CN103755740A - Process for producing 2-chloroethylphosphonicacid through continuous pressurization method - Google Patents
Process for producing 2-chloroethylphosphonicacid through continuous pressurization method Download PDFInfo
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Abstract
The present invention discloses a process for producing 2-chloroethylphosphonicacid through a continuous pressurization method. The process comprises that: pressurized 2-chloroethylphosphonicacid bis(2-chloroethyl)ester is continuously added from the top of a first-stage acidolysis reaction kettle (1), pressurized hydrogen chloride gas is introduced from the bottom of a second-stage acidolysis reaction kettle (2), the hydrogen chloride tail gas discharged from the top of the second-stage acidolysis reaction kettle (2) is treated by a second-stage condenser (4) and then is introduced into the bottom of the first-stage acidolysis reaction kettle (1), the tail gas discharged from the first-stage acidolysis reaction kettle (1) is treated by a condenser (3) and then is subjected to a purification treatment so as to be recovered and applied for the second-stage acidolysis reaction kettle (2), external circulation static mixing devices of the first-stage acidolysis reaction kettle (1) and the second-stage acidolysis reaction kettle (2) are opened during a reaction process, and the 2-chloroethylphosphonicacid product can be continuously obtained from the bottom of the second-stage acidolysis reaction kettle (2). According to the present invention, the high quality 2-chloroethylphosphonicacid can be prepared, and good economic benefits and good social benefits are provided.
Description
(1) technical field
The present invention relates to the novel process that 2 chloroethyl phosphoric acid is produced in a kind of serialization pressurization.
(2) background technology
The commodity ethrel by name of 2 chloroethyl phosphoric acid, is a plant growth regulators, is widely used on the crops such as cotton, rubber, tomato, wheat, paddy rice.The production technique of early stage domestic ethrel is relatively backward, generally adopt normal pressure or negative pressure method to produce, as Chinese patent CN1048043A adopts negative pressure (100-400mmHg), in 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester solution, pass into hydrogen chloride gas, be heated to 160-170 ℃, react 12-15 hour, make the ethrel product of content 75% left and right.Recent year has been studied intermittent pressurized method and has been produced ethrel technique, ethrel content is enhanced, as Chinese patent CN101274944A has reported the method for a kind of intermittent pressurized legal system for ethrel, the method, by hydrogen chloride tail gas control pressure 0.4-0.7MPa, is reacted discharging in 6-18 hour and can be made the ethrel that purity is 80%-90%.Chinese patent CN102766161A has reported a kind of method of preparing ethrel, and the method, in the withstand voltage reactor of 0.05-0.40MPa, is reacted 5-16 hour, and it is 89%-95% that discharging can make ethrel purity, and its yield is 89%.At present, it is all that intermittent pressurized method is produced that the method that existing report technology adopts is prepared ethrel, randomness is very large, be difficult to the stable ethrel product that obtains high-content, yield is on the low side, meanwhile, at high temperature raw material and ethrel product time length longer, cause side reaction under high temperature and the impurity ethylene vinyl profit (H that produces
2c=CHPO (OH)
2) higher, generally all can be greater than 3%, ethylene vinyl profit can be to making the chemical substance of deposits yields poisoning in ethrel field is used, and in the former medicine of high-quality ethrel of China's export, this impurity should be controlled in 0.5%.Therefore, adopt current intermittent pressurized legal system for ethrel, be difficult to obtain the high-quality ethrel product of high-content, low impurity.
(3) summary of the invention
Technical problem solved by the invention is to provide a kind of serialization pressurization to produce the novel process of the 2 chloroethyl phosphoric acid of high-content, low impurity, and this explained hereafter cost is low, and processing unit is simple, is suitable for industrialization.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
A kind of serialization pressurization is produced the technique of 2 chloroethyl phosphoric acid (II), and the device of described process using comprises primary acids solution reaction kettle, first-stage condenser, secondary acidolysis reaction still and secondary condenser; Described primary acids solution reaction kettle and secondary acidolysis reaction still are furnished with respectively an outer circulation static mixer, the enamel pipe that described outer circulation static mixer is in-built filler, the optional one in polytetrafluoroethylene packing, ceramic corrugated filler, ceramic raschig rings filler of described filler, the bottom of described primary acids solution reaction kettle or secondary acidolysis reaction still is connected with the bottom of outer circulation static mixer by recycle pump, and the top of described primary acids solution reaction kettle or secondary acidolysis reaction still is connected with the top of outer circulation static mixer;
Described technique comprises:
In primary acids solution reaction kettle, add continuously raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of pressurization and the hydrogen chloride tail gas A from secondary condenser, make the outer circulation static mixer of primary acids solution reaction kettle be held open state, controlling primary acids solution reaction kettle internal pressure and be 0.3 ~ 1.0MPa, temperature is 120 ~ 200 ℃ and carries out successive reaction, the tail gas that reaction produces passes into first-stage condenser condensation and reclaims after ethylene dichloride, after the excessive purified processing of hydrogen chloride tail gas B the more compressed hydrogen chloride gas recycled that obtains pressurization in secondary acidolysis reaction still, the 2 chloroethyl phosphoric acid crude product that reaction obtains flows out and enters secondary acidolysis reaction still continuously from the bottom of primary acids solution reaction kettle, toward secondary acidolysis reaction still, pass into continuously the hydrogen chloride gas of pressurization simultaneously, make the outer circulation static mixer of secondary acidolysis reaction still be held open state, controlling secondary acidolysis reaction still internal pressure is 0.3 ~ 1.0MPa, temperature is 120 ~ 200 ℃ makes unreacted raw material in 2 chloroethyl phosphoric acid crude product fully react with hydrogenchloride, from secondary acidolysis reaction still bottom, obtain continuously 2 chloroethyl phosphoric acid product, the tail gas that reaction produces passes into secondary condenser, condensation is reclaimed the excessive hydrogen chloride tail gas A obtaining after ethylene dichloride and is passed into continuously primary acids solution reaction kettle.
In the present invention, because the reaction in firsts and seconds acidolysis reaction still is all to carry out under pressurized conditions, therefore need carry out pressure treatment can pass into reactor to the raw material adding (raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester and hydrogen chloride gas).Wherein, the content of 2 chloroethyl phosphoric acid two in raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester-(2-chloroethyl) ester is more than 90%, the two ethyl esters of phosphonic acids shown in formula (III) (2-chloroethyl) (abbreviation dipolymer) are 4% ~ 6%, this dipolymer is carried out acidolysis reaction with hydrogenchloride under pressurized conditions, can make equally 2 chloroethyl phosphoric acid, reaction equation is as follows:
Side reaction equation is:
In the present invention, the purity of the hydrogen chloride gas passing into continuously in secondary acidolysis reaction still is generally more than 99.9%, and the hydrogen chloride tail gas B that the tail gas of discharging in primary acids solution reaction kettle and secondary acidolysis reaction still obtains through condensation process and hydrogen chloride tail gas A are except hydrogenchloride, also unavoidably there is moisture and ethylene dichloride, general hydrogen chloride content more than 97%, ethylene dichloride content below 3%, moisture content is below 800ppm.Due to will be by hydrogen chloride tail gas B reuse to secondary acidolysis reaction still, and reaction in secondary acidolysis reaction still carries out under certain pressure, therefore must utilize compressor to pressurize to pass into secondary acidolysis reaction still to gas.Due under current contractive condition, if be mixed with the ethylene dichloride of 3% left and right in gas to be compressed, can there is explosion safety risk in compression process, and the hydrogen chloride gas of moisture 800ppm corrosion is simultaneously very serious, compressor material corrosion resistance problem can not solve at present, cannot compress.Therefore, hydrogen chloride tail gas B needs to be purified to process to obtaining and reaches required purity requirement (general hydrogen chloride content is more than 99.9% before recycled, ethylene dichloride content is below 10ppm, and moisture content is below 5ppm) hydrogen chloride gas just can carry out recycled.
In technique of the present invention, reaction raw materials need make hydrogen chloride gas excessive when feeding intake, generally making the mol ratio of the hydrogen chloride gas passing in 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester of adding in primary acids solution reaction kettle in the unit time and secondary acidolysis reaction still is 1:2.50-6.50, is preferably 1:4.00 ~ 6.00.
In technique of the present invention, preferably control primary acids solution reaction kettle internal pressure and be 0.40 ~ 0.60MPa, temperature and be 140 ~ 160 ℃ and carry out successive reaction; Preferably controlling secondary acidolysis reaction still internal pressure and be 0.40 ~ 0.60MPa, temperature is 140 ~ 160 ℃ and carries out successive reaction.
In the present invention, in order to guarantee that the 2 chloroethyl phosphoric acid product finally obtaining has the feature of high-content, low impurity from secondary acidolysis reaction still, preferably control the content that flows out 2 chloroethyl phosphoric acid in the 2 chloroethyl phosphoric acid crude product entering secondary acidolysis reaction still continuously from the bottom of primary acids solution reaction kettle more than 80%, in order to take into account production efficiency, in preferred 2 chloroethyl phosphoric acid crude product, the content of 2 chloroethyl phosphoric acid is 80 ~ 85% simultaneously.
Technique of the present invention is a continuous process, the product ethrel crude product of primary acids solution reaction kettle is as the reaction raw materials of secondary acidolysis reaction still, and the tail gas that the reaction of secondary acidolysis reaction still produces simultaneously becomes again the reaction raw materials of primary acids solution reaction kettle after condensation process.For starting this successive processes, those skilled in the art can adopt some preposition steps first to obtain ethrel crude product or hydrogen chloride tail gas A according to practical situation, the present invention is concrete recommends the described following preposition step of process using: first toward disposable 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester that adds respectively in primary acids solution reaction kettle and secondary acidolysis reaction still, and toward the hydrogen chloride gas that passes into continuously pressurization in secondary acidolysis reaction still, controlling secondary acidolysis reaction still internal pressure is that 0.3 ~ 1.0MPa(is preferably 0.40 ~ 0.60MPa), temperature is that 120 ~ 200 ℃ (being preferably 140 ~ 160 ℃) react, the tail gas that reaction produces passes into secondary condenser, condensation is reclaimed the excessive hydrogen chloride tail gas A obtaining after ethylene dichloride and is passed into continuously primary acids solution reaction kettle, controlling primary acids solution reaction kettle internal pressure is that 0.3 ~ 1.0MPa(is preferably 0.40 ~ 0.60MPa), temperature is that 120 ~ 200 ℃ (being preferably 140 ~ 160 ℃) react 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester and hydrogen chloride tail gas A, reaction to 2 chloroethyl phosphoric acid content in the 2 chloroethyl phosphoric acid crude product obtaining reaches after required purity, raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester of pressurization is joined in primary acids solution reaction kettle continuously.
In the present invention, primary acids solution reaction kettle and secondary acidolysis reaction still all can use enamel reaction still, the enamel reaction still of for example 50 ~ 10000L, the preferably enamel reaction still of 1000L ~ 2000L.Conventionally, liquid starting material adds from reactor top, and gas raw material adds from reactor bottom, and product flows out from reactor bottom.According to the difference of enamel reaction still capacity, the flow that primary acids solution reaction kettle Raw 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester adds is continuously 10-2000Kg/h, the flow that in secondary acidolysis reaction still, hydrogen chloride gas passes into is continuously 7-1350Kg/h, and those skilled in the art can carry out as required routine and select.
In the present invention, first-stage condenser and secondary condenser all can be used graphite condenser, and for example heat interchanging area is at the graphite condenser of 5 ~ 25 square metres, and preferably heat interchanging area is at the graphite condenser of 10 ~ 15 square metres.
In the present invention, in order to strengthen contact mass transfer and the reaction of raw material in reactor, described primary acids solution reaction kettle and secondary acidolysis reaction still are furnished with respectively a set of outer circulation static mixer, the enamel pipe that described outer circulation static mixer is in-built filler, general filler is full of enamel pipe, the for example enamel pipe of 50 millimeters of diameters, 2 meters of length, the optional one in polytetrafluoroethylene packing, ceramic corrugated filler, ceramic raschig rings filler of described filler, preferably ceramic ripple packing.In the course of the work, the material in primary acids solution reaction kettle or secondary acidolysis reaction still enters static mixer under recycle pump effect, then gets back to again primary acids solution reaction kettle or secondary acidolysis reaction still inner-outer circulation flow is recommended as 25Kg/h ~ 2500Kg/h.
The present invention is concrete recommends described technique to carry out according to following steps:
(1) by primary acids solution reaction kettle and secondary acidolysis reaction still disposable charging feedstock 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester respectively, the temperature of controlling secondary acidolysis reaction still is 120 ℃ ~ 200 ℃, from secondary acidolysis reaction still bottom, with the flow velocity of 7-1350Kg/h, pass into continuously the hydrogen chloride gas of pressurization, controlling secondary acidolysis reaction still internal pressure is 0.3MPa ~ 1.0MPa, the tail gas that reaction produces enters secondary condenser from the top of secondary acidolysis reaction still, condensation passes into primary acids solution reaction kettle bottom from secondary condenser hydrogen chloride tail gas A out after reclaiming ethylene dichloride, the temperature of controlling primary acids solution reaction kettle is 120 ℃ ~ 200 ℃, pressure is that 0.3MPa ~ 1.0MPa reacts, obtain 2 chloroethyl phosphoric acid crude product,
(2) when in the 2 chloroethyl phosphoric acid crude product that flow out primary acids solution reaction kettle bottom, 2 chloroethyl phosphoric acid content is greater than 80%, raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester of pressurization is added with the flow velocity of 10-2000Kg/h continuously by the top of primary acids solution reaction kettle, open the outer circulation static mixing apparatus of primary acids solution reaction kettle simultaneously, outer circulation flow is 50Kg/h ~ 5000Kg/h, makes 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester and hydrogen chloride tail gas A carry out successive reaction; Primary acids solution reaction kettle top exit is discharged tail gas continuously, and tail gas reclaims ethylene dichloride through first-stage condenser condensation, and the hydrogen chloride gas obtaining after the purified processing of gained hydrogen chloride tail gas B uses gas compressor compression cycle cover for secondary acidolysis reaction still;
(3) the 2 chloroethyl phosphoric acid crude product that the 2 chloroethyl phosphoric acid content flowing out continuously from primary acids solution reaction kettle bottom is greater than 80%, from secondary acidolysis reaction still top, add continuously, controlling secondary acidolysis reaction still pressure is 0.3MPa ~ 1.0MPa, temperature is 120 ℃ ~ 200 ℃, open the outer circulation static mixing apparatus of secondary acidolysis reaction still simultaneously, outer circulation flow is 25Kg/h ~ 2500Kg/h, unreacted 2 chloroethyl phosphoric acid two in 2 chloroethyl phosphoric acid crude product-(2-chloroethyl) ester is fully reacted with the hydrogen chloride gas passing into continuously, secondary acidolysis reaction still top exit is discharged tail gas continuously, the excessive hydrogen chloride tail gas A that tail gas obtains after ethylene dichloride is reclaimed in secondary condenser condensation passes into primary acids solution reaction kettle bottom, secondary acidolysis reaction still bottom obtains 2 chloroethyl phosphoric acid product continuously.
The present invention also provides the purification treating method of a kind of hydrogen chloride tail gas B, and described treatment process is:
(a) by hydrogen chloride tail gas B by condenser deep cooling to-3 ~ 0 ℃, obtain hydrogen chloride tail gas after deep cooling (general hydrogen chloride content more than 98.5%, ethylene dichloride content below 1.4%, moisture content is below 200ppm);
(b) hydrogen chloride tail gas after deep cooling step (a) being obtained passes into vitriol oil drying tower and carries out drying treatment: described vitriol oil drying tower comprises housing and packing layer, it is one of following that filler in described packing layer is selected from: ceramic corrugated filler, ceramic raschig rings filler or ceramic Pall ring filler, the height of described packing layer is 71% ~ 86% of tower height, the tower top of described vitriol oil drying tower is provided with air outlet and vitriol oil entrance, at the bottom of tower, be provided with inlet mouth and vitriol oil outlet, described tower top vitriol oil ingress is provided with spray equipment, the vitriol oil sprays from the vitriol oil entrance of tower top passes into, flow is 80 ~ 1500kg/h, hydrogen chloride tail gas after deep cooling enters vitriol oil drying tower at the bottom of tower, hydrogen chloride tail gas after deep cooling is flowed through, and (in packing layer, the temperature of hydrogen chloride tail gas is generally 3 ~ 10 ℃ to packing layer, this temperature is relevant with the vitriol oil flow of the packing layer of flowing through, higher or lower than this temperature range, the present invention is not affected), (general hydrogen chloride content is more than 98.6% from vitriol oil drying tower air outlet, to obtain hydrogen chloride tail gas after drying treatment, ethylene dichloride content is below 1.3%, water content is below 5ppm),
(c) hydrogen chloride tail gas after drying treatment step (b) being obtained passes into absorbing carbon fiber adnexa, the bed temperature of carbon fiber is 10 ~ 15 ℃ in adsorber, adsorber outlet obtain hydrogen chloride tail gas after adsorption treatment (general hydrogen chloride content more than 99.9%, ethylene dichloride content below 10ppm, water content is below 5ppm).The hydrogen chloride gas recycled that hydrogen chloride tail gas after adsorption treatment can obtain pressurization through compressor compresses is in secondary acidolysis reaction still.
Further, the described condenser of step (a) is enamel chip type condenser, and for example heat interchanging area is the enamel chip type condenser of 5 ~ 10 square metres.
Further, the described cryogenic method of step (a) is: hydrogen chloride tail gas B is passed into enamel chip type condenser, and under the effect of-10～-15 ℃ of chilled brines, deep cooling to gas temperature is-3 ~ 0 ℃.Further again, hydrogen chloride tail gas B passes into enamel chip type condenser with the flow of 4 ~ 750kg/h.
Further, the described filler of step (b) is ceramic corrugated filler.
Further, in the described absorbing carbon fiber adnexa of step (c) PAN-ACF saturated after, by desorption processing, can realize recycling, desorption processing method is: saturated adsorption bed temperature is risen to 100 ~ 150 ℃ (being preferably 130-150 ℃), with nitrogen, sweep and blow simultaneously, while flowing out without ethylene dichloride to adsorber outlet, desorption and regeneration completes.Described absorbing carbon fiber adnexa generally can be equipped with two simultaneously, after an absorption is saturated, switches another and uses, and both hocket.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
A) serialization pressurization is produced ethrel, the technology that adopts two still pressurization continuously feedings and outer circulation static mixing to combine, strengthened the mass transfer of vapour-liquid two-phase, significantly accelerated speed of response, shortened raw material, the product residence time at high temperature, avoided the side reaction of the long-time dehydrochlorination at high temperature occurring of ethrel, thereby make the content of the former medicine of ethrel reach 93% ~ 96%, impurity ethylene vinyl profit content is less than 0.5%, reach the specification of quality of outlet high-quality ethrel, widen outlet channel, there is good economic benefit.
B) serialization pressurization hydrogen chloride tail gas after treatment, can be applied mechanically after compression continuously with gas compressor, significantly cuts down the consumption of hydrogenchloride in ethrel hydrolysis procedure, has good economic benefit.The industrialization automatization control that can realize DCS is produced in serialization simultaneously, simplifies the operation, and has guaranteed quality product, has improved production efficiency.
C) the present invention is by hydrogen chloride tail gas B is dry by freezing deep cooling, the vitriol oil, absorbing carbon fiber is attached, obtain hydrogen chloride content more than 99.9%, ethylene dichloride content below 10ppm, the hydrogen chloride gas of moisture content below 5ppm, solved corrosion-resistant problem and the safety problem of material in gas compression processes.
In a word, the present invention realized low cost, efficient, clean production, meet the industry policy of national sustainable development.
(4) accompanying drawing explanation
Fig. 1 is the process flow diagram that serialization pressurization of the present invention is produced 2 chloroethyl phosphoric acid, and wherein 1 is primary acids solution reaction kettle, and 2 is secondary acidolysis reaction still, 3 is first-stage condenser, 4 is secondary condenser, and 5,6 are ethylene dichloride groove, and 7,8 are outer circulation static mixer.
Fig. 2 is the process flow sheet that the present invention processes hydrogen chloride tail gas B.
(5) embodiment
Below in conjunction with specific examples, the present invention is described further.But protection scope of the present invention is not limited only to this.
The experimental installation that the embodiment of the present invention adopts as shown in Figure 1.
The vitriol oil drying tower that the embodiment of the present invention adopts is ordinary method home-built equipment, comprise housing and packing layer, there are air outlet and sulfuric acid import in drying tower top, tower top vitriol oil ingress is provided with spray equipment, there are inlet mouth and sulfuric acid outlet in bottom, in-built filler, and drying tower diameter is 400mm, height 7m, bed stuffing height 5 ~ 6m.
The absorbing carbon fiber adnexa that the embodiment of the present invention adopts is ordinary method home-built equipment, comprise housing and filled with carbon fibers bed, there are air outlet and inlet mouth in adsorber two ends, interior filling carbon fiber, adsorber diameter 500mm, height 1.6m, carbon fiber bed height 1 ~ 1.5m, described adsorber inlet mouth place also has nitrogen inlet, and place, air outlet has ethylene dichloride to reclaim mouth, and described ethylene dichloride reclaims mouth and is connected with condenser; In adsorption process, be furnished with two cover adsorbers simultaneously, adsorb saturated after, then carry out desorption and regeneration, another set of adsorber carries out adsorption treatment, the two hockets; When adsorber carries out desorption and regeneration, adsorption bed temperature is risen to 100 ~ 150 ℃, with nitrogen, purge simultaneously, while flowing out without ethylene dichloride drop in the condenser being extremely connected with adsorber ethylene dichloride recovery mouth, desorption and regeneration completes, and is cooled to normal temperature, enters sorption cycle operation, as shown in Figure 2, the pipeline that in Fig. 2, flash line represents refers at another pipeline back side.
Example 1:
(1) the secondary acidolysis reaction still of the primary acids solution reaction kettle of 2000L and 1000L is respectively charged into raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of 2000Kg and raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of 1000Kg.In described raw material (I), the content of 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester is 90%, the content of dipolymer (III) is 6%, the temperature of controlling primary acids solution reaction kettle and secondary acidolysis reaction still is 150 ℃, from secondary acidolysis reaction still bottom, pass into 250Kg/h hydrogen chloride gas (purity 99.9%), control primary acids solution reaction kettle and secondary acidolysis reaction still internal pressure and be 0.5MPa.
(2) when in the ethrel crude product that flow out primary acids solution reaction kettle bottom, ethrel content is greater than 80%, raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of pressurization is added from primary acids solution reaction kettle top continuously with the flow of 300Kg/h, in described raw material (I), 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester content is 90%, the content of dipolymer (III) is 6%, primary acids solution reaction kettle internal pressure is 0.5MPa, temperature is 150 ℃, from secondary condenser acidolysis hydrogen chloride tail gas out, passes into primary acids solution reaction kettle bottom.Open the continuous external circulation static mixing apparatus of primary acids solution reaction kettle, static mixer is that diameter 50 mm lengths are the enamel pipe of 2 meters, inside fills ceramic corrugated filler simultaneously, and outer circulation flow is 1000Kg/h.The ethylene dichloride that primary acids solution reaction kettle top exit is discharged continuously and excessive hydrogen chloride tail gas, after ethylene dichloride is reclaimed in first-stage condenser (graphite condensers that heat interchanging area is 15 square metres) condensation, hydrogen chloride tail gas flow is 170Kg/h, this hydrogen chloride tail gas containing hydrogen chloride 97%, containing ethylene dichloride 2.9%, moisture 800ppm, carries out purification process in accordance with the following steps:
1. hydrogen chloride tail gas passes into enamel chip type condenser with the flow of 170kg/h and carries out freezing deep cooling, 8 square metres of condenser heat interchanging areas, condenser skin passes through the chilled brine of-10～-12 ℃, internal layer leads to hydrogen chloride tail gas, after deep cooling, exhaust temperature is-3 ~ 0 ℃, obtains containing hydrogen chloride 98.5%, containing ethylene dichloride 1.4%, the hydrogen chloride tail gas after moisture 198ppm deep cooling.
2. again by step 1. the hydrogen chloride tail gas after deep cooling pass into vitriol oil drying tower, described vitriol oil drying tower diameter 400mm, is highly 7m, in-built ceramic corrugated filler, packed height is 5.5m; Mass concentration 98% vitriol oil sprays from the vitriol oil entrance of tower top passes into, flow is 1000kg/h, ethrel acid hydrolysis tail gas after deep cooling enters vitriol oil drying tower at the bottom of tower, hydrogen chloride tail gas temperature in vitriol oil drying tower packing layer is 3 ~ 10 ℃, from vitriol oil drying tower air outlet, obtain containing hydrogen chloride 98.6%, containing ethylene dichloride 1.3%, the dried hydrogen chloride tail gas of moisture 2.5ppm;
3. more 2. step is passed into absorbing carbon fiber adnexa (absorbing carbon fiber adnexa diameter 500mm through vitriol oil drying tower hydrogen chloride tail gas after treatment, height 1.6m, there are inlet mouth and air outlet in two ends, inlet mouth place is also provided with nitrogen inlet, place, air outlet is also provided with ethylene dichloride and reclaims mouth), the in-built carbon fiber of absorbing carbon fiber adnexa, bed height is 1.5m, absorbing carbon fiber additive process detects 10 ~ 15 ℃ of bed temperatures online, the online adsorber that detects exports water content 2.5ppm in ethrel acid hydrolysis tail gas, ethylene dichloride content 9.5ppm, hydrogen chloride content is 99.9%; In adsorption process, be furnished with two absorbing carbon fiber adnexa simultaneously, after the absorption of absorbing carbon fiber adnexa is saturated, carry out desorption and regeneration, another adsorber carries out adsorption treatment, and the two hockets; When adsorber carries out desorption and regeneration, adsorption bed temperature is risen to 130 ~ 150 ℃, with nitrogen, purge simultaneously, to the aftercondenser that is connected with adsorber ethylene dichloride recovery mouth, without ethylene dichloride, flow out, desorption and regeneration completes, and is cooled to normal temperature, enters sorption cycle operation;
The containing hydrogen chloride 99.9% that 3. step is obtained, containing ethylene dichloride 9.5ppm, the hydrogen chloride gas of moisture 2.5ppm is compressed to 0.5MPa through gas compressor, obtain the hydrogen chloride gas of pressurization after treatment, recycled, to secondary acidolysis reaction still, is effectively utilized the hydrogenchloride in acid hydrolysis tail gas.
(3) 83% the ethrel crude product flowing out continuously from primary acids solution reaction kettle bottom, from secondary acidolysis reaction still top, add continuously, secondary acidolysis reaction still pressure is 0.5MPa, temperature is 150 ℃, and secondary acidolysis reaction still bottom passes into 250Kg/h hydrogen chloride gas, opens the continuous external circulation static mixing apparatus of secondary acidolysis reaction still simultaneously, outer circulation flow is 500Kg/h, static mixer is 50 millimeters of diameters, and length is the enamel pipe of 2 meters, in-built ceramic corrugated filler.The ethylene dichloride that secondary acidolysis reaction still top exit is discharged continuously and excessive hydrogen chloride tail gas, after ethylene dichloride is reclaimed in secondary condenser condensation, pass into primary acids solution reaction kettle bottom, described secondary condenser is that heat interchanging area is the graphite condenser of 10 square metres.Secondary acidolysis reaction still bottom can make the former medicine of 160Kg/h ethrel continuously, and content is 96.0%, impurity ethylene vinyl profit content 0.20%.Yield is 98%.
Example 2:
(1) the secondary acidolysis reaction still of the primary acids solution reaction kettle of 100L and 50L is respectively charged into raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of 100Kg and raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of 50Kg.In described raw material (I), the content of 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester is 90%, the content of dipolymer (III) is 6%, the temperature of controlling primary acids solution reaction kettle and secondary acidolysis reaction still is 160 ℃, from secondary acidolysis reaction still bottom, pass into 7Kg/h hydrogen chloride gas (purity 99.9%), control primary acids solution reaction kettle and secondary acidolysis reaction still internal pressure and be 0.6MPa.
(2) when the ethrel content in crude product flowing out when primary acids solution reaction kettle bottom is greater than 80%, the raw material 2 chloroethyl phosphoric acid ester (I) of pressurization is added from primary acids solution reaction kettle top continuously with the flow of 10Kg/h, in described raw material (I), 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester content is 90%, the content of dipolymer (III) is 6%, primary acids solution reaction kettle internal pressure is 0.6MPa, temperature is 160 ℃, from secondary condenser acidolysis hydrogen chloride tail gas out, passes into primary acids solution reaction kettle bottom.Open the continuous external circulation static mixing apparatus of primary acids solution reaction kettle, static mixer is that 50 millimeters of diameters, length are the enamel pipe of 2 meters, inside fills ceramic corrugated filler simultaneously, and outer circulation flow is 50Kg/h.The ethylene dichloride that primary acids solution reaction kettle top exit is discharged continuously and excessive hydrogen chloride tail gas, after ethylene dichloride is reclaimed in first-stage condenser (graphite condensers that heat interchanging area is 8 square metres) condensation, hydrogen chloride tail gas flow is 4Kg/h, this hydrogen chloride tail gas is carried out to purification process according to the method for embodiment 1, wherein step 2. in the flow of hydrogen chloride tail gas be 4kg/h, the in-built ceramic raschig rings filler of vitriol oil drying tower, vitriol oil spray flux is 80kg/h, moisture content 3.0ppm in the hydrogen chloride tail gas of vitriol oil drying tower air outlet, other operations and parameter are with embodiment 1, the compressed 0.6MPa that makes, the hydrogen chloride tail gas of containing hydrogen chloride 99.9%, recycled is to secondary acidolysis reaction still.
(3) 83% the ethrel crude product flowing out continuously from primary acids solution reaction kettle bottom, from secondary acidolysis reaction still top, add continuously, secondary acidolysis reaction still pressure is 0.6MPa, temperature is 160 ℃, and secondary acidolysis reaction still bottom passes into 7Kg/h hydrogen chloride gas, opens the continuous external circulation static mixing apparatus of secondary acidolysis reaction still simultaneously, static mixer is 50 millimeters of diameters, length is the enamel pipe of 2 meters, inside fills ceramic corrugated filler, and outer circulation flow is 25Kg/h.The ethylene dichloride that secondary acidolysis reaction still top exit is discharged continuously and excessive hydrogen chloride tail gas, after ethylene dichloride is reclaimed in secondary condenser condensation, pass into primary acids solution reaction kettle bottom, described secondary condenser is that heat interchanging area is the graphite condenser of 5 square metres.Secondary acidolysis reaction still bottom can make the former medicine of 5.5Kg/h ethrel continuously, and content is 95.8%, impurity ethylene vinyl profit content 0.30%.Yield is 98.2%.
Example 3:
(1) the secondary acidolysis reaction still of the primary acids solution reaction kettle of 10000L and 5000L is respectively charged into raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of 10000Kg and raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of 5000Kg.In described raw material (I), the content of 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester is 90%, the content of dipolymer (III) is 6%, the temperature of controlling primary acids solution reaction kettle and secondary acidolysis reaction still is 150 ℃, from secondary acidolysis reaction still bottom, pass into 1350Kg/h hydrogen chloride gas (purity 99.9%), control primary acids solution reaction kettle and secondary acidolysis reaction still internal pressure and be 0.5MPa.
(2) when the ethrel content in crude product flowing out when primary acids solution reaction kettle bottom is greater than 80%, raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of pressurization is added from primary acids solution reaction kettle top continuously with the flow of 2000Kg/h, in described raw material (I), 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester content is 90%, the content of dipolymer (III) is 6%, primary acids solution reaction kettle internal pressure is 0.5MPa, temperature is 150 ℃, from secondary condenser acidolysis hydrogen chloride tail gas out, passes into primary acids solution reaction kettle bottom.The continuous external circulation static mixing apparatus of simultaneously opening primary acids solution reaction kettle, outer circulation flow is 5000Kg/h, static mixer is that diameter 50 mm lengths are the enamel pipe of 2 meters, in-built ceramic corrugated filler.The ethylene dichloride that primary acids solution reaction kettle top exit is discharged continuously and excessive hydrogen chloride tail gas, after ethylene dichloride is reclaimed in first-stage condenser (heat interchanging area is the graphite condenser of 25 square metres) condensation, hydrogen chloride tail gas flow is 750Kg/h, this hydrogen chloride tail gas is carried out to purification process according to the method for embodiment 1, wherein step 2. in the flow of hydrogen chloride tail gas be 750kg/h, the in-built ceramic Pall ring filler of vitriol oil drying tower, vitriol oil spray flux is 1400kg/h, water content 4.0ppm in the ethrel acid hydrolysis tail gas of vitriol oil drying tower air outlet, other operations and parameter are with embodiment 1, the compressed 0.5MPa that makes, the hydrogen chloride gas of the pressurization of containing hydrogen chloride 99.9%, recycled is to secondary acidolysis reaction still.
(3) 84% the ethrel crude product flowing out continuously from primary acids solution reaction kettle bottom, from secondary acidolysis reaction still top, add continuously, secondary acidolysis reaction still pressure is 0.5MPa, temperature is 150 ℃, and secondary acidolysis reaction still bottom passes into 1350Kg/h hydrogen chloride gas, opens the continuous external circulation static mixing apparatus of secondary acidolysis reaction still simultaneously, outer circulation flow is 2500Kg/h, static mixer is 50 millimeters of diameters, and length is the enamel pipe of 2 meters, in-built ceramic corrugated filler.The ethylene dichloride that secondary acidolysis reaction still top exit is discharged continuously and excessive hydrogen chloride tail gas, after ethylene dichloride is reclaimed in secondary condenser condensation, pass into primary acids solution reaction kettle bottom, described secondary condenser is that heat interchanging area is the graphite condenser of 15 square metres.Secondary acidolysis reaction still bottom can make the former medicine of 1070Kg/h ethrel continuously, and content is 96.0%, impurity ethylene vinyl profit content 0.25%.Yield is 98.5%.
Claims (9)
1. serialization pressurization is produced a technique for 2 chloroethyl phosphoric acid (II), and the device of described process using comprises primary acids solution reaction kettle, first-stage condenser, secondary acidolysis reaction still and secondary condenser; Described primary acids solution reaction kettle and secondary acidolysis reaction still are furnished with respectively an outer circulation static mixer, the enamel pipe that described outer circulation static mixer is in-built filler, the optional one in polytetrafluoroethylene packing, ceramic corrugated filler, ceramic raschig rings filler of described filler, the bottom of described primary acids solution reaction kettle or secondary acidolysis reaction still is connected with the bottom of outer circulation static mixer by recycle pump, and the top of described primary acids solution reaction kettle or secondary acidolysis reaction still is connected with the top of outer circulation static mixer;
Described technique comprises:
In primary acids solution reaction kettle, add continuously raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester (I) of pressurization and the hydrogen chloride tail gas A from secondary condenser, make the outer circulation static mixer of primary acids solution reaction kettle be held open state, controlling primary acids solution reaction kettle internal pressure and be 0.3 ~ 1.0MPa, temperature is 120 ~ 200 ℃ and carries out successive reaction, the tail gas that reaction produces passes into first-stage condenser condensation and reclaims after ethylene dichloride, after the excessive purified processing of hydrogen chloride tail gas B the more compressed hydrogen chloride gas recycled that obtains pressurization in secondary acidolysis reaction still, the 2 chloroethyl phosphoric acid crude product that reaction obtains flows out and enters secondary acidolysis reaction still continuously from the bottom of primary acids solution reaction kettle, toward secondary acidolysis reaction still, pass into continuously the hydrogen chloride gas of pressurization simultaneously, make the outer circulation static mixer of secondary acidolysis reaction still be held open state, controlling secondary acidolysis reaction still internal pressure is 0.3 ~ 1.0MPa, temperature is 120 ~ 200 ℃ makes unreacted raw material in 2 chloroethyl phosphoric acid crude product fully react with hydrogenchloride, from secondary acidolysis reaction still bottom, obtain continuously 2 chloroethyl phosphoric acid product, the tail gas that reaction produces passes into secondary condenser, condensation is reclaimed the excessive hydrogen chloride tail gas A obtaining after ethylene dichloride and is passed into continuously primary acids solution reaction kettle.
2. serialization pressurization as claimed in claim 1 is produced the technique of 2 chloroethyl phosphoric acid, it is characterized in that: the mol ratio of the hydrogen chloride gas passing in 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester adding in primary acids solution reaction kettle in the unit time and secondary acidolysis reaction still is 1:2.50-6.50.
3. serialization pressurization as claimed in claim 1 is produced the technique of 2 chloroethyl phosphoric acid, it is characterized in that: control from the continuous content that flows out 2 chloroethyl phosphoric acid in the 2 chloroethyl phosphoric acid crude product entering secondary acidolysis reaction still in bottom of primary acids solution reaction kettle and be greater than 80%.
4. serialization pressurization as claimed in claim 1 is produced the technique of 2 chloroethyl phosphoric acid, it is characterized in that: the content of 2 chloroethyl phosphoric acid two in raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester-(2-chloroethyl) ester is more than 90%, and the two ethyl ester content of phosphonic acids (2-chloroethyl) is 4% ~ 6%; The purity of the hydrogen chloride gas passing into continuously in secondary acidolysis reaction still is more than 99.9%.
5. the serialization pressurization as described in one of claim 1 ~ 4 is produced the technique of 2 chloroethyl phosphoric acid, it is characterized in that described technique also comprises following preposition step:
First toward disposable 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester that adds respectively in primary acids solution reaction kettle and secondary acidolysis reaction still, and toward the hydrogen chloride gas that passes into continuously pressurization in secondary acidolysis reaction still, controlling secondary acidolysis reaction still internal pressure is 0.3 ~ 1.0MPa, temperature is 120 ~ 200 ℃ and reacts, the tail gas that reaction produces passes into secondary condenser, condensation is reclaimed the excessive hydrogen chloride tail gas A obtaining after ethylene dichloride and is passed into continuously primary acids solution reaction kettle, controlling primary acids solution reaction kettle internal pressure is 0.3 ~ 1.0MPa, temperature is 120 ~ 200 ℃ reacts 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester and hydrogen chloride tail gas A, reaction to 2 chloroethyl phosphoric acid content in the 2 chloroethyl phosphoric acid crude product obtaining reaches after required purity, raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester of pressurization is joined in primary acids solution reaction kettle continuously.
6. serialization pressurization as claimed in claim 1 is produced the technique of 2 chloroethyl phosphoric acid, it is characterized in that: the content of 2 chloroethyl phosphoric acid two in raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester-(2-chloroethyl) ester is more than 90%, and the two ethyl ester content of phosphonic acids (2-chloroethyl) is 4% ~ 6%; Primary acids solution reaction kettle and secondary acidolysis reaction still are respectively the enamel reaction still of 50 ~ 10000L, and first-stage condenser and secondary condenser are graphite condenser; Described technique is carried out according to following steps:
(1) by primary acids solution reaction kettle and secondary acidolysis reaction still disposable charging feedstock 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester respectively, the temperature of controlling secondary acidolysis reaction still is 120 ℃ ~ 200 ℃, from secondary acidolysis reaction still bottom, with the flow velocity of 7-1350Kg/h, pass into continuously the hydrogen chloride gas of the pressurization of purity more than 99.9%, controlling secondary acidolysis reaction still internal pressure is 0.3MPa ~ 1.0MPa, the tail gas that reaction produces enters secondary condenser from the top of secondary acidolysis reaction still, condensation passes into primary acids solution reaction kettle bottom from secondary condenser hydrogen chloride tail gas A out after reclaiming ethylene dichloride, the temperature of controlling primary acids solution reaction kettle is 120 ℃ ~ 200 ℃, pressure is that 0.3MPa ~ 1.0MPa reacts, obtain 2 chloroethyl phosphoric acid crude product,
(2) when in the 2 chloroethyl phosphoric acid crude product that flow out primary acids solution reaction kettle bottom, 2 chloroethyl phosphoric acid content is greater than 80%, raw material 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester of pressurization is added with the flow velocity of 10-2000Kg/h continuously by the top of primary acids solution reaction kettle, open the outer circulation static mixing apparatus of primary acids solution reaction kettle simultaneously, outer circulation flow is 50Kg/h ~ 5000Kg/h, makes 2 chloroethyl phosphoric acid two-(2-chloroethyl) ester and hydrogen chloride tail gas A carry out successive reaction; Primary acids solution reaction kettle top exit is discharged tail gas continuously, uses gas compressor compression cycle cover for secondary acidolysis reaction still after the purified processing of hydrogen chloride tail gas B that tail gas obtains after ethylene dichloride is reclaimed in first-stage condenser condensation;
(3) the 2 chloroethyl phosphoric acid crude product that the 2 chloroethyl phosphoric acid content flowing out continuously from primary acids solution reaction kettle bottom is greater than 80%, from secondary acidolysis reaction still top, add continuously, controlling secondary acidolysis reaction still pressure is 0.3MPa ~ 1.0MPa, temperature is 120 ℃ ~ 200 ℃, open the outer circulation static mixing apparatus of secondary acidolysis reaction still simultaneously, outer circulation flow is 25Kg/h ~ 2500Kg/h, unreacted 2 chloroethyl phosphoric acid two in 2 chloroethyl phosphoric acid crude product-(2-chloroethyl) ester is fully reacted with the hydrogen chloride gas passing into continuously, secondary acidolysis reaction still top exit is discharged tail gas continuously, the excessive hydrogen chloride tail gas A that tail gas obtains after ethylene dichloride is reclaimed in secondary condenser condensation passes into primary acids solution reaction kettle bottom, secondary acidolysis reaction still bottom obtains 2 chloroethyl phosphoric acid product continuously.
7. the serialization pressurization as described in one of claim 1 ~ 5 is produced the technique of 2 chloroethyl phosphoric acid, it is characterized in that the purification treating method of described hydrogen chloride tail gas B is:
(a) hydrogen chloride tail gas B is passed through to condenser deep cooling to-3 ~ 0 ℃, obtain the hydrogen chloride tail gas after deep cooling;
(b) hydrogen chloride tail gas after deep cooling step (a) being obtained passes into vitriol oil drying tower and carries out drying treatment: described vitriol oil drying tower comprises housing and packing layer, it is one of following that filler in described packing layer is selected from: ceramic corrugated filler, ceramic raschig rings filler or ceramic Pall ring filler, the height of described packing layer is 71% ~ 86% of tower height, the tower top of described vitriol oil drying tower is provided with air outlet and vitriol oil entrance, at the bottom of tower, be provided with inlet mouth and vitriol oil outlet, described tower top vitriol oil ingress is provided with spray equipment; The vitriol oil sprays from the vitriol oil entrance of tower top passes into, flow is 80 ~ 1500kg/h, hydrogen chloride tail gas after deep cooling enters vitriol oil drying tower at the bottom of tower, and the packing layer of flowing through of the hydrogen chloride tail gas after deep cooling, obtains the hydrogen chloride tail gas after drying treatment from vitriol oil drying tower air outlet;
(c) hydrogen chloride tail gas after drying treatment step (b) being obtained passes into absorbing carbon fiber adnexa, and in adsorber, the bed temperature of carbon fiber is 10 ~ 15 ℃, in adsorber outlet, obtains hydrogen chloride gas.
8. serialization pressurization as claimed in claim 7 is produced the technique of 2 chloroethyl phosphoric acid, it is characterized in that the cryogenic method in step (a) is: hydrogen chloride tail gas B is passed into enamel chip type condenser, under the effect of-10 ~-15 ℃ of chilled brines, deep cooling to gas temperature is-3 ~ 0 ℃.
9. serialization pressurization as claimed in claim 7 is produced the technique of 2 chloroethyl phosphoric acid, after it is characterized in that in the described absorbing carbon fiber adnexa of step (c) that PAN-ACF is saturated, by desorption, process and realize regeneration, desorption processing method is: saturated adsorption bed temperature is risen to 100 ~ 150 ℃, with nitrogen, sweep and blow simultaneously, while flowing out without ethylene dichloride to adsorber outlet, desorption and regeneration completes.
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| CN105693768A (en) * | 2016-04-12 | 2016-06-22 | 淮阴师范学院 | Ethephon solid purification method |
| CN112898339A (en) * | 2020-12-28 | 2021-06-04 | 安道麦安邦(江苏)有限公司 | Ethephon continuous production method and production device |
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| CN112898339A (en) * | 2020-12-28 | 2021-06-04 | 安道麦安邦(江苏)有限公司 | Ethephon continuous production method and production device |
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