CN106083924A - A kind of preparation method of 1-hydroxy ethylidene-1,1-diphosphonic acid - Google Patents
A kind of preparation method of 1-hydroxy ethylidene-1,1-diphosphonic acid Download PDFInfo
- Publication number
- CN106083924A CN106083924A CN201610380252.0A CN201610380252A CN106083924A CN 106083924 A CN106083924 A CN 106083924A CN 201610380252 A CN201610380252 A CN 201610380252A CN 106083924 A CN106083924 A CN 106083924A
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- CN
- China
- Prior art keywords
- acetic acid
- reactor
- preparation
- hydroxy ethylidene
- phosphorus trichloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000010792 warming Methods 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 239000011552 falling film Substances 0.000 claims abstract description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000011017 operating method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The present invention relates to chemical technology field, particularly relate to the preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid, comprise the following steps: (1) is by phosphorus trichloride suction reactor, it is heated to 65～75 DEG C, dripping the mixture of acetic acid and water in reactor, tail gas obtains the hydrogen chloride of by-product 30% through three grades of falling film absorption；(2) material in reactor is warming up to 105～115 DEG C of esterifications 2～4 hours after finishing by dropping, and tail gas is condensed obtains chloroacetic chloride；(3) it is passed through steam hydrolysis, be warming up to 120～125 DEG C of Distillation recovery acetic acid.Operating procedure of the present invention is simple, and cost is relatively low, and saves the reaction time, and reduces energy consumption.
Description
Technical field
The present invention relates to chemical technology field, particularly relate to the preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid.
Background technology
1-hydroxy ethylidene-1,1-diphosphonic acid has good complexing and cushioning effect, is widely used industrial, such as recirculated water
Antisludging agent, metal corrosion inhibitor and the washing agent etc. processing.The production method of 1-hydroxy ethylidene-1,1-diphosphonic acid is a lot, with phosphorus trichloride
With the synthetic method that acetic acid is raw material, cost of material is relatively low, becomes the main side of current industrial production 1-hydroxy ethylidene-1,1-diphosphonic acid
Method.
The preparation method of existing 1-hydroxy ethylidene-1,1-diphosphonic acid, is all first according to processing compound, acetic acid and water to be put into reactor
In, under the environment below 45 DEG C, in reactor, drip phosphorus trichloride generation chlorination reaction, after dripping, be warming up to 110
DEG C occur esterification, tail gas condensed chloroacetic chloride；Be passed through steam hydrolysis last target product.The method is due to trichlorine
Changing phosphorus and the reaction of acetic acid being an endothermic reaction, so comparing power consumption, and reaction speed is slower.
Due to water and acetic acid excess in reactor during phosphorus trichloride dropping, therefore phosphorus trichloride first reacts with water, must
Must be when water total overall reaction complete phosphorus trichloride ability and acetic acid reaction, therefore whole process is that first heat release is absorbed heat again, so waits water complete
After portion has reacted, the heat released just dissipates greatly, when phosphorus trichloride again with acetic acid reaction when, just need
Thermal source to be additionally provided reacts for it, therefore adds the reaction time, wastes heat-source energy simultaneously.
Content of the invention
The present invention, in order to overcome the deficiency of above-mentioned technical problem, provides the preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid,
The method operating procedure is simple, and cost is relatively low, and saves the reaction time, and reduces energy consumption.
The technical scheme solving above-mentioned technical problem is as follows:
The preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid, comprises the following steps:
(1) it by phosphorus trichloride suction reactor, is heated to 65～75 DEG C, in reactor, drip the mixing of acetic acid and water
Thing, tail gas obtains the hydrogen chloride of by-product 30% through three grades of falling film absorption, and the mol ratio of described phosphorus trichloride, acetic acid and water is 1:
1.5:1.5；
(2) material in reactor is warming up to 105～115 DEG C of esterifications 2～4 hours after finishing by dropping, and tail gas is through cold
Coagulate to obtain chloroacetic chloride；
(3) it is passed through steam hydrolysis, be warming up to 120～125 DEG C of Distillation recovery acetic acid.
Acetate concentration is more than 98%.
Rate of addition described in step (1) is 30～90kg/h.
The present invention provides the preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid, adds to acetic acid and water droplet in phosphorus trichloride,
During dropping, owing to, in whole course of reaction, phosphorus trichloride is excessive, so owing to the amount of water and acetic acid is not enough, three
Phosphorus chloride drips in reactor, first first reacts with water, owing to the amount of phosphorus trichloride is far longer than the amount of water and acetic acid, and therefore three
Phosphorus chloride and acetic acid just react subsequently, and phosphorus trichloride is exothermic reaction with the reaction of water, the reaction of phosphorus trichloride and acetic acid
Being the endothermic reaction, therefore, heat required during phosphorus trichloride and acetic acid reaction can anti-from phosphorus trichloride and water
Obtain inside the heat that should release, therefore save the reaction time and reduce energy consumption.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further detailed explanation.
Embodiment 1:
The preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid, comprises the following steps:
(1) it by phosphorus trichloride suction reactor, is heated to 65 DEG C, in reactor, drip the mixture of acetic acid and water,
Tail gas obtains the hydrogen chloride of by-product 30% through three grades of falling film absorption, and the mol ratio of described phosphorus trichloride, acetic acid and water is 1:1.5:
1.5；
(2) material in reactor is warming up to 105 DEG C of esterifications 2 hours after finishing by dropping, and tail gas is condensed obtains acetyl
Chlorine；
(3) it is passed through steam hydrolysis, be warming up to 120 DEG C of Distillation recovery acetic acid.
Acetate concentration is more than 98%.
Rate of addition described in step (1) is 30kg/h.
Embodiment 2:
The preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid, comprises the following steps:
(1) it by phosphorus trichloride suction reactor, is heated to 75 DEG C, in reactor, drip the mixture of acetic acid and water,
Tail gas obtains the hydrogen chloride of by-product 30% through three grades of falling film absorption, and the mol ratio of described phosphorus trichloride, acetic acid and water is 1:1.5:
1.5；
(2) material in reactor is warming up to 115 DEG C of esterifications 4 hours after finishing by dropping, and tail gas is condensed obtains acetyl
Chlorine；
(3) it is passed through steam hydrolysis, be warming up to 125 DEG C of Distillation recovery acetic acid.
Acetate concentration is more than 98%.
Rate of addition described in step (1) is 90kg/h.
Embodiment 3:
The preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid, comprises the following steps:
(1) it by phosphorus trichloride suction reactor, is heated to 70 DEG C, in reactor, drip the mixture of acetic acid and water,
Tail gas obtains the hydrogen chloride of by-product 30% through three grades of falling film absorption, and the mol ratio of described phosphorus trichloride, acetic acid and water is 1:1.5:
1.5；
(2) material in reactor is warming up to 110 DEG C of esterifications 3 hours after finishing by dropping, and tail gas is condensed obtains acetyl
Chlorine；
(3) it is passed through steam hydrolysis, be warming up to 123 DEG C of Distillation recovery acetic acid.
Acetate concentration is more than 98%.
Rate of addition described in step (1) is 60kg/h.
Operating procedure of the present invention is simple, and cost is relatively low, and saves the reaction time, and reduces energy consumption.
The above, be only presently preferred embodiments of the present invention, not does any pro forma restriction to the present invention, every depends on
According to any simple modification in the technical spirit of the present invention made above example, equivalent variations, each fall within the guarantor of the present invention
Within the scope of protecting.
Claims (3)
1. the preparation method of a 1-hydroxy ethylidene-1,1-diphosphonic acid, it is characterised in that comprise the following steps:
(1) it by phosphorus trichloride suction reactor, is heated to 65～75 DEG C, in reactor, drip the mixture of acetic acid and water,
Tail gas obtains the hydrogen chloride of by-product 30% through three grades of falling film absorption, and the mol ratio of described phosphorus trichloride, acetic acid and water is 1:1.5:
1.5；
(2) material in reactor is warming up to 105～115 DEG C of esterifications 2～4 hours after finishing by dropping, and tail gas is condensed to be obtained
Chloroacetic chloride；
(3) it is passed through steam hydrolysis, be warming up to 120～125 DEG C of Distillation recovery acetic acid.
2. the preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid according to claim 1, it is characterised in that acetate concentration is more than
98%.
3. the preparation method of a kind of 1-hydroxy ethylidene-1,1-diphosphonic acid according to claim 1, it is characterised in that institute in step (1)
The rate of addition stated is 30～90kg/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610380252.0A CN106083924A (en) | 2016-05-31 | 2016-05-31 | A kind of preparation method of 1-hydroxy ethylidene-1,1-diphosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610380252.0A CN106083924A (en) | 2016-05-31 | 2016-05-31 | A kind of preparation method of 1-hydroxy ethylidene-1,1-diphosphonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106083924A true CN106083924A (en) | 2016-11-09 |
Family
ID=57230866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610380252.0A Pending CN106083924A (en) | 2016-05-31 | 2016-05-31 | A kind of preparation method of 1-hydroxy ethylidene-1,1-diphosphonic acid |
Country Status (1)
| Country | Link |
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| CN (1) | CN106083924A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418883A (en) * | 2002-09-24 | 2003-05-21 | 复旦大学 | Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid |
| CN1827625A (en) * | 2006-03-29 | 2006-09-06 | 傅明珠 | Process for synthesis of hydroxy ethidene diphosphoric acid |
| CN102030776A (en) * | 2009-09-28 | 2011-04-27 | 天津市化学试剂研究所 | Method for preparing hydroxyl-ethidene diphosphoric acid |
| 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) |
-
2016
- 2016-05-31 CN CN201610380252.0A patent/CN106083924A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418883A (en) * | 2002-09-24 | 2003-05-21 | 复旦大学 | Method for producing 1-hydroxy ethylene-1,1-diphosphonic acid |
| CN1827625A (en) * | 2006-03-29 | 2006-09-06 | 傅明珠 | Process for synthesis of hydroxy ethidene diphosphoric acid |
| CN102030776A (en) * | 2009-09-28 | 2011-04-27 | 天津市化学试剂研究所 | Method for preparing hydroxyl-ethidene diphosphoric acid |
| 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) |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161109 |
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| RJ01 | Rejection of invention patent application after publication |