CN102701963B - Method for preparing potassium hydrogen terephthalate - Google Patents
Method for preparing potassium hydrogen terephthalate Download PDFInfo
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- CN102701963B CN102701963B CN201210197826.2A CN201210197826A CN102701963B CN 102701963 B CN102701963 B CN 102701963B CN 201210197826 A CN201210197826 A CN 201210197826A CN 102701963 B CN102701963 B CN 102701963B
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- terephthalic acid
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- potassium hydroxide
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Abstract
The invention discloses a method for preparing potassium hydrogen terephthalate. The method comprises the following steps of: preparing terephthalic acid from alkali-decrement wastewater serving as a raw material by an acidification method, and controlling the acid value of the generated terephthalic acid to be more than or equal to 450(KOH)mg/g and ash content to be less than or equal to 0.11 percent; and performing neutralization reaction on the terephthalic acid and potassium hydroxide, and controlling the molar ratio of the potassium hydroxide to the terephthalic acid to be 1:1.1-1.3. Crystallization mother liquor is recycled in the process, and the potassium hydrogen terephthalate product can be directly used for producing terephthalate whistling powder without being further purified; and production cost is low, waste resources are recycled, and sustainable development is realized.
Description
Technical field: the present invention relates to a kind of method preparing potassium hydrogen terephthalate, particularly a kind of take alkali decrement waste water as the method that potassium hydrogen terephthalate prepared by raw material.
Background technology: potassium hydrogen terephthalate, Potassium Hydrogen Phthalate etc. are as sibilant rale agent, be widely used in fireworks industry, because two carboxyls of potassium hydrogen terephthalate are in contraposition, its oxygenolysis temperature is higher than the Potassium Hydrogen Phthalate at ortho position, therefore, potassium hydrogen terephthalate is more and more used; Because potassium hydrogen terephthalate is comparatively stable, do not fire with naked light, substantially increase the security in fireworks and firecrackers production process.Be subject to accreditation and the favorable comment of user after launch products, the prospect of the market development is very good.But its existing method taking pure terephthalic acid as raw material and carry out producing, the potassium hydrogen terephthalate of production, application cost is relatively high, makes its use be limited to.
Terephthalic acid is hereinafter referred to as PTA, be the basic chemical industry raw material of the polyester such as synthesis polyethylene terephthalate (PET, terylene), polybutylene terephthalate (PBT), produce PTA at present and mainly generally adopt smart p-Xylol (PX) air catalytic oxidation method.Because raw material p-Xylol (PX) price of producing PTA constantly rises, the demand of PTA is huge, although China builds up and have many at tens0000 tons that build and a hundreds of thousands of tonne PTA production equipment, but analyze from the situation of demand, PTA still difficulty meets domestic needs, still needs a large amount of import.
So be raw material production PTA with alkali decrement waste water, then be the problem that people pay close attention to by its production potassium hydrogen terephthalate always.This is because be mixed with the mechanical impuritys such as a small amount of dust in its terephthalic acid made, be not suitable as the raw materials for production of terylene, but still can be used as the raw material of preparation potassium hydrogen terephthalate, significantly can reduce the raw materials for production cost of potassium hydrogen terephthalate like this, make the PTA in alkali decrement waste water be recycled utilization.Meanwhile, adopting feasible effective means to reclaim PTA from alkali decrement waste water, is implement the strategy of sustainable development, realizes the recycling of waste resource, greatly can improve again the biodegradability of follow-up sewage disposal, improves wastewater treatment compliance rate.
It is estimated that every ten thousand square metres of polyester piece goods are by the alkali decrement waste water of generation 30 ~ 50 tons, account for 10 ~ 15% of dyeing waste water total amount, and COD amount accounts for 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, it is estimated and can produce alkali decrement waste water 9.2 hundred million tons, wherein containing PTA about 1,000,000 tons.Because in alkali decrement waste water, Pollutant levels are high, large pH >=12 of alkalescence, microbic resolvability is poor, usually makes the biochemistry pool of Sewage treatment systems, and exposed to damaging is impacted, and makes alkali decrement waste water become dyeing and pollutes heavy, the waste water that intractability is large.
Summary of the invention: the invention provides a kind of method preparing potassium hydrogen terephthalate, it is that raw material first prepares terephthalic acid with alkali decrement waste water, carry out neutralization reaction with alkali afterwards and directly prepare potassium hydrogen terephthalate, crystalline mother solution recycle in technique, product potassium hydrogen terephthalate, without the need to further purification, can be directly used in and produce the agent of benzene sibilant rale; Production cost is low, realizes waste resource recycle, realizes Sustainable development.
The invention provides a kind of method preparing potassium hydrogen terephthalate, it is 1), be that raw material adopts acid-precipitation method to prepare terephthalic acid with alkali decrement waste water, control acid number >=450 (KOH) mg/g of the terephthalic acid generated, ash content≤0.11%;
2), by above-mentioned terephthalic acid and potassium hydroxide carry out neutralization reaction, the mol ratio controlling potassium hydroxide and terephthalic acid is 1:1.1-1.3.
Terephthalic acid of the present invention and potassium hydroxide carry out in neutralization reaction process, control the pH=6-7.5 that its temperature of reaction is 85-105 DEG C, reaction soln, and the mol ratio of preferred potassium hydroxide and terephthalic acid is 1:1.18-1.2.
After neutralization reaction of carrying out described terephthalic acid and potassium hydroxide terminates, the filtrate that the potassium hydrogen terephthalate exsiccation made obtains, reclaims to enter in neutralization reaction operation again and carries out recycle.
Utilize alkali decrement waste water for main raw material, through technological process production potassium hydrogen terephthalate such as precipitation, acid out, washing, neutralization, dehydration and dryings, the filtrate that in technique, exsiccation obtains makes mother liquid recycling, and product potassium hydrogen terephthalate can be directly used in the agent of production potassium hydrogen terephthalate sibilant rale without the need to purifying further.Produce 1 ton of potassium hydrogen terephthalate, can process and reclaim alkali decrement waste water 290 tons, reduce COD and discharge 1.275 tons.Eliminate the pulverizing process that need increase for raw material production potassium hydrogen terephthalate with terylene level PTA, be conducive to energy-saving and emission-reduction.The transformation efficiency of potassium hydrogen terephthalate primary first-order equation reaches more than 95% simultaneously.
If the not treated direct discharge of alkali subtraction amount waste water, particularly causes huge harm to water quality and aquatic organism by environment, and cause valuable PTA resource waste in vain.The present invention reclaims PTA and prepares potassium hydrogen terephthalate from alkali decrement waste water, to the pressure reducing Sewage treatment systems mesophytization pond,
The qualified discharge effect realizing waste water is great, and production technique is simple, and production cost is low, workable, realizes industrialization continuous seepage.
The technological process of production of the present invention is as follows: alkali decrement waste water raw material → catchment equalizing tank → precipitation → acid precipitation reaction → press filtration → terephthalic acid → washing → filtration → neutralization reaction → dehydration → drying products.
Process explanation: first alkali decrement waste water is pooled to water collecting basin, after be sent to equalizing tank pH value suitably regulated.Waste water is sent to settling tank subsequently.In settling tank, add flocculation agent, some impurity in waste water and solid particulate are removed, and then waste water is sent in acidification reaction tower and carries out acid precipitation reaction; After reaction terminates, reaction solution press filtration, obtains PTA product.By terephthalic acid PTA product, carry out washing filtering, remove sodium sulfate wherein.Then PTA and potassium hydroxide are placed in reactor in certain proportion and react, reaction terminates rear feed liquid through centrifuge dehydration, and mother liquor returns reactor, and the product that dehydration obtains, through super-dry, can obtain product potassium hydrogen terephthalate.
What utilize the inventive method to produce detects through national light industry fireworks and crackers safety quality surveillance inspection center potassium hydrogen terephthalate product, and indices all reaches specification of quality.
Name of product: potassium hydrogen terephthalate,
Kind of inspection: entrust,
Production unit: Wanzai County Jian Kun Chemical Co., Ltd.
Client: Wanzai County Administration of Quality and Technology Supervision,
Sample situation: powder,
Test atmosphere condition: temperature: 24 DEG C, humidity: 70%,
With the potassium hydrogen terephthalate product that Wanzai County Jian Kun Chemical Co., Ltd. produces according to the inventive method, through the selective examination of Wanzai County Administration of Quality and Technology Supervision, with every 30 tons of products for radix, 1 kilogram of standard of sampling detects.
Survey report sees the following form 1.
Table 1
| Sequence number | Interventions Requested | Measure unit | Standard or require detected result conclusion |
| 1 | 120 screen residues | ％ | ≤ 10.04 is qualified |
| 2 | Moisture | ％ | ≤ 1.50.15 is qualified |
| 3 | Rate of moisture absorption | ％ | ≤ 30.21 is qualified |
| 4 | Acid number pH | 4-65.1 qualified |
Utilize the raw potassium hydrogen terephthalate product of the inventive method all to reach specification of quality from table inspection numbers illustrated, application fireworks manufacturing enterprise is as sibilant rale agent good product effect.
Embodiment: the present invention is described in further detail below in conjunction with embodiment.
The method of production potassium hydrogen terephthalate of the present invention is that raw material is produced with alkali decrement waste water, first produce terephthalic acid, then carry out neutralization reaction after making solution with potassium hydroxide and water and obtain potassium hydrogen terephthalate, potassium hydrogen terephthalate is filtered, filtrate recovery enters in neutralization reaction device again continues reaction, achieves the recycle of waste liquid.Namely be first alkali decrement waste water is pooled to water collecting basin, be then sent to equalizing tank and pH value is suitably regulated; Subsequently the alkali decrement waste water through regulating is delivered to settling tank; In settling tank, add flocculation agent, some impurity in alkali decrement waste water and solid particulate are removed, obtain the alkali decrement waste water after removal of impurities, then this alkali decrement waste water is sent in acidification reaction tower, carries out acid precipitation reaction, after reaction terminates, obtain reaction solution and carry out press filtration, obtain PTA product.By terephthalic acid PTA product, carry out washing filtering, remove sodium sulfate wherein.Then PTA is direct and potassium hydroxide is placed in reactor in certain proportion and reacts, reaction terminates rear feed liquid and filters through centrifuge dehydration, the filtrate obtained is made mother liquor and is returned in reactor as continuing reaction raw materials again, the product that dehydration obtains, through super-dry, can obtain potassium hydrogen terephthalate product.
Embodiment 1
With Asia-Pacific, Zhejiang Province textile printing and dyeing company limited discharge alkali decrement waste water for raw material of the present invention, the organic content (COD) after testing in this alkali decrement waste water between 30000 ~ 40000mg/L, PH >=12, BODs is 1800; This alkali decrement waste water is pooled to water collecting basin, is then sent to equalizing tank and pH value is suitably regulated; Subsequently the above-mentioned alkali decrement waste water through regulating is delivered to settling tank; In settling tank, add flocculation agent, some impurity in alkali decrement waste water and solid particulate are removed, obtain the alkali decrement waste water after removal of impurities, then this alkali decrement waste water is sent in acidification reaction tower, carries out acid precipitation reaction; After reaction terminates, carrying out press filtration obtaining reaction solution, obtaining PTA product.Then the PTA product that upper step obtains is carried out washing filtering, remove sodium sulfate wherein.Then be that 1:1.18-1.2 ratio is placed in reactor and carries out neutralization reaction with mol ratio by potassium hydroxide and PTA, to control in it and in reaction process, temperature of reaction is 85-105 DEG C, the pH=6-7.5 of reaction soln, control acid number >=450 (KOH) mg/g of the terephthalic acid generated, ash content≤0.11%; After reaction terminates, the feed liquid obtained containing potassium hydrogen terephthalate is filtered through centrifuge dehydration, filtrate recovery is made mother liquor and is returned in reactor and continue recycle, the crystal that obtains of dewatering be potassium hydrogen terephthalate through super-dry, product potassium hydrogen terephthalate can be obtained.
Embodiment 2
Except the situation of following explanation, all the other are identical with embodiment 1, and control PTA and potassium hydroxide carry out in neutralization reaction process, the pH=6.5 of reaction soln, and temperature of reaction is 95 DEG C.
Claims (2)
1. prepare a method for potassium hydrogen terephthalate, it is characterized in that 1), be raw material with alkali decrement waste water, adopt acid-precipitation method to prepare terephthalic acid, alkali decrement waste water be pooled to water collecting basin, and suitable adjust ph; Then the alkali decrement waste water regulated is delivered to settling tank; In settling tank, add flocculation agent, removing impurity and solid particulate, obtain the alkali decrement waste water after removal of impurities, be then sent in acidification reaction tower by the alkali decrement waste water after removal of impurities, carry out acid precipitation reaction; After reaction terminates, obtaining reaction solution press filtration, obtain terephthalate product; By obtained PTA product washing filtering, remove sodium sulfate wherein, obtain terephthalic acid, control acid number >=450 (KOH) mg/g of the terephthalic acid generated, ash content≤0.11%;
2), by 1) terephthalic acid prepared of step and potassium hydroxide carries out neutralization reaction, and the mol ratio controlling potassium hydroxide and terephthalic acid is 1:1.1-1.3;
Described terephthalic acid and potassium hydroxide carry out in neutralization reaction process, control the pH=6-7.5 that its temperature of reaction is 85-105 DEG C, reaction soln;
After neutralization reaction of carrying out described terephthalic acid and potassium hydroxide terminates, the filtrate that the potassium hydrogen terephthalate exsiccation made obtains, recovery enters neutralization reaction operation again and carries out recycle.
2. according to a kind of method preparing potassium hydrogen terephthalate according to claim 1, it is characterized in that described terephthalic acid and potassium hydroxide carry out in neutralization reaction process, the mol ratio controlling potassium hydroxide and terephthalic acid is 1:1.18-1.2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210197826.2A CN102701963B (en) | 2012-06-15 | 2012-06-15 | Method for preparing potassium hydrogen terephthalate |
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| CN201210197826.2A CN102701963B (en) | 2012-06-15 | 2012-06-15 | Method for preparing potassium hydrogen terephthalate |
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| CN102701963A CN102701963A (en) | 2012-10-03 |
| CN102701963B true CN102701963B (en) | 2015-04-29 |
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| CN103819293A (en) * | 2014-01-02 | 2014-05-28 | 万载县建坤化工有限公司 | Firework propellant |
| CN109019977A (en) * | 2018-08-31 | 2018-12-18 | 绍兴众聚环保科技有限公司 | A kind of dyeing alkali decrement waste water pretreating process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956088A (en) * | 1974-05-01 | 1976-05-11 | Barber-Colman Company | Process for the destruction of developed and undeveloped photosensitive film and the recovery of products therefrom |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3956088A (en) * | 1974-05-01 | 1976-05-11 | Barber-Colman Company | Process for the destruction of developed and undeveloped photosensitive film and the recovery of products therefrom |
Non-Patent Citations (4)
| Title |
|---|
| 涤纶废料制笛音剂对苯二甲酸氢钾;王春年;《陕西化工》;19920430(第2期);第31页 * |
| 烟花笛音剂对苯二甲酸氢钾的制备;成本诚等;《湖南化工》;19860829;第35-37页 * |
| 由回收对苯二甲酸一步合成高钾烟花笛音剂;朱卫国等;《化学世界》;19940325;第154-155页 * |
| 碱减量废水中回收对苯二甲酸资源再用的研究;谭书琼;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20070101;第40-71页 * |
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