CN102557109A - Method for synthesizing basic zinc carbonate from waste water in zinciferous sulfhydryl ester production - Google Patents
Method for synthesizing basic zinc carbonate from waste water in zinciferous sulfhydryl ester production Download PDFInfo
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- CN102557109A CN102557109A CN2011104125661A CN201110412566A CN102557109A CN 102557109 A CN102557109 A CN 102557109A CN 2011104125661 A CN2011104125661 A CN 2011104125661A CN 201110412566 A CN201110412566 A CN 201110412566A CN 102557109 A CN102557109 A CN 102557109A
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- zinc
- waste water
- ammonia
- basic zinc
- zinciferous
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Abstract
The invention relates to a method for synthesizing basic zinc carbonate from waste water in zinciferous sulfhydryl ester production, which comprises the following steps: adding ammonia water into the waste water while stirring to regulate the pH value to 5-6; adding ammonium bicarbonate, and filtering to obtain a zinc ammonium carbonate (Zn(NH3)4CO3) solution; and finally carrying out reduced pressure distillation to remove ammonia gas, thereby obtaining the basic zinc carbonate. The technical scheme uses the waste water generated in zinciferous sulfhydryl ester production as the raw material, effectively utilizes the originally useless industrial waste, and relieves the environmental pressure; the yield and purity of the obtained basic zinc carbonate are satisfactory; and the synthesis method is simple to operate, has the advantages of mild reaction conditions and low production cost, and has wide industrial application prospects.
Description
Technical field
The present invention relates to the synthetic field of inorganic chemistry product, be specifically related to the method that a kind of utilization contains the synthetic zinc subcarbonate of thiol esters factory effluent of zine ion.
Background technology
Zinc subcarbonate, mainly as light-duty astringent matter, the well cementation agent in preparation Calamine, Derma-Guard, rubber, latex product raw material and the oil development process.
Synthetic zinc subcarbonate is mainly pickling method and ammonia still process method on the current industrial.The pickling method mainly is that raw material is through acidleach, removal of impurities, neutralization, deposition, dry preparation zinc subcarbonate production technique with smithsonite; But this method is a cleaner with organic precipitant and organic sequestering agent; Impurity such as deironing, manganese, heavy metal, again through filtration, neutralization, deposition and dry zinc subcarbonate, organic solvent toxicity is big, it is big to pollute, operational hazards, loss are many; Be unfavorable for environment protection and safety in production, and damage HUMAN HEALTH and increase production cost.The ammonia still process method mainly prepares the production technique of zinc subcarbonate with POV zinc and agricultural ammonium hydrogencarbonate, but this method side reaction is many, and energy consumption is high, and yield is low, and is not ideal enough.
Thiol esters; Especially contain a small amount of zinc salt in the waste water that PVC thermo-stabilizer raw materials for production thiol esters (like isooctyl mercaptoacetate, Thiovanic acid isobutylate etc.) is produced; Said waste water generally discharges through handling; Like Chinese patent ZL 200810048478.6 disclosed waste water from acetic acid mercapto-isooctyl ester treatment processs, wherein suspended solid and COD etc. are removed through adding medicament.But existing method of wastewater treatment energy consumption is big, with high costs, handle and to be not good at being prone to contaminate environment, and the materials such as zinc salt in the waste water can not get effective recycling, has caused the waste of resource.
Summary of the invention
For overcoming the defective that existing thiol esters factory effluent can not get effective recycling, the purpose of this invention is to provide the method that a kind of utilization contains the synthetic zinc subcarbonate of zinc thiol esters factory effluent.
The method that utilization provided by the invention contains the synthetic zinc subcarbonate of zinc thiol esters factory effluent is: in said waste water, add ammoniacal liquor under stirring, regulating the pH value is 5～6; Add bicarbonate of ammonia again, filter and obtain carbonic acid ammonia zinc (Zn (NH
3)
4CO
3) solution; Remove ammonia through underpressure distillation at last, obtain zinc subcarbonate; Zn in the waste water in molar ratio
2+: ammoniacal liquor: bicarbonate of ammonia=1: 1.0～1.5: 3.0～3.5.
In the aforesaid method, stirred 1～5 hour behind the adding bicarbonate of ammonia, obtain clarifying carbonic acid ammonia zinc solution, said carbonic acid ammonia zinc is zinc carbonate and NH
3The complex compound that forms.
The rotating speed of said stirring is 10～100 rev/mins.
The vacuum tightness that said underpressure distillation removes ammonia is-0.05～-0.09mpa.
The temperature of said underpressure distillation is 40～80 ℃.
The time of said underpressure distillation is 1～5 hour.
Above-mentioned vacuum distillation process can carry out continuously, while drop into carbonic acid ammonia zinc solution, separate out the product zinc subcarbonate.
The said zinc thiol esters factory effluent that contains is for containing Zn
2+Isooctyl mercaptoacetate or the factory effluent of Thiovanic acid isobutylate.
Saidly contain Zn in the zinc thiol esters factory effluent
2+Concentration be 0.4～1.0mol/L.
The reaction equation of compound method according to the invention is described below:
(1)ZnCl
2+3(NH
4)HCO
3+NH
3·H
2O＝Zn(NH
3)
4CO
3+2CO
2+2HCl+3H
2O
(2)5Zn(NH
3)
4CO
3+3H
2O＝2ZnCO
3·3Zn(OH)
2+3CO
2+20NH
3
(3)3Zn(NH
3)
4CO
3+3H
2O＝ZnCO
3·2Zn(OH)
2·H
2O+2CO
2+12NH
3
(4)2Zn(NH
3)
4CO
3+H
2O＝ZnCO
3·Zn(OH)
2+CO
2+8NH
3
Of the present inventionly contain production process reduction a kind of waste water (being the thiol esters reducing waste water) that contains zinc salt that workshop section produced that zinc thiol esters factory effluent is a PVC thermo-stabilizer raw materials for production thiol esters (isooctyl mercaptoacetate, Thiovanic acid isobutylate etc.).Generally speaking; In the synthetic route of said thiol esters; Usually comprising the step that adopts hydrochloric acid, zinc powder reduction, like the disclosed isooctyl mercaptoacetate preparation method of Chinese patent CN 101613309A, is raw material with different monooctyl ester of Mono Chloro Acetic Acid and Sulfothiorine; Prepare title product through salify, hydrolysis, reduction and distillation, isooctyl mercaptoacetate bullion wherein adopts concentrated hydrochloric acid and zinc powder to reduce.Can produce in the said reduction step and contain Zn in a large number
2+And Cl
-Waste water.Usually its pH value is 1～2, and acidity is stronger, and staple is zinc chloride, sodium-chlor, sodium sulfate, zinc sulfate etc.
Various materials in the thiol esters factory effluent can be confirmed its content through conventional method of analysis; As: (1) zinc chloride; Under acidic conditions; With the pentanoic is indicator, uses yellow prussiate of potash standard solution titration to bluish voilet to be yellow-green colour, goes out the zinc content in the thiol esters reducing waste water through consuming yellow prussiate of potash standardized solution volume and cubage; (2) sodium sulfate, the reaction of vitriol and bariumchloride generates barium sulfate precipitate under acidic conditions, after filtering dry weighing, can draw the content of sulfate radical according to the permanent white quality.Determine Zn in the waste water
2+Content after, add proper ammonia and bicarbonate of ammonia again, filter and to obtain carbonic acid ammonia zinc solution, remove ammonia through distillation at last, can obtain zinc subcarbonate.Other impurity such as sodium sulfate, sodium-chlor can not impact reaction in the whole process.
Technical scheme of the present invention is a raw material with the thiol esters reducing waste water; Effectively utilized originally useless trade waste; Alleviated environmental stress, the zinc subcarbonate yield and the purity that obtain all meet the requirements, and; Compound method is easy and simple to handle, reaction conditions is gentle, low production cost, has huge prospects for commercial application.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment 1
Take by weighing 21.6 gram yellow prussiate of potash, the 0.6 gram Tripotassium iron hexacyanide and 0.2 gram soda ash light in the 400ml beaker, with water dissolution, be diluted to 1000ml, place brown bottle, place 1 all after-filtration demarcation; Take by weighing 1 gram pentanoic; Be dissolved in the 100ml vitriol oil, take by weighing the reducing waste water of 3.5 gram Hubei
star chemical industry Ltd isooctyl mercaptoacetate, move in the 250ml volumetric flask; Be diluted with water to scale; Shake up, pipette 25ml liquid to be measured, demarcate with above-mentioned yellow prussiate of potash standardized solution; Do blank test simultaneously, record that zinc ion concentration is 0.8mol/L in the thiol esters reducing waste water.
In the 1000ml four-hole boiling flask of whipping appts, TM is housed; The reducing waste water that adds 200ml Hubei
star chemical industry Ltd isooctyl mercaptoacetate; Under agitation condition, add 4.0mol/L ammoniacal liquor 40ml, regulating the pH value is 6, takes by weighing 40 gram bicarbonate of ammonia; Join in the four-hole boiling flask; Stirred 1 hour, and obtained the carbonic acid ammonia zinc solution of clear, obtain purified carbonic acid ammonia zinc solution through filtration again; Yield reaches 97%, and carbonic acid ammonia zinc solution content reaches 0.24mol/L.
Prepared calcium carbonate ammonia zinc solution with obtaining joins in the 1000ml there-necked flask, connects vacuum pump, heats with electric mantle; Vacuum tightness reaches-0.08mpa, is warming up to 60 ℃, distills 2.5 hours; Carry out press filtration again, filter cake washs with pure water, drying; Obtain the white powder zinc subcarbonate, yield reaches 96%, and zinc content reaches 57.3%.
Embodiment 2
4.0mol/L ammonia volume among the embodiment 1 is adjusted to 50ml, and all the other are constant, and yield is 90%, carbonic acid ammonia zinc solution content 0.2mol/L.
Embodiment 3
Bicarbonate of ammonia consumption among the embodiment 1 is adjusted to 38 grams, and all the other are constant, and yield is 92%, carbonic acid ammonia zinc solution content 0.21mol/L.
Embodiment 4
Temperature among the embodiment 1 is increased to 70 ℃, and all the other are constant, and yield is 95%, and zinc content reaches 56.8%.
Embodiment 5
Vacuum tightness among the embodiment 1 is adjusted to-0.06mpa, and all the other are constant, and yield is 95%, and zinc content reaches 57.0%.
Embodiment 6
Distillation time among the embodiment 1 is adjusted to 1.5 hours, and all the other are constant, and yield is 91%, and zinc content reaches 57.1%.
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on the basis of the present invention, can to some modifications of do or improvement, this is conspicuous as far as these those skilled in the art.Therefore, these modifications or the improvement on the basis of not departing from spirit of the present invention, made all belong to the scope that requirement of the present invention is protected.
Claims (8)
1. a utilization contains the method that zinc thiol esters factory effluent synthesizes zinc subcarbonate, it is characterized in that, stirs in said waste water, to add ammoniacal liquor down, and regulating the pH value is 5～6; Add bicarbonate of ammonia again, filter and obtain carbonic acid ammonia zinc solution; Remove ammonia through underpressure distillation at last, obtain zinc subcarbonate;
Zn in the waste water in molar ratio
2+: ammoniacal liquor: bicarbonate of ammonia=1: 1.0～1.5: 3.0～3.5.
2. method according to claim 1 is characterized in that, stirs 1～5 hour behind the adding bicarbonate of ammonia.
3. method according to claim 2 is characterized in that, the rotating speed of said stirring is 10～100 rev/mins.
4. method according to claim 1 is characterized in that, the vacuum tightness that underpressure distillation removes ammonia is-0.05～-0.09mpa.
5. method according to claim 1 is characterized in that, the temperature of said underpressure distillation is 40～80 ℃.
6. method according to claim 5 is characterized in that, the time of said underpressure distillation is 1～5 hour.
7. according to each described method of claim 1-6, it is characterized in that, saidly contain Zn in the zinc thiol esters factory effluent
2+Concentration be 0.4～1.0mol/L.
8. method according to claim 7 is characterized in that, the said zinc thiol esters factory effluent that contains is the factory effluent of isooctyl mercaptoacetate or Thiovanic acid isobutylate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104125661A CN102557109A (en) | 2011-12-12 | 2011-12-12 | Method for synthesizing basic zinc carbonate from waste water in zinciferous sulfhydryl ester production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104125661A CN102557109A (en) | 2011-12-12 | 2011-12-12 | Method for synthesizing basic zinc carbonate from waste water in zinciferous sulfhydryl ester production |
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Family
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|---|---|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045956A (en) * | 1989-03-27 | 1990-10-10 | 吉林市金刚化工厂 | Produce zinc subcarbonate and active zinc flower with ammonium bicarbonate precipitation method |
| CN1088183A (en) * | 1993-12-09 | 1994-06-22 | 张安沅 | One-stage process of preparing basic zinc carbonate by metathetical reaction |
| RU2258672C1 (en) * | 2004-04-12 | 2005-08-20 | Открытое акционерное общество "Химпром" | Method of preparing basic zinc carbonate from aqueous solutions of chlorine-containing zinc wastes |
-
2011
- 2011-12-12 CN CN2011104125661A patent/CN102557109A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045956A (en) * | 1989-03-27 | 1990-10-10 | 吉林市金刚化工厂 | Produce zinc subcarbonate and active zinc flower with ammonium bicarbonate precipitation method |
| CN1088183A (en) * | 1993-12-09 | 1994-06-22 | 张安沅 | One-stage process of preparing basic zinc carbonate by metathetical reaction |
| RU2258672C1 (en) * | 2004-04-12 | 2005-08-20 | Открытое акционерное общество "Химпром" | Method of preparing basic zinc carbonate from aqueous solutions of chlorine-containing zinc wastes |
Non-Patent Citations (1)
| Title |
|---|
| 杨春等: "《无机合成清洁生产工艺》", 30 September 2004, 化学工业出版社 * |
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Application publication date: 20120711 |