CN106366124A - Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid - Google Patents
Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid Download PDFInfo
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- CN106366124A CN106366124A CN201610799416.3A CN201610799416A CN106366124A CN 106366124 A CN106366124 A CN 106366124A CN 201610799416 A CN201610799416 A CN 201610799416A CN 106366124 A CN106366124 A CN 106366124A
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- waste liquid
- chloroacetic chloride
- production technology
- acetic acid
- deionized water
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- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 239000002699 waste material Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000005516 engineering process Methods 0.000 title claims abstract description 32
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 title abstract 6
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 title abstract 6
- 239000012346 acetyl chloride Substances 0.000 title abstract 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 7
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 54
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 238000004821 distillation Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 239000010865 sewage Substances 0.000 claims description 8
- 238000010025 steaming Methods 0.000 claims description 8
- 239000003039 volatile agent Substances 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 5
- 238000007689 inspection Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 150000001263 acyl chlorides Chemical class 0.000 description 6
- 229920002367 Polyisobutene Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000003839 salts Chemical class 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
Landscapes
- 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 invention discloses a production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid. The production technology is completed by taking the acetyl chloride waste liquid with the mass fraction of 50% to 70%, deionized water and phosphorus trichloride as raw materials according to the following specific steps (please see the steps in the description). The content by HEDP of active ingredients in HEDP produced through the technology is 98% or above; the percent content of a pure acetic acid solution obtained through separation according to the technology ranges from 70% to 90%. The technology for preparing HEDP from the acetyl chloride waste liquid is developed, and compared with a traditional technology, the utilization efficiency of acetyl chloride is increased, the purpose of changing waste materials into things of value is achieved, and the production cost is significantly reduced. According to the production technology, recycling utilization of acetyl chloride containing impurities is achieved, the purity of an acetic acid by-product is high, resources are saved, the generation quantity of three wastes generated in the polyisopropenyl phosphate production process is greatly decreased, and the indexes of the prepared HEDP product all accord with the industrial product indexes.
Description
Technical field
The present invention relates to a kind of production technology of hydroxy ethylene diphosphonic acid is and in particular to a kind of utilize chloroacetic chloride waste liquid system
The production technology of standby hydroxy ethylene diphosphonic acid.
Background technology
Polyisobutylene phosphate be integrate scale inhibition, dispersion, inhibition, etc. multiple performance water treatment agent, before application
Scape is extensive.Its special nature having is thus have special use in industrial circulation water treatment, oil-field flooding, mesohigh boiler
On the way.Existing can produce a large amount of chloroacetic chloride waste liquids with regard to the phosphatic preparation technology of polyisobutylene, waste liquid key component be chloroacetic chloride
And acetic acid, containing less amount of acetic anhydride and acetone.Because chloroacetic chloride is closer to acetone boiling point, very difficult separating-purifying, also difficulty enter
Row biochemical treatment is discharged, and can cause the great wasting of resources.Therefore, develop the recycling of this chloroacetic chloride waste liquid, no
Improve only the utilization ratio of chloroacetic chloride, expand economic benefit, and waste liquid can be reduced and produce.
Hydroxy ethylene diphosphonic acid (hedp) is a kind of organophosphors acids anti-incrustation corrosion inhibitor, frequently as metal and nonmetallic
Abluent, anti-incrustation corrosion inhibitor, application is wide.Therefore development utilization above-mentioned chloroacetic chloride waste liquid prepares the production technology one-tenth of hedp
For research emphasis.
Content of the invention
Present invention aims to the deficiencies in the prior art, a kind of effectively solving chloroacetic chloride waste liquid is now provided to be difficult to back
Receive the drawbacks of process, improve the utilization ratio of chloroacetic chloride, production cost is greatly reduced, turns waste into wealth, developed resource-conserving
Utilization chloroacetic chloride waste liquid prepare the production technology of hydroxy ethylene diphosphonic acid.
For solving above-mentioned technical problem, the technical solution used in the present invention is: one kind prepares hydroxyl using chloroacetic chloride waste liquid
The production technology of ethylidene diphosphonic acid, its innovative point is: the chloroacetic chloride waste liquid with mass fraction as 50-70%, deionized water
It is raw material with Phosphorous chloride., according to step in detail below, complete production technology；Described specifically comprise the following steps that
(1) thoroughly cleaning reactor, check valve, pressure；
(2) by 1000 weight portion chloroacetic chloride waste liquid suction reactor bottoms, open stirring；
(3) it is slowly added dropwise deionized water 200-400 weight portion, 10-50 DEG C of temperature control during Deca, after completion of dropwise addition, stir
Mix 2 hours；
Reaction equation:
Ch3cocl+h2o=ch3cooh+hcl
(ch2co)2o+h2o→2ch3cooh
(4) it is continuously heating to 60-100 DEG C, collect front-end volatiles 120-300 weight portion, deliver to sewage plant and carry out biochemical treatment；
(5) distillation terminates, and obtains acetum, feed liquid sample examination in reactor, and described acetic acid content is 70-90%；
(6) ON cycle water, when material in reactor temperature is down to 30 DEG C, is slowly added dropwise Phosphorous chloride. 1060 weight portion,
Deca process temperature control is at 10-50 DEG C；
(7) after completion of dropwise addition, the slow esterification that heats up, when temperature rises to 105 DEG C, it is incubated 1-4 hour；
Reaction equation:
(8) it is slowly added dropwise 300 parts by weight of deionized water hydrolysis, hydrolysis time 2 hours；
(9) open distillation and dense time liquid reception device, concentrate distillation, receive acetum；
(10) rush steaming to terminate, add 250-400 parts by weight of deionized water, stir；
(11) it is cooled to 95 DEG C, add hydrogen peroxide for decoloration, discharging, inspection.
Further, the chloroacetic chloride waste liquid in described step (2) be containing acetic acid, acetone, acetic anhydride impurity chloroacetic chloride, described
Chloroacetic chloride accounts for the 50-70% of waste liquid gross mass, and described acetic acid accounts for the 20-30% of waste liquid gross mass, and described acetone accounts for the total matter of waste liquid
The 2-6% of amount, described acetic anhydride accounts for the 2-12% of waste liquid gross mass.
Beneficial effects of the present invention are as follows: active component in terms of hedp for the hedp that the present invention produces is more than 98%；This
It is 70%-90% that technique separates the sterling acetum percentage composition obtaining；The present invention has developed using the preparation of chloroacetic chloride waste liquid
The technique of hedp, compared with traditional handicraft, improves the utilization ratio of chloroacetic chloride, realizes turning waste into wealth, significantly reduces production
Cost.By the present invention it is achieved that being recycled of impure chloroacetic chloride, the purity of side-product acetic acid is higher, economizes on resources,
The yield of " three wastes " during greatly reducing polyisobutylene phosphate production, the hedp product index of preparation all meets work
Industry product index.
Brief description
Fig. 1 is the process chart of the present invention.
Specific embodiment
Hereinafter embodiments of the present invention are illustrated by particular specific embodiment, those skilled in the art can be by this explanation
Content disclosed by book understands other advantages and effect of the present invention easily.
It is illustrated in figure 1 the process chart of the present invention；
Embodiment 1
A kind of production technology preparing hydroxy ethylene diphosphonic acid using chloroacetic chloride waste liquid, the second being 50% with mass fraction
Acyl chlorides waste liquid, deionized water and Phosphorous chloride. are raw material, according to step in detail below, complete production technology；Specifically comprise the following steps that
(1) thoroughly cleaning reactor, check valve, pressure；
(2) by 1000 weight portion chloroacetic chloride waste liquid suction reactor bottoms, open stirring, chloroacetic chloride waste liquid be containing acetic acid, third
Ketone, the chloroacetic chloride of acetic anhydride impurity, chloroacetic chloride accounts for the 70% of waste liquid gross mass, and acetic acid accounts for the 20% of waste liquid gross mass, and acetone accounts for useless
The 6% of liquid gross mass, acetic anhydride accounts for the 4% of waste liquid gross mass；
(3) it is slowly added dropwise deionized water 200 weight portion, 10 DEG C of temperature control during Deca, after completion of dropwise addition, stir 2 hours；
Reaction equation:
Ch3cocl+h2o=ch3cooh+hcl
(ch2co)2o+h2o→2ch3cooh
(4) it is continuously heating to 60 DEG C, collect front-end volatiles 120 weight portion, deliver to sewage plant and carry out biochemical treatment；
(5) distillation terminates, and obtains acetum, feed liquid sample examination in reactor, and acetic acid content is 70%；
(6) ON cycle water, when material in reactor temperature is down to 30 DEG C, is slowly added dropwise Phosphorous chloride. 1060 weight portion,
Deca process temperature control is at 10 DEG C；
(7) after completion of dropwise addition, the slow esterification that heats up, when temperature rises to 105 DEG C, it is incubated 1 hour；
Reaction equation:
(8) it is slowly added dropwise 300 parts by weight of deionized water hydrolysis, hydrolysis time 2 hours；
(9) open distillation and dense time liquid reception device, concentrate distillation, receive acetum；
(10) rush steaming to terminate, add 250 parts by weight of deionized water, stir；
(11) it is cooled to 95 DEG C, add hydrogen peroxide for decoloration, discharging, inspection.
Embodiment 2
A kind of production technology preparing hydroxy ethylene diphosphonic acid using chloroacetic chloride waste liquid, the second being 70% with mass fraction
Acyl chlorides waste liquid, deionized water and Phosphorous chloride. are raw material, according to step in detail below, complete production technology；Specifically comprise the following steps that
(1) thoroughly cleaning reactor, check valve, pressure；
(2) by 1000 weight portion chloroacetic chloride waste liquid suction reactor bottoms, open stirring, chloroacetic chloride waste liquid be containing acetic acid, third
Ketone, the chloroacetic chloride of acetic anhydride impurity, chloroacetic chloride accounts for the 52% of waste liquid gross mass, and acetic acid accounts for the 30% of waste liquid gross mass, and acetone accounts for useless
The 6% of liquid gross mass, acetic anhydride accounts for the 12% of waste liquid gross mass；
(3) it is slowly added dropwise deionized water 400 weight portion, 50 DEG C of temperature control during Deca, after completion of dropwise addition, stir 2 hours；
Reaction equation:
Ch3cocl+h2o=ch3cooh+hcl
(ch2co)2o+h2o→2ch3cooh
(4) it is continuously heating to 100 DEG C, collect front-end volatiles 300 weight portion, deliver to sewage plant and carry out biochemical treatment；
(5) distillation terminates, and obtains acetum, feed liquid sample examination in reactor, and acetic acid content is 90%；
(6) ON cycle water, when material in reactor temperature is down to 30 DEG C, is slowly added dropwise Phosphorous chloride. 1060 weight portion,
Deca process temperature control is at 50 DEG C；
(7) after completion of dropwise addition, the slow esterification that heats up, when temperature rises to 105 DEG C, it is incubated 4 hours；
Reaction equation:
(8) it is slowly added dropwise 300 parts by weight of deionized water hydrolysis, hydrolysis time 2 hours；
(9) open distillation and dense time liquid reception device, concentrate distillation, receive acetum；
(10) rush steaming to terminate, add 400 parts by weight of deionized water, stir；
(11) it is cooled to 95 DEG C, add hydrogen peroxide for decoloration, discharging, inspection.
Embodiment 3
A kind of production technology preparing hydroxy ethylene diphosphonic acid using chloroacetic chloride waste liquid, the second being 60% with mass fraction
Acyl chlorides waste liquid, deionized water and Phosphorous chloride. are raw material, according to step in detail below, complete production technology；Specifically comprise the following steps that
(1) thoroughly cleaning reactor, check valve, pressure；
(2) by 1000 weight portion chloroacetic chloride waste liquid suction reactor bottoms, open stirring, chloroacetic chloride waste liquid be containing acetic acid, third
Ketone, the chloroacetic chloride of acetic anhydride impurity, chloroacetic chloride accounts for the 60% of waste liquid gross mass, and acetic acid accounts for the 28% of waste liquid gross mass, and acetone accounts for useless
The 2% of liquid gross mass, acetic anhydride accounts for waste liquid gross mass 10%；
(3) it is slowly added dropwise deionized water 300 weight portion, 30 DEG C of temperature control during Deca, after completion of dropwise addition, stir 2 hours；
Reaction equation:
Ch3cocl+h2o=ch3cooh+hcl
(ch2co)2o+h2o→2ch3cooh
(4) it is continuously heating to 80 DEG C, collect front-end volatiles 210 weight portion, deliver to sewage plant and carry out biochemical treatment；
(5) distillation terminates, and obtains acetum, feed liquid sample examination in reactor, and acetic acid content is 80%；
(6) ON cycle water, when material in reactor temperature is down to 30 DEG C, is slowly added dropwise Phosphorous chloride. 1060 weight portion,
Deca process temperature control is at 30 DEG C；
(7) after completion of dropwise addition, the slow esterification that heats up, when temperature rises to 105 DEG C, it is incubated 3 hours；
Reaction equation:
(8) it is slowly added dropwise 300 parts by weight of deionized water hydrolysis, hydrolysis time 2 hours；
(9) open distillation and dense time liquid reception device, concentrate distillation, receive acetum；
(10) rush steaming to terminate, add 320 parts by weight of deionized water, stir；
(11) it is cooled to 95 DEG C, add hydrogen peroxide for decoloration, discharging, inspection.
Embodiment 4
A kind of production technology preparing hydroxy ethylene diphosphonic acid using chloroacetic chloride waste liquid, the second being 60% with mass fraction
Acyl chlorides waste liquid, deionized water and Phosphorous chloride. are raw material, according to step in detail below, complete production technology；Specifically comprise the following steps that
The relevant devices such as thoroughly cleaning reactor, condenser, check valve, pressure；By 7880kg chloroacetic chloride waste liquid, gc detects acetone
4.8587%, chloroacetic chloride 51.0581%, acetic acid 33.0258%, acetic anhydride 7.2109%, suction reactor bottom, open stirring, cold
Condenser；It is slowly added dropwise 2500kg deionized water, temperature control is less than 40 DEG C；After completion of dropping, it is continuously heating to 100 DEG C, heated up
Cheng Zhong, collects front-end volatiles 1500kg, delivers to sewage plant and carry out biochemical treatment；Feed liquid sampling detection, acetic acid content in reactor
79.8%.Reactor interlayer ON cycle water is lowered the temperature, and when temperature is down to 20 DEG C, is slowly added dropwise Phosphorous chloride. 5300kg, Deca mistake
In journey, keeping temperature is less than 50 DEG C, completion of dropwise addition, the slow esterification that heats up, when temperature rises to 110 DEG C, insulation reaction 2 hours, and delay
Slow addition 1500kg deionized water, is hydrolyzed；After hydrolysis terminates, open distillation and acetic acid reception device, heating distillation, receive
Acetic acid；After concentration terminates, start punching and steam, 125 DEG C of temperature control below, rush after steaming terminates, addition 4000kg water, stir；Cooling
To 95 DEG C, add hydrogen peroxide for decoloration, discharging, after testing, for 60.48%, other indexs all accord with the active quantities that product is counted with acid
Close industrial products to require.
Embodiment 5
A kind of production technology preparing hydroxy ethylene diphosphonic acid using chloroacetic chloride waste liquid, the second being 50% with mass fraction
Acyl chlorides waste liquid, deionized water and Phosphorous chloride. are raw material, according to step in detail below, complete production technology；Specifically comprise the following steps that
The relevant devices such as thoroughly cleaning reactor, condenser, check valve, pressure；By 10000kg chloroacetic chloride waste liquid, gc detects acetone
4.4024%, chloroacetic chloride 64.3530%, acetic acid 25.213%, acetic anhydride 2.9531%, suction reactor bottom, open stirring, condensation
Device；It is slowly added dropwise 2200kg deionized water, temperature control is less than 40 DEG C；After completion of dropping, it is continuously heating to 110 DEG C, temperature-rise period
In, collect front-end volatiles 1450kg, deliver to sewage plant and carry out biochemical treatment；Feed liquid sampling detection, acetic acid content in reactor
81.9%.Reactor interlayer ON cycle water is lowered the temperature, and when temperature is down to 30 DEG C, is slowly added dropwise Phosphorous chloride. 8500kg, Deca mistake
In journey, keeping temperature is less than 40 DEG C, completion of dropwise addition, the slow esterification that heats up, when temperature rises to 110 DEG C, insulation reaction 2 hours, and delay
Slow addition 2500kg deionized water, is hydrolyzed；After hydrolysis terminates, open distillation and acetic acid reception device, heating distillation, receive
Acetic acid；After concentration terminates, start punching and steam, 125 DEG C of temperature control below, rush after steaming terminates, addition 5000kg water, stir；Cooling
To 95 DEG C, add hydrogen peroxide for decoloration, discharging.After testing, the active quantities that product is counted with acid, for 67.15%, continue to add water, and adjust
To 60%, other indexs all meet industrial products requirement to content.
Embodiment 6
A kind of production technology preparing hydroxy ethylene diphosphonic acid using chloroacetic chloride waste liquid, the second being 70% with mass fraction
Acyl chlorides waste liquid, deionized water and Phosphorous chloride. are raw material, according to step in detail below, complete production technology；Specifically comprise the following steps that
The relevant devices such as thoroughly cleaning reactor, condenser, check valve, pressure etc.；By 8000kg chloroacetic chloride waste liquid, (gc detects acetone
3.9185%, chloroacetic chloride 66.2157%, acetic acid 22.3680%, acetic anhydride 3.4378%, suction reactor bottom, open stirring, cold
Condenser；It is slowly added dropwise 2000kg deionized water, temperature control is less than 40 DEG C；After completion of dropping, it is continuously heating to 120 DEG C, heated up
Cheng Zhong, collects front-end volatiles 1450kg, delivers to sewage plant and carry out biochemical treatment；Feed liquid sampling detection, acetic acid content in reactor
85.4%.Reactor interlayer ON cycle water is lowered the temperature, and when temperature is down to 30 DEG C, is slowly added dropwise Phosphorous chloride. 6900kg, Deca mistake
In journey, keeping temperature is less than 50 DEG C, completion of dropwise addition, the slow esterification that heats up, when temperature rises to 110 DEG C, insulation reaction 2 hours, and delay
Slow addition 2000kg deionized water, is hydrolyzed；After hydrolysis terminates, open distillation and acetic acid reception device, heating distillation, receive
Acetic acid；After concentration terminates, start punching and steam, 125 DEG C of temperature control below, rush after steaming terminates, addition 4000kg water, stir；Cooling
To 95 DEG C, add hydrogen peroxide for decoloration, discharging.After testing, for 60.88%, other indexs all accord with the active quantities that product is counted with acid
Close industrial products to require.
Active component in terms of hedp for the hedp that the present invention produces is more than 98%；This technique separates the sterling acetic acid obtaining
Solution percentage composition is 70%-90%；The present invention has developed the technique preparing hedp using chloroacetic chloride waste liquid, with traditional handicraft phase
Ratio improves the utilization ratio of chloroacetic chloride, realizes turning waste into wealth, significantly reduces production cost.By the present invention it is achieved that containing
Being recycled of impurity chloroacetic chloride, the purity of side-product acetic acid is higher, economizes on resources, and greatly reduces polyisobutylene phosphoric acid
The yield of " three wastes " in salt production process, the hedp product index of preparation all meets industrial products index.
Above-described embodiment is presently preferred embodiments of the present invention, is not the restriction to technical solution of the present invention, as long as
The technical scheme that can realize on the basis of above-described embodiment without creative work, is regarded as falling into patent of the present invention
Rights protection scope in.
Claims (2)
1. a kind of using chloroacetic chloride waste liquid prepare hydroxy ethylene diphosphonic acid production technology it is characterised in that: with mass fraction
Chloroacetic chloride waste liquid for 50-70%, deionized water and Phosphorous chloride. are raw material, according to step in detail below, complete production technology；
Described specifically comprise the following steps that
(1) thoroughly cleaning reactor, check valve, pressure；
(2) by 1000 weight portion chloroacetic chloride waste liquid suction reactor bottoms, open stirring；
(3) it is slowly added dropwise deionized water 200-400 weight portion, 10-50 DEG C of temperature control during Deca, after completion of dropwise addition, stirring 2 is little
When；
Reaction equation:
Ch3cocl+h2o=ch3cooh+hcl
(ch2co)2o+h2o→2ch3cooh
(4) it is continuously heating to 60-100 DEG C, collect front-end volatiles 120-300 weight portion, deliver to sewage plant and carry out biochemical treatment；
(5) distillation terminates, and obtains acetum, feed liquid sample examination in reactor, and described acetic acid content is 70-90%；
(6) ON cycle water, when material in reactor temperature is down to 30 DEG C, is slowly added dropwise Phosphorous chloride. 1060 weight portion, Deca
Process temperature control is at 10-50 DEG C；
(7) after completion of dropwise addition, the slow esterification that heats up, when temperature rises to 105 DEG C, it is incubated 1-4 hour；
Reaction equation:
(8) it is slowly added dropwise 300 parts by weight of deionized water hydrolysis, hydrolysis time 2 hours；
(9) open distillation and dense time liquid reception device, concentrate distillation, receive acetum；
(10) rush steaming to terminate, add 250-400 parts by weight of deionized water, stir；
(11) it is cooled to 95 DEG C, add hydrogen peroxide for decoloration, discharging, inspection.
2. a kind of production technology preparing hydroxy ethylene diphosphonic acid using chloroacetic chloride waste liquid according to claim 1, its
Be characterised by: the chloroacetic chloride waste liquid in described step (2) be containing acetic acid, acetone, acetic anhydride impurity chloroacetic chloride, described chloroacetic chloride accounts for
The 50-70% of waste liquid gross mass, described acetic acid accounts for the 20-30% of waste liquid gross mass, and described acetone accounts for the 2- of waste liquid gross mass
6%, described acetic anhydride accounts for the 2-12% of waste liquid gross mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610799416.3A CN106366124A (en) | 2016-08-31 | 2016-08-31 | Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610799416.3A CN106366124A (en) | 2016-08-31 | 2016-08-31 | Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid |
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| Publication Number | Publication Date |
|---|---|
| CN106366124A true CN106366124A (en) | 2017-02-01 |
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| CN201610799416.3A Pending CN106366124A (en) | 2016-08-31 | 2016-08-31 | Production technology for preparing 1-hydroxyethylidene-1,1-diphosphonic acid from acetyl chloride waste liquid |
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| CN (1) | CN106366124A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107721841A (en) * | 2017-11-11 | 2018-02-23 | 山东民基化工有限公司 | A kind of method that pivalic acid is reclaimed in the distillation residual liquid from pivaloyl chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091137A (en) * | 1993-02-16 | 1994-08-24 | 化学工业部天津化工研究院 | The production method of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid |
| CN1616469A (en) * | 2004-09-20 | 2005-05-18 | 张益军 | Method for coproducing acetyl chloride and hydroxy ethylidene diphosphonic acid |
| CN1827625A (en) * | 2006-03-29 | 2006-09-06 | 傅明珠 | Process for synthesis of hydroxy ethidene diphosphoric acid |
| CN1948258A (en) * | 2006-10-28 | 2007-04-18 | 周烜 | Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091137A (en) * | 1993-02-16 | 1994-08-24 | 化学工业部天津化工研究院 | The production method of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid |
| CN1616469A (en) * | 2004-09-20 | 2005-05-18 | 张益军 | Method for coproducing acetyl chloride and hydroxy ethylidene diphosphonic acid |
| CN1827625A (en) * | 2006-03-29 | 2006-09-06 | 傅明珠 | Process for synthesis of hydroxy ethidene diphosphoric acid |
| CN1948258A (en) * | 2006-10-28 | 2007-04-18 | 周烜 | Preparation method and device of acetyl chloride and hydroxy ethylene diphosphonic acid coproduction |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107721841A (en) * | 2017-11-11 | 2018-02-23 | 山东民基化工有限公司 | A kind of method that pivalic acid is reclaimed in the distillation residual liquid from pivaloyl chloride |
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