CN103936600B - Phosphoric acid ester extractant purifies the method for cationic etherifying agent - Google Patents
Phosphoric acid ester extractant purifies the method for cationic etherifying agent Download PDFInfo
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- CN103936600B CN103936600B CN201410152746.4A CN201410152746A CN103936600B CN 103936600 B CN103936600 B CN 103936600B CN 201410152746 A CN201410152746 A CN 201410152746A CN 103936600 B CN103936600 B CN 103936600B
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- extractant
- etherifying agent
- cationic etherifying
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Abstract
The method that the open phosphoric acid ester extractant of the present invention purifies cationic etherifying agent, purification by liquid extraction is carried out as extractant product thick to cationic etherifying agent using phosphate compounds, with the epoxychloropropane and 1 of residual, 3 dichloro 2 propanol in decationize etherifying agent product.While extracting, finally rich in epoxychloropropane and 1 after extracting, the extractant of 3 dichloro 2 propanol regenerates, use alkali liquor that regenerative environ-ment is maintained alkaline environment, extractant after regeneration is circulated use for the extraction of the thick product of cationic etherifying agent, and the epoxychloropropane simultaneously reclaimed is recycled in synthesizing cationic etherifying agent use.Compared with prior art, present invention process is simple, easy and simple to handle, equipment investment few economy, environmental protection.
Description
Technical field
The invention belongs to the purification process of fine chemical product, more particularly, be specifically related to a kind of cation ether
The purification by liquid extraction of agent and renovation process.
Background technology
At present, the cationic etherifying agent major part used by domestic production high-quality modification starch is from external import.But along with shallow lake
The development of the natural product modifying chemical such as powder, as the etherifying agent of a kind of function admirable, 3-chloro-2-hydroxypropyl trimethylammonium
Ammonium chloride (CHPTMAC) consumption will be continuously increased.Therefore, seek the optimum process that CHPTMAC produces,
Significant to the market competitiveness improving China's etherifying agent.But, the cationic etherifying agent that domestic manufacturer produces is thick
Epoxychloropropane (ECH) and 1 in product, 3-bis-chloro-2-propanol (DCP) content is high, respectively reaches 1622mg kg-1With
18472mg·kg-1, product easily crystallizes.The existence of epoxychloropropane and 1,3-bis-chloro-2-propanol makes it easily and starch etc. is handed over
Connection reaction, badly influences the application performance of cationic starch.
Domestic cationic starch manufacturing enterprise mostly uses stripping process removing epoxychloropropane and 1,3-bis-chloro-2-propanol.Vapour
Put forward technique and can effectively reduce the content of organic impurities, but be also faced with energy consumption and (purify one ton of thick products C HPTMAC relatively greatly
Consume 1.0-1.5 ton water vapour), there is generation substantial amounts of containing epoxychloropropane and 1,3-bis-chloro-2-propanol organic wastewater simultaneously
Intractable problem.According to statistics, 1 ton of thick product, 1～1.5 ton of organic wastewater of average generation, dominant therein are often purified
Matter epoxychloropropane and 1,3-bis-chloro-2-propanol toxicity is relatively big, and human body is had carcinogenesis.According to China's integrated wastewater discharge mark
Standard, waste water chloride content < concentration of two kinds of impurity is 1～1.5% for 0.5mg/L, the low-concentration organic waste water that stripping produces,
It is significantly larger than state sewage emission standard.Owing to the impurity content in waste water is the lowest more difficult, therefore process cation ether
The organic wastewater that agent vaporizing extract process produces is relatively difficult, and cost is the highest, and this is also govern Sustainable Development of Enterprises great
Technical bottleneck.Therefore, in order to study more reasonably post-processing approach, reduce ring while effectively removing organic impurities
The pollution in border is the most required major issue solved.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of efficient, economy, the purification cation of environmental protection
The method of etherifying agent.Reduce production cost, reduce because vaporizing extract process uses the problem of environmental pollution brought so that whole work
Skill has good economy and environmental benefit.In conjunction with the application of cationic etherifying agent, extraction process purification is wanted
The extraction coefficient of Seeking Truth slective extraction agent as far as possible is big, and toxicity is little the most nontoxic, extractant can repeatedly use and
Regeneration is easily to be substantially reduced production cost.
For reaching object above, select and investigated multiple extractant, as toluene, dichloromethane, ether, chloroform and
The effect of extracting of several phosphoric acid ester extractant product thick to cationic etherifying agent.Analysis draws phosphoric acid ester extractant ratio
Relatively it is suitable for the purification by liquid extraction of cationic etherifying agent.For this kind of extractants, determine the process conditions of its extraction, examined
Examine the impact on regeneration effect of its technological condition of regeneration, it is determined that optimal technological condition of regeneration.
The technical purpose of the present invention is achieved by following technical proposals:
Phosphoric acid ester extractant purifies the method for cationic etherifying agent, using phosphate compounds as extractant to cation
The thick product of etherifying agent carries out purification by liquid extraction, with the epoxychloropropane and 1 of residual, the chloro-2-of 3-bis-in decationize etherifying agent product
Propanol.While extracting, final rich in epoxychloropropane and 1 after extracting, the extractant of 3-bis-chloro-2-propanol is carried out
Regeneration, uses alkali liquor that regenerative environ-ment maintains alkaline environment, and the extractant after regeneration is for the thick product of cationic etherifying agent
Extraction be circulated use, the epoxychloropropane simultaneously reclaimed be recycled in synthesizing cationic etherifying agent use.
Above-mentioned in technique scheme, the thick product of cationic etherifying agent is 1:(0.4～1 with the volume ratio of extractant).
In technique scheme, extraction temperature is room temperature 20 25 degrees Celsius, and extracting pressure is 1 atmospheric pressure.
In technique scheme, cationic etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, and cationic etherifying agent is thick
In product, epichlorohydrin content is up to 1500mg kg-1Above, 1,3-bis-chloro-2-alcohol content is up to 15472mg kg-1With
On.
In technique scheme, phosphate compounds is selected from tributyl phosphate, three iso-butyl ester of phosphoric acid, tri hexyl phosphate
Or trioctyl phosphate.
In technique scheme, regeneration temperature 60-140 DEG C of extractant, recovery time 2-6h.
In technique scheme, described alkali liquor is the aqueous solution of inorganic base or quaternary ammonium base, and concentration is mass percent
3.8-8.5wt%, described inorganic base is selected from NaOH, KOH or Na2CO3；Described quaternary ammonium base is selected from hydroxide
TBuA, hydroxide ethyl ammonium or tetraethyl ammonium hydroxide.
When stating extraction scheme on the implementation, select three stage countercurrent extraction processes, as shown in Figure 1.Utilize pipeline by three extractions
Take unit to be connected, and by selected extractant and the charging of thick product and discharging direction, to realize in each extraction cells
The counter-current extraction process of extractant and thick product.After the 3rd the final discharging of extraction cells, in thick product, impurity has been expired
Foot product requirement, extractant enters regeneration unit simultaneously, and after regeneration, extractant is back in extraction cells recycle,
Epoxychloropropane is recycled in synthesizing cationic etherifying agent use.
Use above-mentioned three stage countercurrent extraction modes, use continuous operation, or intermittently operated according to actual needs.
Compared with prior art, it is an advantage of the current invention that: 1, technique is simple, easy and simple to handle；2, the few (base of equipment investment
Originally it is zero input)；3, phosphoric acid ester extractant has boiling point height, and in water, dissolubility is little, the feature of stable in properties；4、
After phosphoric acid ester extractant regeneration, using effect is good, economy, environmental protection.
Accompanying drawing explanation
Fig. 1 is three stage countercurrent continuous extraction process schematic in technical solution of the present invention, and wherein A is one-level extraction cells, and B is two
Level extraction cells, C is three grades of extraction cells, and D is regeneration unit, and 1 enters pipeline (light phase feeding pipe) for extractant,
2 is that thick product enters pipeline (heavy phase feeding pipe), and 3 and 6 is thick product connecting line, and 4 and 5 is extractant connecting line,
7 is thick product discharge pipeline (heavy phase discharging pipeline), and 8 is extractant discharging pipeline (light phase discharging pipeline), and 9 is epoxy
Chloropropane discharging pipeline, 10 is extractant reflux pipe.
Detailed description of the invention
Technical scheme is further illustrated below in conjunction with specific embodiment.
Embodiment one
As a example by trioctyl phosphate purifies cationic etherifying agent for extractant:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, epichlorohydrin content is 1622mg kg-1,
1,3-bis-chloro-2-alcohol content is 18472mg kg-1.Extractant is with VThick product: VExtractantThe ratio of=1:0.7,1 continuous extraction
After taking, in cationic etherifying agent, epichlorohydrin content is 15mg kg-1, 1,3-bis-chloro-2-alcohol content is 32mg kg-1；
After 2 continuous extractions, in cationic etherifying agent, epichlorohydrin content is 6mg kg-1, 1,3-bis-chloro-2-alcohol content is
12mg·kg-1。
2, regeneration
The regeneration condition of trioctyl phosphate: concentration is 7%NaOH aqueous solution, temperature 120 DEG C, recovery time 3h,
After recycling 6 times, epoxychloropropane and 1 in the extracted products of regenerating extracting agent, 3-bis-chloro-2-alcohol content still is below
40mg·kg-1.Illustrate that trioctyl phosphate can repeatedly use through regenerative process, it is possible to effectively save use cost.
Embodiment two
As a example by three iso-butyl ester of phosphoric acid purifies cationic etherifying agent for extractant:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, epichlorohydrin content is 1622mg kg-1,
1,3-bis-chloro-2-alcohol content is 18472mg kg-1.Extractant is with VThick product: VExtractantThe ratio of=1:0.8,1 continuous extraction
After taking, in cationic etherifying agent, epichlorohydrin content is 36mg kg-1, 1,3-bis-chloro-2-alcohol content is 70mg kg-1；
After 2 continuous extractions, in cationic etherifying agent, epichlorohydrin content is 10mg kg-1, 1,3-bis-chloro-2-alcohol content is
15mg·kg-1；After 4 continuous extractions, cationic etherifying agent does not detects epoxychloropropane and 1,3-bis-chloro-2-propanol.
2, regeneration
The regeneration condition of three iso-butyl ester of phosphoric acid: concentration is 6%Na2CO3Aqueous solution, temperature 100 DEG C, recovery time 4
H, after recycling 4 times, regenerating extracting agent extracted products in epoxychloropropane and 1,3-bis-chloro-2-alcohol content is still
Less than 50mg kg-1.Illustrate that three iso-butyl ester of phosphoric acid can repeatedly use through regenerative process, it is possible to effectively save make
Use cost.
Embodiment three
As a example by tributyl phosphate purifies cationic etherifying agent for extractant:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, ECH content is 1885mg kg-1, DCP
Content is 23265mg kg-1.Extractant is with VThick product: VExtractantThe ratio of=1:1.1, after 1 continuous extraction, cation
In etherifying agent, epichlorohydrin content is 46mg kg-1, 1,3-bis-chloro-2-alcohol content is 82mg kg-1；2 continuous extractions
After, in cationic etherifying agent, epichlorohydrin content is 18mg kg-1, 1,3-bis-chloro-2-alcohol content content is 25mg kg-1。
2, regeneration
The regeneration condition of tributyl phosphate: concentration is 5% tetrabutylammonium aqueous solution, temperature 120 DEG C, regeneration
Time 6h, after recycling 6 times, epoxychloropropane and 1 in the extracted products of regenerating extracting agent, 3-bis-chloro-2-alcohol content
Less than 50mg kg-1.Illustrate that tributyl phosphate can repeatedly use through regenerative process, it is possible to effectively save use
Cost.
Embodiment four
As a example by tri hexyl phosphate purifies cationic etherifying agent for extractant:
1, extraction
In thick product cationic etherifying agent 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, epichlorohydrin content is 1895mg kg-1,
1,3-bis-chloro-2-alcohol content is 20269mg kg-1.Extractant is with VThick product: VExtractantThe ratio of=1:0.6,1 continuous extraction
After taking, in cationic etherifying agent, epichlorohydrin content is 48mg kg-1, 1,3-bis-chloro-2-alcohol content is 85mg kg-1；
After 2 continuous extractions, in cationic etherifying agent, epichlorohydrin content is 15mg kg-1, 1,3-bis-chloro-2-alcohol content is
25mg·kg-1。
2, regeneration
The regeneration condition of tri hexyl phosphate: concentration is 5% tetraethyl ammonium hydroxide aqueous solution, temperature 100 DEG C, regeneration
Time 6h, after recycling 4 times, epoxychloropropane and 1 in the extracted products of regenerating extracting agent, 3-bis-chloro-2-alcohol content
Less than 50mg kg-1.Illustrate that tri hexyl phosphate can repeatedly use through regenerative process, it is possible to effectively save use
Cost.
When stating four embodiment schemes on the implementation, selecting three stage countercurrent extraction processes, wherein A is one-level
Extraction cells, B is two grades of extraction cells, and C is three grades of extraction cells, and D is regeneration unit, and 1 enters pipeline (gently for extractant
Phase feeding pipe), 2 is that thick product enters pipeline (heavy phase feeding pipe), and 3 and 6 is thick product connecting line, and 4 and 5 are
Extractant connecting line, 7 is thick product discharge pipeline (heavy phase discharging pipeline), 8 for extractant discharging pipeline (light phase go out
Material pipeline), 9 is epoxychloropropane discharging pipeline, and 10 is extractant reflux pipe.Utilize pipeline by three extraction cells phases
Even, and by selected extractant and the charging of thick product and discharging direction, with realize in each extraction cells extractant and
The counter-current extraction process of thick product.After the 3rd the final discharging of extraction cells, in thick product impurity met product want
Asking, extractant enters regeneration unit simultaneously, and after regeneration, extractant is back in extraction cells recycle, epoxy chlorine
Propane cycles uses in synthesizing cationic etherifying agent.
Above the present invention is done exemplary description, it should explanation, in the case of without departing from the core of the present invention,
Any simple deformation, amendment or other those skilled in the art can not spend the equivalent of creative work all to fall
Enter protection scope of the present invention.
Claims (7)
1. phosphoric acid ester extractant purify cationic etherifying agent method, it is characterised in that using phosphate compounds as
Extractant product thick to cationic etherifying agent carries out purification by liquid extraction, with the epoxy chlorine of residual in decationize etherifying agent product
Propane and 1,3-bis-chloro-2-propanol, while extracting, final rich in epoxychloropropane and 1, the chloro-2-of 3-bis-after extracting
The extractant of propanol regenerates, and uses alkali liquor that regenerative environ-ment maintains alkaline environment, and the extractant after regeneration is for sun
The extraction of the thick product of ion etherifying agent is circulated use, and the epoxychloropropane simultaneously reclaimed is recycled to synthesizing cationic etherificate
Using in agent, wherein said cationic etherifying agent is 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, and described cationic etherifying agent is thick
Product is 1:(0.4～1 with the volume ratio of extractant), described phosphate compounds is selected from tributyl phosphate, tricresyl phosphate
Isobutyl ester, tri hexyl phosphate or trioctyl phosphate.
Phosphoric acid ester extractant the most according to claim 1 purifies the method for cationic etherifying agent, it is characterised in that
Extraction temperature is 20 25 degrees Celsius, and extracting pressure is 1 atmospheric pressure.
Phosphoric acid ester extractant the most according to claim 1 purifies the method for cationic etherifying agent, it is characterised in that
Regeneration temperature 60-140 DEG C of described extractant, recovery time 2-6h.
Phosphoric acid ester extractant the most according to claim 1 purifies the method for cationic etherifying agent, it is characterised in that
Described alkali liquor is the aqueous solution of inorganic base or quaternary ammonium base, and concentration is mass percent 3.8-8.5wt%, and described is inorganic
Alkali is selected from NaOH, KOH or Na2CO3；Described quaternary ammonium base is selected from tetrabutylammonium, hydroxide
Ethyl ammonium or tetraethyl ammonium hydroxide.
Phosphoric acid ester extractant the most according to claim 1 purifies the method for cationic etherifying agent, it is characterised in that
When implementing extraction scheme, select three stage countercurrent extraction processes, utilize pipeline three extraction cells to be connected, and by choosing
Determine extractant and the charging of thick product and discharging direction, to realize extractant and the adverse current of thick product in each extraction cells
Extraction process, after the 3rd the final discharging of extraction cells, in thick product, impurity has met product requirement, extracts simultaneously
Agent enters regeneration unit, and after regeneration, extractant is back in extraction cells recycle, and epoxychloropropane is recycled to close
Become in cationic etherifying agent and use.
Phosphoric acid ester extractant the most according to claim 5 purifies the method for cationic etherifying agent, it is characterised in that
Use three stage countercurrent extraction modes, use continuous operation, or intermittently operated according to actual needs.
7. the method purifying cationic etherifying agent according to the phosphoric acid ester extractant one of claim 16 Suo Shu, its feature
Being, in the thick product of cationic etherifying agent, epichlorohydrin content is up to 1500mg kg-1Above, 1,3-bis-chloro-2-propanol contains
Amount up to 15472mg kg-1Above.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57165350A (en) * | 1981-04-03 | 1982-10-12 | Kao Corp | Novel phosphoric ester having quaternary ammonium salt and its preparation |
| EP0371406A1 (en) * | 1988-11-28 | 1990-06-06 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Oxyalkylated quaternary ammonium compounds, processes for production thereof, and plant growth regulating compositions containing said compounds |
| CN1296003A (en) * | 1999-11-10 | 2001-05-23 | 中国石化集团齐鲁石油化工公司 | Process for separation of organic by-products of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride |
| CN101134714A (en) * | 2006-12-06 | 2008-03-05 | 江苏扬农化工集团有限公司 | Method for extraction separation of dichloropropanol from dichloropropanol hydrochloric water solution |
| CN101648927A (en) * | 2009-09-01 | 2010-02-17 | 莫智龙 | Synthesis method of epoxypropyltrimethylammonium chloride |
| CN102659834A (en) * | 2012-05-23 | 2012-09-12 | 东南大学 | Quaternary ammonium class ionic liquid compound containing hydroxy groups and preparation method thereof |
-
2014
- 2014-04-16 CN CN201410152746.4A patent/CN103936600B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57165350A (en) * | 1981-04-03 | 1982-10-12 | Kao Corp | Novel phosphoric ester having quaternary ammonium salt and its preparation |
| EP0371406A1 (en) * | 1988-11-28 | 1990-06-06 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Oxyalkylated quaternary ammonium compounds, processes for production thereof, and plant growth regulating compositions containing said compounds |
| CN1296003A (en) * | 1999-11-10 | 2001-05-23 | 中国石化集团齐鲁石油化工公司 | Process for separation of organic by-products of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride |
| CN101134714A (en) * | 2006-12-06 | 2008-03-05 | 江苏扬农化工集团有限公司 | Method for extraction separation of dichloropropanol from dichloropropanol hydrochloric water solution |
| CN101648927A (en) * | 2009-09-01 | 2010-02-17 | 莫智龙 | Synthesis method of epoxypropyltrimethylammonium chloride |
| CN102659834A (en) * | 2012-05-23 | 2012-09-12 | 东南大学 | Quaternary ammonium class ionic liquid compound containing hydroxy groups and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 改性淀粉油田化学品的研究和应用进展;徐桂云等;《山东轻工业学院学报》;20000925(第03期);第51-54页 * |
| 阳离子魔芋葡甘聚糖的制备与表征;牛春梅等;《精细化工》;20060215(第02期);第188-191页 * |
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