CN104692571A - Comprehensive utilization method for phosphate flame retardant wastewater - Google Patents
Comprehensive utilization method for phosphate flame retardant wastewater Download PDFInfo
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Abstract
The invention relates to a method for treating phosphate flame retardant wastewater and particularly relates to a comprehensive phosphate flame retardant wastewater utilization method integrating energy-saving rectification-evaporation, oriented conversion and other technologies. The method specifically comprises the following steps: (1) effectively separating wastewater components by adopting a rectification-evaporation technology; (2) converting high-concentration phosphate waste liquor into polyphosphates by adopting an oriented conversion technology, and purifying to obtain the industrial grade polyphosphate product, so that the harmless problem of the phosphate waste liquor is solved; (3) using the water obtained by rectification to produce phosphate flame retardant products, and recycling the water; (4) converting inorganic salt solid wastes into recyclable industrial products by virtue of a fractionation and purification method, so that the discharge problem of the inorganic salt solid wastes is solved; and (5) taking the product as fuel in an oriented conversion process in the basis of the characteristic that the rectified low-boiling-point compound is high in heating value. Therefore, the discharge problem is solved, the energy can be saved, and the wastewater treatment cost is reduced.
Description
Technical field
The present invention relates to a kind for the treatment of process of phosphate flame retardant waste water, be specifically related to the phosphoric acid ester wastewater utilization method of the technology such as the rectifying-evaporation of a kind of integrated energy-saving, directed conversion, this technology belongs to field of Environment Protection.
Background technology
Fire retardant is the important auxiliary agent of synthesized polymer material, is the second largest additives for plastics being only second to softening agent at present, has wide market application foreground.Phosphate ester flame retardants is the important branch of flame retardant area, it is lasting that it has flame retardant effect, the distinguishing features such as good with polymeric matrix compatible, water-fast, weather-proof, heat-resisting and resistance to migration, have become one of most important, most widely used fire retardant kind at present.In addition, phosphate flame retardant mostly has the feature such as low cigarette, nontoxic, low halogen (or Halogen), meets the developing direction of fire retardant, thus has good development prospect.
There is a large amount of waste water to produce in phosphate flame retardant production process, for TCPP, TCEP and TDCPP, often obtain 1 ton of product by the factory effluent of generation 1 ~ 5 ton of phosphate ester-containing fire retardant.Phosphoric acid ester waste water is mainly derived from the process such as decomposition and product washing, distillation of catalyzer in fire retardant production process.Lewis acid (Aluminum chloride anhydrous, Magnesium Chloride Anhydrous or titanium tetrachloride etc.) is generally used to make catalyzer in phosphate flame retardant synthesis, need by operations such as alkaline hydrolysis (or acidolysis), washing separation after end of synthesis, catalyzer is separated from product, to improve product purity.In addition, in phosphate flame retardant waste water except phosphate ester-containing flame retardant constituent, also containing compositions such as complete raw material, inorganic salt and the catalyzer of the phosphoric acid ester by product produced in reaction process, unreacted.In general phosphate flame retardant waste water, TP is up to more than 1000mg/L, COD
crmore than 10000mg/L, also containing a certain amount of an alkali metal salt, in environment-protection wastewater process, belong to one of phosphorus-containing wastewater of high difficult degradation.
Domestic research in phosphate flame retardant wastewater processing technology is less at present.Mostly the phosphoric acid ester wastewater processing technology that domestic phosphate flame retardant enterprise adopts in producing is to utilize general wastewater processing technology: i.e. initial oxidation, flocculation sediment dephosphorization, then carry out biochemical treatment after mixing with other waste water, but all do not solve the qualified discharge problem of waste water completely.The patent No. is that the patent of CN101979347A provides a kind of method processing phosphotriester flame retardant wastewater: phosphoric acid ester waste water is adjusted to pH=4 ~ 6 by first acid adding, then hydrogen peroxide is added, oxidizing reaction is carried out under surface catalyst exists, next carries out the operation such as biochemistry, flocculating settling dephosphorization, last qualified discharge.The method is the numerous length of technical process not only, can produce a large amount of phosphorous solid wastes simultaneously, and this method for oxidation is not suitable for high density, wastewater treatment containing the phosphate flame retardant of rock steady structure, is difficult to thoroughly realize qualified discharge problem.The patent No. is the treatment process that CN101704606A discloses a kind of organism P wastewater: first organism P wastewater acid adding is regulated pH=3 ~ 4, add hydrogen peroxide and carry out catalyzed oxidation, then enter micro-electrolysis device to be oxidized further, water outlet again through multistage hydrogen peroxide oxidation, last flocculating settling dephosphorization.The method still adopts oxidation technology, tries hard to organophosphorus to be converted into inorganic phosphorus, then utilizes flocculating settling to be separated by the phosphorus in waste water, thus reach the object of dephosphorization, but technical process is complicated, need repeatedly be oxidized, create a large amount of phosphorous solid wastes equally, cause new pollution." chemical industry environmental protection " proposes " liquid film extraction-acid out sedimentation-complexometric extraction " combination process process organophosphorous fire retardant waste water, waste water COD in interim " research of organophosphate factory effluent pretreatment technology " literary composition in 2012 the 01st
cr, TP clearance can reach 93% and 97% respectively.But this technical matters is complicated, and will use a large amount of solvents and acid solution, easily produce new pollution, processing cost is high, is unfavorable for industrialization.Sichuan University 2005 master thesis " process of flame retardants wastewater and recycling " have studied Fenton process flame retardants wastewater, first the organism in waste water is degraded, then reclaim the aluminum ion in waste water, be made into flocculation agent aluminium chloride ferrum.The method can organism effectively in degrading waste water and reduce colourity, and can reclaim the aluminium element in waste water, has certain using value.But the method is to the flame retardants wastewater containing phosphoric acid ester material, Fenton reagent oxidation effectiveness is not good, and because of the concentration of metal catalyst low, reclaim difficulty and uneconomical, thus its range of application is subject to larger restriction.Propose to adopt the methods such as neutralization, distillation, extraction to carry out treatment research to Acidic flame-retardant agent waste water in " University Of Qingdao's journal (natural science edition) " 02 phase in 2002 " analyzing and processing containing a hydrochloric acid and organic monoacid waste water " literary composition, energy recovery part fire retardant, but this technology energy consumption is high, the rate of recovery is low, and in treating processes, also have new refuse to produce, economy is poor, thoroughly can not solve the problem of outlet of flame retardants wastewater.Wuhan Textile University master thesis " UV/H in 2013
2o
2the research of process two kinds of haloalkyl phosphorus ester simulated wastewaters " in propose and a kind of adopt UV/H
2o
2oxidation style degraded is containing the treatment process of TCEP, TDCP flame retardants wastewater, when pH=7, in waste water, the clearance of TOC can reach 79%, but under the result of gained is only limitted to emulation mode, because real phosphate flame retardant waste water contains other organism and inorganic salt, the degradation effect of phosphoric acid ester can be caused poorer, thus be difficult to the problem of outlet thoroughly solving phosphoric acid ester waste water.
A large amount of experimental studies shows, the organic phosphoric acid ester structure in phosphoric acid ester waste water is very stable, and common method for oxidation is difficult to destroy its structure, is naturally also just difficult to by mode dephosphorization and degradation of organic substances such as flocculation, sedimentations.
In existing phosphate flame retardant method of wastewater treatment, basic ideas are: the structure first being destroyed phosphoric acid ester by means such as oxidations, is translated into inorganic phosphorus, and then goes phosphorus ligands in throw out mode, finally carry out biochemical treatment, qualified discharge.But because phosphoric acid ester has good stability, general method for oxidation is difficult to the structure destroying phosphoric acid ester; And adopt the high-level oxidation technologies such as the Wet Catalytic Oxidation Method of High Temperature High Pressure, even if possible in theory, processing cost is inevitable high, is difficult to realize industrialization.
Along with the demand of market to environmental protection fire retarding agent constantly increases, the market requirement of phosphate flame retardant will be increasing, and China has become phosphate flame retardant big producing country main in the world at present, and the process problem of phosphoric acid ester waste water is also more and more outstanding.Meanwhile, because phosphor resource belongs to valuable Nonrenewable resources, therefore in use comprehensive utilization must be carried out, to save phosphate rock resource as much as possible.Visible, be necessary to develop a kind of efficient, general wastewater processing technology, fundamentally solve the problem of outlet of China's phosphate flame retardant waste water, thus realize the cleanly production of China's phosphate flame retardant industry, be conducive to the health of China's fire retardant industry, Sustainable development.
Summary of the invention
Main purpose of the present invention is exactly solve the deficiency existed in current China phosphate flame retardant wastewater processing technology, based on phosphoric acid ester factory effluent recycling, phosphoric acid ester waste water is converted into the resource of recoverable, thus fundamentally solves a cleanly production difficult problem for China's phosphate flame retardant product.
The invention provides a kind of organic phosphate flame-retardant agent production waste water integrated conduct method, it is characterized in that comprising the steps:
1) entering coupling rectification tower by preparing after phosphate flame retardant generation waste water passes into preheater preheats, controlling bottom temperature 110 DEG C-135 DEG C, collecting tower bottoms continuously;
2) tower bottoms is through insulation centrifugation, filters, obtains white square crystal and filtrate;
3) step 2) middle filtrate decrease temperature crystalline, separating catalyst oxide solid and filtrate;
4) step 3) in filtrate continue in phosphoric acid or liquid caustic soda regulator solution sodium phosphonium ion molar ratio be 1.2-1.6, after sparger atomization, in directed conversion reactor, control temperature 250 DEG C-850 DEG C, reactive polymeric is 15min at least, obtains poly-phosphate crude product.
Above-mentioned steps 2) in the white crystal that obtains of tower bottoms centrifugation be sodium chloride crystal; And rate-determining steps 3) in decrease temperature crystalline temperature be 20-50 DEG C, isolate and obtain catalyst oxidation produce product containing catalyst oxidation thing solid is purified, further can by catalyst oxidation thing and acid-respons, purification, obtain the required catalyzer of phosphoric acid ester synthesis, be recycling in phosphate flame retardant and produce.Described catalyzer comprises one or more mixing in the Lewis acid alkaline metal salts such as magnesium chloride, zinc chloride, titanium tetrachloride, aluminum chloride.
Step 4) described in directed conversion reactor to be selected from the reactors such as fixed bed, fluidized-bed, ebullated bed, agitated bed, rotary kiln the combination of one or more devices, preferred fluidized-bed or ebullated bed.
Described step 1 can be controlled further in the present invention) in the tower middle portion temperature of rectifying tower be 90 DEG C-105 DEG C, tower top temperature is less than 90 DEG C, and collects tower side and overhead product continuously.Collect tower side product be high-purity soft water, can direct reuse to phosphate flame retardant production process.The overhead product collected is mainly containing hydrocarbon small molecular organic compounds, available step 4) in the fuel of directed conversion reaction.
The present invention is achieved in the following ways: (1) coupling rectification.Phosphoric acid ester waste water is pumped into preheater preheats, then enters coupling rectification tower, according to the boiling point difference of component each in waste water, collect product continuously from tower bottom of rectifying tower, side line, top respectively.Wherein, tower reactor still liquid, after insulation centrifugation, obtains the crystal of main sodium chloride-containing, and then after cooling, crystallization, carries out centrifugation, obtain the oxide product of catalyzer after the solid product obtained is purified; Or continue with acid-respons, purification, obtain phosphoric acid ester synthesize needed for catalyzer, carry out catalyst recirculation; Filtrate goes follow-up directed conversion processing.What rectifying tower lateral line discharging obtained is high-purity soft water, directly can be used as the process water that phosphate flame retardant is produced.Overhead collection to mainly containing oxyethane, propylene oxide, epoxy chloropropane and ethanol etc. containing lowly boiling, the small molecules hydrocarbon polymer of high heat energy, directly can be used as the fuel of follow-up directed conversion procedure.(2) directed conversion.The filtrate of tower bottom of rectifying tower gained is after phosphoric acid, liquid caustic soda etc. regulate, after sparger atomization, react rapidly under the condition such as high temperature of directed conversion reactor, be polymerized, obtain poly-phosphate crude product, more purified after obtain poly-phosphate product or the phosphate product of technical grade.(3) recycle.What rectifying tower lateral line discharging obtained is high-purity soft water, can direct cycle to phosphate flame retardant production process, as process waters such as product washings.What rectifying tower tower top obtained mainly contains hydrocarbon small molecular organic compounds, and calorific value is high, is directly used in the fuel of directed conversion reaction.
For thinking of the present invention is described better, below with reference to foregoing, the core contents of the present invention such as rectifying, directed conversion are described:
(1) coupling rectification.As everybody knows, rectifying realizes according to the difference of boiling point, but seldom adopts in the treatment of waste water.The boiling point significant difference of each main component in phosphate flame retardant waste water: phosphate ester element boiling point is higher than 110 DEG C, and the boiling point of the small molecules such as propylene oxide, oxyethane hydrocarbon polymer is no more than 90 DEG C, for rectifying separation provides convenient.Consider Cost Problems, the present invention adopts the conservation measures such as preheater, heat pump and equipment, organically combines with rectifying tower, has given full play to the characteristics of energy saving of heat pump, has solved the Cost Problems of rectifying.Especially, for preventing in rectifying-evaporative process, causing structure or the blocking of interchanger because solid in still liquid is separated out, devising the device of self-timing cleaning heat transfer tube, ensure that interchanger can normally work.
(2) directed conversion.The directed core transformed comprises two aspects: one, suitable feed composition; Two, suitable reaction (polymerization) temperature and reaction times.In the filtrate of the main phosphate ester-containing compound that tower bottom of rectifying tower obtains, phosphorus content is high, but cannot obtain poly-phosphate product by direct reaction, must add phosphoric acid or liquid caustic soda etc. and regulate it.Filtrate after regulating after atomization efficiently, and then need enter directed conversion reactor, to improve the contact area of material, shortens the material residence time in the reactor.The major function of directed conversion reactor is to provide following condition: the temperature of reaction that (1) is higher.Guarantee reconfiguring between the decomposition of phosphate compound and each element.(2) the suitable residence time.Guarantee that the material in reactor can react completely.(3) suitable discharge method.Material after reaction terminates becomes block or sheet, as discharge method is improper, likely causes accumulation of material and blocks discharge port.The dischargers such as conventional track type or rake can play good treatment effect.
Main contents of the present invention: (1), according to the composition of phosphate flame retardant waste water, can be divided into the high boiling compound (as TCPP, TCEP, TDCPP, BDP, RDP, XDP etc.) of phosphate ester-containing structure, containing organic micromolecular low-boiler (as oxyethane, propylene oxide, epoxy chloropropane, low grade aldehyde, alcohol) water and inorganic salt (or oxide compound) four part; (2) utilize heat pump-rectifying coupling technique, each main ingredient in phosphate flame retardant waste water is separated, is easy to subsequent disposal or comprehensive utilization; (3) utilize the technology such as directed conversion, the high boiling compound of phosphate ester-containing is converted into poly-phosphate runic, then carry out purifying and obtain the poly-phosphate product of technical grade; (4) the low organism that boils is used as the fuel of directed conversion reaction, not only thoroughly solves the innoxious problem of this part regenerant, and the energy consumption of directed conversion procedure can be reduced; (5) water separated through rectifying-evaporation is produced for phosphate ester product; (6) reclaim oxide compound or the hydroxide product that the inorganic salt (oxide compound) obtained can obtain synthetic catalyst respectively after substep is purified, or deep processing obtains original catalyst further, carries out recycle.
The problem that the present invention mainly solves is: (1), by adopting rectifying-evaporation technique, realizes effective separation of each component in phosphoric acid ester waste water; (2) by adopting the power-saving technologies such as heat pump, solving the energy consumption problem of rectification working process, significantly reducing cost for wastewater treatment; (3) adopt directed transformation technology, the phosphoric acid ester waste liquid of high density is converted into poly-phosphate, then by the poly-phosphate product obtaining technical grade of purifying, solve an innoxious difficult problem for phosphoric acid ester waste liquid, and the resource utilization realizing phosphoric is recycled; (4) water that rectifying obtains is used for phosphate flame retardant products production, realizes the recycle of water; (5) by the method that fractional separation is purified, inorganic salt solid waste is converted into the technical grade product that resourcebility utilizes, solves the problem of outlet of inorganic salt solid waste; (6) utilize the feature that rectifying low-boiler calorific value is high, used as the fuel of directed conversion procedure, not only solve its problem of outlet, also can save energy, reduce cost for wastewater treatment.By with upper type, this technique achieves the recycling of phosphate flame retardant waste water, without new " three wastes " discharge, thoroughly solve the problem of outlet of phosphate flame retardant waste water, significant to the cleaner production promoting China's phosphate flame retardant industry.
Embodiment
Embodiment 1:
Get TCPP factory effluent 10kg, by analysis: TP=1500mg/L, COD
cr=10200mg/L, TCPP%≤1%, moisture content 94.5%, pH=7.5, appearance colorless is transparent.
After this waste water is pumped into preheater preheats, enter sieve plate distillation column, charging from tower, carry out continuous rectification, collect tower top, tower side sample respectively, when bottom temperature rises to 125 DEG C, stop heating.Still liquid pours out rear rapid filtration, obtains white square crystal; Still liquid continue cooling, crystallization, filtration, the white solid obtained through washing, oven dry after, in white powder.Filtrate regulates with 85% phosphoric acid, 40% liquid caustic soda, then enters directed conversion reactor, and 600 DEG C of reactions after 2 hours, cooling, obtains white loose solid, after recrystallization, oven dry, obtains lenticular pyrophosphate salt.By analysis, tower top is mainly the small molecules alkane derivatives such as propylene oxide, and calorific value is 20000kJ/kg; Tower sides stream COD
cr=85mg/L, TP=0.6mg/L, colorless and odorless; White powdery solids oxide content is 98%; Pyrophosphate salt content is 97%; In white square crystal, sodium chloride content is 98%.Embodiment 2:
Get TCEP phosphoric acid ester waste water 10kg, by analysis: TP=1400mg/l, COD
cr=11000mg/l, TCEP%≤1.5%, moisture content 95.1%, pH=8.1, appearance colorless is transparent, and ester taste is heavier.
After this waste water is pumped into preheater preheats, send into sieve plate distillation column, charging from tower, continuous rectification, collects tower top, tower side sample respectively, when bottom temperature rises to 120 DEG C, stops heating.Still liquid pours out filtered while hot, obtains white square crystal; Filtrate carrying out cools, crystallization, filtration, the solid obtained through washing, dry after, in white powder.Filtrate regulates with acid, alkali, then enters directed conversion reactor, and 650 DEG C of reactions after 1.5 hours, cooling, obtains white flaky solid, after recrystallization, oven dry, obtains lenticular pyrophosphate salt.By analysis, tower top is mainly the small molecules alkane derivatives such as oxyethane, and calorific value is 18000kJ/kg; Cut COD in tower
cr=70mg/L, TP=0.5mg/L, colorless and odorless; White powdery solids oxide content is 98.2%; Pyrophosphate salt content is 96.5%; In white square crystal, sodium chloride content is 98.5%.
Embodiment 3:
Get TDCPP phosphoric acid ester waste water 10kg, by analysis: TP=1600mg/l, COD
cr=10000mg/l, TDCPP%≤0.8%, moisture content 95.5%, pH=7.4, appearance colorless is transparent, and ester taste is heavier.
After this waste water is pumped into preheater preheats, send into stuffing rectification column, charging from tower, carries out continuous rectification, collects tower top, tower side sample respectively, when bottom temperature rises to 128 DEG C, stops heating.Still liquid pours out filtered while hot, obtains white square crystal; Filtrate cooling, crystallization, filtration, solid through washing, dry after, in white powdery solids.Filtrate regulates with acid, alkali, then enters directed conversion reactor, and 850 DEG C of reactions after 2 hours, cooling, obtains white glass-solid, after crushed, obtain hexametaphosphate.By analysis, tower top is mainly the small molecules alkane derivatives such as epoxy chloropropane, and calorific value is 16500kJ/kg; Cut COD in tower
cr=55mg/L, TP=0.7mg/L, colorless and odorless; White powdery solids oxide content is 95.5%; Hexa metaphosphoric acid salts contg is 69% (P
2o
5).
Embodiment 4:
Get BDP phosphoric acid ester waste water 10kg, by analysis: TP=1500mg/L, COD
cr=14000mg/L, moisture content 94.0%, pH8.5, appearance colorless is transparent.
After this waste water is pumped into preheater preheats, send into stuffing rectification column, charging from tower, carries out continuous rectification, collects sample in tower top, tower respectively, when bottom temperature rises to 120 DEG C, stops heating.Still liquid is poured out while hot, obtains white square crystal; Filtrate through cooling, crystallization, filtration, the solid obtained through washing, dry after, in white powdery solids.Filtrate regulates with acid, alkali, then enters directed conversion reactor, and 450 DEG C of reactions after 3 hours, cooling, obtains white loose solid, after recrystallization, oven dry, obtains white powder tri-polyphosphate.By analysis, overhead distillate 8000kJ/kg; Cut COD in tower
cr40mg/L, TP0.4mg/L, colorless and odorless; White powdery solids oxide content is 98.3%; Tripolyphosphate salts contg is 92.0%; White square crystalline content is 97.5%.
Embodiment 5:
Get RDP phosphoric acid ester waste water 10kg, by analysis: TP=1700mg/l, COD
cr=18000mg/l, moisture content 96%, pH=7.1, appearance colorless is transparent.
After this waste water is pumped into preheater preheats, enter stuffing rectification column, charging from tower, carry out continuous rectification, collect tower top, tower side sample respectively, when bottom temperature rises to 135 DEG C, stop heating.Still liquid is poured out, filtered while hot, obtains white square crystal; Filtrate through cooling, crystallization, filtration, the solid obtained through washing, dry after, in white powdery solids.Filtrate regulates with acid, alkali, then enters directed conversion reactor, and 500 DEG C of reactions after 3.5 hours, cooling, obtains white loose solid, after recrystallization, after oven dry, obtains white powder tri-polyphosphate.By analysis, tower top low-boiling-point substance calorific value is 7500kJ/kg; Cut COD in tower
cr=45mg/L, TP=0.5mg/L, colorless and odorless; White powdery solids oxide content is 98.5%; Tripolyphosphate salts contg is 93.5%; White square crystallization sodium chloride content is 97.2%.
Embodiment 6:
The white powdery solids of Example 1-5 gained mixes, sampling analysis, and oxide samples content is 98.2%.Added by solid in dehydrated alcohol, pass into hydrogen chloride gas and fully react, distillation, obtains anhydrous photocatalyst crystals.By analysis, catalyst sample content is 99.2%.
Embodiment 7:
Example 6 gained catalyst sample 1.2g, add and be equipped with in the four-hole boiling flask of phosphorus oxychloride, slowly drip propylene oxide, control temperature of reaction and be no more than 70 DEG C, reaction 15h, then add sheet alkali and be neutralized to Ph=7.5, then add pure water to neutral, layering, upper strata is suspended matter-containing wastewater, upper strata is TCPP crude product, after underpressure distillation dehydration, obtains colourless transparent liquid.Sampling analysis, phosphorus content 9.5%, cl content 32.6%, acid number (mgKOH/g) 0.06%, meets TCPP product standard.
Claims (10)
1. an organic phosphate flame-retardant agent production waste water integrated conduct method, is characterized in that comprising the steps:
1) entering coupling rectification tower by preparing after phosphate flame retardant generation waste water passes into preheater preheats, controlling bottom temperature 110 DEG C-135 DEG C, collecting tower bottoms continuously;
2) tower bottoms is through insulation centrifugation, filters, obtains white square crystal and filtrate;
3) step 2) middle filtrate decrease temperature crystalline, separating catalyst oxide solid and filtrate;
4) step 3) in filtrate continue in phosphoric acid or liquid caustic soda regulator solution sodium phosphonium ion molar ratio be 1.2-1.6, after sparger atomization, in directed conversion reactor, control temperature 250 DEG C-850 DEG C, reactive polymeric is 15min at least, obtains poly-phosphate crude product.
2. method as claimed in claim 1, is characterized in that step 2) in the white square crystal that obtains of still liquid centrifugation be sodium chloride crystal.
3. method as claimed in claim 1, is characterized in that step 3) in decrease temperature crystalline, control temperature is to 20-50 DEG C.
4. method as claimed in claim 1, it is characterized in that step 3) described in be separated after containing catalyst oxidation thing solid purified catalyst oxidation produce product, or with acid-respons, purification, obtain the required catalyzer of phosphoric acid ester synthesis, be recycling in phosphate flame retardant and produce.
5. method as described in as arbitrary in claim 1-4, is characterized in that described catalyzer is one or more mixing in the Lewis acid alkaline metal salts such as magnesium chloride, zinc chloride, titanium tetrachloride, aluminum chloride.
6. method as claimed in claim 1, is characterized in that step 4) described in directed conversion reactor be selected from one or more devices combination in the reactors such as fixed bed, fluidized-bed, ebullated bed, agitated bed, rotary kiln, preferred fluidized-bed or ebullated bed.
7. method as claimed in claim 1, it is characterized in that the further control tower middle portion temperature of described rectifying tower 90 DEG C-105 DEG C, tower top temperature is less than 90 DEG C, collects tower side and overhead product continuously.
8. method as claimed in claim 7, is characterized in that the tower side product collected is high-purity soft water, can direct reuse to phosphate flame retardant production process.
9. method as claimed in claim 7, is characterized in that the overhead product collected is mainly containing hydrocarbon small molecular organic compounds, can be used as step 4 described in claim 1) in the fuel of directed conversion reaction.
10. method as claimed in claim 1, is characterized in that step 4) in gained poly-phosphate crude product can refine purification further and obtain technical grade poly-phosphate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310689337.3A CN104692571B (en) | 2013-12-06 | A kind of method of comprehensive utilization of phosphate flame retardant waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310689337.3A CN104692571B (en) | 2013-12-06 | A kind of method of comprehensive utilization of phosphate flame retardant waste water |
Publications (2)
| Publication Number | Publication Date |
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| CN104692571A true CN104692571A (en) | 2015-06-10 |
| CN104692571B CN104692571B (en) | 2016-11-30 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540915A (en) * | 2015-12-11 | 2016-05-04 | 浙江奇彩环境科技股份有限公司 | Recycling treatment method for phosphate ester fire retardant waste water |
| CN106336059A (en) * | 2016-10-19 | 2017-01-18 | 泰州新安阻燃材料有限公司 | Method for treating wastewater of phosphate fire retardant production process |
| CN108975585A (en) * | 2018-06-22 | 2018-12-11 | 杭州深瑞水务有限公司 | A kind of method of recycling treatment phosphor-containing flame-proof agent production waste water |
| CN110550795A (en) * | 2018-05-30 | 2019-12-10 | 杭州九清科技有限公司 | Process for recovering phenol from phosphorus flame retardant production wastewater |
| CN110937727A (en) * | 2019-12-26 | 2020-03-31 | 河南省科学院化学研究所有限公司 | PROBAN flame-retardant wastewater treatment method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540915A (en) * | 2015-12-11 | 2016-05-04 | 浙江奇彩环境科技股份有限公司 | Recycling treatment method for phosphate ester fire retardant waste water |
| CN105540915B (en) * | 2015-12-11 | 2018-04-27 | 浙江奇彩环境科技股份有限公司 | A kind of recycling processing method of phosphate flame retardant waste water |
| CN106336059A (en) * | 2016-10-19 | 2017-01-18 | 泰州新安阻燃材料有限公司 | Method for treating wastewater of phosphate fire retardant production process |
| CN106336059B (en) * | 2016-10-19 | 2019-06-14 | 泰州瑞世特新材料有限公司 | The processing method of organic phosphate flame-retardant agent producing process waste water |
| CN110550795A (en) * | 2018-05-30 | 2019-12-10 | 杭州九清科技有限公司 | Process for recovering phenol from phosphorus flame retardant production wastewater |
| CN108975585A (en) * | 2018-06-22 | 2018-12-11 | 杭州深瑞水务有限公司 | A kind of method of recycling treatment phosphor-containing flame-proof agent production waste water |
| CN110937727A (en) * | 2019-12-26 | 2020-03-31 | 河南省科学院化学研究所有限公司 | PROBAN flame-retardant wastewater treatment method |
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