CN102617514B - Clean process for using glycerin to synthesize epichlorohydrin - Google Patents
Clean process for using glycerin to synthesize epichlorohydrin Download PDFInfo
- Publication number
- CN102617514B CN102617514B CN201210060543.3A CN201210060543A CN102617514B CN 102617514 B CN102617514 B CN 102617514B CN 201210060543 A CN201210060543 A CN 201210060543A CN 102617514 B CN102617514 B CN 102617514B
- Authority
- CN
- China
- Prior art keywords
- acid
- glycerin
- saponification
- water
- tower
- 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.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Compounds (AREA)
- Fertilizers (AREA)
Abstract
The invention relates to a clean process for using glycerin to synthesize epichlorohydrin, belonging to the technical field of epichlorohydrin. HCl gas and dilute phosphoric acid are produced via hydrolysis of POCl3, and the dilute phosphoric acid produced via the hydrolysis of POCl3 is concentrated into concentrated phosphoric acid. The produced HCl gas is used for chlorination of glycerin to produce dichloro glycerin and byproduct water. The produced dichloro glycerin and lime milk or KOH solution are mixed for saponification to produce epichlorohydrin and saponification wastewater containing CaCl2 or KCl. The saponification wastewater is subjected to multi-effect evaporation and concentration, and the produced neutral condensate water is applied for preparation of the lime milk or KOH solution. The concentrated phosphoric acid is subjected to reaction with the CaCl2 or the KCl in the concentrated saponification wastewater to produce a phosphate fertilizer or a phosphorus/potassium composite fertilizer. Byproduct hydrochloric acid is applied for hydrolysis of POCl3. The hydrolysis of POCl3, glycerin chlorination, saponification of dichloro glycerin and treatment of saponification wastewater are integrated in one system, and intermediates and byproducts in the process can be utilized as mutual resources.
Description
Technical field
The invention belongs to epoxy chloropropane technical field, a kind of synthesizing epoxy chloropropane taking glycerine as raw material, and the clean preparation method of by-product phosphate fertilizer specifically.
Background technology
Epoxy chloropropane is a kind of important basic chemical industry raw material and organic synthesis intermediate, and mainly for the production of epoxy resin, tensio-active agent, medicine, agricultural chemicals, ion exchange resin etc., global consumption is 2,000,000 tons of left and right.
The production method of epoxy chloropropane has propylene high-temperature chlorination process, allyl acetate method and glycerine method.Propylene high-temperature chlorination process and allyl acetate method all have energy consumption high, consume fossil resource, and produce a large amount of reluctant high slat-containing wastewaters.
Along with the cry of energy-saving and emission-reduction is all the more strong, by the trend that renewable resources replaces fossil resource, realizes cleaner production, by-product resource utilization becomes modern chemical industry technical development.So, in recent years, replace the Technology of production of propylene epoxy chloropropane to become the focus that people competitively develop with the large number of biological matter glycerine of biodiesel byproduct.A series of patents such as CN200710019466, CN200480034393, US20080015369, CN200780028732 have all proposed to prepare taking glycerine as raw material the processing method of epoxy chloropropane.Can greatly reduce the discharge (being down to 3～7T waste water/T product by 40～50T waste water/T product) of brine waste although glycerine method replaces propylene method, the waste water saltiness of discharging is up to 15～25%, can not resemble propylene method and process rear discharge.On the other hand, when the glycerin chlorination in glycerine method synthesizing epoxy chloropropane process is prepared glycerin dichlorohydrin, the water of by-product is to separate from system with the form of dilute hydrochloric acid, and its by-product amount is large (0.6～0.7T dilute hydrochloric acid/T product) also, is difficult for processing.In addition, in glycerine method technique, HCl gas raw material used is almost that one can not liquefied gas, is difficult to accumulating, and this makes troubles to production under many circumstances.
Summary of the invention
order of the present inventiona kind of integrated operational path of proposition, by by-product resource utilization, realize the cleaner production of epoxy chloropropane, thereby overcome the deficiencies in the prior art.
technical scheme:
The present invention is achieved through the following technical solutions.Utilize POCl
3hydrolysis produces HCl gas and dilute phosphoric acid, by POCl
3the dilute phosphoric acid simmer down to strong phosphoric acid that hydrolysis produces.Produced HCl gas is produced to glycerin dichlorohydrin for chlorination glycerine, and by-product water.Water separates with dilute hydrochloric acid form.The glycerin dichlorohydrin generating and milk of lime or KOH solution carry out saponification reaction, generate epoxy chloropropane and contain CaCl
2or the saponification waste-water of KCl.Saponification waste-water is concentrated by multiple-effect evaporation, produce neutral solidifying water for preparing lime milk or KOH solution.Contained CaCl during strong phosphoric acid and concentrated saponification is useless
2or KCl reaction, generate CaHPO
4(phosphate fertilizer) or K
2hPO
4(phosphorus potassium complex fertilizer).By-product hydrochloric acid is for POCl
3hydrolysis.Integrated technique process reaction formula is as follows:
POCl
3+3H
2O?→?H
3PO
4+3HCl
2Gly+4HCl?→?2DCP+4?H
2O
2DCP+Ca (OH)
2(or 2KOH) →
2ECH+ CaCl
2(2KCl)+2 H
2o
H
3pO
4+ CaCl
2(2KCl) → CaHPO
4(or K
2hPO
4)+2 HCl
Net reaction is:
POCl
3+ 2Gly+Ca (OH)
2(or 2KOH) →
2ECH+ CaHPO
4(or K
2hPO
4)+HCl+3 H
2o
(Gly: glycerine; DCP: glycerin dichlorohydrin; ECH: epoxy chloropropane)
From a cleaning procedure for glycerine synthesizing epoxy chloropropane, carry out according to following step:
(1) POCl
3hydrolytic process: by POCl
3slowly add in hydrochloric acid the water in hydrochloric acid and POCl
3there is stoichiometric hydrolysis reaction; Hydrolysis temperature is 60～70 DEG C; Along with the consumption of water and the generation of phosphoric acid, make HCl air release that the HCl gas brought in hydrochloric acid and hydrolysis reaction generate out; Control POCl
3with hydrochloric acid ratio, make hydrolysising reacting system H
3pO
4mass concentration is 48～53%; Subsequently solution heating is concentrated into the strong phosphoric acid that mass content is 80% left and right;
(2) glycerin chlorination process: the HCl gas that step (1) reaction is discharged, under the effect of catalyzer, with glycerine generation substitution reaction, generates glycerin dichlorohydrin by-product water; Reaction mixture takes the method for rectifying and extraction to carry out separation and purification, obtains glycerin dichlorohydrin and dilute hydrochloric acid, and dilute hydrochloric acid is as byproduct for treatment;
(3) saponification reaction: enter saponification reaction rectifying tower after the glycerin dichlorohydrin that step (2) is produced mixes with milk of lime or KOH solution, the brine waste that saponification generates is that so-called saponification waste-water is discharged from saponification tower reactor; The epoxy chloropropane generating and water form azeotrope and steam from tower top; After azeotrope condensation through oily water separation, aqueous-phase reflux saponification column, oil phase enters epoxy chloropropane treating tower; Control glycerin dichlorohydrin
:ca(OH)
2(or KOH)=129
:50～60 (mass ratioes), 40～70 DEG C of mixing temperatures; Obtain epoxy chloropropane finished product from epoxy chloropropane treating tower top, the raffinate of discharging from tower reactor is got back to glycerin chlorination workshop section;
(4) saponification waste-water is concentrated: the saponification waste-water that saponification reaction rectifying tower reactor is discharged carries out 3 ~ 5 effect evaporations, obtains concentrated saponification waste-water, makes wherein CaCl
2or KCl mass content is 40 ~ 50%; Multiple-effect evaporation produces neutral solidifying water for preparing lime milk or KOH solution;
(5) by-product resource utilization: the strong phosphoric acid in above-mentioned steps (1) is reacted with the concentrated saponification waste-water in above-mentioned steps (4), the suitable temperature of reaction of strong phosphoric acid and concentrated saponification waste-water is 70～90 DEG C, and product is sent into hot gas flow drying tower and carried out air stream drying; Suitable air stream drying temperature is 140～160 DEG C; Obtain solid CaHPO from cyclonic separator
4(phosphate fertilizer) or K
2hPO
4(phosphorus potassium complex fertilizer); Cyclonic separator tail gas is hydrochloric acid through lime set that condensation obtains, and suitable condensing temperature is 5 ~ 15 DEG C; This lime set is got back in step (1) and is made POCl
3the raw material of hydrolytic process.
Wherein the described hydrochloric acid of step (1) is from concentrated saponification waste-water and POCl in step (5)
3the phosphatase reaction that hydrolysis produces is prepared the by product of phosphate fertilizer process, and its mass concentration is 30～36%.
Wherein in step (2) glycerine react with HCl should be at 100～120 DEG C; Reaction pressure is at 0.5～1.0MPa; Reaction times is 4～6h; Catalyzer used is lipid acid or mineral acid material, is specially acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, suberic acid, zinc chloride, tin tetrachloride, phospho-wolframic acid, silicotungstic acid, germanotungstic acid etc.Preferably hexanodioic acid or phospho-wolframic acid.
The method of taking rectifying and extraction of the glycerin dichlorohydrin wherein wherein producing in step (2) is carried out separation and purification, carries out: (1) is introduced into a cut light tower from the reaction mixture of glycerin chlorination reactor according to following step; That steam from cut light tower top is glycerin dichlorohydrin-HCl-H
2o ternary azeotrope; This ternary azeotrope is sent into extraction tower, carry out counter current contact with organic solvent; Extraction phase is glycerin dichlorohydrin solution, is hydrochloric acid mutually more than extraction; Wherein extracting organic solvent used is that boiling point is less than 155 DEG C of polar solvents.As: 1,2-ethylene dichloride, dibutyl ether, chloroform, diisopropyl ether; Extraction phase containing glycerin dichlorohydrin is sent into desolventizing tower, and solvent steams from tower top, loops back extraction tower, and glycerin dichlorohydrin flows out from tower reactor; The component flowing out from cut light tower still enters glycerin dichlorohydrin rectifying tower in the lump with the component flowing out from desolventizing tower reactor, steams glycerin dichlorohydrin from tower top, and tower reactor obtains the vinasse containing catalyzer, further Distillation recovery catalyzer and Polyglycerine.
the effect of invention:by the present invention program's enforcement, by POCl
3the technological processs such as hydrolysis, glycerin chlorination, glycerin dichlorohydrin saponification and saponification waste-water processing are integrated in a system, the mutual recycling of by product between implementation procedure, in utilizing renewable resources glycerol production epoxy chloropropane, by product phosphoric acid and calcium chloride (or Repone K) are converted into chemical fertilizer-secondary calcium phosphate or potassium hydrogen phosphate, and reclaim hydrochloric acid and can be used as POCl
3the raw material of hydrolysis, reaches energy-saving and emission-reduction, reduces costs, the object of cleaner production.
concrete embodiment
example 1: (taking lime as saponification alkali source, by-product phosphate fertilizer, continuous and steady operation operation)
In hydrolysis kettle, pass into airstream drying tower tail gas lime set 222 ㎏/h(containing 33%HCl, 67%H
2o) (from concentrated saponification waste-water and phosphatase reaction mixture Optimization of Gas Flow Drying) and 155 ㎏/h phosphorus oxychloride, at 60 DEG C of continuous hydrolysis, produce HCl gas 176 ㎏/h, and the by-product dilute phosphoric acid aqueous solution 201 ㎏/h(are containing 48.8%H
3pO
4, 1.4%HCl and 49.8%H
2o(mass ratio)).120 DEG C of heating of this dilute phosphoric acid aqueous solution are condensed into strong phosphoric acid 122.5 ㎏/h(containing 80%H
3pO
4, 0.7%HCl and 19.3%H
2o(mass ratio)), and produce 78.5 ㎏/h dilute hydrochloric acid (containing 2.5%HCl, 97.5%H
2o(mass ratio)).
POCl
3hCl gas 176 ㎏/h that hydrolysis produces, be pressed in glycerin chlorination reactor with reciprocation compressor, with 209 ㎏/h industry glycerol (containing glycerine 96%) with from together with the refining 4 ㎏/h heavy constituent producing of epoxy chloropropane, under 6 ㎏/h catalysis of phosphotungstic acid, 1.0MPa, 100 DEG C of chlorination reaction 6h.Reaction mixture obtains front-end volatiles 129 ㎏/h(23.2% glycerin dichlorohydrin-22.4% hydrogenchloride-54.4% water (mass ratio) through rectifying) and after cut 236 ㎏/h(glycerin dichlorohydrin), and vinasse 30 ㎏/h(is containing catalyzer, further Distillation recovery catalyzer and Polyglycerine).Front-end volatiles containing glycerin dichlorohydrin-hydrogenchloride-water extract with ethylene dichloride, reclaim glycerin dichlorohydrin 30 ㎏/h(containing glycerin dichlorohydrin 97%), and by-product dilute hydrochloric acid 99 ㎏/h(is containing HCl 28%).The glycerin dichlorohydrin and the after cut that merge above-mentioned recovery are total to such an extent that glycerin dichlorohydrin 266 ㎏/h(contains glycerin dichlorohydrin 97%).
The concentrated 78.5 ㎏/h dilute hydrochloric acid producing of above-mentioned dilute phosphoric acid heat is (containing 2.5%HCl, 97.5%H
2o(mass ratio)), in the lime mud producing with milk of lime process for preparation and after, obtain 79 ㎏/h containing 3.8%CaCl
2neutral aqueous solution.It is mixed as milk of lime blending process water 260 ㎏/h with the solidifying water 181 ㎏/h of the neutrality producing from saponification waste-water triple effect evaporation.This process water and 88 ㎏/h lime (are contained to 86%CaO, 8%CaCO
3and 6% lime mud) mixed preparing milk of lime 337 ㎏/h(is containing 18.9%CaO, 1.8%CaCO
3), and discharge lime mud slurry 11 ㎏/h.The milk of lime of preparing and above-mentioned glycerin dichlorohydrin 266 ㎏/h carry out saponification reaction at 70 DEG C, the epoxy chloropropane generating is through the refining 176 ㎏/h(content 99.97% that obtains) and 4 ㎏/h heavy constituent (main component is glycerin dichlorohydrin, be circulated back to glycerin chlorination workshop section), and by-product saponification waste-water 423 ㎏/h(is containing 27.6%CaCl
2, 2.3%CaO and 1.0%CaCO
3).The saponification waste-water of by-product carries out triple effect evaporation by steam heating, produces neutral solidifying water 304 ㎏/h.Concentrated after saponification waste water is that 257.5 ㎏/h(is containing 45.4%CaCl
2, 3.8%CaO and 1.6%CaCO
3).
Above-mentioned strong phosphoric acid 122.5 ㎏/h(is containing H
3pO
480%) react at 70 DEG C with the concentrated useless 257.5 ㎏/h of saponification, product is dry through 140 DEG C of hot gas flows, obtains solid 158 ㎏/h(containing 86%CaHPO from cyclonic separator
4, 6%CaCl
2, 8%H
2o), this solid can be used as slow-release phosphate fertilizer use.Air stream drying tail gas obtains hydrochloric acid 222 ㎏/h(containing HCl 33%, H through 5 DEG C of condensations
2o 67%).This lime set is got back to POCl
3hydrolytic process is made raw material.
example 2: ((taking KOH as saponification alkali source, by-product phosphorus potassium complex fertilizer, continuous and steady operation operation)
In hydrolysis kettle, pass into from saponification waste-water treating processes air stream drying tail gas lime set 158.6 ㎏/h(containing HCl 30.6%, H
2o 69.4%) and 124 ㎏/h phosphorus oxychloride at 70 DEG C of continuous hydrolysis, produce HCl gas 132.8 ㎏/h, and by-product dilute phosphoric acid 149.8 ㎏/h(is containing 52.7%H
3pO
4, 2.2%HCl, 45.1%H
2o).Concentrated 120 DEG C of heating of this dilute phosphoric acid aqueous solution strong phosphoric acid 98 ㎏/h(that obtains is contained to 80%H
3pO
4, 20%H
2o(mass ratio)).
Above-mentioned POCl
3hCl gas 132.8 ㎏/h that hydrolysis produces is pressed in glycerin chlorination reactor with 158.6 ㎏/h industry glycerol (containing glycerine 96%) with from together with the refining 3 ㎏/h heavy constituent producing of epoxy chloropropane with reciprocation compressor, under the catalysis of 6 ㎏/h hexanodioic acid, 0.5MPa, 120 DEG C of chlorination reaction 4h.Reaction mixture obtains front-end volatiles 103 ㎏/h(23.2% glycerin dichlorohydrin-22.4% hydrogenchloride-54.4% water (mass ratio) through rectifying) and after cut 188 ㎏/h(glycerin dichlorohydrin), and vinasse 11.4 ㎏/h(is containing catalyzer, further Distillation recovery catalyzer and Polyglycerine).Front-end volatiles containing glycerin dichlorohydrin-hydrogenchloride-water extract with dibutyl ether, reclaim glycerin dichlorohydrin 24 ㎏/h, and by-product dilute hydrochloric acid 79 ㎏/h(is containing HCl 28%).The glycerin dichlorohydrin and the after cut that merge above-mentioned recovery are total to obtain glycerin dichlorohydrin 212 ㎏/h(97.5%).
The glycerin dichlorohydrin 212 ㎏/h(97.5% generating) carry out saponification reaction with 395 ㎏/h potassium hydroxide solution (containing 25% KOH) at 40 DEG C, the epoxy chloropropane generating is through the refining 141 ㎏/h(99.96% that obtains) and 3 ㎏/h heavy constituent, by-product saponification waste-water 463 ㎏/h(is containing 27.2%KCl, 0.86%KOH).This saponification waste-water is carried out to five effect evaporations, obtains concentrated saponification waste-water 248 ㎏/h(containing 49%KCl, 1.25%KOH), produce neutral solidifying water 280 ㎏/h.
Obtained strong phosphoric acid 98 ㎏/h is reacted at 90 DEG C with the concentrated saponification waste-water 248 ㎏/h of above-mentioned by-product, and it is dry that product enters 135 DEG C of airstream drying towers, obtains solid 187.4 ㎏/h(containing K from cyclonic separator
2hPO
475.3%, H
2o 24.7%).This solid can be used as phosphorus potassium complex fertilizer.Air stream drying tail gas obtains 158.6 ㎏/h dilute hydrochloric acid through 15 DEG C of condensations and (contains HCl 30.6%, H
2o 69.4%).This lime set is got back to POCl
3hydrolytic process is made raw material.
Claims (3)
1. from a cleaning procedure for glycerine synthesizing epoxy chloropropane, it is characterized in that carrying out according to following step:
(1) POCl
3hydrolytic process: by POCl
3slowly add in hydrochloric acid the water in hydrochloric acid and POCl
3there is stoichiometric hydrolysis reaction; Hydrolysis temperature is 60～70 DEG C; Along with the consumption of water and the generation of phosphoric acid, make HCl air release that the HCl gas brought in hydrochloric acid and hydrolysis reaction generate out; Control POCl
3with hydrochloric acid ratio, make hydrolysising reacting system H
3pO
4mass concentration is 48～53%; Subsequently solution heating is concentrated into the strong phosphoric acid that mass content is 80% left and right;
(2) glycerin chlorination process: the HCl gas that step (1) reaction is discharged, under the effect of catalyzer, with glycerine generation substitution reaction, generates glycerin dichlorohydrin by-product water; Reaction mixture takes the method for rectifying and extraction to carry out separation and purification, obtains glycerin dichlorohydrin and dilute hydrochloric acid, and dilute hydrochloric acid is as byproduct for treatment; ;
(3) saponification reaction: enter saponification reaction rectifying tower after the glycerin dichlorohydrin that step (2) is produced mixes with milk of lime or KOH solution, the brine waste that saponification generates is that so-called saponification waste-water is discharged from saponification tower reactor; The epoxy chloropropane generating and water form azeotrope and steam from tower top; After azeotrope condensation through oily water separation, aqueous-phase reflux saponification column, oil phase enters epoxy chloropropane treating tower; Control glycerin dichlorohydrin
:ca(OH)
2or KOH=mass ratio is 129
:50～60,40～70 DEG C of mixing temperatures; Obtain epoxy chloropropane finished product from epoxy chloropropane treating tower top, the raffinate of discharging from tower reactor is got back to glycerin chlorination workshop section;
(4) saponification waste-water is concentrated: the saponification waste-water that saponification reaction rectifying tower reactor is discharged carries out 3 ~ 5 effect evaporations, obtains concentrated saponification waste-water, makes wherein CaCl
2or KCl mass content is 40 ~ 50%; Multiple-effect evaporation produces neutral solidifying water for preparing lime milk or KOH solution;
(5) by-product resource utilization: the strong phosphoric acid in above-mentioned steps (1) is reacted with the concentrated saponification waste-water in above-mentioned steps (4), the suitable temperature of reaction of strong phosphoric acid and concentrated saponification waste-water is 70～90 DEG C, and product is sent into hot gas flow drying tower and carried out air stream drying; Suitable air stream drying temperature is 140～160 DEG C; Obtain solid CaHPO from cyclonic separator
4or K
2hPO
4; Cyclonic separator tail gas is hydrochloric acid through lime set that condensation obtains, and suitable condensing temperature is 5 ~ 15 DEG C; This lime set is got back in step (1) and is made POCl
3the raw material of hydrolytic process;
Wherein in step (2), catalyzer used is lipid acid or mineral acid material;
In hydrochloric acid step (1) wherein described be from step (5) in concentrated saponification waste-water and POCl
3the phosphatase reaction that hydrolysis produces is prepared the by product of phosphate fertilizer process, and its mass concentration is 30～36%;
Wherein in step (2) glycerine react with HCl should be at 100～120 DEG C; Reaction pressure is at 0.5～1.0MPa; Reaction times is 4～6h;
The method of taking rectifying and extraction of the glycerin dichlorohydrin wherein wherein producing in step (2) is carried out separation and purification, carries out: (1) is introduced into a cut light tower from the reaction mixture of glycerin chlorination reactor according to following step; That steam from cut light tower top is glycerin dichlorohydrin-HCl-H
2o ternary azeotrope; This ternary azeotrope is sent into extraction tower, carry out counter current contact with organic solvent; Extraction phase is glycerin dichlorohydrin solution, is hydrochloric acid mutually more than extraction; Wherein extracting organic solvent used is that boiling point is less than 155 DEG C of polar solvents; Extraction phase containing glycerin dichlorohydrin is sent into desolventizing tower, and solvent steams from tower top, loops back extraction tower, and glycerin dichlorohydrin flows out from tower reactor; The component flowing out from cut light tower still enters glycerin dichlorohydrin rectifying tower in the lump with the component flowing out from desolventizing tower reactor, steams glycerin dichlorohydrin from tower top, and tower reactor obtains the vinasse containing catalyzer, further Distillation recovery catalyzer and Polyglycerine.
2. a kind of cleaning procedure from glycerine synthesizing epoxy chloropropane according to claim 1, is characterized in that catalyzer used is acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, suberic acid, zinc chloride, tin tetrachloride, phospho-wolframic acid, silicotungstic acid, germanotungstic acid.
3. a kind of cleaning procedure from glycerine synthesizing epoxy chloropropane according to claim 2, it is characterized in that wherein extracting organic solvent used is 1,2-ethylene dichloride, dibutyl ether, chloroform, diisopropyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210060543.3A CN102617514B (en) | 2012-03-09 | 2012-03-09 | Clean process for using glycerin to synthesize epichlorohydrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210060543.3A CN102617514B (en) | 2012-03-09 | 2012-03-09 | Clean process for using glycerin to synthesize epichlorohydrin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102617514A CN102617514A (en) | 2012-08-01 |
| CN102617514B true CN102617514B (en) | 2014-06-18 |
Family
ID=46557775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210060543.3A Expired - Fee Related CN102617514B (en) | 2012-03-09 | 2012-03-09 | Clean process for using glycerin to synthesize epichlorohydrin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102617514B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044358B (en) * | 2013-01-30 | 2014-07-16 | 淄博永大化工有限公司 | Method for co-producing epoxypropane and epoxy chloropropane |
| CN107935968A (en) * | 2017-10-18 | 2018-04-20 | 江苏索普（集团）有限公司 | A kind of epoxychloropropane preparation method based on biomass glycerol |
| CN107903222A (en) * | 2017-10-18 | 2018-04-13 | 江苏索普（集团）有限公司 | A kind of method that epoxychloropropane is prepared by biomass glycerol |
| CN111138384A (en) * | 2019-12-27 | 2020-05-12 | 浙江巨化技术中心有限公司 | Treatment method for byproduct hydrogen chloride in fluorine-containing olefin production process |
| CN112142690A (en) * | 2020-10-22 | 2020-12-29 | 丹阳市助剂化工厂有限公司 | Process for producing epichlorohydrin by using chlorinated paraffin and chlorine-containing tail gas glycerin method |
| CN113582564A (en) * | 2021-09-06 | 2021-11-02 | 宁波环洋新材料股份有限公司 | Method for processing suspension obtained in production of epoxy chloropropane by glycerol method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157670A (en) * | 2007-11-13 | 2008-04-09 | 武汉理工大学 | Method for synthesizing epichlorohydrin |
| CN101798154A (en) * | 2009-12-30 | 2010-08-11 | 宁波东港电化有限责任公司 | Method for processing wastewater produced in saponification cyclization step in epoxy chloropropane production method |
-
2012
- 2012-03-09 CN CN201210060543.3A patent/CN102617514B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157670A (en) * | 2007-11-13 | 2008-04-09 | 武汉理工大学 | Method for synthesizing epichlorohydrin |
| CN101798154A (en) * | 2009-12-30 | 2010-08-11 | 宁波东港电化有限责任公司 | Method for processing wastewater produced in saponification cyclization step in epoxy chloropropane production method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102617514A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617514B (en) | Clean process for using glycerin to synthesize epichlorohydrin | |
| CN101712661B (en) | Method for producing epoxy chloropropane | |
| CN102145912B (en) | Process for preparing calcium chloride solution by utilizing ammonia soda filtration mother liquor | |
| CN101857210B (en) | Method for producing industrial grade diammonium phosphate from wet-process phosphoric acid | |
| CN106082515B (en) | A kind of incineration treatment technology of glyphosate mother solution | |
| CN107141194B (en) | Equipment and process for jointly producing acid methanol and chloromethane | |
| CN103979594A (en) | Method for preparing calcium chloride product from high-calcium brine obtained by exploiting well and rock salt by using sodium carbonate waste liquid | |
| CN103641748B (en) | A kind of recycle by-product hydrochloric acid prepares the method for methylsulphonic acid | |
| CN106116705B (en) | A kind of many class resourcesization recycling integrated technique of glyphosate mother solution | |
| CN104190104A (en) | Process equipment and method for refining dimethoxymethane in byproducts produced in production of glyphosate by glycine method | |
| CN113827992A (en) | Method for recycling water separated from alkali mother liquor rectification tower top fraction in glyphosate production process | |
| CN105819415B (en) | A kind of production method for the full utilization of resources of phosphorus ore that hydrochloric acid produces calcium hydrogen phosphate fodder | |
| CN1803589A (en) | Method for producing feed grade dicalcium phosphate and industrial grade phosphoric acid by phosphate ore hydrochloric acid reclamation process | |
| CN101462943A (en) | Method for preparing oxalate with co-production products oxalic acid and dihydric phosphate by continuous dehydrogenation of formate | |
| CN102531263B (en) | Method for treating saponified wastewater generated in production process of epoxy compound | |
| CN103665035B (en) | A kind of processing method of glyphosate mother solution | |
| CN208454855U (en) | A kind of continuous reaction system for preparing epoxy chloropropane by using glycerol method | |
| CN103864116B (en) | A kind of method of utilizing cement flue Dust to produce potassium chloride and co-producing calcium carbonate | |
| CN100396599C (en) | Method for producing phosphorous acid and gypsum using hydrochloric acid method | |
| CN108358873A (en) | A method of it being used for the continuous reaction system of preparing epoxy chloropropane by using glycerol method and its is used to prepare epoxychloropropane | |
| CN101955431B (en) | Recovery process of catalyst triethylamine in process of synthesizing glyphosate | |
| CN103848768A (en) | Application method of methylamino formyl chloride decomposition tail gas hydrogen chloride in cartap synthesis | |
| CN206843352U (en) | A kind of 1,4 butynediols purification systems | |
| CN108084032B (en) | A method of methyl triethylammonium hydroxide is prepared using glyphosate mother solution | |
| CN102167301A (en) | Production method for co-production of high-water-solubility feed grade calcium phosphate and purified phosphoric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 213016 Baiyun District, Changzhou, Jiangsu Patentee after: Changzhou University Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120801 Assignee: JIANGXI JUFENG CHEMICAL CO., LTD. Assignor: Changzhou University Contract record no.: 2015360000034 Denomination of invention: Clean process for using glycerin to synthesize epichlorohydrin Granted publication date: 20140618 License type: Exclusive License Record date: 20150429 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140618 Termination date: 20210309 |