CN102701962A - Method for preparing terephthalic acid by using alkali reduction wastewater as raw material - Google Patents
Method for preparing terephthalic acid by using alkali reduction wastewater as raw material Download PDFInfo
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- CN102701962A CN102701962A CN2012101973146A CN201210197314A CN102701962A CN 102701962 A CN102701962 A CN 102701962A CN 2012101973146 A CN2012101973146 A CN 2012101973146A CN 201210197314 A CN201210197314 A CN 201210197314A CN 102701962 A CN102701962 A CN 102701962A
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Abstract
The invention discloses a method for preparing a terephthalic acid by using alkali reduction wastewater as a raw material. The alkali reduction wastewater is used as a raw material. The method comprises an acidification process, in which the pH of a reaction solution is controlled between 3 and 4.1, the reaction temperature is controlled between 70 DEG C and 85 DEG C, and the stirring speed is controlled between 350r/min and 420r/min. By controlling the pH of the solution, the reaction temperature, the stirring speed and the like in an acidification reaction in the reaction process, a terephthalic acid product applied to prepare potassium hydrogen terephthalate can be prepared, the production process is simple, and the production cost is low.
Description
Technical field: the present invention relates to a kind of preparation method of terephthalic acid, particularly a kind of is the feedstock production method of terephthalic acid with the alkali decrement waste water.
Background technology: terephthalic acid is hereinafter to be referred as PTA; Be the basic chemical industry raw material of synthetic polyethylene terephthalate (PET, terylene), polybutylene terephthalate polyester such as (PBT), produce PTA at present and mainly generally adopt smart p-Xylol (PX) air catalytic oxidation method.Along with the Chinese national economy fast continual development, very powerful to the demand of terylene level and engineering plastics PET, the turnout of China PET has surpassed Japan according to statistics, and amount of finish has surpassed the U.S., becomes global PET production, processing and consumption big country.Because it is constantly soaring to produce raw material p-Xylol (PX) price of PTA; The demand of PTA is huge, though China builds up and have many at tens0000 tons that build and a hundreds of thousands of tonne PTA production equipment, analyzes from the situation of demand; PTA still difficulty satisfies domestic needs, still needs a large amount of imports.
So alkali decrement waste water is raw material production PTA is the problem that people pay close attention to always.Adopting feasible effective means from waste water, to reclaim PTA, is to implement the strategy of sustainable development, realizes recycling of waste resources, can improve the biodegradability of follow-up WWT greatly again, improves the wastewater treatment compliance rate.
It is estimated the alkali decrement waste water that per ten thousand square metres of polyester piece goods will produce 30～50 tons, account for 10～15% of dyeing waste water total amount, and COD amount accounts for the dyeing waste water total amount and reaches 50～70%.China's terylene output in 2010 reaches 2,180 ten thousand tons according to incompletely statistics, can produce 9.2 hundred million tons of alkali decrement waste waters approximately, wherein contains about 1,000,000 tons of PTA.Because Pollutant levels are high in the alkali decrement waste water, alkalescence is big, and microbic resolvability is poor, usually makes wrecking property of the biochemistry pool impact of Sewage treatment systems, and it is heavy to make that alkali decrement waste water becomes the dyeing pollution, the waste water that intractability is big.
One Chinese patent application number be 200610053828.9 " a kind of processing of color fiber alkali decremental waste water with reclaim technologies " it is handled dense rare two bursts of waste water branch matter that the alkali decrement process produces; Adopt discoloring agent to decolour earlier; Combine with embrane method through acid-precipitation method then; From alkali decrement waste water, reclaim PTA, the recovery can reach 90%.Though its recovery is high, the PTA range of application of recovery is wider, and it reclaims complex process, and facility investment is big, and production cost is high, is difficult in the suitability for industrialized production of reality, use.
Summary of the invention:It is the feedstock production method of terephthalic acid with the alkali decrement waste water that the present invention provides a kind of; It mainly is raw material with the alkali decrement waste water; Solution pH value through acid precipitation reaction in the control reaction process; Temperature of reaction and stirring velocity etc. are prepared the terephthalate product that can be applicable to prepare terephthaldehyde's potassium hydrogen phthalate, and production technique is simple, and production cost is low.
The present invention is the feedstock production method of terephthalic acid with the alkali decrement waste water, is to be raw material with the alkali decrement waste water, comprises the acid out technological process, the pH=3-4.1 of reaction soln in its control acid precipitation reaction process, and temperature of reaction is 70-85 ℃; Stirring velocity 350-420r/min in the acid out process.
The concentration that preferred control adds acid solution in the acid precipitation reaction process according to the invention is 20-30Wt%, and adding speed is 3.5-4.5ml/min; Said acid solution is a sulphuric acid soln.
After said acid precipitation reaction finished, the terephthalic acid of generation through the filtrating that press filtration obtains, turned back in the acid precipitation reaction device after the recovery again and continues recycle.
The present invention is raw material with the alkali decrement waste water; Produce the novel process of terephthalic acid through technological processs such as deposition, acid out, washing, neutralization, dehydration and dryings; The recovery of PTA reaches 90% in the alkali decrement waste water; PTA acid number>=450 (KOH) mg/g that reclaims, or>=450 (NaOH) mg/g, ash content≤0.11%.
Disodium terephthalate in the alkali decrement waste water is dissolved in the alkaline aqueous solution, and in acid out process neutralisation of sulphuric acid generation neutralization reaction, separates out the throw out PTA and the sodium sulfate that are insoluble in water.
The inventive method changed in the traditional technology acid precipitation reaction mother liquor directly discharging cause contaminated wastewater, the neutralization reaction mother liquid recycling has improved the utilization ratio of raw material sulphuric acid etc.Get rid of conventional process and reclaim high energy consumption, high material-consumption operations such as alkali in the technology dissolves, remove impurity with active carbon.
If the not treated direct discharging of alkali subtraction amount waste water will particularly cause huge harm to water quality and aquatic organism to environment, and cause valuable PTA resource waste in vain.The present invention reclaims PTA from alkali decrement waste water, crystalline mother solution reusable edible in the technology is to reducing the pressure in Sewage treatment systems mesophytization pond; Realize that the standard wastewater discharge effect is great, production technique is simple, and production cost is low; Workable, realize the industriallization continuous production.
The technological process of production of the present invention is following: the alkali decrement waste water raw material → equalizing tank → deposition → acid precipitation reaction that catchments → press filtration → waste water ageing, biochemical treatment → sedimentation discharging.
Process explanation: earlier alkali decrement waste water is pooled to water collecting basin, after be sent to equalizing tank pH value suitably regulated.Alkali decrement waste water is sent to settling tank subsequently.In settling tank, add flocculation agent, make that some impurity and the solid particulate in the alkali decrement waste water is removed, then this alkali decrement waste water is sent to and carries out acid precipitation reaction in the acidification reaction tower; After reaction finished, waste water was sent to press filtration, obtains the thick product of PTA.Through the filtrating that press filtration obtains, turn back to again in the acid precipitation reaction device after the recovery and continue recycle.Waste water was through the sedimentation qualified discharge after waste water was sent to biochemical treatment, biochemical treatment; The mud that settling tank produces is sent to sludge thickener in the lump, handles the back sanitary landfill.
The terephthalate product Institute of Analysis's detection through Jiangxi Province that utilizes the inventive method to produce, each item index all reaches specification of quality.
Name of product: terephthalic acid,
Kind of inspection: entrust,
Client: female chemical industry ltd is built in the Wanzai County,
The sample situation: solid,
Test atmosphere condition: temperature: 24 ℃, humidity: 70%,
The Interventions Requested assay
Ash content 0.11%
Acid number 478 (NaOH) mg/g.
Description of drawings:Fig. 1 is the infrared spectrogram of the terephthalate product of the inventive method production.
Infrared spectrogram by infrared spectrogram of the present invention and standard P TA contrasts; The absorption peak position of spectrogram of the present invention and the absorption peak of standard P TA are about the same; But also has slightly little difference; Show in the PTA product that the present invention reclaims to have small amount of impurities, can be applicable to prepare products such as terephthaldehyde's potassium hydrogen phthalate.
Embodiment:Below in conjunction with embodiment the present invention is done further detailed description.
Production method of terephthalic acid of the present invention is to be that raw material is produced with the alkali decrement waste water, earlier alkali decrement waste water is pooled to water collecting basin, is sent to equalizing tank then pH value is suitably regulated; To deliver to settling tank through the alkali decrement waste water that regulates subsequently; In settling tank, add flocculation agent, make that some impurity and the solid particulate in the alkali decrement waste water is removed, obtain the alkali decrement waste water after the removal of impurities, then this alkali decrement waste water is sent in the acidification reaction tower, carry out acid precipitation reaction; The temperature of reaction of reaction soln is 70-85 ℃ in the control acid precipitation reaction process, the stirring velocity 350-420r/min in the acid precipitation reaction process.As the acid solution that adds in the acid precipitation reaction process of the present invention, and the mass concentration that control adds sulphuric acid soln is 20-30Wt% with sulphuric acid soln, and its rate of addition is 3.5-4.5ml/min; Reaction obtains reaction solution and carries out press filtration after finishing, and obtains the thick product of PTA, through the filtrating that press filtration obtains, turns back in the acid precipitation reaction device after the recovery again and continues recycle, has realized crystalline mother solution reusable edible in the technology.The thick product of PTA is the PTA product through subsequent disposal, and waste water was through the sedimentation qualified discharge after waste water was sent to biochemical treatment, biochemical treatment.
Embodiment1
Alkali decrement waste water with Shaoxing, Zhejiang Province textile printing and dyeing ltd discharging is a raw material of the present invention, through detecting organic content (COD) in this alkali decrement waste water between 10000～40000mg/L, and PH >=12, BODs is 1600; This alkali decrement waste water is pooled to water collecting basin, is sent to equalizing tank then pH value is suitably regulated, it is become about neutrality by strong basicity; Deliver to settling tank with above-mentioned through the alkali decrement waste water that regulates subsequently; In settling tank, add flocculation agent, make that some impurity and the solid particulate in the alkali decrement waste water is removed, obtain the alkali decrement waste water after the removal of impurities, then this alkali decrement waste water is sent in the acidification reaction tower, carry out acid precipitation reaction; In the acid precipitation reaction process; The adding mass concentration is 25% sulphuric acid soln, and control drips the speed of sulphuric acid soln at 4.2ml/min, and temperature of reaction is 80 ℃; Stirring velocity 400-420r/min in the acid precipitation reaction process, and the pH=3-4.1 of reaction soln in the control acid precipitation reaction process.Reaction is carried out press filtration to the reaction solution that obtains containing terephthalic acid after finishing, and obtains the thick product of xln PTA; The press filtration rear filtrate reclaims; The filtrating of reclaiming joins cycling and reutilization in the acid precipitation reaction tower again with the form of mother liquor, is the PTA product to the thick product of the PTA that obtains through subsequent disposal, and waste water is sent to biochemical treatment; The waste water COD of discharging is no more than 800mg/L, and PH is at 7-9 waste material landfill.Conform to quality requirements through detecting the PTA product of producing.
Embodiment2
Except that the situation of following explanation; All the other are identical with embodiment 1, and in the acid precipitation reaction process, the adding mass concentration is 28% sulphuric acid soln; Control drips the speed of sulphuric acid soln at 4 ml/min; Temperature of reaction is 75 ℃, the acid out stirring velocity 390r/min in the reaction process, and the pH=4 of reaction soln in the control acid precipitation reaction process.
Claims (3)
1. one kind is the feedstock production method of terephthalic acid with the alkali decrement waste water, is raw material with the alkali decrement waste water, comprises the acid out technological process, it is characterized in that controlling the pH=3-4.1 of reaction soln in the acid precipitation reaction process, and temperature of reaction is 70-85 ℃; Stirring velocity 350-420r/min in the acid out process.
2. be the feedstock production method of terephthalic acid according to the described alkali decrement waste water of claim 1, it is characterized in that the concentration of control adding acid solution in the said acid precipitation reaction process is 20-30Wt%, adding speed is 3.5-4.5ml/min; Said acid solution is a sulphuric acid soln.
3. be the feedstock production method of terephthalic acid according to the described alkali decrement waste water of claim 1; After it is characterized in that said acid precipitation reaction finishes; The terephthalic acid that generates turns back in the acid precipitation reaction device after the filtrating that press filtration obtains is reclaimed again and continues recycle.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829879A (en) * | 2015-05-09 | 2015-08-12 | 江苏爱特恩东台新材料科技有限公司 | Method for preparing multifunctional rubber assistant by recycling alkali-weight-reduction processing discharged liquor |
Citations (2)
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|---|---|---|---|---|
| US5210292A (en) * | 1989-10-13 | 1993-05-11 | Korea Research Institute Of Chemical Technology | Process for preparing polymer grade terephthalic acid |
| CN101168457A (en) * | 2006-10-23 | 2008-04-30 | 吴江祥盛纺织染整有限公司 | Technique for treating chemical fibre alkali decrement waste water |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210292A (en) * | 1989-10-13 | 1993-05-11 | Korea Research Institute Of Chemical Technology | Process for preparing polymer grade terephthalic acid |
| CN101168457A (en) * | 2006-10-23 | 2008-04-30 | 吴江祥盛纺织染整有限公司 | Technique for treating chemical fibre alkali decrement waste water |
Non-Patent Citations (5)
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| 谭书琼等: "碱减量废水中回收对苯二甲酸资源再用", 《云南化工》, vol. 34, no. 1, 28 February 2007 (2007-02-28), pages 8 - 11 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829879A (en) * | 2015-05-09 | 2015-08-12 | 江苏爱特恩东台新材料科技有限公司 | Method for preparing multifunctional rubber assistant by recycling alkali-weight-reduction processing discharged liquor |
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Application publication date: 20121003 |