CN102874848A - Method for recovering sodium bicarbonate and organic acid sodium salt from cyclohexanone waste alkali solution - Google Patents
Method for recovering sodium bicarbonate and organic acid sodium salt from cyclohexanone waste alkali solution Download PDFInfo
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- CN102874848A CN102874848A CN2012103338400A CN201210333840A CN102874848A CN 102874848 A CN102874848 A CN 102874848A CN 2012103338400 A CN2012103338400 A CN 2012103338400A CN 201210333840 A CN201210333840 A CN 201210333840A CN 102874848 A CN102874848 A CN 102874848A
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- sodium bicarbonate
- clear liquid
- organic acid
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Abstract
The invention provides a method for recovering sodium bicarbonate and organic acid sodium salt from a cyclohexanone waste alkali solution. The method comprises the following steps of: performing gas-liquid contact carbonation reaction on CO2 and the waste alkali solution, precipitating and demixing to obtain clear liquid and concentrated sodium bicarbonate slurry; concentrating and sectioning the concentrated slurry to obtain a crude sodium bicarbonate; and evaporating, concentrating and sectioning the clear liquid to obtain crude organic acid sodium salt, or stirring and mixing raffinate obtained after the clear liquid is evaporated and the concentrated slurry, concentrating and sectioning to obtain the crude organic acid sodium salt. By the method, available resources in the cyclohexanone waste alkali solution are recovered, so that inorganic or organic chemical products such as the sodium bicarbonate and the organic acid sodium salt are obtained, and secondary pollutants are not discharged in the recovering process. Compared with the prior art, the method has the advantages that the whole technological process is short and low in energy consumption, equipment investment and running cost, the added value of the obtained recycled products is high, and social and economic benefits are obvious.
Description
Technical field
The present invention relates to the wastewater from chemical industry comprehensive utilization technique, particularly a kind of method that from the pimelinketone waste lye, reclaims sodium bicarbonate and organic acid sodium salt
Background technology
Pimelinketone is important industrial chemicals.The suitability for industrialized production pimelinketone all adopts cyclohexane liquid phase oxidation technique mostly.This explained hereafter pimelinketone, the selectivity of alcohol, ketone product is generally 75%～85%, and all the other parts transform and generate by product, wherein can directly reclaim lightweight oil and X oil, all the other components must be processed by alkali cleaning, finally form pimelinketone high-concentration waste alkali lye (hereinafter to be referred as waste lye).About 4～60,000 tons of the annual waste lye of discharging of the cyclohexanone production apparatus that one cover is 50,000 ton/years.This waste lye mainly comprises sodium hydroxide, yellow soda ash, also has monocarboxylic acid, di-carboxylic acid, alcohol acid, polycondensate and lower alcohol, ketone, aldehyde, ester type organic and water.Although the polynary complexity of its component wherein is no lack of and contains the Chemicals that can further recycle in a large number.In the last few years, expert both domestic and external and scholar laid particular emphasis on chemical process to processing studying of waste lye in the industry.Its core content is, at utmost extracts the useful resources in the waste lye, reduces simultaneously waste liquid after processing to the pollution of environment.For example: realized industrialized patent of invention " method of zero discharge processing of waste saponification lye of cyclohexanone produced by cyclohexane oxidation technology (ZL200810169750.6) ", through multiple tracks technique, from waste lye, extract yellow soda ash, sodium sulfate, inorganic, the Organic chemical products of acid wet goods of high added value, effectively administered the pollution of relief liquor to environment, have obvious advantage, but it exists still such as: solid-liquid separation difficulty, the defective such as separation costs is too high, technical process is loaded down with trivial details.Again: patent of invention " the solid method of a kind of saponification waste lye and saponification powder (ZL201010244120.8) " discloses " passes through first to add CO with saponification waste lye
2Change its chemical property with auxiliary agent, distill again and make the water qualified discharge; Then filter, filtrate is returned distillation again, and more than the secondary, moisture evaporates fully in the saponification waste lye until make repeatedly; The filter residue drying is solidified generation saponification powder." this patented method exists equally solid-liquid to be difficult to separate, to process that energy consumption is too high, technical process is loaded down with trivial details, is difficult to realize the drawback such as industrialization.For this reason, how to overcome the weak point of above-mentioned existence, being still in the industry, scientific and technical personnel need the again problem of further investigation.
Summary of the invention
The invention provides a kind of method that from the pimelinketone waste lye, reclaims sodium bicarbonate and organic acid sodium salt, purpose is to take full advantage of the resource in the waste lye, with short technical process, lower energy consumption waste lye is processed, from waste lye, obtained to resource utilization inorganic, the Organic chemical products such as sodium bicarbonate and organic acid sodium salt.
Technical solution of the present invention:
One of technical solution of the present invention is with CO
2Unstripped gas and waste lye are realized gas-to-liquid contact, and carbonation reaction occurs, and behind circulating reaction, precipitated and separated obtains clear liquid and the underflow material of separating out the supersaturation sodium bicarbonate, and the underflow material is concentrated section, obtains the crude product sodium bicarbonate; Clear liquid is carried out evaporation concentration, section, obtain the crude product organic acid sodium salt.
Two of technical solution of the present invention is with CO
2Unstripped gas and waste lye are realized gas-to-liquid contact, and carbonation reaction occurs, and behind circulating reaction, precipitated and separated obtains clear liquid and the underflow material of separating out the supersaturation sodium bicarbonate, and the underflow material is inserted underflow material tundish, with for subsequent use; After evaporation raffinate after clear liquid evaporated and described underflow material for subsequent use mix, concentrate section, obtain the crude product organic acid sodium salt.
The concrete technology of one of technical solution of the present invention is:
(A) make waste lye and CO
2Unstripped gas carries out gas-to-liquid contact in Venturi, carry out carbonation reaction, enters in the circulating reaction tank sodium hydroxide that contains in the waste lye and CO
2Reaction generates sodium bicarbonate, and its reaction equation is: NaOH+CO
2==NaHCO
3The yellow soda ash that contains in the waste lye and CO
2Reaction generates sodium bicarbonate, and its reaction equation is: Na
2CO
3+ CO
2+ H
2O==2NaHCO
3
When the pH of above-mentioned reaction solution value reaches 8-8.5, termination reaction;
(B) above-mentioned reaction solution is pumped in the suspension insulation tundish, precipitated and separated, top is clear liquid, the bottom is the underflow material; Clear liquid is pumped into clear liquid insulation tundish, for subsequent use; The underflow material is pumped into underflow material insulation tundish, for subsequent use;
(C) above-mentioned clear liquid for subsequent use is pumped in the evaporating kettle that negative pressure is 20Kpa-95Kpa dewater, when the volume of deviating from the water yield, when reaching the 35-55% that enters evaporating kettle clear liquid volume, stop evaporation; Collect the evaporation raffinate; The recycling condensing water that collection is deviate from is in pimelinketone device;
(D) the above-mentioned evaporation raffinate of collecting is concentrated section, obtain the crude product organic acid sodium salt;
(E) (B) described underflow material for subsequent use is concentrated section, obtain the crude product sodium bicarbonate.
Two concrete technology of technical solution of the present invention is:
(A) make waste lye and CO
2Unstripped gas carries out gas-to-liquid contact in Venturi, carry out carbonation reaction, enters in the circulating reaction tank sodium hydroxide that contains in the waste lye and CO
2Reaction generates sodium bicarbonate, and its reaction equation is: NaOH+CO
2==NaHCO
3The yellow soda ash that contains in the waste lye and CO
2Reaction generates sodium bicarbonate, and its reaction equation is: Na
2CO
3+ CO
2+ H
2O==2NaHCO
3
When the pH of above-mentioned reaction solution value reaches 8-8.5, termination reaction;
(B) above-mentioned reaction solution is pumped in the suspension insulation tundish, precipitated and separated, top is clear liquid, the bottom is the underflow material; Clear liquid is pumped into clear liquid insulation tundish, for subsequent use; The underflow material is pumped into underflow material insulation tundish, for subsequent use;
(C) above-mentioned clear liquid for subsequent use is pumped in the evaporating kettle that negative pressure is 20Kpa-95Kpa dewater, when the volume of deviating from the water yield, when reaching the 35-55% that enters evaporating kettle clear liquid volume, stop evaporation; Collect the evaporation raffinate; The recycling condensing water that collection is deviate from is in pimelinketone device;
(D) with above-mentioned evaporation raffinate, insert after (B) described underflow material tundish and underflow material mix, concentrate section, obtain the crude product organic acid sodium salt.
Beneficial effect of the present invention:
The present invention reclaims the available stock in the pimelinketone waste lye, makes waste lye and carbon dioxide reaction, obtains inorganic, the Organic chemical products such as sodium bicarbonate, organic acid sodium salt; In reclaiming waste lye in the available stock, realize the discharging of non-secondary pollution thing, compare with the pimelinketone spent lye treatment method of prior art, the resource product added value that whole technical process is brief, energy consumption is low, equipment investment is few, working cost is low, obtain is high, has remarkable Social benefit and economic benefit.
Description of drawings
Accompanying drawing 1 is technical process block diagram of the present invention.
Embodiment
The present invention by technical scheme and accompanying drawing as seen, technical scheme one is compared with two: the former is at waste lye and CO
2Carbonation reaction occurs, and after the redeposition layering, the crude product sodium bicarbonate is reclaimed to get in the underflow material section that obtains; The clear liquid that obtains, the raffinate behind the revaporization concentrates section, reclaims to get the crude product organic acid sodium salt.The latter is at waste lye and CO
2After carbonation reaction occurs, the sodium bicarbonate underflow material that obtains behind the precipitated and separated, with together concentrated section of the raffinate that obtains after the clear liquid evaporation, reclaim to get the crude product organic acid sodium salt.And both given processing condition and the processing parameter that sets are basic identical.
Below enumerate embodiment, further specify it:
Embodiment one: extract crude product sodium bicarbonate, crude product organic acid sodium salt from waste lye.
From pimelinketone device, getting volume is the waste lye 1Kg of 810ml, and in the 5000ml three-necked flask, with waste lye and carbon dioxide generation carbonation reaction, the pH value that records reaction solution is 8.3 o'clock, stopped reaction; With the reaction solution precipitated and separated, after a period of time, the solid-liquid two-phase appears in the flask, and the upper strata is clear liquid, and lower floor is the underflow material; The 500ml supernatant liquid is placed in the three-necked flask of 1000ml with the siphon method, the open water ring vacuum pump, keeping the vacuum pressure in the three-necked flask is 60Kpa, collects water of condensation, when the volume of water of condensation reaches 250ml, stops evaporation; To evaporate raffinate and insert in the crucible, in retort furnace, be heated to 110 ℃, obtain crude product organic acid sodium salt 380g; Again the underflow material is inserted in the crucible, in retort furnace, be heated to 110 ℃, obtain crude product sodium bicarbonate 200g.
Embodiment two: extract the crude product organic acid sodium salt from waste lye.
From pimelinketone device, getting volume is the waste lye 1Kg of 810ml, and in the 5000ml three-necked flask, with waste lye and carbon dioxide generation carbonation reaction, the pH value that records reaction solution is 8.5 o'clock, stopped reaction; With the reaction solution precipitated and separated, after a period of time, the solid-liquid two-phase appears in the flask, and the upper strata is clear liquid, and lower floor is the underflow material; The 500ml supernatant liquid is placed in the three-necked flask of 1000ml with the siphon method, the open water ring vacuum pump, keeping the vacuum pressure in the three-necked flask is 60Kpa, collects water of condensation, when the volume of water of condensation reaches 250ml, stop evaporation, the evaporation raffinate is inserted in the 5000ml three-necked flask that the underflow material is housed, after mixing, insert in the crucible, in retort furnace, be heated to 110 ℃, obtain crude product organic acid sodium salt 550g.
To sum up, the inventive method can reach the goal of the invention of expection.
Claims (4)
1. method that reclaims sodium bicarbonate and organic acid sodium salt from the pimelinketone waste lye, it is characterized in that: the method is with CO
2Unstripped gas and described waste lye are realized gas-to-liquid contact, and carbonation reaction occurs, and behind circulating reaction, precipitated and separated obtains clear liquid and the underflow material of separating out the supersaturation sodium bicarbonate, and the underflow material is concentrated section, obtains the crude product sodium bicarbonate; Clear liquid is carried out evaporation concentration, section, obtain the crude product organic acid sodium salt.
2. a kind of method that from the pimelinketone waste lye, reclaims sodium bicarbonate and organic acid sodium salt according to claim 1, it is characterized in that: the concrete technology of the method is:
(A) make waste lye and CO
2Unstripped gas carries out gas-to-liquid contact in Venturi, carry out carbonation reaction, enters in the circulating reaction tank sodium hydroxide that contains in the waste lye and CO
2Reaction generates sodium bicarbonate; The yellow soda ash that contains in the waste lye and CO
2Reaction generates sodium bicarbonate;
When the pH of above-mentioned reaction solution value reaches 8-8.5, termination reaction;
(B) above-mentioned reaction solution is pumped in the suspension insulation tundish, precipitated and separated, top is clear liquid, the bottom is the underflow material; Clear liquid is pumped into clear liquid insulation tundish, for subsequent use; The underflow material is pumped into underflow material insulation tundish, for subsequent use;
(C) above-mentioned clear liquid for subsequent use is pumped in the evaporating kettle that negative pressure is 20Kpa-95Kpa dewater, when the volume of deviating from the water yield, when reaching the 35-55% that enters evaporating kettle clear liquid volume, stop evaporation; Collect the evaporation raffinate; The recycling condensing water that collection is deviate from is in pimelinketone device;
(D) the above-mentioned evaporation raffinate of collecting is concentrated section, obtain the crude product organic acid sodium salt;
(E) (B) described underflow material for subsequent use is concentrated section, obtain the crude product sodium bicarbonate.
3. method that reclaims sodium bicarbonate and organic acid sodium salt from the pimelinketone waste lye is characterized in that:
The method is with CO
2Unstripped gas and waste lye are realized gas-to-liquid contact, and carbonation reaction occurs, and behind circulating reaction, precipitated and separated obtains clear liquid and the underflow material of separating out the supersaturation sodium bicarbonate, and the underflow material is inserted underflow material tundish, with for subsequent use; After evaporation raffinate after clear liquid evaporated and described underflow material for subsequent use mix, concentrate section, obtain the crude product organic acid sodium salt.
4. a kind of method that from the pimelinketone waste lye, reclaims sodium bicarbonate and organic acid sodium salt according to claim 1, it is characterized in that: the concrete technology of the method is:
(A) make waste lye and CO
2Unstripped gas carries out gas-to-liquid contact in Venturi, carry out carbonation reaction, enters in the circulating reaction tank sodium hydroxide that contains in the waste lye and CO
2Reaction generates sodium bicarbonate, the yellow soda ash that contains in the waste lye and CO
2Reaction generates sodium bicarbonate;
When the pH of above-mentioned reaction solution value reaches 8-8.5, termination reaction;
(B) above-mentioned reaction solution is pumped in the suspension insulation tundish, precipitated and separated, top is clear liquid, the bottom is the underflow material; Clear liquid is pumped into clear liquid insulation tundish, for subsequent use; The underflow material is pumped into underflow material insulation tundish, for subsequent use;
(C) above-mentioned clear liquid for subsequent use is pumped in the evaporating kettle that negative pressure is 20Kpa-95Kpa dewater, when the volume of deviating from the water yield, when reaching the 35-55% that enters evaporating kettle clear liquid volume, stop evaporation; Collect the evaporation raffinate; The recycling condensing water that collection is deviate from is in pimelinketone device;
(D) above-mentioned evaporation raffinate is inserted (B) described underflow material tundish, after mixing with the underflow material, concentrate section, obtain the crude product organic acid sodium salt.
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|---|---|---|---|
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| CN2012103338400A CN102874848A (en) | 2012-09-11 | 2012-09-11 | Method for recovering sodium bicarbonate and organic acid sodium salt from cyclohexanone waste alkali solution |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193234A (en) * | 2013-04-12 | 2013-07-10 | 太原理工大学 | Method for preparing magnesium silicide-based powder thermoelectric material by utilizing polysilicon byproduct |
| CN104474881A (en) * | 2014-12-02 | 2015-04-01 | 成都华西堂投资有限公司 | Method for preparing sodium bicarbonate used in purification of flue gas from caprolactam incineration waste alkali |
| CN108996526A (en) * | 2017-06-07 | 2018-12-14 | 中国科学院过程工程研究所 | A kind of preparation method of bulky grain heavy sodium bicarbonate |
| CN112694190A (en) * | 2020-12-08 | 2021-04-23 | 内蒙古工业大学 | Method for treating polyformaldehyde industrial high-alkali/high-organic-matter waste liquid by using boiler tail gas |
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| CN101428915A (en) * | 2008-07-13 | 2009-05-13 | 赵志军 | Method for zero discharge processing of waste saponification lye of cyclohexanone produced by cyclohexane oxidation technology |
| CN101570370A (en) * | 2009-04-26 | 2009-11-04 | 赵志军 | Method for high resource treatment of cyclohexanone waste saponification lye |
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2012
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Patent Citations (4)
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|---|---|---|---|---|
| US3826817A (en) * | 1972-07-26 | 1974-07-30 | Hughes Aircraft Co | Metal halides with low hydroxyl ion contamination |
| CN101428915A (en) * | 2008-07-13 | 2009-05-13 | 赵志军 | Method for zero discharge processing of waste saponification lye of cyclohexanone produced by cyclohexane oxidation technology |
| CN101734825A (en) * | 2008-11-20 | 2010-06-16 | 中国石油化工股份有限公司 | Method for treating wastewater generated by cyclohexanone ammoximation process |
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|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193234A (en) * | 2013-04-12 | 2013-07-10 | 太原理工大学 | Method for preparing magnesium silicide-based powder thermoelectric material by utilizing polysilicon byproduct |
| CN104474881A (en) * | 2014-12-02 | 2015-04-01 | 成都华西堂投资有限公司 | Method for preparing sodium bicarbonate used in purification of flue gas from caprolactam incineration waste alkali |
| CN104474881B (en) * | 2014-12-02 | 2016-06-08 | 成都华西堂投资有限公司 | A kind of caprolactam that utilizes burns the method for converting waste caustic soda for sodium acid carbonate in gas cleaning |
| CN108996526A (en) * | 2017-06-07 | 2018-12-14 | 中国科学院过程工程研究所 | A kind of preparation method of bulky grain heavy sodium bicarbonate |
| CN112694190A (en) * | 2020-12-08 | 2021-04-23 | 内蒙古工业大学 | Method for treating polyformaldehyde industrial high-alkali/high-organic-matter waste liquid by using boiler tail gas |
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Application publication date: 20130116 |