CN200964388Y - Preparation device for acetyl chloride cogeneration hydroxyl ethidene diphosphoric acid - Google Patents
Preparation device for acetyl chloride cogeneration hydroxyl ethidene diphosphoric acid Download PDFInfo
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- CN200964388Y CN200964388Y CN 200620126884 CN200620126884U CN200964388Y CN 200964388 Y CN200964388 Y CN 200964388Y CN 200620126884 CN200620126884 CN 200620126884 CN 200620126884 U CN200620126884 U CN 200620126884U CN 200964388 Y CN200964388 Y CN 200964388Y
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Abstract
The utility model belongs to the field of chemical technology and in particular relates to a preparation apparatus of acetyl chloride joint prepared with hydroxy-ethylidene and diphosphonic acid. The bottom of a hydrolyzing elevated tank, an acetic acid measuring tank, and a trichloride measuring tank are connected with a reaction vessel. A hydrolyzing impacting and steaming condenser is communicated to the reaction vessel at the top. The bottom of the hydrolyzing impacting and steaming condenser is communicated to the top of the hydrolyzing elevated tank. The bottom of a distillation column is communicated to the reaction vessel. The distillation column is communicated to the condensing system at the top, and an acetyl chloride receiving tank is communicated to the bottom of the condensing system, with the bottom of the acetyl chloride receiving tank communicated to the top of distillation column. The condensing system is communicated to the bottom of an absorbing tower which is also communicated to the absorbing fluid bath. The utility model of the preparation apparatus has a reasonable design and can guarantee a sustainable, stable and standardized production, and promote the quality of product acetyl chloride, as well as shorten dripping time of trichloride in the process of HEDP reaction of the trichloride-acetic acid-water method, meanwhile reducing the production amount of hydrogen chloride gas.
Description
Technical field
The utility model belongs to chemical technology field, is specifically related to a kind of preparation facilities of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction.
Background technology
Acetyl Chloride 98Min. is a kind of important organic synthesis intermediate and acetylation reagent; acidylate energy force rate acetic anhydride is strong; be widely used in organic synthesis; can be used for producing agricultural chemicals, medicine, novel complexant for electroplating; and other multiple Minute Organic Synthesis intermediate; pharmaceutically can be used for making 2,4-two chloro-5-fluoro acetophenones (intermediate of Ciprofloxacin), Ibuprofen BP/EP etc.Acetyl Chloride 98Min. also is the catalyzer of carboxylic acid generation chlorination reaction.
The major industry method of Acetyl Chloride 98Min. is Glacial acetic acid-phosphorus trichloride method.Under the normal pressure, excessive phosphorus trichloride slowly adds in the Glacial acetic acid, heat temperature raising, and rectifying gets 98% Acetyl Chloride 98Min., by product phosphorous acid and hydrochloric acid.Its reaction mechanism is comparatively complicated, and side reaction is more.
Principal reaction:
PCl
3+3CH
3COOH→H
3PO
3+3CH
3COCl
Main side reaction:
CH
3COCl+CH
3COOH→(CH
3CO)O
2+HCl
PCl
3+CH
3COOH→CH
3COOPCl
2+HCl
CH
3COCl+H
3PO
3→P(OH)
2OCOCH
3+HCl
2P(OH)
2OCOCH
3→CH
3C(PO
3H
2)
2OCOCH
3
There is following defective in aforesaid method:
1, owing in the production process, dropped into excessive phosphorus trichloride, and technology reaction complexity just itself, make in the finished product Acetyl Chloride 98Min. impurity more.
2, contain a spot of phosphorus impurities in the finished product Acetyl Chloride 98Min., deposit variable muddy when long.
3, contain certain hydroxy ethylene diphosphonic acid acetic ester in the by product phosphorous acid, outward appearance is also bad, has influenced the application to by-product phosphorous acid, and economic benefit is relatively poor.
4,98% Acetyl Chloride 98Min. is purified in 99% process, produce raffinate in the still, raffinate cannot recycle, has produced the three wastes.
5, raw material consumption is too high, with theoretical yield one segment distance is arranged; Industry upslide 830kg Glacial acetic acid, 830kg phosphorus trichloride obtain 1000kg98% Acetyl Chloride 98Min., 440kg phosphorous acid and a small amount of by-product hydrochloric acid.The industrial about 930kg99% Acetyl Chloride 98Min. of purifying out of 1000kg98% Acetyl Chloride 98Min..Promptly throw the 890kg Glacial acetic acid, the 890kg phosphorus trichloride can obtain the 1000kg99% Acetyl Chloride 98Min..
Hydroxy ethylene diphosphonic acid (HEDP) is a kind of organic Tripyrophosphoric acid, because of having the complex performance good to multiple metal ion, the pH value scope of application widely, chemical propertys such as special surfactivity and physiologically active, oxygen uptake, inhibition, low toxicity make its range of application more and more widely.
The production method of HEDP has multiple, and main production methods is with phosphorus trichloride-Glacial acetic acid-water law both at home and abroad.Under the negative pressure operating mode, through drip, heat up (Acetyl Chloride 98Min. is back to reactor simultaneously), insulation, hydrolysis, dash production stage such as steaming and get.
Concrete production technique following (is example with the 2000L reactor): Glacial acetic acid, recovery acetic acid, water are made into 79.58% aqueous acetic acid 1445kg and drop into reactor, under the situation of 45～65 ℃ of controlled temperature, under agitation at the uniform velocity slowly drip 98.5% phosphorus trichloride 1670kg, this process section consumption 8～14h.Slowly heat up, the Acetyl Chloride 98Min. that condensation is got off is back to reactor simultaneously; Present body of paste in reactor, stop Acetyl Chloride 98Min. and reflux, unnecessary Acetyl Chloride 98Min. is received, this moment, temperature in the kettle was approximately 80 ℃; Continue to be warmed up to 118～122 ℃, this process section 14～24h consuming time.Temperature in the kettle is incubated in the time of 118～122 ℃, this process section consumption 1h.110～120 ℃ of controlled temperature are thrown hydrolyzed solution, this process section 1h consuming time.110～140 ℃ of controlled temperature directly towards steam, receive towards the inspissation aqueous acetic acid with towards steaming dilute acetic acid aqueous solution, this process section 8h consuming time in reactor.Throw 500kg water and 3kg hydrogen peroxide, stirring and evenly mixing, this process section 0.5h consuming time.Obtain 1897kg58%HEDP and 3900kg31% hydrochloric acid at last.Adopt major equipment as follows in the technology: gas reactor is through first step condenser (adopting common water coolant), second stage condenser (employing icy salt solution), Acetyl Chloride 98Min. under the absorption of first step graphite falling film absorber is uncooled becomes acetum, second stage graphite falling film absorber absorbing hydrogen chloride gas.Be to reduce raw material consumption, will through falling-film absorber receive acetum, reception unnecessary Acetyl Chloride 98Min., use as reclaiming acetic acid towards the inspissation aqueous acetic acid, dash and steam dilute acetic acid aqueous solution and use as hydrolyzed solution.
The 1000kg58%HEDP raw material consumption is Glacial acetic acid 255kg, 98.5% phosphorus trichloride 882kg in above-mentioned production technique; Under different vacuum and condensing condition, the HEDP reaction times of 2000L reactor is at 32～48h.Phosphorus trichloride-Glacial acetic acid-water law principal reaction is:
PCl
3+3H
2O→H
3PO
3+3HCl
PCl
3+3CH
3COOH→H
3PO
3+3CH
3COCl
CH
3COCl+H
2O→CH
3COOH+HCl
CH
3COCl+H
3PO
3→P(OH)
2OCOCH
3+HCl
2P(OH)
2OCOCH
3→CH
3C(H
2PO
3)
2OCOCH
3
CH
3C(PO
3H
2)
2OCOCH
3+H
2O→HEDP+CH
3COOH
There is following defective in aforesaid method;
1, produced a large amount of by-product hydrochloric acids, under the not smooth situation of hydrochloric acid market sale, can be influential to the production that enlarges HEDP, thus influenced economic benefit.
2, in the dropping process, phosphorus trichloride and water generates intense reaction as generating a large amount of hydrogen chloride gas in the misoperation still, make pressure increase in the system, are prone to accidents.
3, under the negative pressure operating mode, material is overflowed easily in the still, and raw material consumption is from the theoretical ton of 58%HEDP unit consumption Glacial acetic acid 170.5kg, and 98.5% phosphorus trichloride 785kg also has one section gap.
4, Acetyl Chloride 98Min. and the phosphorous acid reaction of passing through of seeing the hydroxy ethylene diphosphonic acid acetic ester from reaction forms, and the water of adding has consumed a part of Acetyl Chloride 98Min. on the contrary.The market value of Acetyl Chloride 98Min. approximately is the twice of Glacial acetic acid, consume the 1000kg Acetyl Chloride 98Min. and could obtain the 765kg Glacial acetic acid, therefrom as can be seen this technology wasted a part can obtainable economic return.
5, integrated artistic overlong time, energy consumption is too big.
6, drip, in the intensification production stage because complicated operation, can not be stable produce the HEDP premium grads.
Summary of the invention
The purpose of this utility model provides a kind of preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction.This preparation method combines production with 99% Acetyl Chloride 98Min. and hydroxy ethylene diphosphonic acid, economize 98% Acetyl Chloride 98Min. and be purified to 99% production stage, make reach 99% content one step of Acetyl Chloride 98Min. finished product of phosphorus trichloride-ice acetic acid method, solved the three wastes in the Acetyl Chloride 98Min. industrial production, the problem that yield is not high; Realized the cleaner production of Acetyl Chloride 98Min. and HEDP; This preparation method has also shortened reaction times, save energy consumption, raising Acetyl Chloride 98Min. and HEDP finished product grade, has reduced the growing amount of low value-added product hydrochloric acid, has improved security and the stability in the reaction process; This preparation method also reduces the raw material consumption of Acetyl Chloride 98Min. and HEDP simultaneously, making full use of under the prerequisite that reclaims acetic acid, raw material consumption is up to unit consumption 98.5% phosphorus trichloride 835kg, the Glacial acetic acid 220kg of 1000kg 58%HEDP and by-product 650kg31% hydrochloric acid, has consumed the 800kg Glacial acetic acid and can obtain 1000kg 99% Acetyl Chloride 98Min. (annotate: the phosphorus trichloride of Acetyl Chloride 98Min. consumption has been deducted) in HEDP raw material consumption.And provide corresponding preparation facilities according to the preparation method of described acetyl chloride and hydroxy ethylene diphosphonic acid coproduction.
The purpose of this utility model is achieved in that
A kind of preparation method of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction is characterized in that adopting following steps:
A) Glacial acetic acid is added reactor after, open to stir, finish the dropping of phosphorus trichloride in reactor under 1～2h normal pressure, the mole number that makes acetic acid in the reactor is 3.0～3.2 times of phosphorus trichloride mole number;
B) open reacting kettle jacketing steam, control jacket steam flow is 30～200kg/h.Make the reactor energy persistently overheating, and by following three operation stepss, make the still internal reaction generate the hydroxy ethylene diphosphonic acid acetic ester, the Acetyl Chloride 98Min. steam that steams in the still is after rectifier unit, condensing works are handled, obtain the liquid Acetyl Chloride 98Min. of content 〉=99%, uncooled Acetyl Chloride 98Min. steam is absorbed by 12～50 ℃ of Glacial acetic acid of absorption tower internal recycle mobile, and hydrogen chloride gas enters the falling film absorption device and forms hydrochloric acid behind the absorption tower.Condensing works adopts three grades of condensations, and water coolant is led in the one-level condensation, and B-grade condensation leads to-10～-20 ℃ of icy salt solutions, three grades of logical-20～-30 ℃ of icy salt solutions of condensation:
Quantity of reflux 100～the 500kg/h of Acetyl Chloride 98Min. in step 2, the control rectifying tower makes final can the stablizing of tower top temperature of rectifying tower keep 0.5h above constant, operation 2～4h, and temperature in the kettle is warming up to 48～65 ℃;
C) under the situation that the tower top temperature in the step 3 begins to descend, the Acetyl Chloride 98Min. that stops rectifying tower refluxing, and temperature in the kettle is 75～100 ℃;
D) continue heating, make temperature in the kettle keep 120 ± 2 ℃, carry out the insulation of hydroxy ethylene diphosphonic acid acetic ester, soaking time 1～2h;
E) with the still internal pressure by normal pressure become-0.01～-the 0.06Mpa vacuum, the hydroxy ethylene diphosphonic acid acetic ester is hydrolyzed, dash to steam and receive simultaneously and reclaim acetum, dash and steam waste water, throw deionized water, obtain the HEDP finished product after throwing hydrogen peroxide decolouring, press filtration 90 ℃ the time in the still.
The absorption liquid that will contain Acetyl Chloride 98Min. is still regarded Glacial acetic acid as and is dropped into next still; The dense acetum that is recovered to can rectifying and dewatering after, as the Glacial acetic acid reuse; Also can be used as the prepared using of the HEDP production of phosphorus trichloride-Glacial acetic acid-water law, can obtain higher economic benefit like this; The dilute acetic acid solution that reclaims uses as the HEDP hydrolyzed solution; Dash steaming waste water and be used for falling film absorption device absorbing hydrogen chloride gas; Adopt the negative pressure operating mode, carry out the hydroxy ethylene diphosphonic acid acetic ester and be hydrolyzed, dash and steam, can reduce the esterolytic fierce degree of hydroxy ethylene diphosphonic acid acetic acid and reduce the consumption of steam.The utility model is at the stage 16～26h consuming time that forms the hydroxy ethylene diphosphonic acid acetic ester, and the hydroxy ethylene diphosphonic acid acetic ester is processed into HEDP stage 8～10h consuming time.
A kind of preparation facilities of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction comprises the reactor of being with stirring system, hydrolysis is towards evaporation condenser, rectifying tower, condenser system, absorption tower, falling film absorption device, hydrolysis header tank, Glacial acetic acid scale tank, phosphorus trichloride scale tank, Acetyl Chloride 98Min. Receiving bin and absorb liquid bath; The bottom of hydrolysis header tank, Glacial acetic acid scale tank, phosphorus trichloride scale tank is connected with reactor; Hydrolysis is communicated with reactor towards the top of evaporation condenser, and hydrolysis is communicated with the top of hydrolysis header tank towards the bottom of evaporation condenser; Rectifier bottoms is communicated with reactor, and the rectifying tower top is communicated with condenser system; The condenser system bottom is communicated with the Acetyl Chloride 98Min. Receiving bin, and Acetyl Chloride 98Min. Receiving bin bottom is communicated with the rectifying tower top, and condenser system is communicated with the bottom, absorption tower; The bottom, absorption tower is communicated with the absorption liquid bath, and the absorption liquid trench bottom is communicated with the top, absorption tower by reflux pump, and the top, absorption tower is communicated with the falling film absorption device.
Preparation method described in the utility model combines production with Acetyl Chloride 98Min. and hydroxy ethylene diphosphonic acid, has improved the quality of finished product Acetyl Chloride 98Min.; Also shorten simultaneously the dropping time of phosphorus trichloride in the HEDP reaction of phosphorus trichloride-Glacial acetic acid-water law, also reduced the generation of 65% hydrogen chloride gas, stable and improved the quality index of finished product HEDP; Also make stability, the production security of reaction also obtain corresponding guarantee; By control, realized the stdn and controlledization of whole HEDP production process to hydrogen chloride gas growing amount and other conditions.Prepare the production equipment of method, reasonable in design, guaranteed the continual and steady and stdn of producing.
Description of drawings
Fig. 1 is a preparation facilities annexation structural representation of the present utility model.
Among the figure: 1. reactor 2. hydrolysis absorb liquid bath 12. stirring systems 13. agitators 14. step-down gears 15. condensers 16. withdrawing fluid under meters 17. gas meters 18. liquid meters towards evaporation condenser 3. rectifying tower 4. condenser systems 5. absorption towers 6. falling film absorption devices, 7. hydrolysis header tanks, 8. Glacial acetic acid scale tanks, 9. phosphorus trichloride scale tanks, 10. Acetyl Chloride 98Min. Receiving bins 11.
Embodiment
A kind of preparation method of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction is characterized in that adopting following steps:
A) Glacial acetic acid is added reactor after, open to stir, finish the dropping of phosphorus trichloride in reactor under 1～2h normal pressure, the mole number that makes acetic acid in the reactor is 3.0～3.2 times of phosphorus trichloride mole number.
B) open reacting kettle jacketing steam, control jacket steam flow is 30～200kg/h., make the reactor can be persistently overheating, and by following three operation stepss:
Quantity of reflux 100～the 500kg/h of Acetyl Chloride 98Min. in step 2, the control rectifying tower makes final can the stablizing of tower top temperature of rectifying tower keep 0.5h above constant, operation 2～4h, and temperature in the kettle is warming up to 48～65 ℃;
Make the still internal reaction generate the hydroxy ethylene diphosphonic acid acetic ester, the Acetyl Chloride 98Min. steam that steams in the still is after rectifier unit, condensing works are handled, obtain the liquid Acetyl Chloride 98Min. of content 〉=99%, uncooled Acetyl Chloride 98Min. steam is absorbed by 12～50 ℃ of Glacial acetic acid of absorption tower internal recycle mobile, and hydrogen chloride gas enters the falling film absorption device and forms hydrochloric acid behind the absorption tower.Condensing works adopts three grades of condensations, and water coolant is led in the one-level condensation, and B-grade condensation leads to-10～-20 ℃ of icy salt solutions, three grades of logical-20～-30 ℃ of icy salt solutions of condensation.
C) under the situation that the tower top temperature in the step 3 begins to descend, stop in the Acetyl Chloride 98Min. backflow still of rectifying tower, temperature in the kettle is 75～100 ℃;
D) continue heating, make temperature in the kettle keep 120 ± 2 ℃, carry out the insulation of hydroxy ethylene diphosphonic acid acetic ester, soaking time 1～2h.
E) with the still internal pressure by normal pressure become-0.01～-the 0.06Mpa vacuum, the hydroxy ethylene diphosphonic acid acetic ester is hydrolyzed, dash to steam and receive simultaneously and reclaim acetum, dash and steam waste water, throw deionized water, obtain the HEDP finished product after throwing hydrogen peroxide decolouring, press filtration 90 ℃ the time in the still.
The absorption liquid that will contain Acetyl Chloride 98Min. still drops into next still as Glacial acetic acid; The dense acetum that is recovered to can rectifying and dewatering after, as the Glacial acetic acid reuse; Also can be used as the prepared using of the HEDP production of phosphorus trichloride-Glacial acetic acid-water law, can obtain higher economic benefit like this; The dilute acetic acid solution that reclaims uses as the HEDP hydrolyzed solution; Dash steaming waste water and be used for falling film absorption device absorbing hydrogen chloride gas; Adopt the negative pressure operating mode, carry out the hydroxy ethylene diphosphonic acid acetic ester and be hydrolyzed, dash and steam, can reduce the esterolytic fierce degree of hydroxy ethylene diphosphonic acid acetic acid and reduce the consumption of steam.The utility model is at the stage 16～26h consuming time that forms the hydroxy ethylene diphosphonic acid acetic ester, and the hydroxy ethylene diphosphonic acid acetic ester is processed into HEDP stage 8～10h consuming time.
A kind of preparation facilities of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction comprises the reactor 1 of being with stirring system 12, hydrolysis is towards evaporation condenser 2, rectifying tower 3, condenser system 4, absorption tower 5, falling film absorption device 6, hydrolysis header tank 7, Glacial acetic acid scale tank 8, phosphorus trichloride scale tank 9, Acetyl Chloride 98Min. Receiving bin 10 and absorb liquid bath 11; The bottom of hydrolysis header tank 7, Glacial acetic acid scale tank 8, phosphorus trichloride scale tank 9 is connected with reactor 1; Reactor 1 bottom is communicated with vapour line; Hydrolysis is communicated with reactor 1 towards the top of evaporation condenser 2, and hydrolysis is communicated with the top of hydrolysis header tank 7 towards the bottom of evaporation condenser 2, and hydrolysis connects vacuum-lines towards the bottom of evaporation condenser 2; Hydrolysis header tank 7 is used to receive the recovery acetic acid that dashes when steaming in the different time, dashes and steam waste water and store hydrolysis with reclaiming dilute acetic acid solution; Rectifying tower 3 bottoms are communicated with reactor 1, and rectifying tower 3 tops are communicated with condenser system 4; Condenser system 4 bottoms are communicated with Acetyl Chloride 98Min. Receiving bin 10, Acetyl Chloride 98Min. Receiving bin 10 bottoms are communicated with rectifying tower 3 tops, on Acetyl Chloride 98Min. Receiving bin 10 and rectifying tower 3 connecting pipelines withdrawing fluid under meter 16 is set and is used to detect the Acetyl Chloride 98Min. quantity of reflux, condenser system 4 is communicated with 5 bottoms, absorption tower; 5 bottoms, absorption tower are communicated with absorption liquid bath 11, absorbing liquid bath 11 bottoms is communicated with 5 tops, absorption tower by reflux pump, 5 tops, absorption tower are communicated with falling film absorption device 6, on the pipeline that is interconnected with falling film absorption device 6 on absorption tower 5 gas meter 17 are set and are used to detect the hydrogen chloride gas flow.Described stirring system 12 comprises agitator 13 and step-down gear 14, and agitator 13 is anchor stirrer or grid agitator, and step-down gear 14 is a cycloidal planetary gear speed reducer.The tower diameter on described rectifying tower 3 and absorption tower 5 is φ 200～600mm.Rectifying tower 3 is φ 50～150mm with the caliber of reactor 1 connecting pipeline; Hydrolysis is φ 75～150mm towards the caliber of evaporation condenser 2 and reactor 1 connecting pipeline; Phosphorus trichloride scale tank 9 is φ 10～50mm with the caliber of reactor 1 connecting pipeline.Described condenser system 4 comprises secondary condenser at least, and it is curved to be provided with the U type between condenser 15 bottoms and the Acetyl Chloride 98Min. Receiving bin 10, and the U type is curved to form fluid-tight, guarantees that Acetyl Chloride 98Min. steam passes through the multi-stage condensing device according to the order of sequence.Reception liquid meter 18 is set on condenser 15 bottoms and Acetyl Chloride 98Min. Receiving bin 10 connecting pipelines is used to detect the Acetyl Chloride 98Min. flow that enters the Acetyl Chloride 98Min. Receiving bin, at condenser system 4 inner condensers 15 two kinds of mode of connection are arranged, first-selected rectifying tower 3 tops are communicated with the first-stage condenser bottom, the first-stage condenser top is communicated with the secondary condenser bottom, the secondary condenser top is communicated with three grades of condenser bottoms, and three grades of condenser overhead are communicated with 5 bottoms, absorption tower; Also can adopt rectifying tower 3 tops to be communicated with the first-stage condenser top, the first-stage condenser bottom is communicated with the secondary condenser top, and the secondary condenser bottom is communicated with three grades of condenser overhead, and three grades of condenser bottoms are communicated with 5 bottoms, absorption tower; The condensation effect of first kind of mode of connection is better than second kind of mode of connection.
Below concrete row for two example two preparation method described in the utility model is illustrated.
The 2190kg Glacial acetic acid is added in 3000 liters of reactors; Start stirring, drip the phosphorus trichloride of 1664kg98.5% in the 1h under the normal pressure, the mole number of acetic acid is 36.41Kmol in the still, and the mole number of phosphorus trichloride is 11.94Kmol.Directly receive the Acetyl Chloride 98Min. that condensation is got off, the hydrogen chloride gas growing amount is stabilized in 35～50kg/h, and 8h consuming time, temperature in the kettle slowly are warmed up to 46 ℃; The quantity of reflux of rectifying tower Acetyl Chloride 98Min. is at 200～300L/h, 2.5h consuming time, and 54 ℃ of temperature in the kettle have realized that the rectifying tower tower top temperature can stablize 0.5h; The quantity of reflux of rectifying tower Acetyl Chloride 98Min. is at 100～150L/h, and when 6h consuming time, 82 ℃ of temperature in the kettle, tower top temperature begins to descend, and stops the backflow of Acetyl Chloride 98Min., finally receives 99.21% finished product Acetyl Chloride 98Min. 1632kg; 120 ± 2 ℃ of temperature in the kettle carry out the insulation 1.5h consuming time of hydroxy ethylene diphosphonic acid acetic ester; Tail gas advances falling-film absorber and absorbs into 1500kg31% hydrochloric acid after the absorption tower absorbs with 20～30 ℃ 400kg Glacial acetic acid, the last absorption liquid 35kg that increased weight; During vacuum in the still-0.03Mpa, the 15% diluted acid 225kg that throws last still recovery is hydrolyzed, dashing steaming receives 70% acetum 650kg, 15% acetic acid 225kg, dashes and steam 700 kilograms of waste water, throw 31% hydrogen peroxide 3kg decolouring 90 ℃ the time in the still, obtain 58%HEDP finished product 1966kg after deionized water 1000kg, the press filtration.Gained HEDP finished product index is: and HEDP 58%, phosphoric acid 0.43%, inferior phosphorus 0.76%, muriate 0.13%, PH (1% aqueous solution) 1.86, density (20 ℃, g/cm
3) 1.43, calcium ion huge legendary turtle value of closing (mg/g) 516; By HG/T 3537-1999 water conditioner hydroxy ethylene diphosphonic acid standard determination gained HEDP finished product is premium grads.The content that detects Acetyl Chloride 98Min. with capillary gas chromatography is 99.2134%.
Embodiment two
The 3360kg Glacial acetic acid is added in 5000 liters of reactors; Start stirring, drip the phosphorus trichloride of 2550kg98.5% in the 1.5h under the normal pressure, the mole number of acetic acid is 55.95Kmol in the still, and the mole number of phosphorus trichloride is 18.29Kmol.Directly receive the Acetyl Chloride 98Min. that condensation is got off, the hydrogen chloride gas growing amount is stabilized in 40～55kg/h, and 11h consuming time, temperature in the kettle slowly are warmed up to 53 ℃; The quantity of reflux of rectifying tower Acetyl Chloride 98Min. is at 250～350L/h, 3.5h consuming time, and 63 ℃ of temperature in the kettle have realized that the rectifying tower tower top temperature can stablize 0.5h; The quantity of reflux of rectifying tower Acetyl Chloride 98Min. is at 100～180L/h, and when 7h consuming time, 95 ℃ of temperature in the kettle, tower top temperature begins to descend, and stops the backflow of Acetyl Chloride 98Min., finally receives 99.16% finished product Acetyl Chloride 98Min. 2500kg; 120 ± 2 ℃ of temperature in the kettle carry out the insulation 2h consuming time of hydroxy ethylene diphosphonic acid acetic ester; Tail gas advances falling-film absorber and absorbs into 2300kg31% hydrochloric acid after the absorption tower absorbs with 20～30 ℃ 800kg Glacial acetic acid, the last absorption liquid 60kg that increased weight; During vacuum in the still-0.03Mpa, throws the 15% diluted acid 345kg that a last still reclaims and is hydrolyzed, dash steam receive 70% acetum 1000kg, 15% acetic acid 345kg, towards 1000 kilograms of steaming waste water; Throw hydrogen peroxide 10kg decolouring 90 ℃ the time in the still, obtain 58%HEDP finished product 3017kg after deionized water 1530kg, the press filtration.Gained HEDP finished product index is: and HEDP 58%, phosphoric acid 0.41%, inferior phosphorus 0.82%, muriate 0.11%, PH (1% aqueous solution) 1.92, density (20 ℃, g/cm
3) 1.44, calcium ion huge legendary turtle value of closing (mg/g) 523; By HG/T 3537-1999 water conditioner hydroxy ethylene diphosphonic acid standard determination gained HEDP finished product is premium grads.The content that detects Acetyl Chloride 98Min. with capillary gas chromatography is 99.1626%.
Claims (5)
1. the preparation facilities of an acetyl chloride and hydroxy ethylene diphosphonic acid coproduction is characterized in that: the reactor (1), hydrolysis that comprise band stirring system (12) are towards evaporation condenser (2), rectifying tower (3), condenser system (4), absorption tower (5), falling film absorption device (6), hydrolysis header tank (7), Glacial acetic acid scale tank (8), phosphorus trichloride scale tank (9), Acetyl Chloride 98Min. Receiving bin (10) and absorption liquid bath (11); The bottom of hydrolysis header tank (7), Glacial acetic acid scale tank (8), phosphorus trichloride scale tank (9) is connected with reactor (1); Hydrolysis is communicated with reactor (1) towards the top of evaporation condenser (2), and hydrolysis is communicated with the top of hydrolysis header tank (7) towards the bottom of evaporation condenser (2); Rectifying tower (3) bottom is communicated with reactor (1), and rectifying tower (3) top is communicated with condenser system (4); Condenser system (4) bottom is communicated with Acetyl Chloride 98Min. Receiving bin (10), and Acetyl Chloride 98Min. Receiving bin (10) bottom is communicated with rectifying tower (3) top, and condenser system (4) is communicated with absorption tower (5) bottom; Bottom, absorption tower (5) is communicated with absorption liquid bath (11), absorbs liquid bath (11) bottom and is communicated with top, absorption tower (5) by reflux pump, and top, absorption tower (5) is communicated with falling film absorption device (6).
2. the preparation facilities of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction according to claim 1, it is characterized in that: described stirring system (12) comprises agitator (13) and step-down gear (14), agitator (13) is anchor stirrer or grid agitator, and step-down gear (14) is a cycloidal planetary gear speed reducer.
3. the preparation facilities of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction according to claim 1, it is characterized in that: the tower diameter of described rectifying tower (3) and absorption tower (5) is φ 200～600mm.
4. the preparation facilities of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction according to claim 1 is characterized in that: rectifying tower (3) is φ 50～150mm with the caliber of reactor (1) connecting pipeline; Hydrolysis is φ 75～150mm towards the caliber of evaporation condenser (2) and reactor (1) connecting pipeline; Phosphorus trichloride scale tank (9) is φ 10～50mm with the caliber of reactor (1) connecting pipeline.
5. the preparation facilities of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction according to claim 1, it is characterized in that: described condenser system (4) comprises secondary condenser at least, is provided with the U type between condenser (15) bottom and the Acetyl Chloride 98Min. Receiving bin (10) and bends.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200620126884 CN200964388Y (en) | 2006-10-28 | 2006-10-28 | Preparation device for acetyl chloride cogeneration hydroxyl ethidene diphosphoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200620126884 CN200964388Y (en) | 2006-10-28 | 2006-10-28 | Preparation device for acetyl chloride cogeneration hydroxyl ethidene diphosphoric acid |
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| Publication Number | Publication Date |
|---|---|
| CN200964388Y true CN200964388Y (en) | 2007-10-24 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675362A (en) * | 2011-05-06 | 2012-09-19 | 江苏大明科技有限公司 | Preparation process of hydroxylethylidene diphosphonic acid (HEDP) |
| CN106316833A (en) * | 2016-08-19 | 2017-01-11 | 周超 | Byproduct hydrogen chloride reusing method |
| CN106390692A (en) * | 2016-11-25 | 2017-02-15 | 湖北博凯医药科技有限公司 | Recycling device of acyl chloride tail gas |
| CN106632469A (en) * | 2016-12-06 | 2017-05-10 | 湖北泰盛化工有限公司 | Hydrogen chloride acidolysis technology and device |
-
2006
- 2006-10-28 CN CN 200620126884 patent/CN200964388Y/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675362A (en) * | 2011-05-06 | 2012-09-19 | 江苏大明科技有限公司 | Preparation process of hydroxylethylidene diphosphonic acid (HEDP) |
| CN106316833A (en) * | 2016-08-19 | 2017-01-11 | 周超 | Byproduct hydrogen chloride reusing method |
| CN106390692A (en) * | 2016-11-25 | 2017-02-15 | 湖北博凯医药科技有限公司 | Recycling device of acyl chloride tail gas |
| CN106632469A (en) * | 2016-12-06 | 2017-05-10 | 湖北泰盛化工有限公司 | Hydrogen chloride acidolysis technology and device |
| CN106632469B (en) * | 2016-12-06 | 2019-06-04 | 湖北泰盛化工有限公司 | A kind of hydrogen chloride acidolysis process and device |
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