CN1057509C - Method for treatment of waste-alkali-liquid from oxidation and saponification of hexamethylene - Google Patents
Method for treatment of waste-alkali-liquid from oxidation and saponification of hexamethylene Download PDFInfo
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- CN1057509C CN1057509C CN 97108229 CN97108229A CN1057509C CN 1057509 C CN1057509 C CN 1057509C CN 97108229 CN97108229 CN 97108229 CN 97108229 A CN97108229 A CN 97108229A CN 1057509 C CN1057509 C CN 1057509C
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Abstract
The present invention discloses a treatment method of oxidizing and saponifying waste alkali with cyclohexane, which uses byproduct hydrochloric acid and waste sulphuric acid for neutralization in two steps, and 10 to 50 portions(volume) of byproduct hydrochloric acid whose concentration is 18 to 31 wt% and 1 to 20 portions(volume) of waste sulphuric acid whose concentration is 80 to 95 wt% are added to each 100 portions of saponified waste alkali; acidity black oil is recycled, and n-octyl alcohol and isomer thereof are used as extraction agents for extracting saponified sewage; the COD of thesaponified waste alkali is reduced by more than 78%, and the recovery rate of the extraction agents reaches more than 97%. The present invention treats waste by waste, eliminates the pollution of byproduct hydrochloric acid and waste sulphuric acid, and treats the pollution of saponified waste alkali; the present invention is especially suitable for applying in petrochemical industry.
Description
The present invention relates to a kind of treatment process of cyclohexane oxidation by product-saponification waste lye, especially utilize in by-product hydrochloric acid and the sulfur waste acid and the treatment process of saponification waste lye.
In the prior art, cyclohexane oxidation is produced pimelinketone, the inevitable part deep oxidation that takes place reacts, produce monocarboxylic acid (for example butyric acid, valeric acid and caproic acid etc.), di-carboxylic acid impurity such as (Succinic Acid, pentanedioic acid, hexanodioic acids etc.), use the aqueous sodium hydroxide solution saponification, thereby produce saponification waste lye and separated with pimelinketone, hexanaphthene and unreacted hexanaphthene.Saponification waste lye contains 10～30% organism, COD3～6 * 10
5Mg/L, this kind waste liquid does not drain in the water if do not add processing, with serious environment pollution.
Adopted incinerating method to handle in the past, and be about to the saponification waste lye heating and be concentrated to a certain degree, but it is combustion-supporting and burn to add fuel material such as heavy oil again, reclaims heat and residue-yellow soda ash.Shortcomings such as though this kind method is still generally adopted at present, because of consuming a large amount of oil fuel, regenerant is few, and utility value is low, and equipment is huge, and investment is many progressively are eliminated.
The clear 47-35412 of Japanese Patent, clear 47-35413 etc. have introduced with in the sulfuric acid and saponification waste lye, again with organic solvent extractions such as MIBK, recovery hexanodioic acid, further be reduced into the method for hexylene glycol after refining, this method has reclaimed useful hexanodioic acid, hexylene glycol etc., has avoided the waste of organic resource in oil fuel and the saponification liquor.But this method technology is comparatively complicated, and cost is higher.
It is extraction agent that the domestic people of having adopts pimelinketone, hexalin, but it only is applicable to the extraction of the saponated sewage that contains high concentration sodium sulfate, in the inventive method in the gained saponated sewage, sodium sulphate content is low, salting out is poor, hexalin, pimelinketone increase because of being dissolved in the saponated sewage loss, therefore should not adopt.
The object of the present invention is to provide a kind ofly saponification waste lye COD to be reduced more than 70%, make full use of by product, and be beneficial to environment protection with in by-product hydrochloric acid and the sulfur waste acid and saponification waste lye and through method of extraction.
The objective of the invention is to realize by the following technical solutions: with in by-product hydrochloric acid and the sulfur waste acid in two steps and saponification waste lye, reclaim black acid liquid, and then be that extraction agent extracts saponated sewage with isooctyl alcohol and isomer thereof, comprise following process: the neutralization of (1) the first step: it is the by-product hydrochloric acid of 18%～31% (weight) that per 100 parts of saponification waste lyes add 10～50 parts of (volume) concentration, thorough mixing under the normal temperature and pressure; The neutralization of (2) second steps: adding 1～20 part of (volume) concentration by 100 parts of saponification waste lyes is that the useless vitriolic metering of 80%～95% (weight) adds sulfur waste acid to pH value≤3 in a step neutralizer, thorough mixing under the normal temperature and pressure, left standstill 10～30 hours, and separated black acid liquid and saponated sewage; (3) extraction: the mixture with a kind of of n-Octanol, isooctyl alcohol and secondary octanol or its any 2～3 kinds any proportioning is made extraction agent, and per 100 parts of saponated sewages add 10～50 parts of (volume) extraction agents, and thorough mixing left standstill 15～60 minutes, separates upper layer of extraction liquid; (4) distillation extraction liquid: 0～-reclaim extraction agent in the temperature range of 40～187 ℃ of the vacuum tightness of 0.096MPa and top temperature.
The present invention's technical scheme preferably is: extraction agent used in the extraction process can once add, and also can the gradation adding repeatedly extract repeatedly, also can carry out continuous countercurrent extraction and reduce more than 50% until the COD of saponification waste-water value, can reach requirement.The indegree that adds of extraction agent depends on appointed condition, adds the mode of extraction agent as adopting gradation in the operation, generally divides 2～4 can reach preferable technique effect.
Compared with prior art, the present invention has following tangible advantage:
1, the present invention in and in the saponification waste lye process, in the first step and use by-product hydrochloric acid, by-product hydrochloric acid as Resins, epoxy production, the used sulfur waste acid of dry chlorine gas is adopted in the neutralization of second step again, thereby reached the purpose of the treatment of wastes with processes of wastes against one another, can eliminate a large amount of by-product hydrochloric acids and useless vitriolic and pollute the pollution that can administer saponification waste lye again, reduce cost greatly, environment protection is played an important role;
2, in the technological process of the present invention, in and layering after reclaim black acid liquid, saponated sewage extracts with organic solvent, so that further reduce COD, just is disposed to the sewage-farm then and handles.Adopt MIBK, acetate, butyric acid ester extraction agent different with Japanese Patent, it is extraction agent that method of the present invention adopts isooctyl alcohol or its isomer, its advantage is that effect of extracting is good, rate of recovery height, can be recycled, the AGS acid (Succinic Acid, pentanedioic acid, hexanodioic acid mixture) of reclaiming is pure, and it has higher using value.
More than the present invention is described in further detail by specific embodiment:
Embodiment 1: get 100 parts of saponification waste lyes, adding 50 parts of concentration is 18% by-product hydrochloric acid, thorough mixing under the normal temperature and pressure, add 1 part of 95% sulfur waste acid again, thorough mixing under normal temperature and pressure is transferred PH≤3 once more, left standstill 24 hours, and separated black acid liquid and saponated sewage.Saponification waste lye COD is 4.5 * 10
5Mg/L, saponated sewage COD are 2.0 * 10
5Mg/L, through neutralization, the COD rate of descent is 55.6%.
Get 100 parts of saponated sewages, add 10 parts of isooctyl alcohol, thorough mixing left standstill 30 minutes, separated upper layer of extraction liquid, twice of lower floor's wastewater reuse isooctyl alcohol re-extract.Extract COD of sewage 8.1 * 10 at last
4Mg/L, extraction COD rate of descent 59.5%.Handle through two steps of neutralization extraction, the total clearance of saponification waste lye COD reaches 82%.
Example 2～14: press embodiment 1 described method, add different umbers, the different concns by-product hydrochloric acid carries out the first step neutralization, add different umbers again, the sulfuric acid of different concns carries out the neutralization of second step, gained saponated sewage, add various extraction agents by different ratios and extract, gained result such as table 1.
Table 1 neutralization and extraction results
| Project implementation example | In and operation | Extraction process | Saponification waste lye | |||||||
| Add HCL | Add H 2SO 4 | In and COD rate of descent (%) | Extraction agent | Extraction agent part/100 part saponated sewage | Extraction COD rate of descent (%) | Last COD (mg/L) | The total clearance of COD (%) | |||
| Concentration % | Part | Concentration % | Part | |||||||
| 1 | 18 | 50 | 80 | 1 | 55.60 | Isooctyl alcohol | 30 | 59.56 | 8.10×10 4 | 82.00 |
| 2 | 25 | 25 | 80 | 10 | 68.50 | Isooctyl alcohol | 10 | 30.46 | 9.86×10 4 | 78.09 |
| 3 | 25 | 25 | 80 | 10 | 68.50 | Isooctyl alcohol | 30 | 62.21 | 5.36×10 4 | 88.10 |
| 4 | 25 | 25 | 80 | 10 | 68.50 | Isooctyl alcohol | 50 | 70.10 | 4.23×10 4 | 90.60 |
| 5 | 25 | 20 | 80 | 12.5 | 70.10 | Isooctyl alcohol | 30 | 67.90 | 4.31×10 4 | 90.40 |
| 6 | 25 | 15 | 80 | 15 | 72.00 | Isooctyl alcohol | 30 | 67.46 | 4.10×10 4 | 90.90 |
| 7 | 25 | 25 | 80 | 10 | 68.50 | Secondary octanol | 10 | 63.37 | 4.91×10 4 | 89.09 |
| 8 | 25 | 25 | 80 | 10 | 68.50 | N-Octanol | 30 | 68.82 | 5.13×10 4 | 88.60 |
| 9 | 25 | 25 | 80 | 10 | 68.50 | Different+second month in a season | 30 | 66.36 | 4.77×10 4 | 89.40 |
| 10 | 25 | 25 | 80 | 10 | 68.50 | Just+second month in a season | 30 | 64.74 | 5.00×10 4 | 88.88 |
| 11 | 25 | 25 | 80 | 10 | 68.50 | Just+different | 30 | 65.09 | 4.95×10 4 | 89.00 |
| 12 | 25 | 25 | 80 | 10 | 68.50 | Just+secondary+different | 30 | 68.55 | 4.46×10 4 | 90.09 |
| 13 | 31 | 10 | 80 | 20 | 70.40 | Isooctyl alcohol | 50 | 69.17 | 4.05×10 4 | 91.00 |
| 14 | 31 | 10 | 95 | 20 | 76.11 | Isooctyl alcohol | 30 | 72.38 | 2.97×10 4 | 93.40 |
According to embodiment 1 described method, collect extraction liquid, be benchmark with the extraction agent that each embodiment was added, the gained extraction liquid distills, and reclaims extraction agent, its rate of recovery purity, the rate of recovery such as table 2.
Table 2 reclaims extraction agent purity and yield
| Embodiment number | Extraction agent | Add weight (g) | Yield (g) | Purity (%) | The rate of recovery (%) | Remarks |
| 15 | Isooctyl alcohol | 482.4 | 477.6 | 99.50 | 98.51 | Air distillation |
| 16 | Isooctyl alcohol | 483.6 | 478.8 | 99.31 | 98.32 | -0.094MPa |
| 17 | N-Octanol | 481.8 | 477.1 | 99.45 | 98.48 | -0.094MPa |
| 18 | Secondary octanol | 479.8 | 475.0 | 98.31 | 97.33 | -0.094MPa |
| 19 | Just+second month in a season | 482.0 | 478.1 | 98.88 | 98.08 | -0.094MPa |
| 20 | Just+different | 481.0 | 477.8 | 99.17 | 98.51 | -0.094MPa |
| 21 | Just+secondary+different | 480.0 | 476.2 | 99.10 | 98.32 | -0.094MPa |
Claims (2)
1, a kind of treatment process of waste-alkali-liquid from oxidation and saponification of hexamethylene with also using organic solvent extraction with saponification waste lye in the acid, the invention is characterized in that the processing saponification waste lye comprises following process:
(1) the first step neutralization: it is the by-product hydrochloric acid of 18%～31% (weight) that per 100 parts of saponification waste lyes add 10～50 parts of (volume) concentration, thorough mixing under the normal temperature and pressure, then
The neutralization of (2) second steps: adding 1～20 part of (volume) concentration by 100 parts of saponification waste lyes is the useless vitriolic metering of 80%～95% (weight), add sulfur waste acid to pH value≤3 in a step neutralizer, thorough mixing under the normal temperature and pressure left standstill 10～30 hours, separate black acid liquid and saponated sewage, then
(3) extraction: the mixture with a kind of of n-Octanol, isooctyl alcohol and secondary octanol or its any 2～3 kinds any proportioning is made extraction agent, per 100 parts of saponated sewages add 10～50 parts of (volume) extraction agents, and thorough mixing left standstill 15～60 minutes, separate upper layer of extraction liquid, then
(4) distillation extraction liquid: 0～-reclaim extraction agent in the temperature range of 40～187 ℃ of the vacuum tightness of 0.096MPa and top temperature.
2, the treatment process of saponification waste lye according to claim 1 is characterized in that the used extraction agent of extraction process can gradation adds, and repeatedly extracts or reduces more than 50% through continuous countercurrent extraction to saponated sewage COD.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97108229 CN1057509C (en) | 1997-09-17 | 1997-09-17 | Method for treatment of waste-alkali-liquid from oxidation and saponification of hexamethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97108229 CN1057509C (en) | 1997-09-17 | 1997-09-17 | Method for treatment of waste-alkali-liquid from oxidation and saponification of hexamethylene |
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| Publication Number | Publication Date |
|---|---|
| CN1177576A CN1177576A (en) | 1998-04-01 |
| CN1057509C true CN1057509C (en) | 2000-10-18 |
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| CN 97108229 Expired - Fee Related CN1057509C (en) | 1997-09-17 | 1997-09-17 | Method for treatment of waste-alkali-liquid from oxidation and saponification of hexamethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100362348C (en) * | 2003-03-28 | 2008-01-16 | 中国石油化工股份有限公司 | Method of assaying total acid total ester in cyclohexane catalytic oxidation, oxygenolysis mixed liquid |
| CN108217802B (en) * | 2018-02-05 | 2021-08-10 | 浙江巴陵恒逸己内酰胺有限责任公司 | Utilization method and utilization system of cyclohexanone saponification waste alkali liquor |
| CN113880292A (en) * | 2021-09-14 | 2022-01-04 | 天津市茂联科技有限公司 | Oil removing process for saponified water |
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Owner name: BALING PETROCHEMICAL CO., LTD., SINOPEC Free format text: FORMER OWNER: YUEYANG PETRO-CHEMICAL GENERAL PLANT, BALING PETRO-CHEMICAL CO Effective date: 20030103 |
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