CN103708572B - Resourceful treatment method for inorganic salts in industrial waste water - Google Patents
Resourceful treatment method for inorganic salts in industrial waste water Download PDFInfo
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Abstract
The invention discloses a resourceful treatment method for inorganic salts in industrial waste water. The method comprises the following steps: evaporating and concentrating waste water to obtain solid salts; carrying out thermal cracking on organic substances in the solid salts into organic gas; introducing the organic gas obtained by thermal cracking into a burning device for full burning, quickly cooling produced tail gas, and exhausting the cooled tail gas; further purifying the thermally-cracked solid salts via high-temperature carbonization to obtain high-purity solid salts, and introducing gas produced by carbonization into the burning device for full burning. According to the method, the flow is simple, the process is mature, industrial utilization is facilitated, and the methd can be applied to treatment of pesticides and even other industrial high-salt waste water. By adopting the method, the purity of the inorganic salts is increased, so that the inorganic salts can be reused. Secondary wastes which are difficult to treat are not produced in a production process, so that waste of resources is reduced, environmental pollution caused by the waste water is lowered, and very good economical and social benefits are achieved.
Description
Technical field
The present invention relates to the recycling processing method of inorganic salt in a kind of trade effluent, particularly relate to the recycling processing method of inorganic salt in a kind of agricultural chemicals high-salt wastewater.
Technical background
Numerous organic or inorganic Chemicals are in its production process, technique tends to because need to produce a large amount of brine wastes, sodium chloride content is wherein higher than 1%, many more than 10%, some even reaches more than 20%, for high-salt wastewater, the high-salt wastewater at present treatment process of maturation mostly is evaporation, will produce so a large amount of by-product abraum salts (NaCl).The sodium chloride content of this salt, more than 70%, contains a large amount of organic or inorganic impurity simultaneously, can not directly be used as industrial raw material salt, more can not be used for ediblely or medical, and most of producer stores away its heap.This salt is stored up not only a large amount of occupied grounds for a long time, and also to environment structure grave danger, salt and impurity very easily run off, and salinization surrounding soil jeopardizes vegetation around, simultaneously to around rivers, water source, rice field etc. pollute.
In some inorganic and organic products production processes, also produce a large amount of high-salt wastewaters, ripe processing mode is also to go out solid salt by evaporation concentration, can not be utilized effectively equally.Therefore, utilize suitable technology and equipment, recycle this high-salt wastewater, for an enterprise, there is far-reaching influence and social benefit.
At present, treatment technology for salt in trade effluent is disclosed less, applicant has applied for the patent of invention that " extracting method of inorganic salt and the resource utilization method of trade effluent in a kind of trade effluent " by name, application number are 201310184084.4, this patent discloses the extracting method of inorganic salt in a kind of trade effluent, step is: by trade effluent evaporation concentration, obtain solid inorganic salt, solid inorganic salt is contacted with oxygen-containing gas at the temperature that is less than or equal to 1000 DEG C, and carbonization obtains high purity inorganic salt.This invention flow process is simple, the high purity that has realized inorganic salt in saliferous trade effluent, especially high salt industrial waste water reclaims, gained inorganic salt can re-use, the wasting of resources and the destruction to environment are avoided, solve to a certain extent a processing difficult problem for high salt industrial waste water, but still there is certain deficiency in this method, in inorganic salt purge process, in high temperature cabonization process, can produce and have these toxic gases of poison gas (such as dioxin etc.) well not process, enter in air and can cause environmental pollution.
Summary of the invention
For above-mentioned deficiency, the invention provides the recycling processing method of inorganic salt in a kind of trade effluent, the method can well be removed the inorganic salt in waste water especially high-salt wastewater, and discharge without poisonous fume in whole process, obtaining highly purified inorganic salt can resource utilization recycle, and meets green, environmental requirement.
The present invention adopts waste water evaporation concentration desalination, and---the high exhaust temperatures after-flame that thermo-cracking (organic substance decomposing is low hydrocarbon thing)---carbonization---produces, the operational path of chilling discharge are processed the inorganic salt in waste water.Objectionable impurities in thorough innoxious waste gas, use thermo-cracking and carbonizing treatment industrial waste salt, organism in salt thoroughly can be removed, and by the high temperature after-flame of waste gas and the treatment technology of chilling, can farthest reduce and burn mephitical generation in organism process, objectionable impurities in the gas that makes to produce is thoroughly innoxious, has reduced environmental pollution.
Concrete technical scheme of the present invention is as follows:
A recycling processing method for inorganic salt in trade effluent, is characterized in that comprising the following steps:
(1) trade effluent is carried out to evaporation concentration, obtain solid salt;
(2) gained solid salt is added to thermal cracker, making the organic substance thermo-cracking in solid salt is organic gas;
(3) organic gas of thermo-cracking gained enters combustion unit and fully burns, and after gained tail gas quenching, discharges;
(4) solid salt after thermo-cracking enters carbonizing plant, by high temperature cabonization, solid salt is further purified, and obtains high-purity solid salt, and the gas that carbonization produces also enters combustion unit and fully burns.
The inventive method is for saliferous trade effluent, and especially pesticide wastewater proposes, and its key is that the salt high purity in waste water is reclaimed, and ensures removal process non-environmental-pollution.The trade effluent of indication of the present invention can be all trade effluents containing inorganic salt, can be also the waste water that above-mentioned waste water obtains after certain processing, and that described processing comprises is concentrated, regulate the operations such as composition, rectifying such as pH, separate raw materials solvent by product.Present method can be both the direct treatment process of saliferous trade effluent, also can be a part for saliferous During Industrial Wastewater Treatment Process, for waste water is comprehensively processed, present method can be combined with other method of wastewater treatment, waste water first can be carried out after other recyclable compositions are removed in pre-treatment enabling again present method, after also can adopting the present invention to remove to desalt, enable again additive method residue waste water is processed.
The factory effluent of the triazine herbicide producing in the preferred pesticide producing process of waste water of the present invention, factory effluent, the organic phosphates weedicide factory effluent etc. of phenoxy carboxylic acid herbicides.Described triazine herbicide waste water is the waste water that directly produces in the production process of terbuthylazine, terbutryn, cyanazine, cyanatryn, atrazine, ametryn, propazine, prometryn, simazine, simetryn, piperazine humulone or hexazinone or waste water after treatment; The factory effluent of described phenoxy carboxylic acid herbicides includes but not limited to 2,4-drips, 2 first 4 chlorine, 2,4-d butyl ester, 2,4-drips different monooctyl ester, cover grass energy (haloxyfop), haloxyfop-r-methyl (haloxyfop-r-methyl), Vi par, Thistrol, 2,4-drips the waste water that propionic acid or 2,4-Embutox directly produce in process of production or carries out waste water after treatment; Described organophosphorus insecticide waste water comprises that in process of preparing glyphosate by glycine method, adding alkali reclaims the mother liquor producing in glyphosate alkaline mother liquor after triethylamine, the intermediate pmida98 preparation process of IDA legal system for the mother liquor producing in glyphosate process or glyphosate.The processing of waste water is included but not limited to concentrate, regulates the operation such as composition, rectifying such as pH, separate raw materials solvent by product.
In above-mentioned recycling processing method, thermo-cracking is carried out under oxygen free condition, and thermo-cracking temperature is 350-550 DEG C.The thermo-cracking time is 5-60min, generally can complete in 5-10min thermo-cracking.Time lengthening does not have much affect to result.
In above-mentioned recycling processing method, carbonization is carried out under the existence of oxygen-containing gas, and oxygen-containing gas is one or more in air, oxygen-rich air and oxygen.Carbonization is carried out at the temperature of 650-750 DEG C.Carbonization time is 10-60min, generally can complete in 10-15min carbonization.Time lengthening does not have much affect to result.
In above-mentioned recycling processing method, the gas of thermo-cracking and the carbonization gained 2-5s that burns at 900-1100 DEG C, discharge after burning gained tail gas quenching to 200 is DEG C following.
In above-mentioned recycling processing method, the method for waste water evaporation concentration is single-effect evaporation, multiple-effect evaporation or MVR evaporation.
In above-mentioned recycling processing method, thermal cracker is tubular type pyrolysis reactor, rotary kiln pyrolysis reactor, bubbling fluidization bed bioreactor, circle transmission bed bioreactor, circulating fluid bed reactor, ablation reactor, rotating cone reactor or vacuum moving-burden bed reactor.
In above-mentioned recycling processing method, carbonizing plant is selected from rotary kiln, vertical incinerator, horizontal incinerator, box-type furnace, fluidizing furnace, grate incinerator or fluidized bed incinerator, preferably rotary kiln.
In above-mentioned recycling processing method, combustion unit is the disclosed roasting kiln for organic gas burning in existing field, for example in waste incineration for the treatment of the dual firing chamber of flue gas.
In above-mentioned recycling processing method, the inorganic salt purity after carbonization is more than 99%.
In above-mentioned recycling processing method, the high purity inorganic salt water wiring solution-forming obtaining, can be as ionogen or for other field.For example, when described inorganic salt are sodium-chlor, gained sodium chloride solution can, for chlorine industry, be preferably ionic membrane caustic soda.
In above-mentioned recycling processing method, when phosphorous in described waste water, for example organic phosphates weedicide factory effluent, in gained high purity inorganic salt, contain trace amounts of phosphorus, the solution being made into need first adopt method of the prior art, the methods such as such as nanofiltration membrane filtration or chemical reagent precipitation are removed after the trace amounts of phosphorus containing, then as ionogen or for other field.
Flow process of the present invention is simple, and technical maturity is applicable to industrialized utilization, can be for agricultural chemicals, the even processing of other industry high-salt wastewater.The present invention first carries out high temperature pyrolysis to the inorganic salt that extract in waste water, carry out again high temperature cabonization, remove a small amount of organic substance wherein containing, improve the purity of inorganic salt, it can be re-used, not only reduce the waste of resource, also reduced the destruction of waste water to environment, there is good economic and social benefit.
The present invention can not produce reluctant secondary refuse, realize the recycling of saliferous trade effluent, especially high salt industrial waste water, solve to a certain extent a processing difficult problem for high salt industrial waste water, efficiently solve the processing problem of the high-salt wastewater producing in pesticide producing, environmental protection and social benefit are outstanding.
Embodiment
Below by specific embodiment, the present invention is further elaborated, should be understood that, following explanation is only in order to explain the present invention, its particular content is not limited.
The effect of the present invention's thermal cracker used is exactly to make a small amount of organic substance generation thermo-cracking in inorganic salt become organic gas.Thermal cracker is a kind of process furnace of temperature controllable, adopts the mode of continuously feeding, interrupted discharging, is low hydrocarbon thing by the organic substance decomposing of cleavable in material, in stove, is subnormal ambient, and the organic gas that organic cracking is produced is drawn.Those skilled in the art can select in prior art the disclosed arbitrary device that meets above-mentioned requirements for the present invention as required, such as tubular type pyrolysis reactor (USC pyrolyzer, SRT pyrolyzer etc.), rotary kiln pyrolysis reactor, bubbling fluidization bed bioreactor, circle transmission bed bioreactor, circulating fluid bed reactor, ablation reactor, rotating cone reactor or vacuum moving-burden bed reactor.
The present invention's combustion unit used can be the disclosed roasting kiln for organic gas burning in existing field, and those skilled in the art can select voluntarily, as the dual firing chamber for the treatment of flue gas in waste incineration.
Carbonization equipment therefor of the present invention can be selected rotary kiln, vertical incinerator, horizontal incinerator, box-type furnace, fluidizing furnace, grate incinerator or fluidized bed incinerator, is preferably rotary kiln.
embodiment 1
Get atrazine production wastewater, waste water is evaporated through MVR, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain sodium chloride content 90.5%, moisture 9.00%, TOC 0.95%, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, obtain high purity salt, sodium chloride content 99.92%, TOC content is 0.004%, the gas that carbonization produces also passes in combustion chamber, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 300Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 2
Get ametryn factory effluent, by waste water through triple effect evaporation, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain KCE content 91.8%, moisture 6.86%, TOC 1.02%, throw to rotary kiln pyrolysis reactor, under starvation, at 400 DEG C of high temperature pyrolysis 8min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 3s, remaining solid is thrown to rotary kiln, under logical oxygen, at 720 DEG C of high temperature cabonization 30min, obtain high purity salt, sodium chloride content 99.96%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 305Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 3
Get simazine factory effluent, waste water is evaporated through MVR, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain sodium chloride content 91.8%, moisture 7.1%, TOC 1.06%, throw to bubbling fluidization bed bioreactor, under starvation, at 450 DEG C of high temperature pyrolysises, time 15min, the organic gas producing passes in dual firing chamber, under 1100 DEG C of high temperature, stop 2s, remaining solid is thrown to fluidized bed incinerator, under blowing air, at 750 DEG C of high temperature cabonization 10min, obtain high purity salt, sodium chloride content 99.98, TOC content is 0.002%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 310Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 4
Get terbutryn factory effluent, waste water is evaporated through MVR, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain sodium chloride content 91.8%, moisture 7.2%, TOC 0.98%, throw to circle transmission bed bioreactor, under starvation, at 480 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2.5s, remaining solid is thrown to fluidizing furnace, under logical oxygen, at 700 DEG C of high temperature cabonization 30min, obtain high purity salt, sodium chloride content 99.94, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 300Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 5
Get terbuthylazine factory effluent, by waste water through triple effect evaporation, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain sodium chloride content 91.3%, moisture 7.7%, TOC 0.99%, throw to circulating fluid bed reactor, under starvation, at 500 DEG C of high temperature pyrolysises, time 5min, the organic gas producing passes in combustion unit, under 1100 DEG C of high temperature, stop 2s, remaining solid is thrown to horizontal incinerator, under blowing air, at 750 DEG C of high temperature cabonization 10min, obtain high purity salt, sodium chloride content 99.91%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 310Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 6
Get cyanazine factory effluent, waste water is evaporated through MVR, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain sodium chloride content 93.1%, moisture 5.62%, TOC 1.25%, throw to ablation reactor, under starvation, at 500 DEG C of high temperature pyrolysises, time 10min, organic gas passes in combustion unit, under 1100 DEG C of high temperature, stop 3s, remaining solid is thrown to grate incinerator, under logical oxygen, at 720 DEG C of high temperature cabonization 15min, obtain high purity salt, sodium chloride content 99.97%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 305Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 7
Get cyanatryn factory effluent, by waste water through triple effect evaporation, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain KCE content 91.4%, moisture 7.23%, TOC 1.34%, throw to rotating cone reactor, under starvation, at 550 DEG C of high temperature pyrolysis 30min, organic gas passes in combustion unit, under 1100 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 750 DEG C of high temperature cabonization 5min, obtain high purity salt, sodium chloride content is more than 99.93%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 310Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 8
Get propazine factory effluent, by waste water through triple effect evaporation, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain KCE content 92.0%, moisture 6.65%, TOC 1.34%, throw to vacuum moving-burden bed reactor, under starvation, at 350 DEG C of high temperature pyrolysis 60min, organic gas passes in combustion unit, under 900 DEG C of high temperature, stop 3s, remaining solid is thrown to rotary kiln, under logical oxygen, at 650 DEG C of high temperature cabonization 50min, obtain high purity salt, sodium chloride content 99.95%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 310Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 9
Get 2, 4-D factory effluent, waste water is evaporated through MVR, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain sodium chloride content 90%, moisture 9.03%, TOC 0.95%, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, obtain high purity salt, sodium chloride content 99.94%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion chamber, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 300Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 10
Get 2, 4-D factory effluent, by waste water through triple effect evaporation, obtain Industrial Salt, get the Industrial Salt 1000Kg of gained, detect to obtain KCE content 92.2%, moisture 6.74%, TOC 1.04%, throw to rotary kiln pyrolysis reactor, under starvation, at 400 DEG C of high temperature pyrolysis 8min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 3s, remaining solid is thrown to rotary kiln, under logical oxygen, at 720 DEG C of high temperature cabonization 30min, obtain high purity salt, sodium chloride content 99.96%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion chamber, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Get above-mentioned steps gained high purity salt 305Kg, be made into 1000L salt solution, gained salt solution enters ion-exchange membrane electrolyzer again and carries out electrolysis, makes liquid caustic soda and chlorine, can be back to use in the middle of production.
embodiment 11
In process of preparing glyphosate by glycine method, add the glyphosate alkaline mother liquor that alkali reclaims phosphorous 1.2% after triethylamine, through MVR evaporation concentration, be cooled to after room temperature, filter.
Get filter cake, obtain Industrial Salt, get the Industrial Salt of gained, detect to obtain sodium chloride content 92.5%, moisture 6.2%, TOC 0.35%, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, obtain higher degree salt, sodium chloride content 99.82%, total phosphorus 0.1%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, after filtering, nanofiltration membrane removes phosphoric acid salt wherein, phosphate radical 0.001% in gained salt solution, gained salt solution is as electrolysis with ion-exchange film salt solution, by Electrowinning caustic soda, chlorine and hydrogen, can be back to use in the middle of production;
Get filtrate, detect phosphorous 5.5%, add solid sodium hydroxide, make sodium mole number: phosphorus mole number=4.0, spray-dried dehydration, must be rich in phosphorus solid materials, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product process recrystallization obtaining, obtain high-purity phosphoric acid sodium, content 99.0%, the gas that carbonization produces also passes in combustion chamber, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
embodiment 12
In process of preparing glyphosate by glycine method, add the glyphosate alkaline mother liquor that alkali reclaims phosphorous 1.4% after triethylamine, through MVR evaporation concentration, be cooled to after room temperature, filter.
Get filter cake, obtain Industrial Salt, get the Industrial Salt of gained, detect to obtain sodium chloride content 92.8%, moisture 6.3%, TOC 0.33%, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, obtain high compared with purity salt, sodium chloride content 99.89%, total phosphorus 0.09%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, after filtering, nanofiltration membrane removes phosphoric acid salt wherein, phosphate radical 0.002% in gained salt solution, gained salt solution is as electrolysis with ion-exchange film salt solution, by Electrowinning caustic soda, chlorine and hydrogen, can be back to use in the middle of production;
Get filtrate, detect phosphorous 6.0%, add magnesium oxide, make (magnesium mole number × 2): phosphorus mole number=2.1, spray-dried dehydration, must be rich in phosphorus solid materials, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product process recrystallization obtaining, obtain high purity magnesium pyrophosphate, content 99.3%, the gas that carbonization produces also passes in combustion chamber, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
embodiment 13
In process of preparing glyphosate by glycine method, add the glyphosate alkaline mother liquor that alkali reclaims phosphorous 2.0% after triethylamine, through MVR evaporation concentration, be cooled to after room temperature, filter.
Get filter cake, obtain Industrial Salt, get the Industrial Salt of gained, detect to obtain sodium chloride content 92.6%, moisture 6.9%, TOC 0.38%, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, obtain higher degree salt, sodium chloride content 99.87%, total phosphorus 0.07%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, after filtering, nanofiltration membrane removes phosphoric acid salt wherein, phosphate radical 0.001% in gained salt solution, gained salt solution is as electrolysis with ion-exchange film salt solution, by Electrowinning caustic soda, chlorine and hydrogen, can be back to use in the middle of production;
Get filtrate, detect phosphorous 7.1%, add sodium hydroxide, make sodium mole number: phosphorus mole number=1.7, spray-dried dehydration, must be rich in phosphorus solid materials, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product process recrystallization obtaining, obtain high purity tripoly phosphate sodium STPP, content 99.6%, the gas that carbonization produces also passes in combustion chamber, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
embodiment 14
In process of preparing glyphosate by glycine method, add the glyphosate alkaline mother liquor that alkali reclaims phosphorous 2.2% after triethylamine, through MVR evaporation concentration, be cooled to after room temperature, filter.
Get filter cake, obtain Industrial Salt, get the Industrial Salt of gained, detect to obtain sodium chloride content 94.9%, moisture 4.2%, TOC 0.28%, throw to tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, obtain higher degree salt, sodium chloride content 99.86%, total phosphorus 0.07%, TOC content is 0.003%, the gas that carbonization produces also passes in combustion unit, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, remove phosphoric acid salt wherein through adding calcium chloride precipitation, phosphate radical 0.002% in gained salt solution, gained salt solution is as electrolysis with ion-exchange film salt solution, by Electrowinning caustic soda, chlorine and hydrogen, can be back to use in the middle of production;
Get filtrate, detect phosphorous 6.8%, add copper hydroxide, make (copper mole number × 2): phosphorus mole number=1.9, spray-dried dehydration, must be rich in phosphorus solid materials, throw to vacuum moving-burden bed reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 DEG C of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product process recrystallization obtaining, obtain high purity cupric pyrophosphate, content 99.1%, the gas that carbonization produces also passes in combustion chamber, with at high temperature fully burning together with the organic gas of thermo-cracking, the tail gas quenching to 200 producing DEG C following rear discharge.
Above-described embodiment is only exemplary the inventive method have been carried out enumerating; in addition to the above methods; in prior art, the evaporating concentrating method of disclosed other waste water, waste water are removed organic method and also be may be used in the present invention, within also all belonging to protection domain of the present invention.
Claims (14)
1. a recycling processing method for inorganic salt in trade effluent, is characterized in that comprising the following steps:
(1) trade effluent is carried out to evaporation concentration, obtain solid salt;
(2) gained solid salt is added to thermal cracker, making the organic substance thermo-cracking in solid salt is organic gas;
(3) organic gas of thermo-cracking gained enters combustion unit and fully burns, and after gained tail gas quenching, discharges;
(4) solid salt after thermo-cracking enters carbonizing plant, by high temperature cabonization, solid salt is further purified, and obtains high-purity solid salt, and the gas that carbonization produces also enters combustion unit and fully burns;
Thermo-cracking is carried out under oxygen free condition, and thermo-cracking temperature is 350-550 DEG C; Carbonization is carried out under the existence of oxygen-containing gas, at the temperature of 650-750 DEG C.
2. recycling processing method according to claim 1, is characterized in that: described trade effluent is the waste water of direct generation in pesticide producing process or waste water after treatment.
3. recycling processing method according to claim 2, is characterized in that: described trade effluent is the waste water that directly produces in the production process of triazine herbicide, organophosphorus insecticide or waste water after treatment.
4. recycling processing method according to claim 3, is characterized in that: described triazine herbicide waste water comprises the waste water that directly produces in the production process of terbuthylazine, terbutryn, cyanazine, cyanatryn, atrazine, ametryn, propazine, prometryn, simazine, simetryn, piperazine humulone or hexazinone or waste water after treatment; Described organophosphorus insecticide waste water comprises that in process of preparing glyphosate by glycine method, adding alkali reclaims the mother liquor producing in glyphosate alkaline mother liquor after triethylamine, the intermediate pmida98 preparation process of IDA legal system for the mother liquor producing in glyphosate process or glyphosate.
5. recycling processing method according to claim 1, is characterized in that: the gas of thermo-cracking and the carbonization gained 2-5s that burns at 900-1100 DEG C, discharge after burning gained tail gas quenching to 200 is DEG C following.
6. recycling processing method according to claim 1 or 5, is characterized in that: described oxygen-containing gas is air and/or oxygen.
7. recycling processing method according to claim 1, is characterized in that: described oxygen-containing gas is oxygen-rich air.
8. recycling processing method according to claim 1 or 5, is characterized in that: the thermo-cracking time is 5-60min; Carbonization time is 10-60min.
9. recycling processing method according to claim 8, is characterized in that: the thermo-cracking time is 5-10min; Carbonization time is 10-15min.
10. recycling processing method according to claim 1, is characterized in that: the method for trade effluent evaporation concentration is single-effect evaporation, multiple-effect evaporation or MVR evaporation; Carbonizing plant is selected from rotary kiln, vertical incinerator, horizontal incinerator, box-type furnace, fluidizing furnace, grate incinerator or fluidized bed incinerator; Thermal cracker is tubular type pyrolysis reactor, rotary kiln pyrolysis reactor, bubbling fluidization bed bioreactor, circle transmission bed bioreactor, circulating fluid bed reactor, ablation reactor, rotating cone reactor or vacuum moving-burden bed reactor; Combustion unit is the roasting kiln for organic gas burning.
11. according to the recycling processing method described in claim 1 or 10, it is characterized in that: carbonizing plant is rotary kiln.
12. according to the recycling processing method of claim 1, it is characterized in that: the inorganic salt purity after carbonization is more than 99%; Described high purity inorganic salt water wiring solution-forming, as ionogen.
13. according to the recycling processing method of claim 12, it is characterized in that: when described inorganic salt are sodium-chlor, gained sodium chloride solution is for chlorine industry.
14. recycling processing methods according to claim 12, it is characterized in that: when phosphorous in described waste water, in gained high purity inorganic salt, contain trace amounts of phosphorus, the solution being made into first adopts chemical precipitation agent or nanofiltration membrane to remove by filter after the trace amounts of phosphorus containing, then as ionogen.
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