CN1126730C - Process for separating terephthalic acid from its waste and purifying it - Google Patents
Process for separating terephthalic acid from its waste and purifying it Download PDFInfo
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- CN1126730C CN1126730C CN 01113738 CN01113738A CN1126730C CN 1126730 C CN1126730 C CN 1126730C CN 01113738 CN01113738 CN 01113738 CN 01113738 A CN01113738 A CN 01113738A CN 1126730 C CN1126730 C CN 1126730C
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Abstract
The present invention relates to a method for separating and purifying phthalic acid waste materials, which is a method for separating and purifying outwards expelled waste materials in the production process of terephthalic acid. The present invention has the following purifying scheme: 75 to 98% of sulfuric acid and 50 to 95% of nitric acid are respectively added in an acid tank according to a volume ratio of 1: 1 to 9: 1 and form mixed acid through stirring; solid terephthalic acid waste materials are added in the mixed acid; paste generated in the steps is filtered by a filtering net at negative pressure; filter cakes are sent in a water washing pool after being concentrated; the filter cakes separated in the process are washed by desalted water in the water washing pool for generating terephthalic acid solid wet filter cakes which are sent to a drier for being dried for 20 to 40 minutes for obtaining terephthalic acid solid finished products.
Description
The present invention relates to separation, the method for purification of Production of Terephthalic Acid process China and foreign countries' waste discharge material, belong to the recycling of chemical industry waste.Especially the method utilized of the waste material in the Production of Terephthalic Acid process.
Terephthaldehyde's acid waste products part is because in pure terephthalic acid's device production process, its oxidation unit, refined unit and wind send and system such as feed bin, the terephthalic acid solid raw material that effluxes during because of run, drip, leak or accidental state; Another part be must efflux in the production process of device own contain terephthalic acid and other organic acid by product.These contaminated outer discharges finally enter ground trench system or the inflow wastewater disposal basin in the production equipment district and precipitate.At present, each para-phthalic acid (pta) this class waste material that all is not recycled is all taked irregularly to salvage and the direct mode of pack, as the waste product material with extremely low price export trade.From raising the condition of production of sub-petro-chemical corporation 600,000 t/a pure terephthalic acid devices, the various waste material amounts that efflux every year have 5000～9000 tons approximately.Because of the composition of this waste material very unstable, wherein not only contain multiple metal ions such as iron, aluminium, cobalt, manganese, sodium, sometimes also carry foreign material such as a small amount of tiny silt and vegetation rod secretly, color has yellow, black, grey etc. multiple, can not directly use as the raw material of producing softening agent or synthon.Terephthaldehyde's acid content in terephthaldehyde's acid waste products is generally between 50～60% (m/m), and water-content is at 40～30% (m/m), about 10% (m/m) of other foreign matter content.
At present, to the recovery of this type of waste material with utilize method to be: it is molten with terephthaldehyde's acid waste products alkali at first to add excessive highly basic (NaOH), after making terephthalic acid and alkali reaction wherein, generate water-soluble terephthalic acid sodium salt, metal ions such as iron wherein, aluminium then generate ironic hydroxide and aluminum hydroxide precipitation (silt wherein also forms precipitation).Separate obtaining the terephthalic acid sodium solution after filtration, isolated solids is a waste material.For isolated solution, add excessive 75% dilute sulphuric acid again and under 80 ℃, carry out acid out, filtering separation, thereby obtain the terephthalic acid solid material of yellow-white; Isolated metabisulfite solution (sulfuric acid that contains the excessive adding of part) is as discharge of wastewater.The solid material gets the finished product material after further washing, filtration, drying, about 95% (m/m) of terephthaldehyde's acid content wherein can be used as the raw material of producing softening agent, can not use as the raw material of synthon; The waste water that filters out with efflux after waste water in the acid out process mixes.The wastewater discharge of finished product material per ton is up to 6～8t; The direct material raw materials consumption expense of finished product material per ton is on average up to 1150 yuan in the production process.
It is long that present recovery technology exists operational path, and wastewater discharge is big, liquid waste concentration height, thereby defectives such as intractability is big, processing cost height.And the higher raw materials such as caustic soda of a large amount of dilute sulphuric acids that add and price all can't cycling and reutilization, and the waste of resource is more serious, and total production cost is higher.Another insoluble problem is: because raw material alkali is when molten, need to add excessive caustic soda, thereby a large amount of sodium ions of bringing into, be difficult to separate clean by washing process, cause the finished product material after illumination, to present yellow spotting immediately, not only influence the sale of finished product, also the production to downstream softening agent product has disadvantageous effect.
The separating and purifying method that the purpose of this invention is to provide a kind of simple and direct, efficient, cost is low, quantity of wastewater effluent is little terephthaldehyde's acid waste products.
The scheme that separation of the present invention is purified is:
A. complex acid is molten with acid: the sulfuric acid with 75%～98% and 50%～95% nitric acid joined respectively and become nitration mixture in the acid tank after stirring in 1: 1 by volume～9: 1, again solid terephthaldehyde acid waste products is added in this nitration mixture sour solubility temperature continuously stirring 20～40 minutes between 20 ℃～80 ℃;
B. vacuum filtration: the slurry that above process is generated filters with filtering net under negative pressure, and filter cake is sent into washing pool after concentrating;
C. washing: the isolated filter cake of above process is washed the ratio of de-salted water and filter cake more than 1: 1 with de-salted water in washing pool, wash temperature is 30 ℃～50 ℃, washed 10～20 minutes, carry out the suction filtration first time, filter cake behind the suction filtration is added water carry out secondary washing, carry out the suction filtration second time afterwards, generate the terephthalic acid solid wet cake and deliver to moisture eliminator;
D. with the terephthalic acid solid wet cake of above generation below room temperature to 121 ℃ dry 20～40 minutes, obtain the terephthalic acid solid finished product.The filtering net that suction filtration is used is 200～500 purpose terylene filter clothes.Take the pressure reduction suction filtration, the negative pressure of suction filtration is 200～500mmH
2The O post.
The invention has the advantages that simple and direct efficient, the little solid finished product material after drying of quantity of wastewater effluent of technology, wherein about 95% (mm) of terephthaldehyde's acid content can be used as the raw materials for production of multiple PVC CABLE MATERIALS softening agent product.Compare with existing technology, the present invention has not only saved the molten unit of alkali in the former technology, and the acid solution of acid after molten recycles after both can having handled, also can export trade, thereby greatly reduce concentration of wastewater, and quantity of wastewater effluent is less than 20% of former technology; Simultaneously, the raw and auxiliary material cost that consumes in the production only is 1/5th of this product price, and product per ton is saved direct material than existing technology and taken 800-900 unit, and economic benefit and environmental benefit are obvious.
The invention will be further described below in conjunction with embodiment:
Embodiment 1: get black terephthalic acid solid waste material 100g.
(1) acid is joined with acid molten
Get 75% dilute sulphuric acid 90mL earlier, join in the beaker of 500mL, get rare nitric acid 10mL of 50% again, slowly join in the beaker of 500mL,, under normal temperature, normal pressure, stir with original dilute sulphuric acid in the beaker.
The beaker that nitration mixture is housed for preparing is placed on heats, on the water-bath heater of temperature control, add load weighted terephthaldehyde's acid waste products while stirring, open warming-in-water simultaneously and be controlled at 78 ℃.After 30 minutes heated and stirred, sour cementing bundle.
(2) vacuum filtration
With sour cementing bundle disposed slurry, under continuous whipped state, keep the solid terephthalic acid in the feed liquid to be suspended state, use B then, built-in 400 orders, model are the filtration of bleeding of the terylene filter cloth of 621-90, aspiration vacuum level is the 200mm water column.The dark red filtrate that suction filtration goes out evaporates after collecting; The white of draining (having yellow) filter cake is weighed after collecting, and quality is 61g.
(3) washing, drying
With the terephthalic acid cake 61g that obtains in the vacuum filtration process, put into the beaker of 200mL, but and beaker is placed on the water-bath heater of temperature control, heating; Add the 122g de-salted water, stir on the limit, and the limit is warming up to 45 ℃.Keep under 45 ℃ of states agitator treating to use B after 15 minutes, built-in 400 orders, model be 621-90 wash the synthetic fibre filter cloth, under the negative pressure of 500mm water column, the filtration of once bleeding.To the filter cake after draining in the B, stop suction; Spray the 6g de-salted water more uniformly, carry out the secondary suction filtration.The acid wash liquid of suction filtration gained is collected back 135mL altogether once more, as dissolving, the bath water of vaporizer still slag; The terephthalic acid solid filter cake of the white after draining is put into baking oven, and baking is 30 minutes under 121 ℃ of states.In the finished product material after the oven dry, terephthaldehyde's acid content is 95.5% by analysis, and quality is 54.8g.
Embodiment 2: the terephthalic acid solid waste material 1000g of extracting yellow.
(1) complex acid is molten with acid
Measure 98% dilute sulphuric acid 800mL with measuring tank, join in the beaker of 2000mL, measure rare nitric acid 400mL of 95% again, slowly join in rare sulphur, under normal temperature, normal pressure, stir.
The beaker that nitration mixture is housed for preparing is placed on can heats, on the water-bath heater of temperature control, add 1000g terephthaldehyde's acid waste products of weighing while stirring, it is molten to carry out acid at normal temperatures and pressures, after 20 minutes heated and stirred, and sour cementing bundle.
(2) vacuum filtration
With the slurry behind the sour cementing bundle, under continuous whipped state, keep the solid terephthalic acid in the feed liquid to be suspended state, use B then, built-in 400 orders, model are the filtration of bleeding of the terylene filter cloth of 621-90, aspiration vacuum level is the 500mm water column.Standby with decolorizing with activated carbon behind the red filtrate collection that suction filtration goes out, the white after draining (having faint yellow) filter cake is weighed after collecting, and quality is 681g.
(3) washing, drying
With the terephthalic acid cake 681g that obtains in the vacuum filtration process, put into the beaker of 2000mL, but and beaker is placed on the water-bath heater of temperature control, heating; Add the 2000g de-salted water, stir on the limit, and the limit is warming up to 30 ℃.Keep under 30 ℃ of states agitator treating to use B after 15 minutes, built-in 400 orders, model are the terylene filter cloth of 621-90, under the negative pressure of 200mn water column, and the filtration of once bleeding.To the filter cake after draining in the B, stop suction, spray 100g (mL) de-salted water more uniformly, carry out the secondary suction filtration.After the acid wash liquid of twice suction filtration gained is collected, as dissolving, the bath water of molten still of acid or vaporizer still slag; The terephthalic acid solid filter cake of the white after draining is put into baking oven, and baking is 40 minutes under 90 ℃ of states.By analysis, terephthaldehyde's acid content is 96.5% in the finished product material, and quality is 600.5g.
Embodiment 3: get terephthaldehyde's waste material 10kg: wherein black waste material and each 3kg of yellow waste material, gray solid waste material 4kg.
(1) complex acid is molten with acid
Measure 92% dilute sulphuric acid 8000mL (the mother liquor 1100mL that behind evaporation or decolorizing with activated carbon, reclaims in the example several times before wherein containing) altogether earlier, join in the garden cylindricality enamelled vessel of homemade 20L, get 75% nitric acid 2000mL again, slowly join in the enamelled vessel of 20L, with the vitriol oil in the bucket, under normal temperature, normal pressure, stir.
In the enamelled vessel that nitration mixture is housed for preparing (in-built electrical well heater), stir on the limit, the limit adds terephthaldehyde's acid waste products, and the temperature of opening electric heater intensification and control solution simultaneously is between 60～70 ℃.After 40 minutes heated and stirred, sour cementing bundle.
(2) vacuum filtration
With the slurry behind the sour cementing bundle, under continuous whipped state, keep the solid terephthalic acid in the feed liquid to be suspended state, use B then, built-in 400 orders, model are the filtration of in batches bleeding of the terylene filter cloth of 621-90, and aspiration vacuum level is 400mm water column (adopting the suction of small-sized electric vacuum pump).The dark red filtrate that suction filtration goes out evaporates after collecting; White after draining (having yellow) filter cake is weighed after collecting, and quality is 6.45kg.
(3) washing, drying
With the terephthalic acid cake 6.45kg that obtains in the vacuum filtration process, put into the porcelain enamel barrel that 20L had cleaned, add the 16kg de-salted water, stir on the limit, and the limit is opened electric heater and is warming up to 35～40 ℃.Keep under this state of temperature agitator treating to use B after 15 minutes, built-in 400 orders, model are the terylene filter cloth of 621-90, under the negative pressure of 500mm water column, bleed in batches and filter and the washing suction filtration.After the acid wash liquid of twice suction filtration gained is collected, as dissolving, the bath water of vaporizer still slag; The terephthalic acid solid filter cake of the white after draining is put into baking oven, and baking is 35 minutes under 110 ℃ of states.By analysis, terephthaldehyde's acid content is 96.1% in the finished product material, and quality is 5.68kg.
Claims (3)
1. the separating and purifying method of terephthaldehyde's acid waste products is characterized in that the scheme of separating purification is:
A. complex acid is molten with acid: the sulfuric acid with 75%～98% and 50%～95% nitric acid joined respectively and become nitration mixture in the acid tank after stirring in 1: 1 by volume～9: 1, again solid terephthaldehyde acid waste products is added in this nitration mixture sour solubility temperature continuously stirring 20～40 minutes between 20 ℃～80 ℃;
B. vacuum filtration: the slurry that above process is generated filters with filtering net under negative pressure, and filter cake is sent into washing pool after concentrating;
C. washing: the isolated filter cake of above process is washed with de-salted water in washing pool, the ratio of de-salted water and filter cake is more than 1: 1, wash temperature is 30 ℃～50 ℃, washed 10～20 minutes, carry out the suction filtration first time, filter cake behind the suction filtration is added water carry out secondary washing, carry out the suction filtration second time afterwards, generate the terephthalic acid solid wet cake and deliver to moisture eliminator;
D. with the terephthalic acid solid wet cake of above generation below room temperature to 121 ℃ dry 20～40 minutes, obtain the terephthalic acid solid finished product.
2. the separating and purifying method of terephthaldehyde's acid waste products according to claim 1 is characterized in that the filtering net that suction filtration is used is 200～500 purpose terylene filter clothes.
3. the separating and purifying method of terephthaldehyde's acid waste products according to claim 1 and 2 is characterized in that taking the pressure reduction suction filtration, and the negative pressure of suction filtration is 200～500mmH
2The O post.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01113738 CN1126730C (en) | 2001-06-29 | 2001-06-29 | Process for separating terephthalic acid from its waste and purifying it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01113738 CN1126730C (en) | 2001-06-29 | 2001-06-29 | Process for separating terephthalic acid from its waste and purifying it |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1338451A CN1338451A (en) | 2002-03-06 |
| CN1126730C true CN1126730C (en) | 2003-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 01113738 Expired - Fee Related CN1126730C (en) | 2001-06-29 | 2001-06-29 | Process for separating terephthalic acid from its waste and purifying it |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104649897A (en) * | 2015-03-03 | 2015-05-27 | 常州市博洋新材料科技有限公司 | Method for purifying terephthalic acid from terephthalic acid residues |
| CN104829030B (en) * | 2015-05-12 | 2016-10-19 | 苏州苏净环保工程有限公司 | Containing para-phthalic sodium and the process of the waste water of 1,4-butanediol and recovery method |
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