CN103524291B - A kind of method for continuously synthesizing of chloroparaffin - Google Patents
A kind of method for continuously synthesizing of chloroparaffin Download PDFInfo
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- CN103524291B CN103524291B CN201310428106.7A CN201310428106A CN103524291B CN 103524291 B CN103524291 B CN 103524291B CN 201310428106 A CN201310428106 A CN 201310428106A CN 103524291 B CN103524291 B CN 103524291B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a kind of method for continuously synthesizing of chloroparaffin, comprise the following steps: (1) adds the mixture of tetracol phenixin and iron powder in the reactor, described volume of mixture is 10 ~ 30% of reactor volume, and in mixture, the mass ratio of tetracol phenixin and iron powder is 1:0.1 ~ 1; (2) to reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 40 ~ 50:1 and the mixture of catalyzer, and to control temperature of reaction be 90 ~ 150 DEG C, by passing into alkene to reactor continuously from reactor bottom, to control reaction pressure be that 0.5 ~ 1.2MPa reacts simultaneously; (3) to collect from the reaction solution of reactor top overflow and namely rectifying obtain chloroparaffin product.The present invention has simple to operate, and facility investment is few, and production efficiency is high, catalyzer does not need the advantage being separated reusable edible.
Description
Technical field
The present invention relates to a kind of method for continuously synthesizing of chloroparaffin.
Background technology
Tetracol phenixin is the byproduct producing methane chloride, is prohibited for clean-out system as Ozone Depleting Substances.The way solving the outlet of a large amount of tetracol phenixin the most feasible is exactly as industrial chemicals, is converted into non-ODS material.Tetracol phenixin and alkene carry out telomerization, generate chloroparaffin, then fluoridize further as fluoric ether, be widely adopted.This synthetic method must just can be carried out in the presence of a catalyst, and bibliographical information is more, and catalyzer mainly contains superoxide, metal inorganic salt and nitrile, metal carbonyl, alkyl phosphite and metal chloride etc.
Superoxide is as catalyzer, and telomerization is too violent, restive, has explosion hazard, should not carry out industrialization; Metal inorganic salt and nitrile catalyst system, need just can obtain higher product yield at low pressures, do not possess industrialization prospect; Metal carbonyl is expensive, and toxicity is large, is difficult to industrialization; There is the degree of depth and telomerize in alkyl phosphite and metal chloride catalyst system, easily generates a large amount of tarry superpolymer, reduces equipment heat transfer efficiency, waste raw material.After researchist improves alkyl phosphite and metal chloride catalyst system, have developed with the catalyst system of alkyl phosphite and reduced iron powder to prepare chloroparaffin, alleviate the degree that the degree of depth telomerizes, under lower temperature, pressure, also can obtain higher yields.
But preparing chloroparaffin with the catalyst system of alkyl phosphite and reduced iron powder in prior art is all based on autoclave rhythmic reaction, have that facility investment is large, technique is loaded down with trivial details, reaction efficiency is low, the shortcomings such as the difficult recovery of catalyzer, greatly hinder industrialization process.
As US Patent No. 6313360 discloses the preparation method of 1,1,1,3,3-pentachloropropane (HCC-240fa), in lining tetrafluoroethylene autoclave, with iron powder and tributyl phosphate for catalyst preparing 1,1,1,3,3-pentachloropropane, the reaction times reaches 9 hours.Weak point is this reaction is batch production, complex operation, long reaction time, and production efficiency is low; Lining tetrafluoroethylene autoclave manufacturing expense is high; During iron powder dispersed and catalyst recovery in the solution, the problem of occluding device and pipeline not easily solves.
Summary of the invention
The object of the invention is the defect overcoming above-mentioned prior art, provide a kind of simple to operate, facility investment is few, the continuous synthesis technique that production efficiency is high, catalyzer does not need the chloroparaffin being separated reusable edible.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of method for continuously synthesizing of chloroparaffin, comprises the following steps:
(1) add the mixture of tetracol phenixin and iron powder in the reactor, described volume of mixture is 10 ~ 30% of reactor volume, and in mixture, the mass ratio of tetracol phenixin and iron powder is 1:0.1 ~ 1;
(2) to reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 40 ~ 50:1 and the mixture of catalyzer, and to control temperature of reaction be 90 ~ 150 DEG C, by passing into alkene to reactor continuously from reactor bottom, to control reaction pressure be that 0.5 ~ 1.2MPa reacts simultaneously;
(3) to collect from the reaction solution of reactor top overflow and namely rectifying obtain chloroparaffin product.
Further:
Iron powder order number described in step (1) is 100 ~ 500.
Volume of mixture described in step (1) is 15 ~ 25% of reactor volume.
The mass ratio of the tetracol phenixin described in step (1) and iron powder is 1:0.3 ~ 0.5.
Temperature of reaction described in step (2) is 110 ~ 120 DEG C, and reaction pressure is 0.8 ~ 1.0MPa.
The mol ratio of the tetracol phenixin described in step (2) and catalyzer is 45 ~ 47:1.
Catalyzer described in step (2) is the one in triethyl phosphate, triethyl-phosphite, n-Butyl Amine 99, Isopropylamine.
Alkene described in step (2) is the one in ethene, vinylchlorid, vinylidene chloride, vinylbenzene.
In reaction process, in order to iron powder can be allowed to be in recurrent state, fully to contact with the catalyzer that bottom adds continuously, preferably in reaction process, the reaction solution in reactor is drawn from reactor bottom and turn back to reactor from top again, circulate.
In a preferred embodiment of the invention, in reaction process, the reaction solution containing iron powder is drawn by reactor bottom, after recycle pump circulates, squeeze into reactor again, to reaction system, add the mixture of tetracol phenixin, catalyzer and alkene simultaneously from reactor bottom continuously.Iron powder slowly declines under gravity, under the catalyzer co-catalysis added with bottom, tetracol phenixin and olefine reaction, generate chloroparaffin, reaction solution is drawn continuously finally by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin recycled, obtain chloroparaffin product, carrying out continuously of realization response simultaneously.The present invention has simple to operate, and facility investment is few, and production efficiency is high, catalyzer does not need the advantage being separated reusable edible.
When reacting beginning, first add tetracol phenixin, iron mixture that volume is 10 ~ 30% of reactor volume, and make iron powder be in recurrent state, iron powder can be made fully to contact with material and from the liquid catalyst that reactor bottom adds continuously, improve the efficiency of reaction.The mass ratio of tetracol phenixin and iron powder is 1:0.1 ~ 1, preferred 1:0.3 ~ 0.5.It is suitable that iron particle size will be selected, and excessive then surface-area is little, and catalyst effect is poor, too small then unsuitable sedimentation, and cause catalyzer to run off from overflow port with product, general order number selects 100 ~ 500, and preferably 200 ~ 300.
The continuous synthesis of temperature of reaction on chloroparaffin has important impact.Temperature is too low, then speed of response is too slow, and a large amount of alkene unreacted, causes the waste of material; Temperature of reaction is too high, then aggravate side reaction.Therefore, in the present invention, temperature of reaction controls at 90 ~ 150 DEG C, preferably 110 ~ 120 DEG C.
In reaction process, catalyzer, in continuous decomposition, needs to keep there are enough catalyzer in reaction solution, reaction just can be made constantly to carry out.Therefore, in the present invention, the mol ratio of tetracol phenixin and catalyzer is 40 ~ 50:1, preferably 45 ~ 47:1.
Reaction pressure in the present invention is that the amount of alkene by passing into reactor controls, when pass into reactor alkene amount very little time, reaction pressure is too low, and the density loss of alkene in reaction system, causes speed of reaction to decline, the efficiency of impact reaction; When the amount of the alkene passing into reactor is too many, reaction pressure is too high, and the concentration of alkene in reaction system rises, and cause speed of reaction too fast, temperature should not control, and local temperature is too high, and by product increases.Therefore, it is 0.5 ~ 1.2MPa that the intake by controlling alkene in the present invention makes reaction pressure control, and is preferably 0.8 ~ 1.0MPa.
Reactor material of the present invention can adopt the material such as carbon steel, stainless steel, the reactor types that reactor types can adopt this areas such as tower, autoclave conventional.
Compared with prior art, the present invention has the following advantages:
1, simple to operate, facility investment is few, and production efficiency is high, achieves operate continuously, and catalyzer does not need to be separated reusable edible, is applicable to large-scale industrial production;
2, reaction yield is high, and selectivity is good, and yield reaches as high as 89.3%, and selectivity reaches as high as 99.7%.
Embodiment
By the following examples more specific description is carried out to the present invention, but the present invention is not limited to described embodiment.
Embodiment 1:
Be with at volume 10L in the stainless steel reactor of outer circulation, add 2L tetracol phenixin, 300 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.3.Start recycle pump, the reaction solution containing iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 47:1 and the mixed solution of triethyl-phosphite, heating up and controlling temperature of reaction is 100 DEG C, and pass through to reactor, to pass into ethene control reaction pressure continuously from reactor bottom is that 1.0MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro bromopropane product simultaneously, 1,1,1,3-tetrachloro propane recovering rate 85.3%, selectivity 97.6%.
Embodiment 2:
Be with at volume 10L in the stainless steel reactor of outer circulation, add 2L tetracol phenixin, 500 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.1.Start recycle pump, the reaction solution containing iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 40:1 and the mixed solution of triethyl-phosphite, heating up and controlling temperature of reaction is 120 DEG C, and pass through to reactor, to pass into ethene control reaction pressure continuously from reactor bottom is that 1.2MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro bromopropane product simultaneously, 1,1,1,3-tetrachloro propane recovering rate 83.7%, selectivity 93.6%.
Embodiment 3:
Be with at volume 10L in the stainless steel reactor of outer circulation, add 1L tetracol phenixin, 400 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.8.Start recycle pump, the reaction solution containing iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 50:1 and the mixed solution of triethyl-phosphite.Heating up and controlling temperature of reaction is 150 DEG C, and pass through to reactor, to pass into ethene control reaction pressure continuously from reactor bottom is that 0.5MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro bromopropane product simultaneously, 1,1,1,3-tetrachloro propane recovering rate 83.7%, selectivity 90.1%.
Embodiment 4:
Be with at volume 10L in the stainless steel reactor of outer circulation, add 2L tetracol phenixin, 100 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:1.Start recycle pump, the reaction solution containing iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 45:1 and the mixed solution of triethyl-phosphite.Heating up and controlling temperature of reaction is 90 DEG C, and pass through to reactor, to pass into ethene control reaction pressure continuously from reactor bottom is that 0.8MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro bromopropane product simultaneously, 1,1,1,3-tetrachloro propane recovering rate 89.3%, selectivity 98.2%.
Embodiment 5:
Be with at volume 10L in the carbon steel reactor of outer circulation, add 3L tetracol phenixin, 200 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.7.Start recycle pump, the reaction solution containing iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 45:1 and the mixed solution of triethyl-phosphite, heating up and controlling temperature of reaction is 110 DEG C, and pass through to reactor, to pass into ethene control reaction pressure continuously from reactor bottom is that 1.1MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3-tetrachloro bromopropane product simultaneously, 1,1,1,3-tetrachloro propane recovering rate 84.3%, selectivity 97.5%.
Embodiment 6:
Be with at volume 10L in the carbon steel reactor of outer circulation, add 1.5L tetracol phenixin, 200 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.3.Start recycle pump, the reaction solution containing iron powder is drawn by reactor bottom, after recycle pump pressurization, then squeeze into reactor since reactor head.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 46:1 and the mixed solution of triethyl phosphate, heating up and controlling temperature of reaction is 120 DEG C, and pass through to reactor, to pass into vinylidene chloride control reaction pressure continuously from reactor bottom is that 0.9MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3,3,3-chlordene bromopropane product simultaneously, 1,1,1,3,3,3-chlordene propane recovering rate 84.6%, selectivity 99.5%.
Embodiment 7:
Be with at volume 10L in the carbon steel reactor of outer circulation, add 2L tetracol phenixin, 250 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.5.Start recycle pump, drawn by the reaction solution containing iron powder by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head, heating up and controlling temperature of reaction is 100 DEG C.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 45:1 and the mixed solution of triethyl phosphate, and pass through to reactor, to pass into vinylchlorid control reaction pressure continuously from reactor bottom is that 0.8MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,1,1,3,3-pentachloropropane product simultaneously, 1,1,1,3,3-pentachloropropane yield 88.5%, selectivity 99.7%.
Embodiment 8:
Be with at volume 10L in the stainless steel reactor of outer circulation, add 2.5L tetracol phenixin, 300 order iron mixtures, the mass ratio of tetracol phenixin and iron powder is 1:0.4.Start recycle pump, drawn by the reaction solution containing iron powder by reactor bottom, after recycle pump pressurization, then squeeze into reactor from reactor head, heating up and controlling temperature of reaction is 110 DEG C.To reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 47:1 and the mixed solution of triethyl phosphate.Pass through to reactor, to pass into vinylbenzene control reaction pressure continuously from reactor bottom is that 1.0MPa reacts simultaneously.Reaction solution is drawn continuously by reactor top overflow port, through rectifying, reclaims unreacted tetracol phenixin, obtains 1,3,3,3-tetra-chloro-3-phenyl-propane product simultaneously, 1,3,3,3-tetra-chloro-3-phenyl-propane yield 85.3%, selectivity 99.4%.
Claims (4)
1. a method for continuously synthesizing for chloroparaffin, is characterized in that, comprises the following steps:
(1) add the mixture of tetracol phenixin and iron powder in the reactor, described volume of mixture is 15 ~ 25% of reactor volume, and in mixture, the mass ratio of tetracol phenixin and iron powder is 1:0.3 ~ 0.5, and iron powder order number is 100 ~ 500;
(2) to reactor, adding mol ratio continuously from reactor bottom is the tetracol phenixin of 45 ~ 47:1 and the mixture of catalyzer, and to control temperature of reaction be 90 ~ 150 DEG C, pass through to reactor, to pass into alkene control reaction pressure continuously from reactor bottom is that 0.5 ~ 1.2MPa reacts simultaneously, being drawn from reactor bottom by reaction solution in reactor in reaction process turns back to reactor from top again, circulates;
(3) to collect from the reaction solution of reactor top overflow and namely rectifying obtain chloroparaffin product.
2. the method for continuously synthesizing of chloroparaffin according to claim 1, it is characterized in that the temperature of reaction described in step (2) is 110 ~ 120 DEG C, reaction pressure is 0.8 ~ 1.0MPa.
3. the method for continuously synthesizing of chloroparaffin according to claim 1, is characterized in that the catalyzer described in step (2) is the one in triethyl phosphate, triethyl-phosphite, n-Butyl Amine 99, Isopropylamine.
4. the method for continuously synthesizing of chloroparaffin according to claim 1, is characterized in that the alkene described in step (2) is the one in ethene, vinylchlorid, vinylidene chloride, vinylbenzene.
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| CN105218299B (en) * | 2015-09-30 | 2020-03-31 | 巨化集团技术中心 | Continuous preparation method for producing chlorohydrocarbon from carbon tetrachloride and olefin |
| CN105622330A (en) * | 2016-01-26 | 2016-06-01 | 巨化集团技术中心 | Continuous preparation method of chlorohydrocarbons |
| CN114835554B (en) * | 2021-02-02 | 2024-12-20 | 中国科学院宁波材料技术与工程研究所 | A preparation method of 1,1,1,3-tetrachloropropane |
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| CN101362070A (en) * | 2007-08-09 | 2009-02-11 | 宏大化纤技术装备有限公司 | Reaction device with outer circulation device and method for controlling the reaction process |
| CN101558031A (en) * | 2006-10-11 | 2009-10-14 | 霍尼韦尔国际公司 | Process for the manufacture of 1,1,1,3,3-pentachloropropane |
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| EP2463261A3 (en) * | 2009-06-24 | 2012-12-19 | Tokuyama Corporation | Process of making a chlorinated hydrocarbon |
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| CN101558031A (en) * | 2006-10-11 | 2009-10-14 | 霍尼韦尔国际公司 | Process for the manufacture of 1,1,1,3,3-pentachloropropane |
| CN101362070A (en) * | 2007-08-09 | 2009-02-11 | 宏大化纤技术装备有限公司 | Reaction device with outer circulation device and method for controlling the reaction process |
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