) in temperature of reaction be 50 ~ 180 DEG C, preferably 70 ~ 140 DEG C; Step 2) in reaction times be 0.5 ~ 5h, preferably 0.8 ~ 3.5h.
Especially, described in be two (trichloromethyl) benzene, when its corresponding phthalic acid reacts in the presence of a catalyst, in general, step 2) in temperature of reaction be 50 ~ 300 DEG C, preferably 70 ~ 160 DEG C, more preferably 110 ~ 120 DEG C; Step 2) in reaction times be 0.8 ~ 1.6h, preferably 1.0 ~ 1.3h; Described is two (trichloromethyl) benzene, when reacting in the presence of a catalyst with water, in general, step 2) in temperature of reaction be 50 ~ 150 DEG C, preferably 70 ~ 130 DEG C, more preferably 80 ~ 110 DEG C; Step 2) in reaction times be 0.5 ~ 2h, preferably 0.8 ~ 1.2h.
Especially, described is to chlorine (trichloromethyl) benzene, when reacting in the presence of a catalyst with Chlorodracylic acid, in general, step 2) in temperature of reaction be 40 ~ 200 DEG C, preferably 70 ~ 130 DEG C; Step 2) in reaction times be 0.7 ~ 1.5h, preferably 0.9 ~ 1.2h; Described is to chlorine (trichloromethyl) benzene, when reacting in the presence of a catalyst with water, in general, step 2) in temperature of reaction be 50 ~ 150 DEG C, preferably 70 ~ 130 DEG C; Step 2) in reaction times 0.5 ~ 2h, preferably 0.8 ~ 1.3h.
Especially, described is equal three (trichloromethyl) benzene, when reacting in the presence of a catalyst with trimesic acid, in general, step 2) in temperature of reaction be 60 ~ 300 DEG C, preferably 120 ~ 160 DEG C; Step 2) in reaction times be 0.5 ~ 4h, preferably 1 ~ 2.5h; Described is equal three (trichloromethyl) benzene, when reacting in the presence of a catalyst with water, in general, step 2) in temperature of reaction be 60 ~ 180 DEG C, preferably 95 ~ 140 DEG C; Step 2) in reaction times 0.5 ~ 5h, preferably 1 ~ 3.5h.
Especially, described for benzenyl trichloride and phenylformic acid react in the presence of a catalyst time, in general, step 2) in temperature of reaction be 60 ~ 150 DEG C, preferably 100 ~ 120 DEG C; Step 2) in reaction times be 0.5 ~ 1.5h, preferably 0.9 ~ 1.1h; Described for benzenyl trichloride and water react in the presence of a catalyst time, in general, step 2) in temperature of reaction be 70 ~ 130 DEG C, preferably 95 ~ 110 DEG C; Step 2) in reaction times 0.6 ~ 1.5h, preferably 0.9 ~ 1.2h.
Production method of the present invention, preferably to step 2) gas that produces in reaction carries out condensation process, and the backflow of the phlegma that obtains enters reactive system; Optionally further vent gas treatment is carried out to noncondensable gas.
Production method of the present invention, preferably carries out condensed in two stages process to the gas produced in reaction.
Production method of the present invention, during the gas employing condensed in two stages process produced in reaction process, as much as possible the condensation of chloroformyl substituted benzene to be got off, tail gas hydrogen chloride gas then still keeps gaseous phase to discharge condenser system as non-condensable gas, therefore, preferably, the condensing temperature of one-level condensation is the arbitrary temperature in the boiling point lower than chloroformyl substituted benzene, the interval range higher than the fusing point of chloroformyl substituted benzene; The condensing temperature of B-grade condensation is the fusing point 5 ~ 30 DEG C lower than chloroformyl substituted benzene; preferably lower than the fusing point 10 ~ 20 DEG C of chloroformyl substituted benzene; the phlegma that one-level condensation obtains passes back into reactor; noncondensable gas enters B-grade condensation; the phlegma that B-grade condensation obtains passes back into reactor, and noncondensable gas is discharged.Such as, when preparing Isosorbide-5-Nitrae-two (chloroformyl) benzene, one-level condensing temperature preferably 84 ~ 91 DEG C, B-grade condensation temperature preferably 50 ~ 75 DEG C; During preparation 1,3-bis-(chloroformyl) benzene, one-level condensing temperature preferably 48 ~ 55 DEG C, B-grade condensation temperature preferably 15 ~ 40 DEG C.It will be appreciated by those skilled in the art that the phlegma that condensation obtains is mainly chloroformyl substituted benzene, may also containing a small amount of reaction mass, such as trichloromethyl substituted benzene.
Production method of the present invention, the gas of discharging reactive system carries out condensation process, the noncondensable gas of discharging after condensation process, first can be collected in unified process again in surge tank.Described noncondensable gas main ingredient is hydrogen chloride gas, can adopt such as with other conventional treatment method such as water or alkali liquor absorption, preferably adopts the catalytic oxidation of hydrogen chloride (Deacon reaction) method process, can prepare chlorine.
Production method of the present invention, the reaction times refers to the reaction times that reaction mass is total in each stage reactor.
Production method of the present invention, preferably, reaction mass is enter adjacent next stage reactor successively by the mode of overflow from first step reactor.
Described in the application, trichloromethyl substituted benzene structural formula is (X)
ac
6h
6-a-b(CCl
3)
b, corresponding aromatic acid structural formula is (X)
ac
6h
6-a-b(COOH)
b, in the above-claimed cpd structural formula described in the application, X is alkyl or chlorine or bromine or fluorine atom, a be selected from 0,1,2,3,4 or 5 integer, b be selected from 1,2,3 or 4 integer, and a+b=6.Corresponding aromatic acid described in the application refers to that the substituting group on described aromatic acid parent nucleus is in identical or corresponding the position of substitution with the substituting group on described trichloromethyl substituted benzene parent nucleus; Substituent X on described aromatic acid parent nucleus can be identical with the substituent X on described trichloromethyl substituted benzene parent nucleus, also can be different, the substituent X on preferred described aromatic acid parent nucleus be identical with the substituent X on described trichloromethyl substituted benzene parent nucleus.
Production method of the present invention, step 2) in reacting by heating system to certain temperature carry out to maintain reaction, described certain temperature is temperature of reaction.
Another object of the present invention is to provide a kind of continuous production device of chloroformyl substituted benzene.
A kind of continuous production device of chloroformyl substituted benzene; comprise feed proportioning system, reactive system, condenser system; described reactive system comprises more than the 2 grades reactors be connected in series; described condenser system is composed in series by two-stage or the above condenser of two-stage; in described reactive system, the opening for feed of first step reactor is connected with the discharge port of feed proportioning system; in described reactive system, the pneumatic outlet of each stage reactor is connected with condenser system import, is connected with liquid returning tube between any reactor in the condensate outlet of described condenser system and reactive system.
Those skilled in the art can understand the import that namely condenser system import that the above condenser of described two-stage is composed in series refers to first-stage condenser, and namely the noncondensable gas relief outlet of condenser system refers to the noncondensable gas relief outlet of last step condenser.Phlegma in described condenser system can to pass back in reactive system in any one reactor by liquid returning tube.
Condenser system of the present invention, is preferably composed in series by condensed in two stages device.
The condenser system be composed in series by condensed in two stages device of the present invention, specifically comprises first-stage condenser and secondary condenser, and wherein first-stage condenser is single condenser, and secondary condenser is that two condensers compose in parallel.The phlegma that described first-stage condenser condensation obtains is back to reactive system, and noncondensable gas enters secondary condenser; The phlegma that in secondary condenser, condensation obtains is back to reactive system, and noncondensable gas discharges condenser system, optionally enters exhaust treatment system further.
Condenser system of the present invention, can be equipped with 1 to multiple according to the number of reactor, such as, often supporting condenser system can be housed stage reactor; Also can share a set of condenser system by staged reactor, condensation process is unified to the gas that reactor produces.
The continuous production device of described chloroformyl substituted benzene, comprises exhaust treatment system further, and exhaust treatment system is connected with the noncondensable gas relief outlet of described condenser system.The noncondensable gas that condenser system is discharged enters exhaust treatment system.
The continuous production device of described chloroformyl substituted benzene, comprises purification system further, and purification system is connected with the discharge port of last step reactor in described reactive system.Discharging in reactive system enters purification system.
Reactive system of the present invention, preferably includes 2 ~ 10 grades of reactors be connected in series, and more preferably comprises 2 ~ 5 grades of reactors be connected in series.
Feed proportioning system of the present invention, comprises more than 2 batching kettles, in parallel or be connected in series, preferably include 2 batching kettles to be connected in series, batching kettle feeds intake and after mixing, material enters next batching kettle, from next batching kettle continuous discharge, enter reactive system.
Further, in order to realize feed proportioning system better to the stability of reactive system convey materials and continuity, preferably on the pipeline of the discharge port of the opening for feed and feed proportioning system that connect first step reactor, flow rate control device is installed.
Namely the discharge port that those skilled in the art can understand described feed proportioning system refers to the discharge port of the batching kettle be directly connected with the opening for feed of reactive system first step reactor.
Exhaust treatment system of the present invention, preferably includes gas buffer tank, enters gas buffer tank, then carries out unifying process, be connected with such as the catalytic oxidation of hydrogen chloride reaction unit after preferred surge tank after the unified collection of all noncondensable gases.
Chloroformyl substituted benzene purifying crude system of the present invention can be general purification device, such as vacuum distillation apparatus, rectifier unit, molecular distillation apparatus or recrystallization device.
The continuous production device of chloroformyl substituted benzene of the present invention; product groove can also be comprised; product groove is connected in the middle of described reactive system and described purification system; namely in reactive system, last step reactor discharge port connects product groove, enters purification system again after the discharging of reactive system enters product groove.
Product groove of the present invention can be more than one or two.
Batching kettle of the present invention and reactor are all preferred with whipping appts.
The continuous production device of chloroformyl substituted benzene of the present invention, described each system can also be that two or more sets are in parallel, to meet need of production.
Device of the present invention, feed proportioning system enters reactive system after preparing material, after reaction mass has reacted in reactive system, optionally enter discharging after purification system, pneumatic outlet in reactive system connects condenser system, and the noncondensable gas of discharging after condenser system can enter exhaust treatment system.
The mode that is connected in series of reactor described in the application and the mode that is connected in series of batching kettle etc. are the classical tandem mode of connection in this area, it can be such as the series connection of above-below direction, also can be the series connection in horizontal direction, the application preferably connects mutually successively with potential difference nature press over system.
The continuous production device of chloroformyl substituted benzene of the present invention; be applicable to trichloromethyl substituted benzene and water reacts; or trichloromethyl substituted benzene aromatic acid corresponding to it reacts; chloroformyl substituted benzene can also be prepared for trichloromethyl substituted benzene and corresponding ester reaction etc., and the reaction of similar substance.
Device of the present invention may be used for the continuous production method realizing the substituted benzene of chloroformyl described in the present invention, preferably, specifically comprises the steps:
1) prepare burden: feed proportioning system reaction mass being added more than 2 batching kettle compositions is prepared burden, and is (X) at structural formula
ac
6h
6-a-b(CCl
3)
bthe state that melts completely of trichloromethyl substituted benzene under, be (X) with water or described structural formula
ac
6h
6-a-b(COOH)
bcorresponding aromatic acid and catalyzer, stir;
2) reacting: by step 1) the reaction mass continuous print that mixes delivers in the reactive system that is made up of more than 2 grades reactors in series and reacts, reacting by heating system to certain temperature is carried out to maintain reaction, reaction mass enters adjacent next stage reactor successively from first step reactor, from last step reactor continuous discharge, obtain chloroformyl substituted benzene crude product;
3) process of the gas produced in reactive system: the gas produced in reaction enters condenser system, phlegma enters reactive system from condensate outlet by liquid returning tube backflow, carries out further vent gas treatment to the noncondensable gas of discharging from condenser system; Preferred condenser system is made up of condensed in two stages device, and first the gas produced in reaction enter first-stage condenser, and the backflow of chloroformyl substituted benzene phlegma enters reactive system, and noncondensable gas enters secondary condenser after discharging one-level condenser system; The phlegma that in secondary condenser, condensation obtains also passes back into reactive system by liquid returning tube, and noncondensable gas carries out further vent gas treatment;
4) optional, carry out purifying to gained chloroformyl substituted benzene crude product, such as rectifying, distillation, molecular distillation or recrystallization etc. are further purified step.
Compared with prior art, beneficial effect of the present invention is embodied in:
1) method and apparatus for adopting trichloromethyl substituted benzene and corresponding aromatic acid or water to carry out acyl chloride reaction to prepare chloroformyl substituted benzene provided by the invention; the continuous prodution of chloroformyl substituted benzene can be realized; production capacity is large, equipment is little; improve production output; reduce production cost; the stable of chloroformyl substituted benzene quality can be ensured; material reaction is complete; the product purity of preparation is high; namely can obtain high-purity chloro formyl radical substituted benzene by further simple purification step, purity reaches more than 99.95%.
2) trichloromethyl substituted benzene of the present invention and corresponding aromatic acid or water successive reaction, on the one hand compared with batch production, entering of air in reinforced process can be avoided, because the air entered finally can enter hydrogen chloride tail gas, be unfavorable for the recycling of tail gas, be particularly unfavorable for the catalytic oxidation treatment of tail gas; On the other hand while obtaining product continuously, also byproduct hydrogen chloride can be produced by continuous print, be conducive to the disposal and utilization of byproduct hydrogen chloride, particularly be conducive to the supporting operation of continuous treatment flow process with hydrogenchloride, such as, the continuous treatment flow process that continuous print catalytic oxidation treatment (Deacon reaction) prepares chlorine carried out to hydrogenchloride.
3) the present invention preferably adds chloroformyl substituted benzene solution as solvent in the process of batching, because trichloromethyl substituted benzene and corresponding aromatic acid are difficult to dissolve each other, add target product chloroformyl substituted benzene as solvent, trichloromethyl substituted benzene, corresponding aromatic acid and acyl chlorides three is made to form suspension, chloroformyl substituted benzene all has solvency action for trichloromethyl substituted benzene and aromatic acid on the one hand, be convenient to the Homogeneous phase mixing of reaction mass, in the production process of serialization, have more the effect being convenient to mass transport; On the other hand; adding of solvent; batch temperature can be reduced; particularly batch temperature is reduced for the trichloromethyl substituted benzene that fusing point is higher and there is the safer advantage of operation; and due to the target product that the solvent adopted is exactly reaction, therefore adding of solvent chloroformyl substituted benzene the purity of product is not affected.
4) continuous production method of the present invention and device have taken into full account the environmental protection problem in production process, condensed in two stages process (condensed in two stages device) is adopted to the gas produced in reaction, one-level condensation process temperature is more than the fusing point of product, substantially the condensation of chloroformyl substituted benzene is got off, uncooled chloroformyl substituted benzene and hydrogenchloride enter B-grade condensation, condensing temperature is below the fusing point of product, the chloroformyl substituted benzene of volatilization obtains sufficient trapping, chloroformyl substituted benzene results in blockage after can be avoided to enter pipeline, the condensed fluid simultaneously obtained passes back into reactor recycling again, product yield reaches more than 95%, and B-grade condensation is employing two condenser parallel connection uses, condensation effect is good, and service efficiency is high.
5) the inventive method is compared with traditional chloroformyl substituted benzene production method such as sulfur oxychloride method etc., by product is few, burden is not caused to environment, the gas overflowed from chloroformyl substituted benzene synthesis reactor, reclaimed by condensation, chloroformyl substituted benzene and a small amount of reaction mass are again back in reactor and utilize further; Byproduct hydrogen chloride carries out unifying to collect aftertreatment.
Accompanying drawing explanation
Fig. 1 is the continuous production device schematic diagram of chloroformyl substituted benzene of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
In following examples, the purity of aromatic acid is 99.5%.
Embodiment 1
With reference to accompanying drawing 1, adopt Isosorbide-5-Nitrae-two (trichloromethyl) benzene to be raw material, carry out acyl chloride reaction with Isosorbide-5-Nitrae-phthalic acid, concrete steps are as follows:
(1) prepare burden: by 43.2Kg 1, 4-bis-(trichloromethyl) benzene adds in batching kettle 12, add 10.8Kg1, 4-bis-(chloroformyl) benzene is as solvent, and raised temperature makes 1, after 4-bis-(trichloromethyl) benzene dissolves completely, according to 1, 1.01 times of 4-bis-(trichloromethyl) benzene mole number add 1, 4-phthalic acid 22.17Kg, again according to 1, 0.25% of 4-bis-(trichloromethyl) benzene weight adds ferric chloride catalyst 0.11Kg, after reaction mass mixes in batching kettle 12, namely valve 14 is opened, by material continus convergence to batching kettle 13, valve-off 14 again after conveying, batching kettle 12 continues batching, to ensure the continuity of preparing burden,
(2) feed proportioning system to prepare after material from batching kettle 13 continus convergence to A reactor 1, and control reaction mass to enter first step reactor 1 flow from batching kettle 13, to ensure the continuous feeding of batching kettle 13 pairs of reactive systems by flow rate control device 15; Reaction system to 120 DEG C in heating first step reactor maintains reaction and carries out, enter second stage reactor 2 continuously by pipeline 11 after material overflow in first step reactor 1 and continue reaction, reaction system to 130 DEG C in the reactor of the heating second stage maintains reaction and carries out, from the second stage reactor continuous discharge reactive system, obtain Isosorbide-5-Nitrae-two (chloroformyl) benzene crude product;
(3) process of the gas produced in reactive system: the gas produced in reaction enters condenser system from the pneumatic outlet of each stage reactor by condenser system import.The gas produced in first step reactor 1 enters supporting condenser system, this condenser system comprises first-stage condenser 3, secondary condenser 5 and 6, first gas in reactor 1 enter first-stage condenser 3, condensing temperature is 85 DEG C, in first-stage condenser 3, phlegma passes back into reactor 1 from condensate outlet 10a by liquid returning tube 9a, and noncondensable gas enters secondary condenser 5 or 6, and condensing temperature is 52 DEG C; In secondary condenser, phlegma passes back into reactor 1 from condensate outlet 10c and 10d by liquid returning tube 9b respectively, and noncondensable gas 19 enters exhaust treatment system by noncondensable gas relief outlet; The gas produced in second stage reactor 2 enters supporting condenser system, this condenser system comprises first-stage condenser 4, secondary condenser 7 and 8, first gas in reactor 2 enter first-stage condenser 4, condensing temperature is 85 DEG C, in first-stage condenser 4, phlegma passes back into reactor 2 from condensate outlet 10b by liquid returning tube 9c, and noncondensable gas enters secondary condenser 7 or 8, and condensing temperature is 52 DEG C; In secondary condenser, phlegma passes back into reactor 2 from condensate outlet 10e and 10f by liquid returning tube 9d respectively, and noncondensable gas 19 enters exhaust treatment system by noncondensable gas relief outlet; Here, flow rate control device is known in those skilled in the art, such as flowrate control valve, does not repeat them here.
(4) product purification: 1; 4-bis-(chloroformyl) benzene crude product enters crude product groove 17 and 18 continuously by pipeline 16 from second stage reactor 2; purification system is connected again after crude product groove; discharging after rectifying; obtain polymerization-grade Isosorbide-5-Nitrae-two (chloroformyl) benzene, purity is 99.96%; with Isosorbide-5-Nitrae-two (trichloromethyl) the benzene rate of collecting for 95.7%.
In the embodiment of the present invention, for the secondary condenser in condenser system, two condenser cross-references in parallel, when in arbitrary condenser, coagulum is too many, blocking pipe, when affecting gas circulation (whether affect gas circulation can be judged by the pressure reduction such as measuring condenser-air import and pneumatic outlet), then enable another condenser, temperature-boosting measure is taked to this condenser simultaneously, Melting And Solidification thing, recycled in order to next time.With the supporting condenser system first-stage condenser 3 of A reactor, secondary condenser 7 and 8 is example, the concrete operations flow process of condenser system: after gas enters first-stage condenser 3 in A reactor, major part chloroformyl substituted benzene is condensed into liquid return to reactor, noncondensable gas enters secondary condenser 5 further, chloroformyl substituted benzene is condensed into solid, when in secondary condenser 5, solids is too many, when affecting gas circulation, then close the valve that gas enters secondary condenser 5, open the valve that gas enters secondary condenser 6 simultaneously, and temperature-boosting measure is taked to secondary condenser 5, Melting And Solidification thing is back to reactor, the secondary condenser 5 handled well is stand-by, treat that secondary condenser 6 occurs that coagulum is too many, when affecting gas circulation, enter using state, the secondary condenser of parallel connection like this realizes uninterruptedly recycling, the tail gas of discharging in secondary condenser is unified enters exhaust treatment system.
Embodiment 2
Adopt 1,3-bis-(trichloromethyl) benzene to be raw material, carry out acyl chloride reaction with 1,3-phthalic acid.
1,3-bis-(chloroformyl) benzene of 12.65Kg is added as solvent during batching.
The mol ratio of 1,3-bis-(trichloromethyl) benzene and 1,3-phthalic acid is 1:1.03, then adds ferric chloride catalyst 0.14Kg according to 0.28% of 1,3-bis-(trichloromethyl) benzene weight
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is with embodiment 1.
1,3-bis-(chloroformyl) benzene crude product be obtained by reacting, obtain polymerization-grade 1,3-bis-(chloroformyl) benzene through rectifying purifying, purity is 99.95%, with 1, the 3-phthalic acid rate of collecting for 96.1%.
Embodiment 3
Adopt Isosorbide-5-Nitrae-two (trichloromethyl) benzene to be raw material, carry out acyl chloride reaction with water;
Isosorbide-5-Nitrae-two (chloroformyl) benzene of 750Kg is added as solvent during batching.
The mol ratio of Isosorbide-5-Nitrae-two (trichloromethyl) benzene and water is 1:2.08, then adds ferric chloride catalyst 8.1Kg according to 0.27% of Isosorbide-5-Nitrae-two (trichloromethyl) benzene weight.
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is with embodiment 1.
Isosorbide-5-Nitrae-two (chloroformyl) the benzene crude product be obtained by reacting, obtain polymerization-grade Isosorbide-5-Nitrae-two (chloroformyl) benzene through rectifying, purity is 99.96%, with Isosorbide-5-Nitrae-two (trichloromethyl) the benzene rate of collecting for 95.6%.
Embodiment 4
Adopt 1,3-bis-(trichloromethyl) benzene to be raw material, carry out acyl chloride reaction with water;
1,3-bis-(chloroformyl) benzene of 14.53Kg is added as solvent during batching.
The mol ratio of 1,3-bis-(trichloromethyl) benzene and water is 1:2.1, then adds ferric chloride catalyst 3.5Kg according to 6% of 1,3-bis-(trichloromethyl) benzene weight.
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is with embodiment 1.
1,3-bis-(chloroformyl) benzene crude product be obtained by reacting, obtain polymerization-grade 1,3-bis-(chloroformyl) benzene through rectifying purifying, purity is 99.97%, with 1, the 3-phthalic acid rate of collecting for 95.7%.
Embodiment 5
The present embodiment is characterised in that reactive system comprises three reactor, and every stage reactor is all equipped with condenser system.
Adopt Isosorbide-5-Nitrae-two (trichloromethyl) benzene to be raw material, carry out acyl chloride reaction with Isosorbide-5-Nitrae-phthalic acid.
Isosorbide-5-Nitrae-two (chloroformyl) benzene of 12.65Kg is added as solvent during batching.
The mol ratio of Isosorbide-5-Nitrae-two (trichloromethyl) benzene and Isosorbide-5-Nitrae-phthalic acid is 1:1.07, then adds ferric chloride catalyst 0.05Kg according to 0.09% of Isosorbide-5-Nitrae-two (trichloromethyl) benzene weight.
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is substantially identical with embodiment 1, difference is that reactive system comprises three reactor, 1 is obtained from third stage reactor continuous discharge, 4-bis-(trichloromethyl) benzene crude product, the gas that described third stage reactor produces enters the condenser system phlegma comprising secondary condenser and passes back into third stage reactor, and the never solidifying gas discharge outlet of noncondensable gas enters exhaust treatment system.
Isosorbide-5-Nitrae-two (chloroformyl) the benzene crude product be obtained by reacting, obtain polymerization-grade Isosorbide-5-Nitrae-two (chloroformyl) benzene through rectifying, purity is 99.99%, with Isosorbide-5-Nitrae-two (trichloromethyl) the benzene rate of collecting for 97.4%.
Embodiment 6
The present embodiment is characterised in that reactive system comprises three reactor, and three reactor is equipped with a set of condenser system altogether.
Adopt 1,3-bis-(trichloromethyl) benzene to be raw material, carry out acyl chloride reaction with 1,3-phthalic acid;
1,3-bis-(chloroformyl) benzene of 500Kg is added as solvent during batching.
The mol ratio of 1,3-bis-(trichloromethyl) benzene and 1,3-phthalic acid is 1:1.01, then adds ferric chloride catalyst 4.6Kg according to 0.23% of 1,3-bis-(trichloromethyl) benzene weight.
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is substantially identical with embodiment 5, and difference is that the gas of three reactor generation in reactive system all enters same set of condenser system and carries out condensation process.
1,3-bis-(chloroformyl) benzene crude product be obtained by reacting, obtain polymerization-grade 1,3-bis-(chloroformyl) benzene through rectifying, purity is 99.98%, with 1,3-bis-(trichloromethyl) the benzene rate of collecting for 97.2%.
Embodiment 7
The present embodiment is characterised in that reactive system comprises two-stage reactor, and every stage reactor is all equipped with condenser system.
Adopting chlorine (trichloromethyl) benzene is raw material, carries out acyl chloride reaction with Chlorodracylic acid.
Add during batching 21.25Kg to chlorine (chloroformyl) benzene as solvent.
Be 1:1.05 to the mol ratio of chlorine (trichloromethyl) benzene and Chlorodracylic acid, then add ferric chloride catalyst 0.21Kg according to 0.25% of chlorine (trichloromethyl) benzene weight.
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is with embodiment 1.
Be obtained by reacting to chlorine (chloroformyl) benzene, after rectifying, purity is 99.96%, with to chlorine (trichloromethyl) the benzene rate of collecting for 96.4%.
Embodiment 8
The present embodiment is characterised in that reactive system comprises two-stage reactor, and every stage reactor is all equipped with condenser system.
Adopt equal three (trichloromethyl) benzene to be raw material, carry out acyl chloride reaction with trimesic acid.
Equal three (chloroformyl) benzene of 23.75Kg is added as solvent during batching.
The molar ratio of equal three (trichloromethyl) benzene and trimesic acid is 1:1.08, then adds ferric chloride catalyst 0.27Kg according to 0.28% of equal three (trichloromethyl) benzene weight.
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is with embodiment 1.
Equal three (chloroformyl) benzene be obtained by reacting, after rectifying, purity is 99.95%, with equal three (trichloromethyl) benzene rate of collecting for 97.1%.
Embodiment 9
The present embodiment is characterised in that reactive system comprises two-stage reactor, and every stage reactor is all equipped with condenser system.
Employing benzenyl trichloride is raw material, carries out acyl chloride reaction with phenylformic acid.
Benzenyl trichloride and benzoic mol ratio are 1:1.03, then add ferric chloride catalyst 0.23Kg according to 0.23% of benzenyl trichloride weight.
The consumption of reactant and operating procedure are in table one.Concrete operations flow process is substantially identical with embodiment 1, and difference is: because benzenyl trichloride fusing point is low, be in molten state under room temperature, therefore need not additionally heat up when preparing burden or add solvent.
Be obtained by reacting to chlorine (chloroformyl) benzene, after rectifying, purity is 99.98%, with the benzenyl trichloride rate of collecting for 97.3%.
In above embodiment, the measuring method of chloroformyl substituted benzene purity is vapor-phase chromatography or liquid phase chromatography.
Yield described in the application refers to that crude product chloroformyl substituted benzene is converted to sterling chloroformyl substituted benzene and adopts the gauge of the raw material of stoichiometric mole ratio deficiency to calculate the mass ratio of available in theory chloroformyl substituted benzene.In 8 hours, the purity of each embodiment products therefrom after rectifying and yield, in shown in table one.
It should be noted that the situation that this accompanying drawing describes is a kind of comparatively perfect embodiment, the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.Such as, in the present invention, reactor can also be more than 3 grades, also can be connected in parallel by two or more and form in every stage reactor; The liquid obtained after secondary condenser condensation, also all can reflux and enter a reactor, also can separately enter these similar accommodations such as respective reactor, all belong to protection scope of the present invention.
Table one, each embodiment concrete technology condition
Claims (20)
1. a continuous production method for chloroformyl substituted benzene, comprises the following steps:
1) prepare burden: each reaction mass is added in batching kettle, under being at trichloromethyl substituted benzene the state melted completely, to water or corresponding aromatic acid and catalyst mix, stir;
2) reacting: by step 1) the reaction mass continuous print that mixes delivers in the reactive system that is made up of more than 2 grades reactors in series and reacts; reacting by heating system to certain temperature is carried out to maintain reaction; reaction mass enters adjacent next stage reactor successively from first step reactor; from last step reactor continuous discharge, obtain chloroformyl substituted benzene crude product.
2. method according to claim 1, is characterized in that further, to the chloroformyl substituted benzene crude product of gained, optional carry out rectifying, distillation, molecular distillation or recrystallization be further purified step.
3. the method according to any one of claim 1-2; it is characterized in that; in the process of batching, as solvent, trichloromethyl substituted benzene is melted completely by raised temperature and/or the target product chloroformyl substituted benzene that adds reaction, preferably the add-on of the described chloroformyl substituted benzene as solvent is 20% ~ 30% of trichloromethyl substituted benzene weight.
4. the method according to any one of claim 1-3, it is characterized in that, the molar ratio of described trichloromethyl substituted benzene and corresponding aromatic acid is 1:1 ~ 1:1.1, and the molar ratio of preferred trichloromethyl substituted benzene and corresponding aromatic acid is 1:1.01 ~ 1:1.03; Or the molar ratio of described trichloromethyl substituted benzene and water is 1:2 ~ 1:2.2, preferred 1:2.03 ~ 1:2.05.
5. the method according to any one of claim 1-4, is characterized in that, the catalyzer of described reaction is Lewis acid, preferred iron trichloride; Especially, step I) in for trichloromethyl substituted benzene react to water time preferably also there is a small amount of corresponding aromatic acid.
6. the method according to any one of claim 1-5, is characterized in that, described step 1) in catalyst charge be 0.01% ~ 10% of trichloromethyl substituted benzene weight, be preferably trichloromethyl substituted benzene weight 0.2% ~ 0.3%.
7. the method according to any one of claim 1-6, is characterized in that, described for trichloromethyl substituted benzene aromatic acid corresponding to it react in the presence of a catalyst time, step 2) in temperature of reaction be 40 ~ 300 DEG C, preferably 85 ~ 120 DEG C; And/or the reaction times is 0.5 ~ 4h, preferably 0.8 ~ 2.5h;
Or described for trichloromethyl substituted benzene and water react in the presence of a catalyst time, step 2) in temperature of reaction be 50 ~ 180 DEG C, preferably 70 ~ 140 DEG C; And/or the reaction times is 0.5 ~ 5h, preferably 0.8 ~ 3.5h.
8. method according to claim 7, it is characterized in that, described trichloromethyl substituted benzene is two (trichloromethyl) benzene, when its corresponding phthalic acid reacts in the presence of a catalyst, step 2) in temperature of reaction be 50 ~ 300 DEG C, preferably 70 ~ 160 DEG C, more preferably 110 ~ 120 DEG C; And/or the reaction times is 0.8 ~ 1.6h, preferably 1.0 ~ 1.3h;
Or described trichloromethyl substituted benzene is two (trichloromethyl) benzene, when reacting in the presence of a catalyst with water, step 2) in temperature of reaction be 50 ~ 150 DEG C, preferably 70 ~ 130 DEG C, more preferably 80 ~ 110 DEG C; And/or the reaction times is 0.5 ~ 2h, preferably 0.8 ~ 1.2h;
Or described trichloromethyl substituted benzene is to chlorine (trichloromethyl) benzene, when reacting in the presence of a catalyst with Chlorodracylic acid, step 2) in temperature of reaction be 40 ~ 200 DEG C, preferably 70 ~ 130 DEG C; And/or the reaction times is 0.7 ~ 1.5h, preferably 0.9 ~ 1.2h;
Or described trichloromethyl substituted benzene is to chlorine (trichloromethyl) benzene, when reacting in the presence of a catalyst with water, step 2) in temperature of reaction be 50 ~ 150 DEG C, preferably 70 ~ 130 DEG C; And/or reaction times 0.5 ~ 2h, preferably 0.8 ~ 1.3h;
Or described trichloromethyl substituted benzene is equal three (trichloromethyl) benzene, when reacting in the presence of a catalyst with trimesic acid, step 2) in temperature of reaction be 60 ~ 300 DEG C, preferably 120 ~ 160 DEG C; And/or the reaction times is 0.5 ~ 4h, preferably 1 ~ 2.5h;
Or described trichloromethyl substituted benzene is equal three (trichloromethyl) benzene, when reacting in the presence of a catalyst with water, step 2) in temperature of reaction be 60 ~ 180 DEG C, preferably 95 ~ 140 DEG C; And/or reaction times 0.5 ~ 5h, preferably 1 ~ 3.5h;
Or described trichloromethyl substituted benzene is benzenyl trichloride, when reacting in the presence of a catalyst with phenylformic acid, step 2) in temperature of reaction be 60 ~ 150 DEG C, preferably 100 ~ 120 DEG C; And/or the reaction times is 0.5 ~ 1.5h, preferably 0.9 ~ 1.1h;
Or described trichloromethyl substituted benzene is benzenyl trichloride, when reacting in the presence of a catalyst with water, step 2) in temperature of reaction be 70 ~ 130 DEG C, preferably 95 ~ 110 DEG C; And/or reaction times 0.6 ~ 1.5h, preferably 0.9 ~ 1.2h.
9. the method according to any one of claim 1-8, is characterized in that, to described step 2) gas that produces in reaction carries out condensation process, and the backflow of the phlegma that obtains enters reactive system; Noncondensable gas optionally carries out further vent gas treatment after discharging.
10. method according to claim 9, is characterized in that, to described step 2) reaction in produce gas carry out condensed in two stages process.
11. methods according to claim 10, is characterized in that, described in when carrying out condensed in two stages process, the condensing temperature of one-level condensation is the arbitrary temperature in the boiling point lower than chloroformyl substituted benzene, the interval range higher than the fusing point of chloroformyl substituted benzene; The condensing temperature of B-grade condensation is the fusing point 5 ~ 30 DEG C lower than chloroformyl substituted benzene, preferably lower than the fusing point 10 ~ 20 DEG C of chloroformyl substituted benzene.
The continuous production device of 12. 1 kinds of chloroformyl substituted benzenes; comprise feed proportioning system, reactive system, condenser system; it is characterized in that; described reactive system comprises more than the 2 grades reactors be connected in series; described condenser system is composed in series by two-stage or the above condenser of two-stage; in described reactive system, the opening for feed of first step reactor is connected with the discharge port of feed proportioning system; in described reactive system, the pneumatic outlet of each stage reactor is connected with condenser system import, is connected with liquid returning tube between any reactor in the condensate outlet of described condenser system and reactive system.
13. devices according to claim 12, is characterized in that, described condenser system is composed in series by condensed in two stages device, comprise first-stage condenser and secondary condenser, wherein first-stage condenser is single condenser, and secondary condenser is that two condensers compose in parallel.
14. devices according to claim 12 or 13, it is characterized in that, comprise exhaust treatment system further, exhaust treatment system is connected with the noncondensable gas relief outlet of described condenser system.
15. devices according to any one of claim 12-14, it is characterized in that, comprise purification system further, purification system is connected with the discharge port of last step reactor in described reactive system.
16. devices according to any one of claim 12-15, it is characterized in that, described reactive system comprises 2 ~ 10 grades of reactors be connected in series, and preferably includes 2 ~ 5 grades of reactors be connected in series.
17. devices according to any one of claim 12-16, is characterized in that, described feed proportioning system, comprise more than 2 batching kettles, in parallel or be connected in series, and preferably include two batching kettles and are connected in series.
18. devices according to any one of claim 14-17, is characterized in that described exhaust treatment system comprises gas buffer tank, is connected with the catalytic oxidation of hydrogen chloride reaction unit after preferred surge tank.
19. devices according to any one of claim 15-18, it is characterized in that, described purification system is general purification device, such as vacuum distillation apparatus, rectifier unit, molecular distillation apparatus or recrystallization device.
20. devices according to any one of claim 15-19, it is characterized in that, can also comprise product groove, product groove is connected in the middle of described reactive system and described purification system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510073134.0A CN104592012A (en) | 2015-02-11 | 2015-02-11 | Continuous production method and device for chloroformyl substituted benzenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510073134.0A CN104592012A (en) | 2015-02-11 | 2015-02-11 | Continuous production method and device for chloroformyl substituted benzenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104592012A true CN104592012A (en) | 2015-05-06 |
Family
ID=53118122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510073134.0A Pending CN104592012A (en) | 2015-02-11 | 2015-02-11 | Continuous production method and device for chloroformyl substituted benzenes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104592012A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104998513A (en) * | 2015-07-21 | 2015-10-28 | 苏州市兴鲁空分设备科技发展有限公司 | Carbon dioxide rectification emission-reducing process and apparatus thereof |
| CN108191646A (en) * | 2018-01-08 | 2018-06-22 | 江苏振方生物化学有限公司 | A kind of preparation process for recycling parachlorobenzoic-acid parachlorobenzoyl chloride |
| CN110665449A (en) * | 2019-09-26 | 2020-01-10 | 保定加合精细化工有限公司 | Equipment for continuously producing ethylene sulfide |
| CN113307735A (en) * | 2021-05-07 | 2021-08-27 | 江苏方圆芳纶研究院有限公司 | Novel recrystallization process of phthaloyl chloride and bis (trichloromethyl) benzene |
| CN114516780A (en) * | 2021-12-21 | 2022-05-20 | 宿迁市科莱博生物化学有限公司 | Preparation method of 3,4, 5-trifluorobromobenzene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508115A (en) * | 2002-12-13 | 2004-06-30 | 上海群力化工有限公司 | High-purity benzoyl chloride synthesizing process |
| CN102976918A (en) * | 2011-09-05 | 2013-03-20 | 三菱瓦斯化学株式会社 | Making method for aromatic polycarboxylic acid polyacylchloride |
| CN104230612A (en) * | 2014-09-30 | 2014-12-24 | 烟台裕祥精细化工有限公司 | Continuous synthesis device and synthesis method for acyl chloride |
-
2015
- 2015-02-11 CN CN201510073134.0A patent/CN104592012A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508115A (en) * | 2002-12-13 | 2004-06-30 | 上海群力化工有限公司 | High-purity benzoyl chloride synthesizing process |
| CN102976918A (en) * | 2011-09-05 | 2013-03-20 | 三菱瓦斯化学株式会社 | Making method for aromatic polycarboxylic acid polyacylchloride |
| CN104230612A (en) * | 2014-09-30 | 2014-12-24 | 烟台裕祥精细化工有限公司 | Continuous synthesis device and synthesis method for acyl chloride |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104998513A (en) * | 2015-07-21 | 2015-10-28 | 苏州市兴鲁空分设备科技发展有限公司 | Carbon dioxide rectification emission-reducing process and apparatus thereof |
| CN104998513B (en) * | 2015-07-21 | 2017-07-21 | 苏州市兴鲁空分设备科技发展有限公司 | Carbon dioxide rectifying emission-reducing process and device |
| CN108191646A (en) * | 2018-01-08 | 2018-06-22 | 江苏振方生物化学有限公司 | A kind of preparation process for recycling parachlorobenzoic-acid parachlorobenzoyl chloride |
| CN110665449A (en) * | 2019-09-26 | 2020-01-10 | 保定加合精细化工有限公司 | Equipment for continuously producing ethylene sulfide |
| CN113307735A (en) * | 2021-05-07 | 2021-08-27 | 江苏方圆芳纶研究院有限公司 | Novel recrystallization process of phthaloyl chloride and bis (trichloromethyl) benzene |
| CN114516780A (en) * | 2021-12-21 | 2022-05-20 | 宿迁市科莱博生物化学有限公司 | Preparation method of 3,4, 5-trifluorobromobenzene |
| CN114516780B (en) * | 2021-12-21 | 2024-03-29 | 科莱博(江苏)科技股份有限公司 | Preparation method of 3,4, 5-trifluoro-bromobenzene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104592012A (en) | Continuous production method and device for chloroformyl substituted benzenes | |
| CN108752161B (en) | Method for synthesizing monochloro-o-xylene in continuous flow microchannel reactor | |
| CN102093209A (en) | Method for preparing aromatic dimethyl chloride | |
| CN108794321A (en) | The method that aromatic carboxylic-acid compound is synthesized in continuous flow micro passage reaction | |
| CN108997284B (en) | Method for synthesizing chlorophthalic anhydride in continuous flow micro-channel reactor | |
| CN104829415B (en) | A kind of method synthesizing hexafluoro-1,3-butadiene | |
| CN103819337B (en) | A kind of trifunctional pentaerythritol acrylate preparation method | |
| CN103342642B (en) | Process for continuously producing dimethyl adipate through reaction-rectification method | |
| CN108610314B (en) | Method for synthesizing biphenyl dianhydride in continuous flow microchannel reactor | |
| CN108997285B (en) | Method for synthesizing benzophenone tetracarboxylic dianhydride in continuous flow microchannel reactor | |
| CN103570760B (en) | Hydroxy ethylene diphosphonic acid production unit and method thereof | |
| CN107488108B (en) | Synthesis method of chlorophenoxyacetic acid or chlorophenol | |
| CN103755520A (en) | Method for producing substituted benzyl alcohol, substituted benzaldehyde and substituted benzyl acid through oxidizing substituted methylbenzene with air based on gas-liquid-solid heterogeneous reaction separation synchronization reactor | |
| CN104513161A (en) | Preparation method of pentaerythritol tetraacrylate mixture | |
| CN104591958B (en) | The method and apparatus of continuous prodution trichloromethyl substituted benzene | |
| CN104478698B (en) | A kind of method of continuous seepage stearyl chloride | |
| CN1332922C (en) | Method for synthesizing 2,2 dimethyl-3-(2,2-ethylene dichloride) cyclopropane carboxyacyl chloride | |
| CN110229129A (en) | A kind of device and method thereof preparing 4- chloride anhydride | |
| CN110922313A (en) | Method for continuously producing aromatic ketone | |
| CN110790631B (en) | Device for producing fluorinated alkane through liquid phase method pipelining continuous separation | |
| CN111004086A (en) | Continuous production process of 1-chloro-3-methyl-2-butene | |
| CN109364869A (en) | A kind of device of gas-liquid countercurrent method continuous production chloro thing | |
| CN110746264B (en) | Device for continuously synthesizing fluoroalkane in pipeline manner by liquid phase method | |
| CN109096057A (en) | A kind of technical process of tower continuous chlorination production parachlorophenol | |
| CN201793508U (en) | Device for producing dichloroethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150506 |
|
| RJ01 | Rejection of invention patent application after publication |