CN102659968A - Hydrolysis technology for acrylic weak-acid cation exchange resin - Google Patents
Hydrolysis technology for acrylic weak-acid cation exchange resin Download PDFInfo
- Publication number
- CN102659968A CN102659968A CN2012101534384A CN201210153438A CN102659968A CN 102659968 A CN102659968 A CN 102659968A CN 2012101534384 A CN2012101534384 A CN 2012101534384A CN 201210153438 A CN201210153438 A CN 201210153438A CN 102659968 A CN102659968 A CN 102659968A
- Authority
- CN
- China
- Prior art keywords
- reaction
- hydrolysis
- acid
- exchange resin
- stainless steel
- 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.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydrolysis technology for acrylic weak-acid cation exchange resin. The technology comprises hydrolysis reaction of two parts, namely basic hydrolysis reaction and acid hydrolysis reaction, wherein the basic hydrolysis reaction is operated in a stainless steel reaction kettle, the acid hydrolysis reaction is operated in an enameled reaction kettle, and excessive 10 percent of NaOH in basic hydrolysis and excessive 30 percent of H2SO4 in acid hydrolysis are kept; and the air pressure in the reaction kettles is improved by closing exhaust valves of the reaction kettles, and the pressure in the kettles is also raised together with rise of material temperature. By the technology, the production costs of related products can be effectively reduced, the production efficiency is improved, and the treatment cost of waste water produced by waste acid and waste base can be greatly reduced.
Description
Technical field
The invention belongs to functional high molecule material ion exchange resin field, be specially a kind of method for hydrolysis that can under the low pressure condition, produce vinylformic acid slightly acidic sun sub-exchange resin.
Background technology
Prior art thinks that the vinylformic acid weakly acidic cation-exchange resin is a kind of ROHM spherical spheres with crosslinking structure.Having higher quality exchange capacity and volume-exchange amount, simultaneously, also possess less acid, alkali body variable quantity transition and higher physical strength, is a kind of ion-exchange material of excellent performance.The common method for making of this exchange resin is to be monomer by methyl acrylate or vinyl cyanide; Utilize divinylbenzene, iso-cyanuric acid triallyl ester etc. as linking agent; With toluene, gasoline, acetic ester etc. is pore-creating agent; With BPO, Diisopropyl azodicarboxylate etc. is initiator, and suspension polymerization obtains the polymkeric substance Archon in dispersing salt solution, obtains the vinylformic acid weakly acidic cation-exchange resin through hydrolysis again.
At present, hydrolysis all is to be employed in the reaction that is hydrolyzed under the condition of normal pressure to the polymkeric substance Archon.In order to satisfy the condition that it reacts completely, with 25% the NaOH aqueous solution of polymkeric substance Archon volume twice or 60% aqueous sulfuric acid.Hydrolysis reaction is more than 20 hours under 100 ℃ of-120 ℃ of temperature.The main drawback of this hydrolysis reaction is that temperature of reaction is low, and acid, alkali use excessive big, long reaction time.
Summary of the invention
The technical problem that the present invention solved is to provide a kind of hydrolysis process of vinylformic acid weakly acidic cation-exchange resin; This novel hydrolysis process can effectively improve hydrolysising reacting temperature; Thereby reduce the usage quantity of acid, alkali, shorten the reaction times, to solve the shortcoming in the above-mentioned background technology.
The technical problem that the present invention solved adopts following technical scheme to realize:
A kind of hydrolysis process of vinylformic acid weakly acidic cation-exchange resin comprises two-part hydrolysis reaction, is respectively macromolecule alkali for hydrolysis and acid hydrolytic reaction, and wherein, macromolecule alkali for hydrolysis is arranged in stainless steel cauldron, and reaction formula is:
Wherein, CH
2The consumption of=CH-CN and two kinds of raw materials of NaOH is 500:377 by reaction formula;
And acid hydrolytic reaction is arranged in glassed steel reaction vessels, and reaction formula is:
Wherein, CH
2=CH-CN and H
2SO
4The consumption of these two kinds of raw materials is 500:642 by reaction formula.
In said process, basic hydrolysis adopts the theoretical usage quantity of NaOH excessive 10%, by the calculating that feeds intake of 500Kg Archon, can be made into 2000 liters of concentration and be 17% the NaOH aqueous solution.
H is adopted in acid hydrolysis
2SO
4Theoretical use excessive 30%; By the calculating that feeds intake of 500Kg Archon, can be made into 1700 liters of concentration and be 30% H
2SO
4The aqueous solution.
If under condition of normal pressure, the said ratio material is the temperature of reaction that can't reach more than 120 ℃.In order to reach this purpose, can take the method for off-response still vent valve to improve the reaction kettle internal gas pressure, with the rising of temperature of charge, the still internal pressure also rises, control still internal pressure 0.2-0.5Mpa.The material hydrolysising reacting temperature can reach 130-160 ℃, is very beneficial for hydrolysis reaction and carries out, and the reaction times only need be kept and just can be realized that hydrolysis was complete in 8-10 hours.
In the present invention, in macromolecule alkali for hydrolysis, said stainless steel cauldron preferred volume is 5m
3Stainless steel cauldron, adopt material 304 or 316 stainless steels, applying pressure>=1Mpa, simultaneously, the stainless steel cauldron of its stainless steel cauldron side sideband 10 ㎡ refluxes.
In the present invention, in acid hydrolytic reaction, said glassed steel reaction vessels preferred volume is 3m
3, applying pressure>=1Mpa, simultaneously, with the glassed steel reaction vessels of 10 ㎡ refluxes.
Beneficial effect: hydrolysis reaction technology is compared under this technology and the traditional condition of normal pressure, has with acid, alkali number and reduces more than 40%, and the shortening hydrolysis time is more than 8 hours, product color characteristics such as obviously bleach.Thereby reduce production costs, enhance productivity, improve the quality of products, significantly reduce spent acid, the cost for wastewater treatment that alkali produces.
Embodiment
In conjunction with examples of implementation the present invention is further detailed:
Embodiment one:
One, batching: 1, polyacrylonitrile Archon (20-60 order): 500Kg;
2, NaOH sheet alkali: 390kg;
3, clear water: 2250Kg;
4, clear infusion: 1kg.
Two, flow process:
1, the 2250kg clear water is injected, in the stainless steel water solution reaction kettle of ability >=1Mpa pressure, open and stir slowly adding 390Kg sheet alkali;
2, drop into polyacrylonitrile Archon 500Kg, slowly be warming up to 85 ℃-90 ℃, note the control heat release;
3,90-100 ℃ of dimension temperature closed drain tap and is warming up to 135 ℃-140 ℃ after 1 hour, and the still internal pressure reaches about 0.5Mpa;
4, at 135 ℃-140 ℃, insulation, pressurize 10 hours;
5, after insulation finished in 10 hours, be cooled to 60 ℃, blowing, washing.Transfer h type resin to hydrochloric acid or sulfuric acid again, be washed till neutrality, remove free-water, the packing warehouse-in;
6, this macropore weakly acidic cation-exchange resin that makes, its key technical indexes is: weight exchange capacity >=10.0mmol/g; The volume-exchange amount is >=4.5mmol/ml that soda acid volume change transition is 75%, intensity (mill back percentage of head rice) >=9.5%.
Embodiment two:
One, batching
1, polyacrylonitrile Archon: 500kg;
2,98% sulfuric acid: 510kg;
3, clear water: 1200kg;
4, skimmer: 0.8kg.
Two, flow process
1, metering water 1200kg drops into the sulfonation reaction still, adds skimmer;
2, slowly add 510kg sulfuric acid, sulfonation still chuck adds cooling;
3, about 80 ℃ add Archon 500kg, slowly heat up;
4,116 ℃-118 ℃ are incubated 1 hour, note heat release and temperature control;
5, close all drain taps and be warming up to 140 ℃-160 ℃, pressure 0.4Mpa, heat-insulation pressure keeping 6 hours;
6, tie up in warm end, cooling, blowing, the washing extremely, pack and put in storage;
7, this macropore weakly acidic cation-exchange resin that makes, its key technical indexes is: >=10.0mmol/g; The volume-exchange amount is >=4.5mmol/ml that soda acid volume change transition is 52-55%, intensity (mill back percentage of head rice) >=9.5%.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The scope of the present invention is required by the appended claims and their equivalents define
.
Claims (3)
1. the hydrolysis process of a vinylformic acid weakly acidic cation-exchange resin comprises two-part hydrolysis reaction, is respectively macromolecule alkali for hydrolysis and acid hydrolytic reaction, it is characterized in that macromolecule alkali for hydrolysis is arranged in stainless steel cauldron, and reaction formula is:
Wherein, CH
2The consumption of=CH-CN and two kinds of raw materials of NaOH is 500:377 by reaction formula;
And acid hydrolytic reaction is arranged in glassed steel reaction vessels, and reaction formula is:
Wherein, CH
2=CH-CN and H
2SO
4The consumption of these two kinds of raw materials is 500:642 by reaction formula;
In said process, basic hydrolysis NaOH is excessive 10%, acid hydrolysis H
2SO
4Excessive 30%; Simultaneously, take the method for off-response still vent valve to improve the reaction kettle internal gas pressure, with the rising of temperature of charge, the still internal pressure also rises, control still internal pressure 0.2-0.5Mpa, and the material hydrolysising reacting temperature reaches 130-160 ℃, and the reaction times is 8-10 hours.
2. the hydrolysis process of a kind of vinylformic acid weakly acidic cation-exchange resin according to claim 1 is characterized in that, in macromolecule alkali for hydrolysis, said stainless steel cauldron preferred volume is 5m
3Stainless steel cauldron, adopt material 304 or 316 stainless steels, applying pressure>=1Mpa, simultaneously, the stainless steel cauldron of its stainless steel cauldron side sideband 10 ㎡ refluxes.
3. the hydrolysis process of a kind of vinylformic acid weakly acidic cation-exchange resin according to claim 1 is characterized in that, in acid hydrolytic reaction, said glassed steel reaction vessels preferred volume is 3m
3, applying pressure>=1Mpa, simultaneously, with the glassed steel reaction vessels of 10 ㎡ refluxes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101534384A CN102659968A (en) | 2012-05-17 | 2012-05-17 | Hydrolysis technology for acrylic weak-acid cation exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101534384A CN102659968A (en) | 2012-05-17 | 2012-05-17 | Hydrolysis technology for acrylic weak-acid cation exchange resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102659968A true CN102659968A (en) | 2012-09-12 |
Family
ID=46769565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101534384A Pending CN102659968A (en) | 2012-05-17 | 2012-05-17 | Hydrolysis technology for acrylic weak-acid cation exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659968A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281609A (en) * | 1999-03-30 | 2000-10-10 | Nippon Steel Chem Co Ltd | Cation exchange resin |
| CN1320647A (en) * | 2001-01-05 | 2001-11-07 | 南京大学 | Process for preparing macroreticular weakly acidic cationic exchange resin of acrylic series |
| US7166645B2 (en) * | 2003-05-19 | 2007-01-23 | Lanxess Deutschland Gmbh | Process for the alkaline saponification of crosslinked acrylonitrile bead polymers |
| CN101310860A (en) * | 2007-02-24 | 2008-11-26 | 朗盛德国有限责任公司 | Monodisperse weakly-acidic cation exchangers |
| CN102234353A (en) * | 2011-04-20 | 2011-11-09 | 安徽美佳新材料股份有限公司 | Preparation method of D113 dilute acid acrylic cation-exchange resin |
-
2012
- 2012-05-17 CN CN2012101534384A patent/CN102659968A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281609A (en) * | 1999-03-30 | 2000-10-10 | Nippon Steel Chem Co Ltd | Cation exchange resin |
| CN1320647A (en) * | 2001-01-05 | 2001-11-07 | 南京大学 | Process for preparing macroreticular weakly acidic cationic exchange resin of acrylic series |
| US7166645B2 (en) * | 2003-05-19 | 2007-01-23 | Lanxess Deutschland Gmbh | Process for the alkaline saponification of crosslinked acrylonitrile bead polymers |
| CN101310860A (en) * | 2007-02-24 | 2008-11-26 | 朗盛德国有限责任公司 | Monodisperse weakly-acidic cation exchangers |
| CN102234353A (en) * | 2011-04-20 | 2011-11-09 | 安徽美佳新材料股份有限公司 | Preparation method of D113 dilute acid acrylic cation-exchange resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103864332B (en) | A kind of preparation method of collapse protection type naphthalene water reducer | |
| CN106115724B (en) | A kind of preparation method of high mode lithium silicate aqueous solution | |
| CN103694405B (en) | A kind of preparation method of Macroporous weak acid cation exchange resin | |
| CN102071267A (en) | Method for coproducing xylose, white carbon black and active carbon from rice hulls | |
| CN105294907A (en) | Preparation method of highly acid styrene series macroporous cation exchange resin | |
| CN101219812A (en) | Method for producing vectolite with waste and old lithium ion battery | |
| CN105234344B (en) | A kind of lost foam casting special cooling coating and preparation method thereof | |
| CN101633627B (en) | Process for producing 3-(N,N-diallyl)amino-4-p-methoxyacetanilide | |
| CN103059180A (en) | Suspension polymerization preparation method of polystyrene/meerschaum particle | |
| CN107057004A (en) | A kind of high density high adsorption is except nitrate nitrogen resin and preparation method thereof | |
| CN102659968A (en) | Hydrolysis technology for acrylic weak-acid cation exchange resin | |
| CN106188400B (en) | A kind of preparation process of polystyrene multi-component copolymer high molecular material | |
| CN104628605B (en) | A kind of naphthalene continuous catalysis method of sulfonating and device thereof | |
| CN203072835U (en) | Syrup heater | |
| CN102234353A (en) | Preparation method of D113 dilute acid acrylic cation-exchange resin | |
| CN105924344B (en) | A kind of preparation method that zinc stearate is prepared using glyceryl tristearate | |
| CN205313117U (en) | Magnesium hydroxide preparation facilities | |
| CN103936993A (en) | Method for preparing methyl silicone oil by utilizing sulfuric acid | |
| CN203976680U (en) | A kind of refining plant of high purity taurine | |
| CN105418402A (en) | Production technology of salicylic acid | |
| CN106632804A (en) | Green preparation method of cation exchange resin | |
| CN113943006A (en) | High-reinforcement white carbon black and preparation method and application thereof | |
| CN101891616A (en) | Continuous acylation production process of tributyl acetocitrate | |
| CN108102354A (en) | A kind of well lid anticorrosion material and preparation method thereof | |
| CN109046262A (en) | Heavy metals removal agent and preparation method thereof in a kind of Chinese medicine extract |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120912 |