CN104671570A - Method for treating aluminum-containing wastewater in preparation process of 6-oxo-8-chloro ethyl caprylate - Google Patents
Method for treating aluminum-containing wastewater in preparation process of 6-oxo-8-chloro ethyl caprylate Download PDFInfo
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- CN104671570A CN104671570A CN201410808222.6A CN201410808222A CN104671570A CN 104671570 A CN104671570 A CN 104671570A CN 201410808222 A CN201410808222 A CN 201410808222A CN 104671570 A CN104671570 A CN 104671570A
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Abstract
The invention relates to a method for treating aluminum-containing wastewater in a preparation process of 6-oxo-8-chloro ethyl caprylate, and belongs to the field of industrial wastewater treatment and green production. The technical problem to be solved in the invention is to provide the method for treating aluminum-containing wastewater in a preparation process of 6-oxo-8-chloro ethyl caprylate. The method comprises the following steps: by taking aluminum trichloride as a catalyst, performing addition reaction on 6-oxo-6-oxo ethyl caproate and ethylene in a dichloroethane solution, and hydrolyzing the aluminum trichloride to prepare a target product. According to the technical scheme adopted by the invention, compared with the prior art, direction wastewater emission is avoided, and aluminum trichloride hexahydrate solids can be recycled, so that the method is very remarkable in saving water resources and achieving environmental friendliness.
Description
Technical field
The present invention relates to a kind of method processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process, belong to the field of Industrial Wastewater Treatment and green production.
Background technology
One of synthetic method of Thioctic Acid, be starting raw material by hexanodioic acid, building-up process comprises the operations such as esterification, chloride, addition, reduction, chloro, cyclization, hydrolysis and acidifying.Wherein, the 6-chloro-6-oxo ethyl hexanoate that addition reaction is obtained through esterification, chloride by hexanodioic acid, reacts with Addition on ethylene and prepares 6-oxo-8-chloroctanoic acid ethyl ester, then through reduction and chloro, obtained intermediate 6,8-dichloro-octanoic acid ethyl ester.
In above-mentioned technique, addition reaction adopts 6-chlorine 6-oxo ethyl hexanoate and ethene to be raw material usually, be catalyzer with aluminum chloride, in dichloroethane solution, addition reaction occur, then addition liquid is put into water, aluminum chloride complex compound is hydrolyzed, preparation 6-oxo-8-chloroctanoic acid ethyl ester.For making to react completely, need add 1.5 times of theoretical amount aluminum chlorides, in hydrolytic process, aluminum chloride complex decomposes and excessive aluminum chloride meet water all can heat release in a large number.And in existing conventional production process, adopt and addition reaction liquid is put into excessive water be hydrolyzed, and lead to icy salt solution cooling with reacting kettle jacketing, although can solve cooling problem, owing to adding excessive water coolant, cause wastewater flow rate to increase, cooling efficiency is low.
By the process modification (see CN102731307A) of present invention applicant, the preparation method of the 6-oxo-8-chloroctanoic acid ethyl ester used take aluminum chloride as catalyzer, in dichloroethane solution, 6-chloro-6-oxo ethyl hexanoate and ethene generation addition reaction, obtained object after aluminum chloride hydrolysis, it is characterized in that, addition reaction liquid mixes with water in hydrolysis kettle, hydrolysis kettle arranges recycle pump and circulating line, circulating line connects graphite condenser, the mixture of reaction solution and water enters after graphite condenser cools by recycle pump, return again in hydrolysis kettle, continuous circulation is until hydrolysis reaction terminates.The method overcomes addition reaction product in old technique and is hydrolyzed the many technological problemses produced, and improves cooling efficiency, and the temperature of effective controlled hydrolysis reaction, shortens hydrolysis time and improve reaction yield, reducing hydrolysis water and waste water quantity discharged.
But, still there is large (the such as throwing 6-chloro-6-oxo ethyl hexanoate 100kg participation reaction of aluminium wastewater amount in above-mentioned prior art, produce 1.4 ~ 1.6 tons of waste water), aluminium composition low (Baumé gravity about 13), the defect of recycling treatment difficulty.
Therefore, expect that finding one can either carry out aluminum ions recovery to aluminium wastewater, can realize again the method for cycling utilization of wastewater.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method and apparatus processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process.
In 6-oxo-8-chloroctanoic acid ethyl ester preparation process, aluminium wastewater comprises aluminum ion usually, is removed by aluminum ion wherein traditionally, discharges after reaching emission standard.Due to aluminum ions throwing out, very unfavorable to water circulation use, often need complicated pre-treatment just can recycle.In addition, because conventional process aluminium wastewater is not thorough, cause the heavy contamination to environment in discharge, be therefore badly in need of wanting a kind of new method to carry out process aluminium wastewater.
But, present inventor improves the ratio of aluminium salt in water by reducing water consumption when chancing on hydrolysis, its convergence is made to be similar to state of saturation, after hydrolysis terminates, organic phase and aqueous phase separation, namely secondary saturated sour water obtains six water aluminum chloride solids after distilling a small amount of moisture, mother liquid recycle, and distilled water then returns and does down batch hydrolysis water use.Therefore, the present invention proposes a kind of method that aluminium wastewater can be recycled through simple process.
A kind of method processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process provided by the invention, take aluminum chloride as catalyzer, in dichloroethane solution, 6-chloro-6-oxo ethyl hexanoate and ethene generation addition reaction, obtained object product after aluminum chloride hydrolysis, the method for described process aluminium wastewater comprises the following steps:
(1), that this aluminium wastewater is concentrated in container;
(2), appropriate water is removed;
(3), water temperature is down to less than 30 DEG C and separates out six water aluminum chloride solids;
(4), the removing aluminium wastewater mother liquor six water aluminum chloride solids of separating out, drying solid also reclaims;
(5), by the aluminium wastewater mother liquor that step (4) obtains apply mechanically, distilled water then returns does circulation hydrolysis use.
A kind of method processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process provided by the invention, described step (1) container is concentration kettle.
A kind of method processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process provided by the invention, described step (2) boils off the water yield and is about the 25%-50% often criticizing hydrolysis gained aluminium wastewater weight.
A kind of method processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process provided by the invention, described step (3) water temperature is down to less than 25 DEG C.
A kind of method processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process provided by the invention, described step (3) water temperature is down to 15 DEG C-20 DEG C.
A kind of method processing aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process provided by the invention, is characterized in that, in described method, the weight ratio of 6-chloro-6-oxo ethyl hexanoate and water is 1: 2.9 ~ 3.8.
Present invention also offers a kind of equipment of aluminium wastewater recycle, described equipment comprises:
Concentration kettle, input aluminium wastewater, boils off appropriate water;
Cold analysis tank, directly connects strainer, is cooled by the concentrated solution of aluminium wastewater;
Strainer, the six water aluminum chloride solids that removing aluminium wastewater mother liquor is separated out;
Circulating line, applies mechanically aluminium wastewater mother liquor, and distilled water then returns does circulation hydrolysis use.
Present invention also offers a kind of equipment of aluminium wastewater recycle, its feature also comprises the pipeline order of connection and is: concentration kettle, cold analysis tank, strainer; Strainer pipeline is connected with concentration kettle, for Recycling Mother Solution.
The present invention, owing to adopting above technical scheme, makes it compared with prior art, both to avoid direct discharging of waste water, and recyclable six water aluminum chloride solids, therefore have very significant meaning for saving water resource and environmental protection again.It is also advantageous in that:
1. aluminium wastewater Baumé gravity can reach more than 30, and after distilling a small amount of water, cold analysis obtains six water aluminum chlorides, and technique is simple, and cost is low, and resource utilization is with the obvious advantage.
2. distill the water obtained and return technique use, cold analysis mother liquid recycle, form closed cycle, waste acid water zero release.
3. the water yield than originally significantly reduces, and the various energy consumptions of electric energy, kinetic energy are also significantly reduced, and labour intensity reduces, and production cost declines.Such as, the water yield ratio that the present invention uses is 6-chloro-6-oxo ethyl hexanoate: the water yield=1: the water yield ratio used in 2.9 ~ 3.8, CN102731307A is 1: 10 ~ 12.
4. the significantly minimizing of the water yield, makes unit hydrolysis ability on year-on-year basis increase more than 4 times, improves throughput.
5., under the state of remaining unchanged of refrigeration capacity, the significantly minimizing of the water yield, the refrigerating speed of water speeds, and control same hydrolysis temperature and hydrolysis material, its hydrolysis effect is constant.
6. this mode is hydrolyzed the material of generation, and the reaction through follow-up processing step is verified, yield, quality keep stable.
Accompanying drawing explanation
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated, wherein:
Fig. 1 is aluminium wastewater processing technological flow figure of the present invention (Thioctic Acid aluminium wastewater processing technological flow figure);
Fig. 2 is aluminium wastewater treatment facility figure of the present invention;
Fig. 3 be the present invention relates to Thioctic Acid addition, hydrolysis, reduction reaction equipment figure.
Embodiment
Embodiment 1
According to CN102731307A, the similar preparation method of 6-oxo-8-chloroctanoic acid ethyl ester, puts into 3M by 1050kg water
3in hydrolysis kettle, pass into icy salt solution in hydrolysis kettle chuck, hydrolysis kettle arranges recycle pump and circulating line, circulating line connects graphite condenser, in hydrolysis kettle, material enters graphite condenser through recycle pump, passes into icy salt solution in graphite condenser, and after material cooling, recirculation returns in hydrolysis kettle.With chuck and graphite condenser by below the cooling water circulation to 10 in hydrolysis kettle DEG C, for subsequent use.
1280Kg ethylene dichloride is added in 1500L reactor, drop into 450Kg aluminum chloride, stir, icy salt solution chuck is cooled to 10 DEG C ~ 18 DEG C, drip 360kg 6-chloro-6-oxo ethyl hexanoate, interior temperature control, at 20 DEG C ~ 25 DEG C, passes into ethene and obtains addition reaction liquid after 3 hours.Reaction solution puts into hydrolysis kettle 1050kg water for subsequent use, stirs, after reaction solution enters graphite condenser cooling by recycle pump, return again in hydrolysis kettle, temperature less than 35 DEG C in controlling, continuous circulation 60 minutes, leaves standstill 1 hour after hydrolysis reaction completes, layering, upper strata is 6-oxo-8-chloroctanoic acid ethyl ester liquid, in lower floor's aluminium wastewater suction concentration kettle, after boiling off 375kg water, lower the temperature less than 30 DEG C and separate out solid, dry content 96% 6 water aluminum chloride 320kg.Aluminium wastewater mother liquid recycle, distilled water then returns and does down batch hydrolysis water use.
By in 6-oxo-8-chloroctanoic acid ethyl ester liquid suction 1500L reactor, less than 35 DEG C drip POTASSIUM BOROHYDRIDE ammonia soln (40kg POTASSIUM BOROHYDRIDE+120kg 17% ammoniacal liquor), and in controlling, temperature less than 35 DEG C, is incubated 3 hours.Layering, organic layers with water is washed till neutrality, and 0.1MPa heating under reduced pressure concentrates, and to temperature 110 DEG C end, obtains the 6-hydroxyl-8-chloroctanoic acid ethyl ester concentrated solution 363kg of content 92%.
Embodiment 2
Upper batch distilled water is put into 3M
3in hydrolysis kettle, moisturizing is to 1050kg, icy salt solution is passed in hydrolysis kettle chuck, hydrolysis kettle arranges recycle pump and circulating line, circulating line connects graphite condenser, in hydrolysis kettle, material enters graphite condenser through recycle pump, passes into icy salt solution in graphite condenser, and after material cooling, recirculation returns in hydrolysis kettle.With chuck and graphite condenser by below the cooling water circulation to 10 in hydrolysis kettle DEG C, for subsequent use.
1280Kg ethylene dichloride adds in 1500L reactor, drops into 450Kg aluminum chloride, stirs, icy salt solution chuck is cooled to 10 DEG C ~ 18 DEG C, drip 360kg 6-chloro-6-oxo ethyl hexanoate, interior temperature control, at 20 DEG C ~ 25 DEG C, passes into ethene and obtains addition reaction liquid after 3 hours.Reaction solution puts into hydrolysis kettle 1050kg water for subsequent use, stirs, after reaction solution enters graphite condenser cooling by recycle pump, return again in hydrolysis kettle, temperature less than 35 DEG C in controlling, continuous circulation 60 minutes, 1 hour is left standstill after hydrolysis reaction completes, layering, upper strata is 6-oxo-8-chloroctanoic acid ethyl ester liquid, in lower floor's aluminium wastewater suction concentration kettle, merge with upper batch mother liquor, after boiling off 750kg water, lower the temperature less than 30 DEG C and separate out solid, dry content 96% 6 water aluminum chloride 790kg.Aluminium wastewater mother liquid recycle, distilled water then returns and does down batch hydrolysis water use.
By in 6-oxo-8-chloroctanoic acid ethyl ester liquid suction 1500L reactor, less than 35 DEG C drip POTASSIUM BOROHYDRIDE ammonia soln (40kg POTASSIUM BOROHYDRIDE+120kg 17% ammoniacal liquor), and in controlling, temperature less than 35 DEG C, is incubated 3 hours.Layering, organic layers with water is washed till neutrality, and 0.1MPa heating under reduced pressure concentrates, and to temperature 110 DEG C end, obtains the 6-hydroxyl-8-chloroctanoic acid ethyl ester concentrated solution 368kg of content 91%.
Embodiment 3
1350kg water is put into 3M
3in hydrolysis kettle, pass into icy salt solution in hydrolysis kettle chuck, hydrolysis kettle arranges recycle pump and circulating line, circulating line connects graphite condenser, in hydrolysis kettle, material enters graphite condenser through recycle pump, passes into icy salt solution in graphite condenser, and after material cooling, recirculation returns in hydrolysis kettle.With chuck and graphite condenser by below the cooling water circulation to 10 in hydrolysis kettle DEG C, for subsequent use.
1280Kg ethylene dichloride is added in 1500L reactor, drop into 450Kg aluminum chloride, stir, icy salt solution chuck is cooled to 10 DEG C ~ 18 DEG C, drip 360kg 6-chloro-6-oxo ethyl hexanoate, interior temperature control, at 20 DEG C ~ 25 DEG C, passes into ethene and obtains addition reaction liquid after 3 hours.Reaction solution puts into hydrolysis kettle 1350kg water for subsequent use, stirs, after reaction solution enters graphite condenser cooling by recycle pump, return again in hydrolysis kettle, temperature less than 35 DEG C in controlling, continuous circulation 60 minutes, leaves standstill 1 hour after hydrolysis reaction completes, layering, upper strata is 6-oxo-8-chloroctanoic acid ethyl ester liquid, in lower floor's aluminium wastewater suction concentration kettle, after boiling off 540kg water, lower the temperature less than 20 DEG C and separate out solid, dry content 96% 6 water aluminum chloride 500kg.Aluminium wastewater mother liquid recycle, distilled water then returns and does down batch hydrolysis water use.
By in 6-oxo-8-chloroctanoic acid ethyl ester liquid suction 1500L reactor, less than 35 DEG C drip POTASSIUM BOROHYDRIDE ammonia soln (40kg POTASSIUM BOROHYDRIDE+120kg17% ammoniacal liquor), and in controlling, temperature less than 35 DEG C, is incubated 3 hours.Layering, organic layers with water is washed till neutrality, and 0.1MPa heating under reduced pressure concentrates, and to temperature 110 DEG C end, obtains the 6-hydroxyl-8-chloroctanoic acid ethyl ester concentrated solution 361kg of content 90%.
Upper batch distilled water is put into 3M
3in hydrolysis kettle, moisturizing, to 1350kg, recycles.
Although the present invention discloses as above with preferred embodiment; so itself and be not used to limit the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when doing a little amendment and perfect, therefore protection scope of the present invention is when being as the criterion of defining with claims.
Claims (8)
1. one kind processes the method for aluminium wastewater in 6-oxo-8-chloroctanoic acid ethyl ester preparation process, take aluminum chloride as catalyzer, in dichloroethane solution, 6-chloro-6-oxo ethyl hexanoate and ethene generation addition reaction, obtained object product after aluminum chloride hydrolysis, is characterized in that the method for described process aluminium wastewater comprises the following steps:
(1), that this aluminium wastewater is concentrated in container;
(2) water that, distillation removing is appropriate;
(3), water temperature is down to less than 30 DEG C and separates out six water aluminum chloride solids;
(4), the removing aluminium wastewater mother liquor six water aluminum chloride solids of separating out, drying solid also reclaims;
(5), by the aluminium wastewater mother liquor that step (4) obtains apply mechanically, after collecting the distilled water described in step (2), return the hydrolysis making next batch and use.
2. the method for claim 1, is characterized in that, described step (1) container is concentration kettle.
3. the method for claim 1, is characterized in that, described step (2) boils off the water yield and is about the 25%-50% often criticizing hydrolysis gained aluminium wastewater weight.
4. the method for claim 1, is characterized in that, described step (3) water temperature is down to less than 25 DEG C.
5. method as claimed in claim 4, it is characterized in that, described step (3) water temperature is down to 15 DEG C-20 DEG C.
6. 6-oxo-8-chloroctanoic acid ethyl ester preparation method as claimed in claim 1, it is characterized in that, in described method, the weight ratio of 6-chloro-6-oxo ethyl hexanoate and water is 1: 2.9 ~ 3.8.
7. an equipment for aluminium wastewater recycle, described equipment comprises:
Concentration kettle, input aluminium wastewater, boils off appropriate water;
Cold analysis tank, directly connects strainer, is cooled by the concentrated solution of aluminium wastewater;
Strainer, the six water aluminum chloride solids that removing aluminium wastewater mother liquor is separated out;
Circulating line, applies mechanically aluminium wastewater mother liquor, and distilled water then returns does circulation hydrolysis use.
8. equipment as claimed in claim 6, it is characterized in that, also comprising the pipeline order of connection is: concentration kettle, cold analysis tank, strainer; Strainer pipeline is connected with concentration kettle, for Recycling Mother Solution.
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| CN201410808222.6A CN104671570A (en) | 2014-12-24 | 2014-12-24 | Method for treating aluminum-containing wastewater in preparation process of 6-oxo-8-chloro ethyl caprylate |
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| CN201410808222.6A CN104671570A (en) | 2014-12-24 | 2014-12-24 | Method for treating aluminum-containing wastewater in preparation process of 6-oxo-8-chloro ethyl caprylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800850A (en) * | 2016-02-04 | 2016-07-27 | 三峡大学 | Method for producing AlCl3.6H2O from aluminum wastewater containing formaldehyde and dichloroethane |
| CN106966901A (en) * | 2016-01-13 | 2017-07-21 | 江苏同禾药业有限公司 | A kind of preparation method of 6- hydroxyls -8- Lipase Catalyzed Resolution of Racemic Ethyl |
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| CN101837998A (en) * | 2010-04-27 | 2010-09-22 | 中国神华能源股份有限公司 | Method for evaporating, concentrating and crystallizing solution of aluminum chloride |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1063468A (en) * | 1991-01-22 | 1992-08-12 | 山西大学 | From the waste water of producing anthraquinone, reclaim the method for aluminum compound |
| JPH0592189A (en) * | 1991-09-30 | 1993-04-16 | Nec Corp | Treatment of washing waste water |
| CN1857999A (en) * | 2005-05-02 | 2006-11-08 | 黄中杰 | Recovering and utilizing method for aluminum trichloride solution in chemical production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966901A (en) * | 2016-01-13 | 2017-07-21 | 江苏同禾药业有限公司 | A kind of preparation method of 6- hydroxyls -8- Lipase Catalyzed Resolution of Racemic Ethyl |
| CN105800850A (en) * | 2016-02-04 | 2016-07-27 | 三峡大学 | Method for producing AlCl3.6H2O from aluminum wastewater containing formaldehyde and dichloroethane |
| CN105800850B (en) * | 2016-02-04 | 2018-11-02 | 三峡大学 | It is a kind of to produce AlCl using containing the aluminium waste water of formaldehyde and dichloroethanes3·6H2The method of O |
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Application publication date: 20150603 |