CN1884079A - Method for reclaiming byproduct sodium chloride in production of epoxy resin - Google Patents
Method for reclaiming byproduct sodium chloride in production of epoxy resin Download PDFInfo
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- CN1884079A CN1884079A CN 200610021092 CN200610021092A CN1884079A CN 1884079 A CN1884079 A CN 1884079A CN 200610021092 CN200610021092 CN 200610021092 CN 200610021092 A CN200610021092 A CN 200610021092A CN 1884079 A CN1884079 A CN 1884079A
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- sodium chloride
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Abstract
The invention discloses a byproduct NaCl recycling method in the epoxide resin manufacturing course, which comprises the following steps: allocating over-saturated salt solution; acidifying; sedimenting the separated NaCl solution; watering; separating; evolving solid NaCl. The invention improves recycling rate by over 98 percent, which is benefit to protect environment.
Description
Technical field
The present invention relates to a kind of method that reclaims Resins, epoxy production process by product NaCl, more properly say, relating to a kind of is catalyzer with NaOH, with dihydroxyphenyl propane and epoxy chloropropane is main raw material, is the recovery method that extraction solvent is produced the by product sodium-chlor in bisphenol A-type (being the E type) the Resins, epoxy process with toluene (or benzene, dimethylbenzene etc.).
Background technology
Because universal E type epoxy resin cured product has mechanical property height, adhesive property excellence, cure shrinkage is little and characteristics such as manufacturability, electrical property, good stability, therefore in thermosetting resin, over-all properties the best of Resins, epoxy and cured article thereof.
Resins, epoxy and cured article thereof are mainly as coating, glue paste, electronic apparatus material, engineering plastics and aspects such as matrix material, civil material.In the every field of national economy, be widely used.
The Resins, epoxy technological development develops to high performance, high added value, the security of environment protection and production in paying attention to developing.
E type Resins, epoxy is to be catalyzer with NaOH, with dihydroxyphenyl propane and epoxy chloropropane is main raw material, with toluene (or benzene, dimethylbenzene etc.) is that extraction solvent is produced bisphenol A-type (being the E type) Resins, epoxy, do in the catalyzer one-step synthesis technology product per ton (resin) at sodium hydroxide and take by-product salt pin out of (in process of production, solids behind separating ring epoxy resins and the recovery solvent is referred to as the salt pin) reach 300-350kg, this salt pin mainly contains following material and content thereof:
| Sequence number | Title | Content (wt%) | States of matter |
| 1 | Sodium-chlor | 80-85 | Solid |
| 2 | Spent resin | 5-13 | Solid |
| 3 | Dihydroxyphenyl propane | 5-8 | Solid |
| 4 | Solvent | ≈2 | Infiltration is in solid |
This " refuse " resource need reclaim and utilize, and on the contrary, if with the discarded loss of this resource, then both caused the wasting of resources, brings the severe contamination to surface water again, the havoc ecotope.
Yet, up to now, adopt filtration method, centrifuging, suction method, water-soluble method, WATER-WASHING METHOD, azeotropic dehydration to isolate by product NaCl usually, as waste treatment, as following table:
| Sequence number | Method | Advantage | Shortcoming |
| 1 | Filtration method | Being fit to general solid-liquid separates | Inapplicable salt pin separate solid composition separates with permeation liquid |
| 2 | Centrifuging | Being fit to general solid-liquid separates | Only separate the perviousness solvent, can not the separate solid composition |
| 3 | Suction method | Being fit to general solid-liquid separates | Inapplicable salt pin solids component separates |
| 4 | Water-soluble method | Being fit to salt pin solid-liquid separates | A large amount of NaCl saturated solutions need boiling or vacuum salt production to isolate solid NaCl |
| 5 | WATER-WASHING METHOD | Both can the separate solid spent resin, dihydroxyphenyl propane, can obtain solid NaCl again, and saturated NaCl salt solution can utilize again | Consume hydrochloric acid and NaOH, do not bring by-product salt (NaCl) into but there is any impurity |
But above-mentioned the whole bag of tricks is the needs of incompatibility modern production, in order to economize on resources, protect environment, and some scientific research personnel have done following research:
Qiu Peng (chemical industry Technological Economy, 2004,22 (8), 42-44,47) on periodical has introduced isolated salt loading liquid evaporation concentration has been obtained crystallization, can be used as Industrial Salt and sell, but this method will expend a large amount of heat energy;
Department scape (Anhui chemical industry, 2003, (1) on periodical, 42-44) (the salt slag repeatedly washs through reclaiming toluene the technology of Jie Shaoing, separate through the automatic vacuum whizzer, through vacuum rake dryer piptonychia benzene) obtain meeting the NaCl that chlorine industry requires, but process and equipment are all complicated.
Above-mentioned two kinds of methods are applicable to the production of ton E type Resins, epoxy; because of its salt pin amount big; adopt the NaCl in the water-soluble method recovery salt pin; must investment one overlap vacuum salt production equipment, the product that manufactures industry salt, ability balance E type Resins, epoxy production profit and loss point; but general manufacturer had only kiloton E type Resins, epoxy production equipment; then can not balanced production profit and loss point, produce uneconomical, if all the Law on Environmental Protection regulation is run counter in dischargings again.The result causes medium and small sized enterprises to change the line of production or close, and causes China to have the tackiness agent of extensive use and the Resins, epoxy of system raw materials for varnish mainly to rely on import.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art and provide a kind of fairly simple method to reclaim the byproduct sodium chloride that brings in the production of E type Resins, epoxy, this method is rate of recovery height not only, and is fit to middle-size and small-size E type Resins, epoxy manufacturing enterprise more and uses.
The object of the present invention is achieved like this:
The recovery method of byproduct sodium chloride during a kind of Resins, epoxy is produced, it comprises the steps:
(1) raw material solid salt is added water and be configured to supersaturated brine solution;
(2) add hydrochloric acid in the salt brine solution in step (1) and carry out agitator treating, leave standstill solution and remove its upper strata floating matter, these floating matters are meant density spent resin and the dihydroxyphenyl propane lighter than water in the salt pin composition, and adding sodium hydroxide solution adjusting salt brine solution pH value again is 7-8, obtains the sodium-chlor precipitation;
(3) sodium-chlor of isolating in the salt brine solution precipitates;
(4) water or weak brine clean isolated sodium-chlor precipitation in (3) step, leave standstill solution and remove its upper strata floating matter, these floating matters are remaining density spent resin and dihydroxyphenyl propanes lighter than water in the sodium-chlor precipitation, obtain sodium chloride saturated solution and sedimentary solid sodium chloride;
(5) separate sodium chloride saturated solution and solid sodium chloride;
(6) adding the hydrochloric acid conditioning solution pH value in sodium chloride saturated solution is 6-7, separates out solid sodium chloride;
(7) isolate solid sodium chloride in the step (6).
Wherein, the concentration of the hydrochloric acid that adds in the salt brine solution in step (1) is 10%; The concentration of the sodium hydroxide solution that uses in the step (2) is 35-40%; The concentration of the hydrochloric acid that adds in the sodium chloride saturated solution in step (6) is 10%;
For more economically, will in step (3), be back in the step (2) by the remaining clear liquid of sodium-chlor post precipitation of isolating; Also remaining clear liquid isolate solid sodium chloride in step (7) after can be back in the step (4).
The technology of the byproduct sodium chloride that brings in the designed recovery E type Resins, epoxy production of the present invention, cost is low, and energy consumption is few, and the rate of recovery can reach more than 98%; Pickle solution, washing water recycle by regenerating to reach in handling by-product salt process, near zero release, avoid pollution to surface water, help environmental protection, the present invention is because of low for equipment requirements, is fit to middle-size and small-size E type Resins, epoxy manufacturing enterprise more and reclaims byproduct sodium chloride.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further details, but the present invention has more than and is limited to these examples:
Embodiment: technological process of the present invention:
The 50kg clean water is added in the 100l volume stirring tank, open and stir, mixing speed 80-100 rev/min, the by-product salt from the production of E type Resins, epoxy that adds 35kg is configured to supersaturated brine solution, reinforced finishing, add 10% hydrochloric acid 3kg again,, stop to stir through 30 minutes washing, left standstill 5-10 minute, pickling still upper strata floating matter is spent resin and dihydroxyphenyl propane, after upper strata spent resin and other solid impurities are cleaned out, saturated brine is moved out to the pickle solution accumulator tank, and adding 35-40% sodium hydrate regulator solution PH is 7-8, produce the sodium-chlor precipitation in the solution, the oyster sodium-chlor of isolating then in the salt brine solution that is precipitates, wherein, isolate the remaining clear liquid of sodium-chlor post precipitation and can do the liquid circulation use of dissolved salt pin, reuse, in fact, the operation of hydro-oxidation sodium washings regeneration just.
After pickling, obtain oyster salt (work in-process salt), in volume 100L stirring tank, add clean water 50kg, open and stir, mixing speed 80-100 rev/min, add 35kg work in-process salt, under agitation condition, washed 30 minutes, stop to stir, static 5-10 minute, remove the floating matter on water body upper strata, separate sodium chloride saturated solution and solid sodium chloride finished product then, shift out Nacl saturated solution to water lotion again and reclaim in the storage tank, with concentration is that 10% Hcl solution regulator solution pH value is to 6-7, this moment, water lotion reclaimed washings AUTOMATIC ZONING in the storage tank, and the supernatant liquid recycling use is as wash medium next time, separate out the solid sodium chloride finished product at the bottom of reclaiming storage tank, white, loose, free from extraneous odour, water-content wherein add the pH value of hydrochloric acid conditioning solution generally below 6%, separating impurity makes the clarifying operation of saturated brine also can be referred to as the regeneration of water lotion.
For the advantage of present method is described in further detail, do following 8 examples constantly according to the method in the foregoing description below, and do simultaneous test with prior art, specifically reclaim sodium-chlor processing condition such as table 1:
Table 1
| Operation | The control project | Controlling index | Control method |
| Pickling | PH value | PH＝3-4 | Add 10% acid adjusting |
| Hold time (t) h | T＝0.5h | ||
| Washing | Hold time (t) h | T＝0.5h | |
| Acid washing water regeneration | PH value | Add alkali, PH=8 | Add 40% alkali adjusting |
| Add acid, PH=3-4 | Add 10% acid adjusting | ||
| The washing water reuse | PH value | Add alkali, PH=8 | Add 40% alkali adjusting |
| Add acid, PH=6 | Add 10% acid adjusting |
Then, according to above-mentioned processing condition, simultaneous test and acid washing test example case such as table 2:
Table 2
| The test sequence number | Service water kg | Raw material salt kg | ～10％ (wt) HCl，kg | Pickling salt kg | The outward appearance form and aspect | ～10％ (wt) HCl，kg | Service water kg | Pickling salt kg | The outward appearance form and aspect |
| Comparative Examples 1 | 50 | 33.5 | / | / | Slightly redly | 3 | / | 20.6 | Oyster |
| Embodiment 1 | 50 | 34.8 | 3 | 31.6 | Oyster | / | / | / | / |
| Embodiment 2 | 50 | 34.8 | 3 | 32.6 | Oyster | / | / | / | / |
| Embodiment 3 | 50 | 37.3 | 3 | 39.3 | Oyster | / | / | / | / |
| Embodiment 4 | 50 | 34.9 | 5 | 38 | Oyster | / | / | / | / |
| Comparative Examples 2 | 50 | 35.2 | Add alkali to strong basicity | / | Near black | 9 | / | 38.9 | Oyster |
| Comparative Examples 3 | 50 | 37.8 | Add acid to neutral | / | Slightly redly | 2 | / | 38.3 | Oyster |
| Contrast | 50 | 35 | Add acid extremely | / | Pale yellow | / | 50 | 37.6 | Whiter |
| Example 4 | Slightly acidic | Green | |||||||
| Embodiment 5 | 50 | 34 | 3 | 33.2 | Oyster | / | / | / | / |
| Embodiment 6 | 50 | 35 | 3 | 37 | Oyster | / | / | / | / |
| Embodiment 7 | 50 | 34.8 | 3 | 38 | Oyster | / | / | / | / |
| Embodiment 8 | 50 | 34 | 3 | 27 | Oyster | / | / | / | / |
Continuation is washed the oyster work in-process salt after pickling among the embodiment 1-8 in the table 2 once more and is obtained finished product, and the experimental result of this finished product is as follows:
| The embodiment sequence number | Service water kg | Pickling salt kg | Product NaCl | The outward appearance form and aspect |
| Embodiment 1 | 50 | 36 | 24.3 | Whiter |
| Embodiment 2 | 50 | 41 | 42.3 | Whiter |
| Embodiment 3 | 50 | 31.3 | 34.8 | Whiter |
| Embodiment 4 | 50 | 35.3 | 26.3 | Whiter |
| Embodiment 5 | 50 | 36 | 34.5 | Whiter |
| Embodiment 6 | 50 | 34.2 | 31 | Whiter |
| Embodiment 7 | 50 | 41 | 42 | Whiter |
| Embodiment 8 | 50 | 36.8 | 40 | Whiter |
Above result proves that this technology can remove spent resin and glycerine that the attached product salt of Resins, epoxy is carried secretly preferably, and the salt outward appearance of handling does not contain the toluene taste for white; Cost recovery is low, does not cause the pollution to surface water; The test favorable repeatability, device amplifies easily.
Claims (6)
1, the recovery method of byproduct sodium chloride is characterized in that comprising the steps: during a kind of Resins, epoxy was produced
(1) raw material solid salt is added water and be configured to supersaturated brine solution;
(2) add hydrochloric acid in the salt brine solution in step (1) and carry out agitator treating, leave standstill solution and remove its upper strata floating matter, adding sodium hydroxide solution adjusting salt brine solution pH value again is 7-8, obtains the sodium-chlor precipitation;
(3) sodium-chlor of isolating in the salt brine solution precipitates;
(4) water or weak brine clean isolated sodium-chlor precipitation in (3) step, leave standstill solution and remove its upper strata floating matter, obtain sodium chloride saturated solution and sedimentary solid sodium chloride;
(5) separate sodium chloride saturated solution and solid sodium chloride;
(6) adding the hydrochloric acid conditioning solution pH value in sodium chloride saturated solution is 6-7, separates out solid sodium chloride;
(7) isolate solid sodium chloride in the step (6).
2,, it is characterized in that the concentration of the hydrochloric acid that adds in the salt brine solution in step (1) is 10% according to the method described in the claim 1.
3,, it is characterized in that the concentration of the middle sodium hydroxide solution that uses of step (2) is 35-40% according to the method described in the claim 1.
4,, it is characterized in that the concentration of the hydrochloric acid that adds in the sodium chloride saturated solution in step (6) is 10% according to the method described in the claim 1.
5,, it is characterized in that the remaining clear liquid of sodium-chlor post precipitation of isolating is back in the step (2) in step (3) according to the method described in the claim 1.
6, according to the method described in the claim 1, remaining clear liquid is back in the step (4) after it is characterized in that isolating solid sodium chloride in step (7).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100210927A CN100417593C (en) | 2006-06-01 | 2006-06-01 | Method for reclaiming byproduct sodium chloride in production of epoxy resin |
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|---|---|---|---|
| CNB2006100210927A CN100417593C (en) | 2006-06-01 | 2006-06-01 | Method for reclaiming byproduct sodium chloride in production of epoxy resin |
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| CN1884079A true CN1884079A (en) | 2006-12-27 |
| CN100417593C CN100417593C (en) | 2008-09-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102292372A (en) * | 2008-12-18 | 2011-12-21 | 陶氏环球技术有限责任公司 | Method of separating solid salt from epoxy resin solutions |
| CN102557164A (en) * | 2010-12-15 | 2012-07-11 | 益海天成(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| CN102849755A (en) * | 2012-10-17 | 2013-01-02 | 安徽理工大学 | Purification method for industrial byproduct salt and purification device therefor |
| US8466257B2 (en) | 2008-02-22 | 2013-06-18 | Dow Global Technologies Llc | Process and apparatus for purifying solid salt compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU526597A1 (en) * | 1974-11-05 | 1976-08-30 | Предприятие П/Я А-3732 | Calcium Chloride Preparation Method |
| US4747917A (en) * | 1987-03-02 | 1988-05-31 | Olin Corporation | Scale-free process for purifying concentrated alkali metal halide brines containing sulfate ions as an impurity |
| ES2336812T3 (en) * | 2004-10-22 | 2010-04-16 | Akzo Nobel N.V. | METHOD FOR CRSTALIZING SOLUBLE SALTS OF DIVAL ANIONS FROM SALMUERA. |
-
2006
- 2006-06-01 CN CNB2006100210927A patent/CN100417593C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8466257B2 (en) | 2008-02-22 | 2013-06-18 | Dow Global Technologies Llc | Process and apparatus for purifying solid salt compositions |
| CN102292372A (en) * | 2008-12-18 | 2011-12-21 | 陶氏环球技术有限责任公司 | Method of separating solid salt from epoxy resin solutions |
| CN102292372B (en) * | 2008-12-18 | 2013-06-05 | 陶氏环球技术有限责任公司 | Method of separating solid salt from epoxy resin solutions |
| TWI495498B (en) * | 2008-12-18 | 2015-08-11 | Dow Global Technologies Llc | Method of separating solid salt from epoxy resin solutions |
| CN102557164A (en) * | 2010-12-15 | 2012-07-11 | 益海天成(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| CN102557164B (en) * | 2010-12-15 | 2013-12-11 | 益海嘉里(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| CN102849755A (en) * | 2012-10-17 | 2013-01-02 | 安徽理工大学 | Purification method for industrial byproduct salt and purification device therefor |
| CN102849755B (en) * | 2012-10-17 | 2014-04-02 | 安徽理工大学 | Purification method for industrial byproduct salt and purification device therefor |
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| CN100417593C (en) | 2008-09-10 |
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