CN103665034A - Method for realizing continuous hydrolysis in production process of hydroxyl ethylidene diphosphonic acid - Google Patents
Method for realizing continuous hydrolysis in production process of hydroxyl ethylidene diphosphonic acid Download PDFInfo
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- CN103665034A CN103665034A CN201310635598.7A CN201310635598A CN103665034A CN 103665034 A CN103665034 A CN 103665034A CN 201310635598 A CN201310635598 A CN 201310635598A CN 103665034 A CN103665034 A CN 103665034A
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Abstract
The invention provides a method for realizing continuous hydrolysis of acetylated hydroxyl ethylidene diphosphonic acid in the production process of hydroxyl ethylidene diphosphonic acid. The method comprises the following steps: phosphorus trichloride and glacial acetic acid are subjected to continuous tubular reaction and then enter a gas liquid separator to be separated, and a liquid-phase intermediate product acetylated hydroxyl ethylidene diphosphonic acid is sprayed from the top of a hydrolysis tower and encounters water vapor which ascends from the bottom of the tower to perform hydrolysis. The process realizes continuous hydrolysis of the acetylated hydroxyl ethylidene diphosphonic acid, and the obtained product has high quality and stable performance.
Description
Technical field
The invention belongs to water treatment agent field, a kind of hydroxy ethylene diphosphonic acid production process hydrolysis continuous process is provided.
Background technology
HEDP is as water conditioner, Stability Analysis of Structures, and facile hydrolysis, at 250 ℃, through 216h hydrolysis, percent hydrolysis is only 50%; Anticorrosion-antiscaling effect is good; and to have good corrosion mitigating effect be a kind of cathode type inhibiter; in middle high rigidity and basicity water quality; the HEDP of low concentration and two valence metal ions act on metallic surface and form precipitation protective membrane, and corrosion inhibition rate can reach more than 90%, to the scale inhibition performance of carbonate, can reach more than 50%; in deionized water medium; the HEDP of higher concentration mainly forms chemisorbed film in metallic surface, also have certain corrosion mitigating effect, as the HEDP corrosion inhibition rate of 40mg/L can reach more than 90%.Compatibility is good, compound with other water conditioners such as polycarboxylate, zinc salts, has obvious synergy.As with polycarboxylate compound use, the successful of resistance calcium carbonate scale is improved, can bring up to more than 70% from 50%; With zinc salt compound use, to the corrosion mitigating effect of carbon steel, can bring up to more than 98% from 90%.Use metering low, toxicity is low.
HEDP is one of regeneration product of inorganic phosphorus as water conditioner, in phosphine system formula as a kind of main ingredient, be widely used in the industrial circulating cooling water systems such as electric power, chemical industry, metallurgy, chemical fertilizer and in, scale inhibition and the inhibition of low pressure boiler, oil-field flooding and pipe laying; In light and textile industries, can make metal and nonmetallic clean-out system, bleaching and dyeing industrial peroxide stabiliser and laking agent, the complexing agent of cyanideless electro-plating industry.
Production technique how to improve HEDP improves its production capacity, improves its quality product, to meet the demand of various circles of society to water treatment agent, is the matter of utmost importance in current its industrial production.HEDP generally has 4 synthetic routes, (1) phosphorus trichloride, Glacial acetic acid and water reaction; (2) ortho-phosphoric acid, aceticanhydride and excess acetyl chloride; (3) phosphorous acid and aceticanhydride reaction; (4) ortho-phosphoric acid and aceticanhydride reaction.The synthetic method of industrial conventional simple economy is the reaction that (1) phosphorus trichloride, Glacial acetic acid and water are raw material.But synthetic method in sum all adopts intermittent type still reaction, whole building-up process is all that production efficiency is low with batch reactor esterification, hydrolysis, distillation, energy consumption is large, it is large that production process produces a large amount of wastewater treatments load, and blowdown, pollution treatment intensity are high, and product performance less stable.
In order to change the shortcoming of traditional technology, the invention provides a kind of hydroxy ethylene diphosphonic acid production process hydrolysis continuous process, be intended to reasonable energy utilization and reduce product cost, boost productivity, increase the stability of product.
Summary of the invention
The technique way taked is in order to achieve the above object: take phosphorus trichloride, Glacial acetic acid is raw material, pumps into according to a certain percentage tubular reactor, carries out Hybrid Heating continuous reaction.Reaction product out enters gas-liquid separator separates from tubular reactor, and gaseous component Acetyl Chloride 98Min. and hydrogenchloride enter condensing tower and at overhead condensation, obtains the Acetyl Chloride 98Min. of high density, and hydrogenchloride enters multistage absorption device manufacture grade hydrochloric acid.Liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid drenches and the hydrolysis of meeting of rising high-temperature water vapor at the bottom of tower from hydrolysis tower top spray with certain speed, in tower reactor, collects to obtain hydroxy ethylene diphosphonic acid, acetic acid steam from tower top through condensation recovery.
Above-mentioned is 5 ~ 15:1 from tower top spray liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid with hypogene water steam mass flow ratio.
At the bottom of above-mentioned tower, the top hole pressure of water vapor is 0.2 ~ 0.5MPa.
The temperature out of above-mentioned water vapor is 120 ~ 160 ℃.
The tower height of above-mentioned hydrolysis tower is 10 ~ 30 meters.
The stage number of above-mentioned hydrolysis tower is 5 ~ 20.
Excellent characteristics of the present invention is the serialization that has realized whole production process, boosts productivity, and save energy cost, reduces occupation area of equipment; Improve on the other hand the stability of product performance, improved the appearance luster of product.
Specific embodiment
Embodiment 1
Take phosphorus trichloride and Glacial acetic acid as raw material, according to the ratio of 1:3.5, pump into tubular reactor, carry out Hybrid Heating continuous reaction.Reaction product out enters gas-liquid separator separates from tubular reactor, and gaseous component enters condensing tower and obtains Acetyl Chloride 98Min. at tower top, and hydrogenchloride enters multistage absorption device manufacture grade hydrochloric acid.Liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid is from the hydrolysis of meeting of hydrolysis tower tower top spray and rising high-temperature water vapor; gained target product hydroxy ethylene diphosphonic acid and holding tank at the bottom of liquefaction water vapor formation solution inflow tower, the vaporization of by product acetic acid enters condensate recycling device from tower top.
Wherein, high-temperature water vapor temperature is 120 ℃, at the bottom of tower, with top hole pressure 0.5MPa, sprays into hydrolysis tower; The mass flux ratio of acetylize hydroxy ethylene diphosphonic acid and high-temperature steam is 10:1; Hydrolysis tower height is 12 meters, and stage number is 6.
Embodiment 2
Take phosphorus trichloride and Glacial acetic acid as raw material, according to the ratio of 1:3.5, pump into tubular reactor, carry out Hybrid Heating continuous reaction.Reaction product out enters gas-liquid separator separates from tubular reactor, and gaseous component enters condensing tower and obtains Acetyl Chloride 98Min. at tower top, and hydrogenchloride enters multistage absorption device manufacture grade hydrochloric acid.Liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid is from the hydrolysis of meeting of hydrolysis tower tower top spray and rising high-temperature water vapor; gained target product hydroxy ethylene diphosphonic acid and holding tank at the bottom of liquefaction water vapor formation solution inflow tower, the vaporization of by product acetic acid enters condensate recycling device from tower top.
Wherein, high-temperature water vapor temperature is 130 ℃, at the bottom of tower, with top hole pressure 0.4MPa, sprays into hydrolysis tower; The mass flux ratio of acetylize hydroxy ethylene diphosphonic acid and high-temperature steam is 15:1; Hydrolysis tower height is 15 meters, and stage number is 6.
Embodiment 3
Take phosphorus trichloride and Glacial acetic acid as raw material, according to the ratio of 1:3.5, pump into tubular reactor, carry out Hybrid Heating continuous reaction.Reaction product out enters gas-liquid separator separates from tubular reactor, and gaseous component enters condensing tower and obtains Acetyl Chloride 98Min. at tower top, and hydrogenchloride enters multistage absorption device manufacture grade hydrochloric acid.Liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid is from the hydrolysis of meeting of hydrolysis tower tower top spray and rising high-temperature water vapor; gained target product hydroxy ethylene diphosphonic acid and holding tank at the bottom of liquefaction water vapor formation solution inflow tower, the vaporization of by product acetic acid enters condensate recycling device from tower top.
Wherein, high-temperature water vapor temperature is 140 ℃, at the bottom of tower, with top hole pressure 0.2MPa, sprays into hydrolysis tower; The mass flux ratio of acetylize hydroxy ethylene diphosphonic acid and high-temperature steam is 8:1; Hydrolysis tower height is 18 meters, and stage number is 7.
Embodiment 4
Take phosphorus trichloride and Glacial acetic acid as raw material, according to the ratio of 1:3.5, pump into tubular reactor, carry out Hybrid Heating continuous reaction.Reaction product out enters gas-liquid separator separates from tubular reactor, and gaseous component enters condensing tower and obtains Acetyl Chloride 98Min. at tower top, and hydrogenchloride enters multistage absorption device manufacture grade hydrochloric acid.Liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid is from the hydrolysis of meeting of hydrolysis tower tower top spray and rising high-temperature water vapor; gained target product hydroxy ethylene diphosphonic acid and holding tank at the bottom of liquefaction water vapor formation solution inflow tower, the vaporization of by product acetic acid enters condensate recycling device from tower top.
Wherein, high-temperature water vapor temperature is 140 ℃, at the bottom of tower, with top hole pressure 0.3MPa, sprays into hydrolysis tower; The mass flux ratio of acetylize hydroxy ethylene diphosphonic acid and high-temperature steam is 10:1; Hydrolysis tower height is 20 meters, and stage number is 8.
Embodiment 5
Take phosphorus trichloride and Glacial acetic acid as raw material, according to the ratio of 1:3.5, pump into tubular reactor, carry out Hybrid Heating continuous reaction.Reaction product out enters gas-liquid separator separates from tubular reactor, and gaseous component enters condensing tower and obtains Acetyl Chloride 98Min. at tower top, and hydrogenchloride enters multistage absorption device manufacture grade hydrochloric acid.Liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid is from the hydrolysis of meeting of hydrolysis tower tower top spray and rising high-temperature water vapor; gained target product hydroxy ethylene diphosphonic acid and holding tank at the bottom of liquefaction water vapor formation solution inflow tower, the vaporization of by product acetic acid enters condensate recycling device from tower top.
Wherein, high-temperature water vapor temperature is 140 ℃, at the bottom of tower, with top hole pressure 0.5MPa, sprays into hydrolysis tower; The mass flux ratio of acetylize hydroxy ethylene diphosphonic acid and high-temperature steam is 12:1; Hydrolysis tower height is 26 meters, and stage number is 10.
Claims (6)
1. hydroxy ethylene diphosphonic acid production process hydrolysis continuous process, is characterized in that, take phosphorus trichloride, Glacial acetic acid is raw material, pumps into tubular reactor, carries out Hybrid Heating continuous reaction; Reaction product out enters gas-liquid separator separates from tubular reactor, and gaseous component enters condensing tower and at tower top, obtains the Acetyl Chloride 98Min. of concentration >=90%, and hydrogenchloride enters multistage absorption device manufacture grade hydrochloric acid; Liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid drenches and the hydrolysis of meeting of rising high-temperature water vapor from hydrolysis tower top spray, in tower reactor, collects to obtain hydroxy ethylene diphosphonic acid, acetic acid steam from tower top through condensation recovery.
2. hydroxy ethylene diphosphonic acid production process hydrolysis continuous process according to claim 1, is characterized in that, from tower top spray liquid phase intermediate product acetylize hydroxy ethylene diphosphonic acid, is 5 ~ 15:1 with hypogene water steam mass flow ratio.
3. hydroxy ethylene diphosphonic acid production process hydrolysis continuous process according to claim 1, is characterized in that, at the bottom of tower, the top hole pressure of water vapor is 0.2 ~ 0.5MPa.
4. hydroxy ethylene diphosphonic acid production process hydrolysis continuous process according to claim 1, is characterized in that, the temperature out of water vapor is 120 ~ 160 ℃.
5. hydroxy ethylene diphosphonic acid production process hydrolysis continuous process according to claim 1, is characterized in that, the tower height of hydrolysis tower is 10 ~ 30 meters.
6. hydroxy ethylene diphosphonic acid production process hydrolysis continuous process according to claim 1, is characterized in that, the stage number of hydrolysis tower is 5 ~ 10.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311596A (en) * | 2014-09-14 | 2015-01-28 | 山东省泰和水处理有限公司 | 2-phosphonobutane-1,2,4-tricarboxylic acid production hydrolysis continuous technology |
| CN106588979A (en) * | 2016-10-28 | 2017-04-26 | 河南清水源科技股份有限公司 | Synthesis method for multistage power-free bubble-type (hydroxyethylidene)diphosphonic acid |
| 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 |
| CN115845758A (en) * | 2021-09-24 | 2023-03-28 | 浙江医药股份有限公司新昌制药厂 | Continuous reaction device and method for preparing phosphoric acid diester compound through continuous reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875594A (en) * | 2012-10-20 | 2013-01-16 | 山东省泰和水处理有限公司 | Continuous synthesis technique of hydroxyethylidenediphosphonic acid |
| CN103265576A (en) * | 2013-05-22 | 2013-08-28 | 山东省泰和水处理有限公司 | Low-concentration acetic acid concentrating process for hydroxyl ethylidene diphosphonic acid production process |
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2013
- 2013-12-03 CN CN201310635598.7A patent/CN103665034A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875594A (en) * | 2012-10-20 | 2013-01-16 | 山东省泰和水处理有限公司 | Continuous synthesis technique of hydroxyethylidenediphosphonic acid |
| CN103265576A (en) * | 2013-05-22 | 2013-08-28 | 山东省泰和水处理有限公司 | Low-concentration acetic acid concentrating process for hydroxyl ethylidene diphosphonic acid production process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311596A (en) * | 2014-09-14 | 2015-01-28 | 山东省泰和水处理有限公司 | 2-phosphonobutane-1,2,4-tricarboxylic acid production hydrolysis continuous technology |
| CN106588979A (en) * | 2016-10-28 | 2017-04-26 | 河南清水源科技股份有限公司 | Synthesis method for multistage power-free bubble-type (hydroxyethylidene)diphosphonic acid |
| CN106588979B (en) * | 2016-10-28 | 2018-11-27 | 河南清水源科技股份有限公司 | A kind of multi-stage non-powered bubble type hydroxy ethylene diphosphonic acid synthetic method |
| 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 |
| CN115845758A (en) * | 2021-09-24 | 2023-03-28 | 浙江医药股份有限公司新昌制药厂 | Continuous reaction device and method for preparing phosphoric acid diester compound through continuous reaction |
| CN115845758B (en) * | 2021-09-24 | 2024-10-08 | 浙江医药股份有限公司新昌制药厂 | Continuous reaction device and method for preparing phosphoric acid diester compound by continuous reaction |
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Application publication date: 20140326 |