CN102897963A - Method for utilizing cyclohexanone waste alkali liquor as resource - Google Patents
Method for utilizing cyclohexanone waste alkali liquor as resource Download PDFInfo
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- CN102897963A CN102897963A CN2012103119047A CN201210311904A CN102897963A CN 102897963 A CN102897963 A CN 102897963A CN 2012103119047 A CN2012103119047 A CN 2012103119047A CN 201210311904 A CN201210311904 A CN 201210311904A CN 102897963 A CN102897963 A CN 102897963A
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- waste lye
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- pimelinketone
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Abstract
The invention provides a method for utilizing cyclohexanone waste alkali liquor as a resource. According to the invention, sulfuric acid or sulfur dioxide is added into waste alkali liquor with a residual temperature of 80-90 DEG C; a chemical reaction is carried out until a reaction liquid is neutral; the reaction is terminated; the reaction liquid is subjected to flash-evaporation dehydration in a flash evaporation tank under a negative pressure state; obtained condensate water is collected and is reused in a cyclohexanone device; and residual liquid obtained by flash-evaporation is subjected to solid-liquid separation and extraction, such that sodium sulfate or sodium sulfite, and organic acid sodium salt are obtained. According to the invention, waste alkali liquor residual heat is sufficiently utilized, and the above inorganic and organic chemical products are obtained by recovery. Compared with a cyclohexanone waste alkali liquor treatment method in prior arts, a pollution problem is solved, and the entire process flow is short and energy-saving. The method has the advantages of high resource product added value, low equipment investment, and low operation cost. The method has substantial social and economic benefits.
Description
Technical field
The present invention relates to harmless treatment and the comprehensive utilization technique of wastewater from chemical industry, particularly a kind of pimelinketone waste lye resource utilization method.
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 to generate by products, wherein except lightweight oil and X oil can directly reclaim, all the other components form the high-concentration waste alkali lye that is in a large number sticky shape, has acid smell by alkali cleaning.This waste lye component very complex 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.After testing, undressed waste lye COD value is up to 600 g/L, about 4～60,000 tons of the annual waste lye of discharging of the cyclohexanone production apparatus that a cover is 50,000 ton/years.Waste lye not only has corrodibility, and can havoc ecotope and groundwater resource.For this reason, this waste lye has become the environmental protection bottleneck of restriction pimelinketone industry development.Method to present Treatment of Cyclohexanone waste lye (hereinafter to be referred as waste lye) mainly contains burning method and chemical method.The main drawback of burning method is to produce secondary pollution, and its pollutent is such as SO
2, oxynitride, dust etc. all exceed standard far away, finally can not solve preferably environmental issue.In the last few years, expert both domestic and external and scholar laid particular emphasis on chemical method were studied.The inventive method of external disclosed processing waste lye is to carry out chemical reaction with sulfuric acid and waste lye; Reclaim Organic chemical products and sodium sulfate from waste lye, the added value of products obtained therefrom is higher; But its drawback is directly to make sulfuric acid and waste lye generation neutralization reaction, make the pH value of waste lye reach the acid state of 2-3, produce again that a large amount of corrodibility is strong, COD value height, the acidifying sewage that smell is large, the acidifying sewage disposal is improper, can cause serious secondary pollution to environment equally.Domestic patent of invention of having authorized " a kind of method of Treatment of Cyclohexanone saponification waste lye " (ZL201010248629.X) discloses and " has passed into the sulfurous gas that absorbs for waste lye in waste lye; The evaporation waste lye extracts S-WAT; Again pass into sulfurous gas in the waste lye raffinate, separation and Extraction goes out saponified oil; Concentrated raffinate--the saturated solution of sodium bisulfite extracts S-WAT ".This patent has can effectively administer waste lye to the pollution of environment, and S-WAT, the saponification wet goods that can extract high added value from waste lye is inorganic, the obvious advantage such as Organic chemical products.This patented technology is in the last few years, adopts chemical means to process the most advanced method of described waste lye.But the applicant finds that by further research and practice it still has the following disadvantages, as: the waste heat of waste lye is underused; Energy consumption is relatively also higher; Technical process is loaded down with trivial details; Also have the halfway potentially contaminated problem of acidifying waste water control, this is still the problem that scientific and technical personnel in the industry need to continue seeking breakthrough.
Summary of the invention
The invention provides a kind of resource utilization method of pimelinketone waste lye, purpose is to take full advantage of the waste heat of waste lye, with short technical process, lower energy consumption waste lye is processed, and resource utilization ground obtains inorganic, the Organic chemical products such as sodium sulfate, S-WAT and organic acid sodium salt from waste lye.
Technical solution of the present invention:
One of technical solution of the present invention is 80-90 ℃ waste lye with remaining temperature, adds sulfuric acid and carries out neutralization reaction, and the control reaction solution is converted to neutrality by alkalescence, termination reaction; Make this reaction solution enter the interior flash-evaporation dehydration of flash tank of negative pressure state, the recycling condensing water that collection is deviate from is in pimelinketone device, and the raffinate with flash vaporization carries out solid-liquid separation again, extracts to obtain sodium sulfate and organic acid sodium salt.
Two of technical solution of the present invention is 80-90 ℃ waste lye with remaining temperature, passes into sulfur dioxide gas, reacts, and the control reaction solution is converted to neutrality by alkalescence, termination reaction; Make this reaction solution enter the interior flash-evaporation dehydration of flash tank of negative pressure state, the recycling condensing water that collection is deviate from is in pimelinketone device, and the raffinate with flash vaporization carries out solid-liquid separation again, extracts to obtain S-WAT and organic acid sodium salt.
The concrete technology of one of technical scheme of the present invention is:
A, the sodium hydroxide that contains in the described waste lye and mass concentration are that the sulfuric acid of 50-98% carries out neutralization reaction, generate sodium sulfate and water;
Its reaction equation is:
2NaOH+H
2SO
4==Na
2SO
4+2H
2O
B, the yellow soda ash that contains in the described waste lye generates sodium sulfate, water and carbonic acid gas with sulfuric acid reaction;
Its reaction equation is:
Na
2CO
3+H
2SO
4==Na
2SO
4+?H
2O+CO
2
When the pH value of the reaction solution of above-mentioned two chemical reactions reaches 6-8, termination reaction;
C enters the reaction solution of above-mentioned insulation in the flash tank that negative pressure is 20Kpa-95Kpa and to carry out flash-evaporation dehydration, when the volume of deviating from the water yield reaches the 35-55% that enters flash tank waste lye volume, stops evaporation; The recycling condensing water that collection is deviate from is in pimelinketone device.
D carries out solid-liquid separation with above-mentioned flash tank evaporation raffinate, extracts and obtains sodium sulfate;
E concentrates above-mentioned solid-liquid separation raffinate, and section obtains organic acid sodium salt.
Two concrete technology of technical scheme of the present invention is:
A, the sodium hydroxide that contains in the described waste lye and sulfur dioxide gas precursor reactant generate S-WAT and water;
Its reaction equation is:
2NaOH+SO
2==Na
2SO
3+H
2O
B, the yellow soda ash that contains in the described waste lye and sulfur dioxide gas precursor reactant generate S-WAT and carbonic acid gas; Its reaction equation is:
Na
2CO
3+SO
2==Na
2SO
3+CO
2
When the pH value of the reaction solution of above-mentioned two chemical reactions reaches 6-8, termination reaction;
C enters the reaction solution of above-mentioned insulation in the flash tank that negative pressure is 20Kpa-95Kpa and to carry out flash-evaporation dehydration, when the volume of deviating from the water yield reaches the 35-55% that enters flash tank waste lye volume, stops evaporation; The recycling condensing water that collection is deviate from is in pimelinketone device.
D carries out solid-liquid separation with above-mentioned flash tank evaporation raffinate, extracts and obtains S-WAT;
E concentrates above-mentioned solid-liquid separation raffinate, and section obtains organic acid sodium salt.
Beneficial effect of the present invention:
The present invention carries out recycling treatment to the pimelinketone waste lye, take full advantage of the waste lye exhaust temperature and be 80-90 ℃ waste heat, make waste lye and sulfuric acid, or react with sulfurous gas, and employing flash process, extract and obtain sodium sulfate or S-WAT, organic acid sodium salts etc. are inorganic, Organic chemical products, in reclaiming waste lye in the available stock, reach the discharging of non-secondary pollution thing, compare with the pimelinketone spent lye treatment method of prior art, whole technical process is brief, energy consumption is low, and the resource product added value of obtaining is high, and equipment investment is few, working cost is low, has remarkable Social benefit and economic benefit.
Description of drawings
Accompanying drawing is technical process block diagram of the present invention.
Embodiment
The present invention by technical scheme and accompanying drawing as seen,
Technical scheme one and two differences only are: the former adds the sulfuric acid react with in waste lye, extracts and obtains sodium sulfate, organic acid sodium salt; The latter passes into the sulfurous gas react with in waste lye, extract to obtain S-WAT, organic acid sodium salt.
Technical scheme one is with two something in common: both have identical technical qualification, and handled is the same waste lye; The pH value of reaction end is identical, is 6-8; The flash tank that same employing negative pressure is 20Kpa-95Kpa carries out flash-evaporation dehydration to reaction solution, and when the volume of deviating from the water yield reaches the 35-55% that enters flash tank waste lye volume, stops evaporation, collects the water of condensation of deviating from and all is back in the pimelinketone device; To evaporate equally raffinate and carry out solid-liquid separation; Equally the solid-liquid separation raffinate is concentrated, section obtains identical organic acid sodium salt product.
Below enumerate embodiment, further specify it:
Embodiment one: waste lye and sulfuric acid reaction extract sodium sulfate, organic acid sodium salt.
From pimelinketone device, getting volume is 810ml, and temperature is 85 ℃ waste lye 1Kg, waste lye is inserted while hot in the three-necked flask of the 2000ml that is incubated by electric heating cover, and the dropping mass concentration is 50% sulfuric acid, and the pH value that records reaction solution is 7 o'clock, stops acid adding; Keeping the temperature of reaction solution is 80-85 ℃, the open water ring vacuum pump, and keeping the vacuum pressure in the three-necked flask is 60Kpa, collects water of condensation, when the volume of water of condensation reaches 350ml, stops evaporation; To evaporate raffinate and carry out vacuum filtration with sand core funnel, the filter cake that obtains is sodium sulfate, and weight in wet base is 150 g; The suction filtration raffinate is placed on again and is heated to 130 ℃ in the retort furnace, the powder material that obtains is organic acid sodium salt, and quality is 380 g.
Embodiment two: S-WAT, organic acid sodium salt are extracted in waste lye and sulfurous gas reaction.
From pimelinketone device, getting volume is 810ml, and temperature is 85 ℃ waste lye 1Kg, waste lye is inserted while hot in the three-necked flask of the 2000ml that is incubated by electric heating cover, pass into sulfur dioxide gas and waste lye and carry out blistering reaction, the pH value that records reaction solution is 7, stops ventilation; Keeping the temperature of reaction solution is 80-85 ℃, the open water ring vacuum pump, and keeping the vacuum pressure in the three-necked flask is 60 Kpa; Collect water of condensation, when the volume of water of condensation reaches 350ml, stop evaporation; To evaporate raffinate and carry out vacuum filtration with sand core funnel, the filter cake that obtains is S-WAT, and weight in wet base is 120 g; The suction filtration raffinate is placed on again and is heated to 130 ℃ in the retort furnace, the powder material that obtains is organic acid sodium salt, and quality is 400 g.
To sum up, the inventive method can reach the goal of the invention of expection.
Claims (4)
1. the resource utilization method of a pimelinketone waste lye is characterized in that: be 80-90 ℃ waste lye with remaining temperature, add sulfuric acid and carry out neutralization reaction that the control reaction solution is converted to neutrality by alkalescence, termination reaction; Make this reaction solution enter the interior flash-evaporation dehydration of flash tank of negative pressure state, the recycling condensing water that collection is deviate from is in pimelinketone device again, and the raffinate with flash vaporization carries out solid-liquid separation again, extracts to obtain sodium sulfate and organic acid sodium salt.
2. the resource utilization method of a kind of pimelinketone waste lye according to claim 1, it is characterized in that: the concrete technology of described method is:
The sodium hydroxide that contains in A, the described waste lye and mass concentration are that the sulfuric acid of 50-98% carries out neutralization reaction, generate sodium sulfate and water;
The yellow soda ash that contains in B, the described waste lye generates sodium sulfate, water and carbonic acid gas with sulfuric acid reaction;
When the pH value of the reaction solution of above-mentioned two chemical reactions reaches 6-8, termination reaction;
C, the reaction solution of above-mentioned insulation entered in the flash tank that negative pressure is 20Kpa-95Kpa carry out flash-evaporation dehydration, when the volume of deviating from the water yield reaches the 35-55% that enters flash tank waste lye volume, stop evaporation; The recycling condensing water that collection is deviate from is in pimelinketone device;
D, above-mentioned flash tank evaporation raffinate is carried out solid-liquid separation, extract and obtain sodium sulfate;
E, above-mentioned solid-liquid separation raffinate is concentrated, section obtains organic acid sodium salt.
3. the resource utilization method of a pimelinketone waste lye is characterized in that: be 80-90 ℃ waste lye with remaining temperature, pass into sulfur dioxide gas, react, the control reaction solution is converted to neutrality by alkalescence, termination reaction; Make this reaction solution enter the interior flash-evaporation dehydration of flash tank of negative pressure state, the recycling condensing water that collection is deviate from is in pimelinketone device again, and the raffinate with flash vaporization carries out solid-liquid separation again, extracts to obtain S-WAT and organic acid sodium salt.
4. the resource utilization method of a kind of pimelinketone waste lye according to claim 3, it is characterized in that: the concrete technology of described method is:
The sodium hydroxide that contains in A, the described waste lye and sulfur dioxide gas precursor reactant generate S-WAT and water;
The yellow soda ash that contains in B, the described waste lye and sulfur dioxide gas precursor reactant generate S-WAT and carbonic acid gas;
When the pH value of the reaction solution of above-mentioned two chemical reactions reaches 6-8, termination reaction;
C, the reaction solution of above-mentioned insulation entered in the flash tank that negative pressure is 20Kpa-95Kpa carry out flash-evaporation dehydration, when the volume of deviating from the water yield reaches the 35-55% that enters flash tank waste lye volume, stop evaporation; The recycling condensing water that collection is deviate from is in pimelinketone device;
D, above-mentioned flash tank evaporation raffinate is carried out solid-liquid separation, extract and obtain S-WAT;
E, above-mentioned solid-liquid separation raffinate is concentrated, section obtains organic acid sodium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103119047A CN102897963A (en) | 2012-08-29 | 2012-08-29 | Method for utilizing cyclohexanone waste alkali liquor as resource |
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|---|---|---|---|
| CN2012103119047A CN102897963A (en) | 2012-08-29 | 2012-08-29 | Method for utilizing cyclohexanone waste alkali liquor as resource |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439309A (en) * | 2014-06-25 | 2016-03-30 | 中国石油化工股份有限公司 | Treatment method of methanol-to-olefin (MTO) waste alkali liquid |
| CN105669346A (en) * | 2016-03-03 | 2016-06-15 | 中国天辰工程有限公司 | Method for comprehensively recycling cyclohexanone device waste oil |
| CN113548770A (en) * | 2021-07-14 | 2021-10-26 | 刘炳鑫 | Cyclohexanone-containing sewage treatment process and device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5346620A (en) * | 1993-08-31 | 1994-09-13 | Basf Corporation | Process for waste water treatment by removal of sodium sulfate |
| CN1293223A (en) * | 1999-10-18 | 2001-05-02 | 巴陵石化鹰山石油化工厂 | Process for evaporating, concentrating and drying waste saponifying alkali solution |
| CN101955284A (en) * | 2010-08-06 | 2011-01-26 | 赵志军 | Method of treating cyclohexanone saponification waste alkali liquor |
-
2012
- 2012-08-29 CN CN2012103119047A patent/CN102897963A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5346620A (en) * | 1993-08-31 | 1994-09-13 | Basf Corporation | Process for waste water treatment by removal of sodium sulfate |
| CN1293223A (en) * | 1999-10-18 | 2001-05-02 | 巴陵石化鹰山石油化工厂 | Process for evaporating, concentrating and drying waste saponifying alkali solution |
| CN101955284A (en) * | 2010-08-06 | 2011-01-26 | 赵志军 | Method of treating cyclohexanone saponification waste alkali liquor |
Non-Patent Citations (2)
| Title |
|---|
| 朱兆华: "环己酮生产中皂化废碱液的中和处理与综合利用", 《化工环保》, vol. 20, no. 4, 31 December 2000 (2000-12-31), pages 36 - 39 * |
| 李惠友等: "环己烷氧化废碱液化学处理工艺概述", 《精细石油化工》, no. 5, 30 September 2000 (2000-09-30), pages 5 - 8 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439309A (en) * | 2014-06-25 | 2016-03-30 | 中国石油化工股份有限公司 | Treatment method of methanol-to-olefin (MTO) waste alkali liquid |
| CN105439309B (en) * | 2014-06-25 | 2018-01-23 | 中国石油化工股份有限公司 | A kind of processing method of methanol-to-olefins spent lye |
| CN105669346A (en) * | 2016-03-03 | 2016-06-15 | 中国天辰工程有限公司 | Method for comprehensively recycling cyclohexanone device waste oil |
| CN113548770A (en) * | 2021-07-14 | 2021-10-26 | 刘炳鑫 | Cyclohexanone-containing sewage treatment process and device |
| CN113548770B (en) * | 2021-07-14 | 2023-11-21 | 刘炳鑫 | Process and device for treating sewage containing cyclohexanone |
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Application publication date: 20130130 |