CN1948258A - Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction - Google Patents
Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction Download PDFInfo
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- CN1948258A CN1948258A CN 200610097146 CN200610097146A CN1948258A CN 1948258 A CN1948258 A CN 1948258A CN 200610097146 CN200610097146 CN 200610097146 CN 200610097146 A CN200610097146 A CN 200610097146A CN 1948258 A CN1948258 A CN 1948258A
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Abstract
The present invention belongs to the field of chemical technology, in the concrete, it relates to a preparation method for simultaneously producing acetyl chloride and hydroxyethylidene diphosphonate and its equipment. Said method includes the following steps: adding glacial acetic acid and phosphorus trichloride according to the mole ratio of 3.0-3.2:1 in a reaction still, adopting continuous three-stage heating mode: 40-55 deg.C, 48-65 deg.C and 55-100 deg.C to make them produce reaction in the still so as to form hydroxyethylidene diphosphonate acetate and produce acetyl chloride vapor, making said acetyl chloride vapor be passed through rectification device and condensation device so as to obtain the liquid acetyl chloride whose content is greater than 99%.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method and a device for co-producing hydroxyl ethylidene diphosphonic acid by using acetyl chloride.
Background
Acetyl chloride is an important organic synthesis intermediate and an acetylation reagent, has stronger acylation capability than acetic anhydride, can be widely used for organic synthesis, can be used for producing pesticides, medicines, novel electroplating complexing agents and other various fine organic synthesis intermediates, and can be used for preparing 2, 4-dichloro-5-fluoro acetophenone (ciprofloxacin intermediate), ibuprofen and the like in medicine. Acetyl chloride is also a catalyst for the chlorination of carboxylic acids.
The main industrial method of acetyl chloride is the glacial acetic acid-phosphorus trichloride method. Under normal pressure, excessive phosphorus trichloride is slowly added into glacial acetic acid, heated and rectified to obtain 98% acetyl chloride, by-products of phosphorous acid and hydrochloric acid. The reaction mechanism is complex, and side reactions are more.
The main reaction:
the main side reaction:
the above method has the following disadvantages:
1. in the production process, excessive phosphorus trichloride is added, and the reaction of the process is complex, so that the finished acetyl chloride product has more impurities.
2. The finished acetyl chloride product contains a small amount of phosphorus impurities and is easy to become turbid after long-term storage.
3. The by-product phosphorous acid contains a certain amount of hydroxy ethylidene diphosphonic acid acetate, the appearance is not good, the application of the by-product phosphorous acid is influenced, and the economic benefit is poor.
4. In the process of purifying 98 percent acetyl chloride to 99 percent, residual liquid in the kettle is generated, the residual liquid can not be recycled, and three wastes are generated.
5. The unit consumption of raw materials is too high, and a distance is kept from the theoretical yield; a commercial charge of 830kg of glacial acetic acid and 830kg of phosphorus trichloride gave 1000kg of 98% acetyl chloride, 440kg of phosphorous acid and a small amount of by-product hydrochloric acid. 1000kg of 98% acetyl chloride can be purified industrially to approximately 930kg of 99% acetyl chloride. Namely, 890kg of glacial acetic acid and 890kg of phosphorus trichloride were added to obtain 1000kg of 99% acetyl chloride.
Hydroxy ethylidene diphosphonic acid (HEDP) is an organic polyphosphoric acid, and has good complexing performance on various metal ions, a wide pH value application range, special surface activity and chemical characteristics such as physiological activity, oxygen absorption, corrosion inhibition, low toxicity and the like, so that the application range of the HEDP is more and more extensive.
The HEDP production method has various methods, and the main production method at home and abroad is a phosphorus trichloride-glacial acetic acid-water method. Under the negative pressure working condition, the product is obtained by the production steps of dripping, heating (acetyl chloride flows back to the reaction kettle at the same time), heat preservation, hydrolysis, flushing and steaming and the like.
The specific production process is as follows (taking 2000L reaction kettle as an example): 1445kg of acetic acid aqueous solution with the concentration of 79.58% prepared from glacial acetic acid, recycled acetic acid and water is put into a reaction kettle, 1670kg of phosphorus trichloride with the concentration of 98.5% is slowly dripped at a constant speed under stirring under the condition of controlling the temperature to be 45-65 ℃, and the process consumes 8-14 hours. Slowly heating, and refluxing the condensed acetyl chloride to the reaction kettle; stopping the reflux of acetyl chloride when the paste is present in the reaction kettle, and receiving the redundant acetyl chloride, wherein the temperature in the reaction kettle is about 80 ℃; and continuously heating to 118-122 ℃, wherein the process takes 14-24 hours. And (3) preserving the temperature of the kettle at 118-122 ℃, wherein the process consumes 1 hour. Controlling the temperature to be 110-120 ℃, and feeding a hydrolysis solution, wherein the process takes 1 h. Controlling the temperature to be 110-140 ℃, directly injecting steam into the reaction kettle, receiving the injection-steamed concentrated acetic acid aqueous solution and the injection-steamed dilute acetic acid aqueous solution, and consuming 8 hours in the process period. Adding 500kg of water and 3kg of hydrogen peroxide, stirring and uniformly mixing, wherein the process period takes 0.5 h. 1897kg of 58% HEDP and 3900kg of 3 l% hydrochloric acid are obtained. The process adopts the following main equipment: the gas in the kettle passes through a first-stage condenser (adopting common cooling water), a second-stage condenser (adopting brine ice), a first-stage graphite falling film absorber absorbs the uncondensed acetyl chloride to form an acetic acid solution, and a second-stage graphite falling film absorber absorbs hydrogen chloride gas. In order to reduce the unit consumption of raw materials, the acetic acid solution received by the falling film absorber, the received redundant acetyl chloride and the flushing and steaming concentrated acetic acid aqueous solution are used as recovered acetic acid, and the flushing and steaming diluted acetic acid aqueous solution is used as hydrolysate.
In the production process, the unit consumption of 1000kg of 58 percent HEDP raw materials is 255kg of glacial acetic acid and 882kg of 98.5 percent phosphorus trichloride; under different vacuum and condensation conditions, the HEDP reaction time of a 2000L reaction kettle is 32-48 h.
The main reaction of phosphorus trichloride-glacial acetic acid-water method is:
the above method has the following drawbacks;
1. a large amount of hydrochloric acid as a by-product is generated, and under the condition that the hydrochloric acid is not sold in the market, the method has the influence on expanding the production of HEDP, thereby influencing the economic benefit.
2. In the dropping process, phosphorus trichloride reacts violently with water, and if the operation is not proper, a large amount of hydrogen chloride gas can be generated in the kettle, so that the pressure in the system is increased, and accidents are easy to happen.
3. Under the negative pressure working condition, materials in the kettle are easy to escape, the unit consumption of the raw materials is separated from the unit consumption of 170.5kg glacial acetic acid per 58 percent HEDP theoretical ton, and a gap exists between 785kg phosphorus trichloride 98.5 percent.
4. From the reaction, it appears that the hydroxyethylidene diphosphonic acid acetate is formed by the reaction of acetyl chloride and phosphorous acid, the water added instead consuming a portion of the acetyl chloride. The market price of acetyl chloride is approximately twice that of glacial acetic acid, 765kg of glacial acetic acid can be obtained by consuming 1000kg of acetyloxy, and it can be seen that the process wastes a part of the economic gain that can be obtained.
5. The whole process time is too long, and the energy consumption is too large.
6. In the production steps of dripping and heating, because the operation is complicated, HEDP high-quality products cannot be stably produced.
Disclosure of Invention
The invention aims to provide a method and a device for preparing acetyl chloride and co-producing hydroxyethylidene diphosphonic acid. The preparation method combines 99% of acetyl chloride and hydroxyethylidene diphosphonic acid for production, saves the production step of purifying 98% of acetyl chlorideto 99%, ensures that the content of the acetyl chloride finished product of the phosphorus trichloride-glacial acetic acid method reaches 99% by one step, and solves the problems of three wastes and low yield in the industrial production of the acetyl chloride; realizing the clean production of acetyl chloride and HEDP; the preparation method also shortens the reaction time, saves the energy consumption, improves the grade of acetyl chloride and HEDP finished products, reduces the generation amount of low value-added product hydrochloric acid, and improves the safety and stability in the reaction process; the preparation method simultaneously reduces the raw material consumption of acetyl chloride and HEDP, and on the premise of fully utilizing the recovered acetic acid, the highest raw material consumption is 1000kg of 58% HEDP, the byproduct consumption of 650kg of 31% hydrochloric acid is 98.5% of phosphorus trichloride 835kg, glacial acetic acid is 220kg, and the consumption of 800kg of glacial acetic acid can obtain 1000kg of 99% acetyl chloride (note: the phosphorus trichloride consumed by acetyl chloride is deducted from the consumption of the HEDP raw material). And provides a corresponding preparation device according to the preparation method of acetyl chloride coproduced with hydroxyethylidene diphosphonic acid.
The purpose of the invention is realized as follows:
a preparation method of acetyl chloride and hydroxyethylidene diphosphonic acid is characterized by comprising the following steps:
a) adding glacial acetic acid into a reaction kettle, starting stirring, and finishing dropwise adding phosphorus trichloride into the reaction kettle under normal pressure for 1-2 h to ensure that the mole number of acetic acid in the reaction kettle is 3.0-3.2 times of that of phosphorus trichloride;
b) and (3) starting steam of a jacket of the reaction kettle, and controlling the flow of the steam of the jacket to be 30-200 kg/h. The reaction kettle can be continuously heated, hydroxy ethylidene diphosphonic acid acetate is generated in the reaction kettle through the following three operation steps, acetyl chloride vapor evaporated in the reaction kettle is treated by a rectifying device and a condensing device to obtain liquid acetyl chloride with the content of more than or equal to 99%, uncondensed acetyl chloride vapor is absorbed by glacial acetic acid flowing in an absorption tower at the temperature of 12-50 ℃, and hydrogen chloride gas enters a falling film absorption device after passing through the absorption tower to form hydrochloric acid. The condensing device adopts three-stage condensation, cooling water is introduced into the first-stage condensation, brine ice at the temperature of-10 to-20 ℃ is introduced into the second-stage condensation, and brine ice at the temperature of-20 to-30 ℃ is introduced into the third-stage condensation:
directly receiving liquid acetyl chloride, controlling the amount of hydrogen chloride gas generated by reaction in a kettle to be stable at 30-60 kg/h, operating for 8-12 h, and heating the temperature in the kettle to 40-55 ℃;
step two, controlling the reflux amount of acetyl chloride in the rectifying tower to be 100-500 kg/h, keeping the tower top temperature of the rectifying tower unchanged for more than 0.5h, operating for 2-4 h, and heating the temperature in the kettle to 48-65 ℃;
step three, under the condition that the temperature of the tower top in the step two is kept unchanged, the reflux amount of acetyl chloride is reduced to 50-250 kg/h, the operation is carried out for 5-8 h, and the temperature in the kettle is raised to 55-100 ℃;
c) stopping the acetyl chloride reflux of the rectifying tower under the condition that the temperature of the tower top in the third step begins to decrease, wherein the temperature in the kettle is 75-100 ℃;
d) continuously heating to keep the temperature in the kettle at 120 +/-2 ℃, and carrying out heat preservation on the hydroxyethylidene diphosphonic acid acetate for 1-2 h;
e) changing the pressure in the kettle from normal pressure to vacuum of-0.01 to-0.06 Mpa, hydrolyzing the hydroxyethylidene diphosphonic acid acetate, steaming, receiving and recovering acetic acid solution, steaming waste water, adding deionized water, adding hydrogen peroxide at 90 ℃ in the kettle for decolorization, and performing filter pressing to obtain a HEDP finished product.
Putting the absorption liquid containing acetyl chloride into the next kettle as glacial acetic acid; the recovered concentrated acetic acid solution can be recycled as glacial acetic acid after rectification and dehydration; the method can also be used as a raw material for HEDP production of a phosphorus trichloride-glacial acetic acid-water method, so that higher economic benefit can be obtained; the recovered dilute acetic acid solution is used as HEDP hydrolysate; the flushing and steaming wastewater is used for absorbing hydrogen chloride gas by a falling film absorption device; the hydroxyethylidene diphosphonic acid acetate is hydrolyzed and steamed under the negative pressure working condition, so that the hydrolysis severity of the hydroxyethylidene diphosphonic acid acetate can be reduced, and the consumption of steam can be reduced. The method takes 16-26 hours in the stage of forming the hydroxyethylidene diphosphonic acid acetate, and takes 8-10 hours in the stage of processing the hydroxyethylidene diphosphonic acid acetate into HEDP.
A preparation device for acetyl chloride coproduction of hydroxyl ethylidene diphosphonic acid comprises a reaction kettle with a stirring system, a hydrolysis flushing and steaming condenser, a rectifying tower, a condensing system, an absorption tower, a falling film absorption device, a hydrolysis elevated tank, a glacial acetic acid metering tank, a phosphorus trichloride metering tank, an acetyl chloride receiving tank and an absorption liquid tank; the bottoms of the hydrolysis overhead tank, the glacial acetic acid metering tank and the phosphorus trichloride metering tank are connected with the reaction kettle; the top of the hydrolysis flushing and steaming condenser is communicated with the reaction kettle, and the bottom of the hydrolysis flushing and steaming condenser is communicated with the top of the hydrolysis elevated tank; the bottom of the rectifying tower is communicated with the reaction kettle, and the top of the rectifying tower is communicated with the condensing system; the bottom of the condensation system is communicated with an acetyl chloride receiving tank, the bottom of the acetyl chloride receiving tank is communicated with the top of the rectifying tower, and the condensation system is communicated with the bottom of the absorption tower; the bottom of the absorption tower is communicated with an absorption liquid tank, the bottom of the absorption liquid tank is communicated with the top of the absorption tower through a reflux pump, and the top of the absorption tower is communicated with a falling film absorption device.
The preparation method combines acetyl chloride and hydroxyethylidene diphosphonic acid for production, thereby improving the quality of the finished product of acetyl chloride; meanwhile, the dropping time of phosphorus trichloride in the HEDP reaction of the phosphorus trichloride-glacial acetic acid-water method is shortened, the generation amount of 65% hydrogen chloride gas is reduced, and the quality index of the finished product HEDP is stabilized and improved; the stability of the reaction and the production safety are correspondingly guaranteed; the standardization and the controllability of the whole HEDP production process are realized by controlling the generation amount of the hydrogen chloride gas and other conditions. The production device matched with the preparation method has reasonable design and ensures the continuous stability and standardization of production.
Drawings
FIG. 1 is a schematic view showing the connection structure of a manufacturing apparatus according to the present invention.
In the figure: 1. reaction kettle 2, hydrolysis flushing condenser 3, rectifying tower 4, condensing system 5, absorption tower 6, falling film absorption device 7, hydrolysis head tank 8, glacial acetic acid metering tank 9, phosphorus trichloride metering tank 10, acetyl chloride receiving tank 11, absorption tank 12, stirring system 13, stirrer 14, speed reducer 15, condenser 16, reflux liquid flowmeter 17, gas flowmeter 18, liquid flowmeter
Detailed Description
A preparation method of acetyl chloride and hydroxyethylidene diphosphonic acid is characterized by comprising the following steps:
a) adding glacial acetic acid into a reaction kettle, starting stirring, and finishing dropwise adding phosphorus trichloride into the reaction kettle under normal pressure for 1-2 h, so that the mole number of acetic acid in the reaction kettle is 3.0-3.2 times of that of phosphorus trichloride.
b) And (3) starting steam of a jacket of the reaction kettle, and controlling the flow of the steam of the jacket to be 30-200 kg/h. The reaction kettle can be continuously heated, and the following three operation steps are carried out:
directly receiving liquid acetyl chloride, controlling the amount of hydrogen chloride gas generated by reaction in a kettle to be stable at 30-60 kg/h, operating for 8-12 h, and heating the temperature in the kettle to 40-55 ℃;
step two, controlling the reflux amount of acetyl chloride in the rectifying tower to be 100-500 kg/h, keeping the tower top temperature of the rectifying tower unchanged for more than 0.5h, operating for 2-4 h, and heating the temperature in the kettle to 48-65 ℃;
step three, under the condition that the temperature of the tower top in the step two is kept unchanged, the reflux amount of acetyl chloride is reduced to 50-250 kg/h, the operation is carried out for 5-8 h, and the temperature in the kettle is raised to 55-100 ℃;
the method comprises the following steps of enabling hydroxyl ethylidene diphosphonic acid acetate to be generated through reaction in a kettle, processing acetyl chloride vapor evaporated from the kettle through a rectifying device and a condensing device to obtain liquid acetyl chloride with the content being more than or equal to 99%, absorbing uncondensed acetyl chloride vapor through glacial acetic acid flowing in an absorption tower at the temperature of 12-50 ℃, and enabling hydrogen chloride gas to enter a falling film absorption device after passing through the absorption tower to form hydrochloric acid. The condensing device adopts three-stage condensation, cooling water is introduced into the first-stage condensation, brine ice at the temperature of minus 10 to minus 20 ℃ is introduced into the second-stage condensation, and brine ice at the temperature of minus 20 to minus 30 ℃ is introduced into the third-stage condensation.
c) Stopping the acetyl chloride of the rectifying tower from refluxing into the kettle under the condition that the temperature of the tower top begins to decrease in the third step, wherein the temperature in the kettle is 75-100 ℃;
d) and continuously heating to keep the temperature in the kettle at 120 +/-2 ℃, and carrying out heat preservation on the hydroxyethylidene diphosphonic acid acetate for 1-2 h.
e) Changing the pressure in the kettle from normal pressure to vacuum of-0.01 to-0.06 Mpa, hydrolyzing the hydroxyethylidene diphosphonic acid acetate, steaming, receiving and recovering acetic acid solution and steaming waste water, adding deionized water, adding hydrogen peroxide at 90 ℃ in the kettle for decolorization, and performing filter pressing to obtain a HEDP finished product.
Putting the absorption liquid containing acetyl chloride into the next kettle as glacial acetic acid; the recovered concentrated acetic acid solution can be recycled as glacial acetic acid after rectification and dehydration; the method can also be used as a raw material for HEDP production of a phosphorus trichloride-glacial acetic acid-water method, so that higher economic benefit can be obtained; the recovered dilute acetic acid solution is used as HEDP hydrolysate; the flushing and steaming wastewater is used for absorbing hydrogen chloride gas by a falling film absorption device; the hydroxyethylidene diphosphonic acid acetate is hydrolyzed and steamed under the negative pressure working condition, so that the hydrolysis severity of the hydroxyethylidene diphosphonic acid acetate can be reduced, and the consumption of steam can be reduced. The method takes 16-26 hours in the stage of forming the hydroxyethylidene diphosphonic acid acetate, and takes 8-10 hours in the stage of processing the hydroxyethylidene diphosphonic acid acetate into HEDP.
A preparation device for acetyl chloride coproduction of hydroxyl ethylidene diphosphonic acid comprises a reaction kettle 1 with a stirring system 12, a hydrolysis flushing and steaming condenser 2, a rectifying tower 3, a condensing system 4, an absorption tower 5, a falling film absorption device 6, a hydrolysis elevated tank 7, a glacial acetic acid metering tank 8, a phosphorus trichloride metering tank 9, an acetyl chloride receiving tank 10 and an absorption liquid tank 11; the bottoms of the hydrolysis overhead tank 7, the glacial acetic acid metering tank 8 and the phosphorus trichloride metering tank 9 are connected with the reaction kettle 1; the bottom of the reaction kettle 1 is communicated with a steam pipeline; the top of the hydrolysis flushing and steaming condenser 2 is communicated with the reaction kettle 1, the bottom of the hydrolysis flushing and steaming condenser 2 is communicated with the top of the hydrolysis elevated tank 7, and the bottom of the hydrolysis flushing and steaming condenser 2 is connected with a vacuum pipeline; the hydrolysis head tank 7 is used for receiving the recovered acetic acid and the steam flushing waste water during steam flushing and storing the recovered dilute acetic acid solution for hydrolysis at different time; the bottom of the rectifying tower 3 is communicated with the reaction kettle 1, and the top of the rectifying tower 3 is communicated with the condensing system 4; the bottom of the condensing system 4 is communicated with an acetyl chloride receiving tank 10, the bottom of the acetyl chloride receiving tank 10 is communicated with the top of the rectifying tower 3, a reflux liquid flowmeter 16 is arranged on a communication pipeline between the acetyl chloride receiving tank 10 and the rectifying tower 3 and used for detecting acetyl chloride reflux amount, and the condensing system 4 is communicated with the bottom of the absorption tower 5; the bottom of the absorption tower 5 is communicated with an absorption liquid tank 11, the bottom of the absorption liquid tank 11 is communicated with the top of the absorption tower 5 through a reflux pump, the top of the absorption tower 5 is communicated with a falling film absorption device 6, and a gas flow meter 17 is arranged on a pipeline for mutually communicating the absorption tower 5 and the falling film absorption device 6 and is used for detecting the flow rate of hydrogen chloride gas. The stirring system 12 comprises a stirrer 13 and a speed reducer 14, wherein the stirrer 13 is an anchor stirrer or a frame stirrer, and the speed reducer 14 is a cycloidal pin gear speed reducer. The tower diameters of the rectifying tower 3 and the absorption tower 5 are 200-600 mm. The pipe diameter of a connecting pipeline between the rectifying tower 3 and the reaction kettle 1 is phi 50-150 mm; the pipe diameter of a connecting pipeline between the hydrolysis steaming condenser 2 and the reaction kettle 1 is phi 75-150 mm; the pipe diameter of the connecting pipeline between the phosphorus trichloride metering tank 9 and the reaction kettle 1 is phi 10-50 mm. Condensing system 4 includes the second grade condenser at least, is provided with the U type between 15 bottoms of condenser and acetyl chloride receiving tank 10 and bends, and the U type is bent can form the liquid seal, guarantees that acetyl chloride steam passes through multistage condenser in proper order. A receiving liquid flowmeter 18 is arranged on a communication pipeline between the bottom of the condenser 15 and the acetyl chloride receiving tank 10 and is used for detecting the flow of acetyl chloride entering the acetyl chloride receiving tank, the condenser 15 in the condensing system 4 has two connection modes, the top of the first-choice rectifying tower 3 is communicated with the bottom of a first-class condenser, the top of the first-class condenser is communicated with the bottom of a second-class condenser, the top of the second-class condenser is communicated with the bottom of a third-class condenser, and the top of the third-class condenser is communicated with the bottom of; the top of the rectifying tower 3 can also be communicated with the top of the first-stage condenser, the bottom of the first-stagecondenser is communicated with the top of the second-stage condenser, the bottom of the second-stage condenser is communicated with the top of the third-stage condenser, and the bottom of the third-stage condenser is communicated with the bottom of the absorption tower 5; the first connection is better in condensation than the second connection.
The preparation process according to the invention is illustrated below by means of two specific examples.
Example 1
Adding 2190kg of glacial acetic acid into a 3000-liter reaction kettle; and (3) starting stirring, and dripping 1664kg of 98.5% phosphorus trichloride under normal pressure within 1h, wherein the mole number of acetic acid in the kettle is 36.41Kmol, and the mole number of the phosphorus trichloride is 11.94 Kmol. Directly receiving the condensed acetyl chloride, wherein the generation amount of hydrogen chloride gas is stabilized at 35-50 kg/h, the time is taken for 8h, and the temperature in the kettle is slowly increased to 46 ℃; the reflux amount of acetyl chloride of the rectifying tower is 200-300L/h, the time is 2.5h, the temperature in the kettle is 54 ℃, and the top temperature of the rectifying tower can be stabilized for 0.5 h; the reflux amount of acetyl chloride in the rectifying tower is 100-150L/h, the time is 6h, when the temperature in the kettle is 82 ℃, the temperature at the top of the tower begins to drop, the reflux of the acetyl chloride is stopped, and 1632kg of 99.21 percent finished product acetyl chloride is finally received; the temperature in the kettle is 120 +/-2 ℃, and the heat preservation time for the hydroxyethylidene diphosphonic acid acetate is 1.5 h; absorbing the tail gas by using 400kg of glacial acetic acid at the temperature of 20-30 ℃ through an absorption tower, and then absorbing the tail gas into 1500kg of 31% hydrochloric acid in a falling film absorber, wherein the weight of the absorption liquid isincreased by 35 kg; putting 225kg of 15 percent dilute acid recovered in a kettle for hydrolysis when the vacuum in the kettle is-0.03 Mpa, steaming to obtain 650kg of 70 percent acetic acid solution, 225kg of 15 percent acetic acid and 700 kg of steaming waste water, putting 3kg of 31 percent hydrogen peroxide in the kettle for decolorization when the temperature in the kettle is 90 ℃, 1000kg of deionized water and 1966kg of 58 percent HEDP finished product after filter pressing. The indexes of the obtained HEDP finished product are as follows: HEDP 58%, phosphoric acid 0.43%, phosphorous 0.76%, chloride 0.13%, pH (1% aqueous solution) 1.86, density (20 ℃, g/cm)3)1.43, calcium ion chelate value (mg/g) 516;the HEDP finished product is judged to be a superior product according to HG/T3537-1999 water treatment agent hydroxyethylidene diphosphonic acid standard. The acetyl chloride content was 99.2134% by capillary gas chromatography.
Example two
Adding 3360kg of glacial acetic acid into a 5000L reaction kettle; starting stirring, dripping 2550kg of 98.5 percent phosphorus trichloride under normal pressure within 1.5h, wherein the mole number of acetic acid in the kettle is 55.95Kmol, and the mole number of the phosphorus trichlorideIt was 18.29 Kmol. Directly receiving the condensed acetyl chloride, wherein the generation amount of hydrogen chloride gas is stabilized at 40-55 kg/h, the time is 11h, and the temperature in the kettle is slowly increased to 53 ℃; the reflux amount of acetyl chloride of the rectifying tower is 250-350L/h, the time is 3.5h, the temperature in the kettle is 63 ℃, and the top temperature of the rectifying tower can be stabilized for 0.5 h; the reflux amount of acetyl chloride in the rectifying tower is 100-180L/h, the time is 7h, when the temperature in the kettle is 95 ℃, the temperature at the top of the tower begins to drop, the reflux of the acetyl chloride is stopped, and finally, 2500kg of 99.16% of finished acetyl chloride is obtained; the temperature in the kettle is 120 +/-2 ℃, and the heat preservation time for the hydroxyethylidene diphosphonic acid acetate is 2 hours; absorbing the tail gas by using 800kg of glacial acetic acid at the temperature of 20-30 ℃ in an absorption tower, and then absorbing the tail gas into 2300kg of 31% hydrochloric acid in a falling film absorber, wherein the weight of the absorption liquid is increased by 60 kg; when the vacuum in the kettle is-0.03 Mpa, putting 345kg of 15 percent dilute acid recovered in a kettle for hydrolysis, and carrying out flash evaporation to obtain 1000kg of 70 percent acetic acid solution, 345kg of 15 percent acetic acid and 1000kg of flash evaporation waste water; 10kg of hydrogen peroxide and 1530kg of deionized water are added into the kettle at 90 ℃ for decolorization, and 58% HEDP finished product 3017kg is obtained after filter pressing. The indexes of the obtained HEDP finished product are as follows: HEDP 58%, phosphoric acid 0.41%, phosphorous 0.82%, chloride 0.11%, pH (1% aqueous solution) 1.92, density (20 ℃, g/cm)3)1.44, calcium ion sequestration value (mg/g) 523; the HEDP finished product is judged to be a superior product according to HG/T3537-1999 water treatment agent hydroxyethylidene diphosphonic acid standard. The acetyl chloride content was 99.1626% by capillary gas chromatography.
Claims (10)
1. A preparation method of acetyl chloride and hydroxyethylidene diphosphonic acid is characterized by comprising the following steps:
a) adding glacial acetic acid into a reaction kettle, starting stirring, and finishing dropwise adding phosphorus trichloride into the reaction kettle under normal pressure for 1-2 h to ensure that the mole number of acetic acid in the reaction kettle is 3.0-3.2 times of that of phosphorustrichloride;
b) the method comprises the following steps of starting jacket steam of a reaction kettle, controlling the flow of the jacket steam to enable the reaction kettle to be heated continuously, enabling the reaction kettle to react to generate hydroxyethylidene diphosphonate acetate, processing acetyl chloride vapor evaporated from the kettle by a rectifying device and a condensing device to obtain liquid acetyl chloride with the content of more than or equal to 99%, absorbing uncondensed acetyl chloride vapor by absorption liquid flowing in an absorption tower at the temperature of 12-50 ℃, and enabling hydrogen chloride gas to enter a falling film absorption device after passing through the absorption tower to form hydrochloric acid:
directly receiving liquid acetyl chloride, controlling the amount of hydrogen chloride gas generated by reaction in a kettle to be stable at 30-60 kg/h, operating for 8-12 h, and heating the temperature in the kettle to 40-55 ℃;
step two, controlling the reflux amount of acetyl chloride in the rectifying tower to be 100-500 kg/h, keeping the tower top temperature of the rectifying tower unchanged for more than 0.5h, operating for 2-4 h, and heating the temperature in the kettle to 48-65 ℃;
step three, under the condition that the temperature of the tower top in the step two is kept unchanged, the reflux amount of acetyl chloride is reduced to 50-250 kg/h, the operation is carried out for 5-8 h, and the temperature in the kettle is raised to 55-100 ℃;
c) stopping acetyl chloride reflux of the rectifying tower under the condition that the temperature of the tower top in the third step begins to decrease, wherein the temperature in the kettle is 75-100 ℃;
d) continuously heating to keep the temperature in the kettle at 120 +/-2 ℃, and carrying out heat preservation on the hydroxyethylidene diphosphonic acid acetate for 1-2 h;
e) changing the pressure in the kettle from normal pressure to vacuum of-0.01 to-0.06 Mpa, hydrolyzing the hydroxyethylidene diphosphonic acid acetate, steaming, receiving and recovering an acetic acid solution and steaming waste water; adding deionized water, adding hydrogen peroxide at 90 ℃ in the kettle for decolorization, and performing filter pressing to obtain a HEDP finished product.
2. The method for preparing acetyl chloride and hydroxyethylidene diphosphonic acid as claimed in claim 1, wherein the method comprises the following steps: the steam flow of the reaction kettle jacket is 30-200 kg/h.
3. The method for preparing acetyl chloride and hydroxyethylidene diphosphonic acid as claimed in claim 1, wherein the method comprises the following steps: the condensing device adopts three-stage condensation, cooling water is introduced into the first-stage condensation, brine ice at the temperature of minus 10 to minus 20 ℃ is introduced into the second-stage condensation, and brine ice at the temperature of minus 20 to minus 30 ℃ is introduced into the third-stage condensation.
4. The method for preparing acetyl chloride and hydroxyethylidene diphosphonic acid as claimed in claim 1, wherein the method comprises the following steps: and the absorption liquid of the absorption tower adopts glacial acetic acid.
5. The method for preparing acetyl chloride and hydroxyethylidene diphosphonic acid as claimed in claim 1, wherein the method comprises the following steps: the content of the hydrogen peroxide is 31 percent, and the mole number of the hydrogen peroxide is 1.5 multiplied by 10 of that of the phosphorus trichloride-3～4×10-3And (4) doubling.
6. A preparation device for acetyl chloride coproduction of hydroxyl ethylidene diphosphonic acid is characterized in that: comprises a reaction kettle (1) with a stirring system (12), a hydrolysis flash condenser (2), a rectifying tower (3), a condensing system (4), an absorption tower (5), a falling film absorption device (6), a hydrolysis head tank (7), a glacial acetic acid metering tank (8), a phosphorus trichloride metering tank (9), an acetyl chloride receiving tank (10) and an absorption liquid tank (11); the bottoms of the hydrolysis overhead tank (7), the glacial acetic acid metering tank (8) and the phosphorus trichloride metering tank (9) are connected with the reaction kettle (1); the top of the hydrolysis flushing and steaming condenser (2) is communicated with the reaction kettle (1), and the bottom of the hydrolysis flushing and steaming condenser (2) is communicated with the top of the hydrolysis elevated tank (7); the bottom of the rectifying tower (3) is communicated with the reaction kettle (1), and the top of the rectifying tower (3) is communicated with the condensing system (4); the bottom of the condensing system (4) is communicated with an acetyl chloride receiving tank (10), the bottom of the acetyl chloride receiving tank (10) is communicated with the top of the rectifying tower (3), and the condensing system (4) is communicated with the bottom of the absorption tower (5); the bottom of the absorption tower (5) is communicated with an absorption liquid tank (11), the bottom of the absorption liquid tank (11) is communicated with the top of the absorption tower (5) through a reflux pump, and the top of the absorption tower (5) is communicated with a falling film absorption device (6).
7. The apparatus for preparing acetylchloride and hydroxyethylidene diphosphonic acid as claimed in claim 6, wherein: the stirring system (12) comprises a stirrer (13) and a speed reducer (14), wherein the stirrer (13) is an anchor stirrer or a frame stirrer, and the speed reducer (14) is a cycloidal pin gear speed reducer.
8. The apparatus for preparing acetyl chloride and hydroxyethylidene diphosphonic acid as claimed in claim 6, wherein: the tower diameters of the rectifying tower (3) and the absorption tower (5) are phi 200-600 mm.
9. The apparatus for preparing acetyl chloride and hydroxyethylidene diphosphonic acid as claimed in claim 6, wherein: the pipe diameter of a connecting pipeline between the rectifying tower (3) and the reaction kettle (1) is phi 50-150 mm; the pipe diameter of a connecting pipeline between the hydrolysis steaming condenser (2) and the reaction kettle (1) is phi 75-150 mm; the pipe diameter of a connecting pipeline between the phosphorus trichloride metering tank (9) and the reaction kettle (1) is phi 10-50 mm.
10. The apparatus for preparing acetyl chloride and hydroxyethylidene diphosphonic acid as claimed in claim 6, wherein: the condensing system (4) at least comprises a secondary condenser, and a U-shaped bend is arranged between the bottom of the condenser (15) and the acetyl chloride receiving tank (10).
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| CN101386628B (en) * | 2008-10-29 | 2010-12-15 | 河南清水源科技股份有限公司 | Hydroxylethylidene diphosphonic acid with arsenic content <=3ppm and preparation technique thereof |
| WO2011023280A1 (en) * | 2009-08-28 | 2011-03-03 | Synthon B.V. | Process for making 1-hydroxyalkylidene-1,1-biphosphonic acids |
| CN102278868A (en) * | 2011-08-02 | 2011-12-14 | 济南圣泉集团股份有限公司 | Exhaust gas recycling technology and device in isothiocyanate preparation |
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| CN106366124A (en) * | 2016-08-31 | 2017-02-01 | 南通联膦化工有限公司 | Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid |
| CN107602611A (en) * | 2017-09-11 | 2018-01-19 | 南通意特化工有限公司 | A kind of production technology that hydroxy ethylene diphosphonic acid is prepared using chloroacetic chloride waste liquid |
| CN109956969A (en) * | 2019-04-25 | 2019-07-02 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of hydroxy ethylene diphosphonic acid |
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| CN1043044C (en) * | 1993-02-16 | 1999-04-21 | 化学工业部天津化工研究院 | Method for preparation of hydroxy-ethylene-diphosphonic acid |
| CN1616469A (en) * | 2004-09-20 | 2005-05-18 | 张益军 | Method for coproducing acetyl chloride and hydroxy ethylidene diphosphonic acid |
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| CN101386628B (en) * | 2008-10-29 | 2010-12-15 | 河南清水源科技股份有限公司 | Hydroxylethylidene diphosphonic acid with arsenic content <=3ppm and preparation technique thereof |
| WO2011023280A1 (en) * | 2009-08-28 | 2011-03-03 | Synthon B.V. | Process for making 1-hydroxyalkylidene-1,1-biphosphonic acids |
| CN102278868A (en) * | 2011-08-02 | 2011-12-14 | 济南圣泉集团股份有限公司 | Exhaust gas recycling technology and device in isothiocyanate preparation |
| CN103570760A (en) * | 2013-11-25 | 2014-02-12 | 山东化友化学有限公司 | Method for producing etidronic acid |
| CN103570760B (en) * | 2013-11-25 | 2015-12-09 | 山东化友化学有限公司 | Hydroxy ethylene diphosphonic acid production unit and method thereof |
| CN106366124A (en) * | 2016-08-31 | 2017-02-01 | 南通联膦化工有限公司 | Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid |
| CN107602611A (en) * | 2017-09-11 | 2018-01-19 | 南通意特化工有限公司 | A kind of production technology that hydroxy ethylene diphosphonic acid is prepared using chloroacetic chloride waste liquid |
| CN109956969A (en) * | 2019-04-25 | 2019-07-02 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of hydroxy ethylene diphosphonic acid |
| CN111318244A (en) * | 2020-02-26 | 2020-06-23 | 青岛长荣化工科技有限公司 | Phosphonate ester hydrolysis device and method |
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Application publication date: 20070418 Assignee: Nanjing Chemical Engineering Institute Changzhou Wujin Water Quality Stabilizer Factory Assignor: Zhou Hui Contract record no.: 2010320000097 Denomination of invention: Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction Granted publication date: 20081217 License type: Exclusive License Record date: 20100222 |
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