CN103710036A - Treatment method for phosphorus-containing waste materials in pesticide production - Google Patents
Treatment method for phosphorus-containing waste materials in pesticide production Download PDFInfo
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Abstract
The invention discloses a treatment method for phosphorus-containing waste materials in pesticide production. The treatment method comprises the steps of adding dry solid-state phosphorus-containing waste materials or phosphorus-containing solid materials obtained by dehydration of liquid-state phosphorus-containing waste materials into a thermal cracking device to turn solid-state organic substances to organic gas by thermal cracking, introducing the organic gas into a combustion device for full combustion, quenching tail gas obtained by combustion, and then discharging the tail gas; adding the solid-state phosphorus-containing waste materials or/and the phosphorus-containing solid materials after thermal cracking into a carbonization device, further purifying by high-temperature carbonization to obtain high-purity phosphates, and further introducing gas produced by carbonization into the combustion device for full combustion. According to the method disclosed by the invention, the phosphorus element in waste liquid with high content of phosphorus can be well recycled, the use of expensive medicaments is avoided, and phosphorus in the waste materials can be turned to high-purity phosphates; furthermore, secondary wastes which are difficult to treat can not be produced in the whole process, the emission of toxic waste gas is avoided, and the method is further in line with green and environment-friendly requirements.
Description
Technical field
The present invention relates to a kind of method of processing the phosphorous waste material producing in pesticide producing process, more specifically, relate to and a kind of the phosphorous waste material producing in pesticide producing process is carried out to the processing such as thermo-cracking, carbonization, reclaim the method for phosphor resource.
Technical background
Some organic or inorganic products have the participation of phosphoric in preparation process, so in production process, meeting produces phosphorus-containing waste slag, phosphorous by product, contains in phosphorous waste material, especially the pesticide producing processes such as phosphorus waste liquid, can produce a large amount of phosphorous waste materials.Pressure based on two aspects of resources and environment, since the end of the nineties in last century, people begin one's study and from phosphorous waste, remove and reclaim the technology of phosphorus, and have obtained certain progress.At present, more, the phosphor-removing effect of domestic and international application is preferably biological process and chemical method relatively.Wherein biological process floor space is large, and conventionally need to use chemical dephosphorization method to carry out pre-treatment, and the method is high and not ideal enough containing the phosphor-removing effect of the material of organophosphorus for phosphorus content.
Applicant has applied for the patent of invention that " a kind for the treatment of process of glyphosate mother solution " by name, application number are 201210384860.0 in 2012, this patent comprises the following steps: regulate glyphosate mother solution pH, isolate triethylamine, remaining mother liquor is concentrated through multiple-effect evaporation, obtain filter cake, filter cake is removed organism by washing, obtains inorganic salt; Filtrate, through 600-900 ℃ of burning, obtains pyrophosphate salt; This invented technology is simple, realized the recycling of chlorine, phosphorus and triethylamine in glyphosate mother solution, the wasting of resources and the destruction to environment have been avoided, solved to a certain extent a processing difficult problem for phosphorous pesticide producing waste liquid, but still there is certain deficiency in this method: 1, the only processing of applicable and glyphosate mother solution of the method, does not have universality; 2, the method water is difficult to all organic substances in inorganic salt to remove; 3, the flue gas producing in the method filtrate burning process contains toxic gas, and the method has only been utilized the physics heat of these flue gases, the toxic substance in flue gas is not processed, and drains in air and can cause environmental pollution.
Summary of the invention
For overcoming the above-mentioned problems in the prior art, the invention provides the treatment process of phosphorous waste material in the stronger pesticide producing of a kind of more environmental protection, universality, the method can well be processed the phosphorus in waste material, the phosphoric acid salt obtaining can also be recycled, and strengthened the processing to toxic gas, avoided the discharge of poisonous fume, more green, environmental protection.
The concrete technical scheme of the present invention is as follows:
The treatment process of phosphorous waste material in a kind of pesticide producing, it is characterized in that step comprises: the phosphorous solid materials obtaining adds in thermal cracker or/and liquid phosphorous waste material dewaters by dry solid-state phosphorous waste material, making solid-state organic substance thermo-cracking is organic gas, organic gas is introduced to fully burning in combustion unit, after burning gained tail gas quenching, discharge; Solid-state phosphorous waste material after thermo-cracking, or/and phosphorous solid materials adds in carbonizing plant, is further purified by high temperature cabonization, obtains high-purity phosphoric acid salt, and the gas that carbonization produces is also introduced combustion unit and fully burnt.
Phosphorous waste material of the present invention can be pesticide material, the phosphorous waste material of liquid state directly producing in pesticide intermediate or pesticide producing process is (mother liquor for example or/and solid-state phosphorous waste material, waste water, waste residue, by product etc.), also can be that the phosphorous waste material of liquid state that obtains after treatment of the phosphorous waste material of above-mentioned direct generation is or/and solid-state phosphorous waste material, described solid-state phosphorous waste material comprises phosphorus-containing waste slag or/and phosphorous by product, the phosphorous waste material of described liquid towards is or/and the processing of solid-state phosphorous waste material includes but not limited to concentration, processed, regulate pH to process, extraction treatment, rectification process, remove not phosphorous raw material, by product, the processing of solvent.
Concrete, the phosphorous waste material of the present invention includes but not limited to the mother liquor and the waste water that in glyphosate production process, produce, the phosphorous acid by product and the waste water that in acetochlor production process, produce, the phosphorus-containing wastewater producing in acephate production process and by product, the organophosphorus waste liquid producing in Chlorpyrifos 94 production process, the phosphorus-containing waste slag producing in Stam F-34 production process and waste liquid, the phosphorous by product and the waste liquid that in grass ammonium phosphine production process, produce, Provado, chlorimuronethyl, triazophos, Malathion, Trichlorphon, SD-1750, the phosphorous waste material producing in the pesticide producing such as Rogor and acephatemet, phosphorus trichloride, phosphorus oxychloride, phosphoric acid, the phosphorous waste material producing in the phosphorous raw material that the agricultural chemicals such as phosphorous acid and dimethylphosphite is required or the production process of intermediate.
Preferably, the phosphorous waste material of the present invention be in glyphosate or glyphosate intermediate production process, directly produce containing phosphorus waste liquid or after treatment containing phosphorus waste liquid, most preferably be at least one in following mother liquor: 1. in process of preparing glyphosate by glycine method, add alkali and reclaim the glyphosate alkaline mother liquor after triethylamine, 2. IDA legal system is for the mother liquor producing in glyphosate process, 3. the mother liquor producing in the intermediate pmida98 preparation process of glyphosate, 4. above-mentioned 1., 2., the 3. mother liquor of three kinds of mother liquors gained after dechloratation salt is processed.
The inventive method is to propose for the phosphorous waste material producing in pesticide producing (containing phosphorus waste liquid, phosphorus-containing waste slag, phosphorous by product), and its key is that the phosphorus in phosphorous waste material is fully reclaimed.Present method can be both the direct treatment process of phosphorous waste material, also can be a part for phosphorous waste disposal process, for waste water is comprehensively processed, composition in waste water is carried out to the comprehensive utilization of resources and recovery, present method can be combined with other method of wastewater treatment, waste material first can be carried out after other recyclable compositions are removed in pre-treatment enabling again present method, also can adopt the present invention to remove to enable again additive method after dephosphorization residue waste water is processed.
The phosphorous waste material of the present invention is if solid-state waste residue, by product, or the words of phosphorous waste water only, can directly adopt aforesaid method to process, if also have other compositions in waste water, such as chloride salts such as sodium-chlor etc., when processing, will first chloride salt be concentrated and be removed, further dewatering and recovery phosphorus containing components.
When phosphorous waste material is the phosphorous waste material of liquid state that contains chloride salt, adopt the phosphorous waste material of following step process:
(1) by phosphorous waste material evaporation concentration, filter after being cooled to room temperature, get filter cake, obtain solid salt;
(2) by filtrate dehydration, obtain phosphorous solid materials;
(3) adopt respectively separately following method to process the phosphorous solid materials of the solid salt of step (1) and step (2): solid salt or phosphorous solid materials are added to thermal cracker, making the organic substance thermo-cracking in solid salt or phosphorous solid materials is organic gas, organic gas is introduced to fully burning in combustion unit, after burning gained tail gas quenching, discharge; Solid salt after thermo-cracking or phosphorous solid materials enter carbonizing plant, by high temperature cabonization, are further purified, and obtain high purity chloride salt after solid salt carbonization; After solid materials carbonization, obtain high-purity phosphoric acid salt, the gas that carbonization produces is also introduced combustion unit and is fully burnt.
In treatment process of the present invention, be also included in before liquid phosphorous waste material dehydration obtains phosphorous solid materials, regulate the step of the ratio of phosphorus and metal ion in liquid phosphorous waste material, this step is preferably carried out after dechloratation salt.Metal ion in phosphorous waste material can be one or more in sodium ion, potassium ion, calcium ion, magnesium ion, cupric ion, aluminum ion, zine ion and tin ion.The high-purity phosphoric acid salt obtaining after carbonization of the present invention is the mixture of orthophosphoric acid salt, pyrophosphate salt, poly-phosphate and metaphosphate, by adjusting the ratio of phosphorus and metal ion, can to phosphate mixt take a certain phosphoric acid salt as main.
When (metal ion mole number * metal ion price): when the ratio of phosphorus mole number is 3.0-4.5, the phosphoric acid salt finally obtaining be take orthophosphoric acid salt as main.When (metal ion mole number * metal ion price): when the ratio of phosphorus mole number is 1.9-2.2, the phosphoric acid salt finally obtaining be take pyrophosphate salt as main.When (metal ion mole number * metal ion price): when the ratio of phosphorus mole number is 1.5-1.8, the phosphoric acid salt finally obtaining be take poly-phosphate as main.When (metal ion mole number * metal ion price): when the ratio of phosphorus mole number is 0.9-1.2, the phosphoric acid salt finally obtaining be take metaphosphate as main.
In treatment process of the present invention, also comprise the step that high-purity phosphoric acid salt recrystallization that carbonization is obtained is further purified.Phosphoric acid salt purity after recrystallization is more than 98%.
In treatment process of the present invention, the high purity chloride salt of gained can be made into salt solution for chlorine industry.In the salt of gained, also contain micro-phosphorus, in order to meet the requirement of chlorine industry, by the salt solution being made into, through method of the prior art, methods such as nanofiltration membrane filtration or chemical reagent precipitation is removed the phosphorus in salt solution, gained salt solution is used further to chlorine industry, for example ionic membrane salt solution.
In treatment process of the present invention, thermo-cracking is carried out under oxygen free condition, and thermo-cracking temperature is 350-550 ℃.The thermo-cracking time is 5-60min, generally in 5-10min thermo-cracking, can complete.Time lengthening does not have much affect to result.
In treatment process of the present invention, 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 ℃.Carbonization time is 10-60min, generally in 10-15min carbonization, can complete.Time lengthening does not have much affect to result.
In treatment process of the present invention, the gas that thermo-cracking and carbonization the produce 2-5s that burns at 900-1100 ℃, discharge after burning gained tail gas quenching to 200 is ℃ following.
In treatment process of the present invention, the mode of evaporation concentration is single-effect evaporation, multiple-effect evaporation or MVR evaporation.
In treatment process of the present invention, solid-state phosphorous waste material is dried or the liquid phosphorous waste material equipment used that dewaters is the disclosed drying plant for dry moisture wet feed in existing field, as spray drying device.
In treatment process of the present invention, 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 treatment process of the present invention, carbonizing plant is rotary kiln, vertical incinerator, horizontal incinerator, box-type furnace, fluidizing furnace, grate incinerator or fluidized bed incinerator, preferably rotary kiln.
In treatment process of the present invention, 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.
Method of the present invention has very strong universality, goes in the processing of nearly all phosphorous pesticide waste liquid, waste residue, by product.For the phosphorus in waste material is recycled with phosphatic form, avoid the discharge of toxic gas simultaneously, the present invention adopts the mode of thermo-cracking+carbonization+vent gas treatment to process waste material, first make phosphorous waste material without aquation, after phosphorous by product or phosphorus-containing waste slag are dry, can directly use, liquid phosphorous waste material will carry out processed, then water-free phosphorous waste material is first removed labile organism by thermo-cracking, by carbonization, remove again the organism of difficult volatilization, and salify, the gas that thermo-cracking and carbonization produce all enters combustion unit and carries out vent gas treatment, tail gas after processing is thoroughly without poisoning, meet emission standard.
The inventive method can well be recycled height containing the phosphoric in phosphorus waste liquid, avoided the use of expensive medicament, and the phosphorus in waste material can change highly purified phosphoric acid salt into, as materials such as orthophosphoric acid salt, pyrophosphate salt and poly-phosphate., while containing the inorganic salt such as sodium-chlor in waste material, can also to this part salt, reclaim simultaneously meanwhile, obtain highly purified muriate inorganic salt.The muriate that processing obtains and phosphoric acid salt can be used for, in other Chemical Manufacture, having realized making full use of of resource.And in whole process, can not produce reluctant secondary refuse, without poisonous fume discharge, meet green, environmental requirement.
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 thermal cracker that the present invention is 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, by the organic substance decomposing of cleavable in material, is low hydrocarbon thing, 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, 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 as required.
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 in waste incineration for the treatment of the dual firing chamber of flue gas.
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
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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ 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, in gained salt solution, phosphate radical 0.001%, 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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ following rear discharge.
embodiment 2
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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ 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, in gained salt solution, phosphate radical 0.002%, 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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ following rear discharge.
embodiment 3
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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ 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, in gained salt solution, phosphate radical 0.001%, 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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ following rear discharge.
embodiment 4
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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ following rear discharge.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, through adding calcium chloride precipitation, remove phosphoric acid salt wherein, in gained salt solution, phosphate radical 0.002%, 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 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ 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 ℃ following rear discharge.
embodiment 5
IDA legal system is for the mother liquor producing in glyphosate process, phosphorous dope after membrane concentration reclaims glyphosate, detect phosphorous 2.1%, add sodium hydroxide, make sodium mole number: phosphorus mole number=1.2, spray-dried dehydration, must be rich in phosphorus solid materials, throw to rotary kiln pyrolysis reactor, under starvation, at 350 ℃ of high temperature pyrolysises, time 60min, the organic gas producing passes in combustion unit, under 900 ℃ of high temperature, stop 5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 650 ℃ of high temperature cabonization 60min, by the solid product process recrystallization obtaining, obtain Sodium Trimetaphosphate with High Purity, 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 ℃ following rear discharge.
embodiment 6
IDA legal system is for the mother liquor producing in glyphosate process, phosphorous dope after membrane concentration reclaims glyphosate, detect phosphorous 2.1%, add tin protoxide, make (tin mole number * 2): phosphorus mole number=1.2, spray-dried dehydration, must be rich in phosphorus solid materials, throw to rotary kiln pyrolysis reactor, under starvation, at 350 ℃ of high temperature pyrolysises, time 60min, the organic gas producing passes in combustion unit, under 900 ℃ of high temperature, stop 5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 650 ℃ of high temperature cabonization 60min, by the solid product process recrystallization obtaining, obtain high purity stannous 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 ℃ following rear discharge.
embodiment 6
The mother liquor producing in the intermediate pmida98 preparation process of glyphosate, through MVR evaporation concentration, is cooled to after room temperature, filters.
Get filter cake, obtain Industrial Salt, get the Industrial Salt of gained, detect to obtain sodium chloride content 92.0%, moisture 6.5%, TOC 0.55%, throw to tubular type pyrolysis reactor, under starvation, at 380 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ of high temperature cabonization 15min, obtain higher degree salt, sodium chloride content 99.85%, 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 ℃ 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, in gained salt solution, phosphate radical 0.001%, 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 10.0%, add potassium hydroxide, make potassium mole number: phosphorus mole number=2.0, spray-dried dehydration, must be rich in phosphorus solid materials 800Kg, throw to bubbling fluidization bed bioreactor, under starvation, at 420 ℃ of high temperature pyrolysises, time 45min, the organic gas producing passes in combustion unit, under 1100 ℃ of high temperature, stop 3.5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 750 ℃ of high temperature cabonization 10min, by the solid product process recrystallization obtaining, obtain high purity potassium pyrophosphate, content 99.2%, 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 ℃ following rear discharge.
embodiment 7
The phosphorus waste liquid that contains by producing in acetochlor production process, through MVR evaporation concentration, is cooled to after room temperature, filters.
Get filter cake, obtain Industrial Salt, get the Industrial Salt of gained, detect to obtain sodium chloride content 91.3%, moisture 5.6%, TOC 0.72%, throw to tubular type pyrolysis reactor, under starvation, at 350 ℃ of high temperature pyrolysises, time 45min, the organic gas producing passes in combustion unit, under 1100 ℃ of high temperature, stop 4s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ of high temperature cabonization 30min, obtain higher degree salt, sodium chloride content 99.86%, total phosphorus 0.06%, 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 ℃ 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, in gained salt solution, phosphate radical 0.002%, 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 10.1%, add phosphoric acid, make sodium mole number: phosphorus mole number=4.5, spray-dried dehydration, must be rich in phosphorus solid materials 800Kg, throw to bubbling fluidization bed bioreactor, under starvation, at 420 ℃ of high temperature pyrolysises, time 45min, the organic gas producing passes in combustion unit, under 1100 ℃ of high temperature, stop 3.5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 750 ℃ of high temperature cabonization 10min, by the solid product process recrystallization obtaining, obtain high-purity phosphoric acid sodium, content 98.2%, 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 ℃ following rear discharge.
embodiment 8
Phosphorus waste liquid will be contained in phosphorous acid production process, add sodium hydroxide, make sodium mole number: phosphorus mole number=1.5, spray-dried dehydration, must be rich in phosphorus solid materials, throw to circulating fluid bed reactor, under starvation, at 550 ℃ of high temperature pyrolysises, time 5min, the organic gas producing passes in combustion unit, under 1050 ℃ of high temperature, stop 5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 680 ℃ of high temperature cabonization 20min, obtain high purity trimer acid sodium, content 98.5%, 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 ℃ following rear discharge.
embodiment 9
Phosphorous 2.5% the waste liquid by producing in Chlorpyrifos 94 production process, through three-effect evaporation and condensation, is cooled to after room temperature, filters.
Get filter cake, obtain Industrial Salt, get the Industrial Salt of gained, detect to obtain sodium chloride content 91.2%, moisture 6.3%, TOC 0.56%, throw to tubular type pyrolysis reactor, under starvation, at 380 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 2s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ of high temperature cabonization 15min, obtain higher degree salt, sodium chloride content 99.85%, total phosphorus 0.09%, 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 ℃ 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, in gained salt solution, phosphate radical 0.001%, 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 10.2%, add sodium hydroxide, make sodium mole number: phosphorus mole number=0.9, spray-dried dehydration, must be rich in phosphorus solid materials, throw to ablation reactor, under starvation, at 480 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1050 ℃ of high temperature, stop 5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ of high temperature cabonization 38min, by the solid product process recrystallization obtaining, obtain Sodium Trimetaphosphate with High Purity, content 98.2%, 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 ℃ following rear discharge.
embodiment 10
By the solid waste producing in Stam F-34 production process, be broken for the particle that particle diameter is 30-2000 μ m, with phosphorous acid, regulate sodium mole number: phosphorus mole number=1.8, after mixing, spray-dried dehydration, must be rich in phosphorus solid materials, throw to rotating cone reactor, under starvation, at 400 ℃ of high temperature pyrolysises, time 30min, the organic gas producing passes in combustion unit, under 1000 ℃ of high temperature, stop 3.5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 700 ℃ of high temperature cabonization 38min, by the solid product process recrystallization obtaining, obtain high purity tripoly phosphate sodium STPP, content 98.4%, 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 ℃ following rear discharge.
embodiment 11
By the phosphorous solid waste producing in phosphate production, be broken for the particle that particle diameter is 30-2000 μ m, use sodium hydroxide to regulate sodium mole number: phosphorus mole number is=3.0, spray-dried dehydration, must be rich in phosphorus solid materials, throw to circle transmission bed bioreactor, under starvation, at 500 ℃ of high temperature pyrolysises, time 10min, the organic gas producing passes in combustion unit, under 1100 ℃ of high temperature, stop 2.5s, remaining solid is thrown to rotary kiln, under logical oxygen, at 720 ℃ of high temperature cabonization 15min, by the solid product process recrystallization obtaining, obtain high-purity phosphoric acid sodium, content 98.1%, 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 ℃ following rear discharge.
Claims (10)
1. the treatment process of phosphorous waste material in a pesticide producing, it is characterized in that step comprises: the phosphorous solid materials obtaining adds in thermal cracker or/and liquid phosphorous waste material dewaters by dry solid-state phosphorous waste material, making solid-state organic substance thermo-cracking is organic gas, organic gas is introduced to fully burning in combustion unit, after burning gained tail gas quenching, discharge; Solid-state phosphorous waste material after thermo-cracking, or/and phosphorous solid materials adds in carbonizing plant, is further purified by high temperature cabonization, obtains high-purity phosphoric acid salt, and the gas that carbonization produces is also introduced combustion unit and fully burnt.
2. treatment process according to claim 1, it is characterized in that: described phosphorous waste material refers to pesticide material, the phosphorous waste material of liquid state directly producing in pesticide intermediate or pesticide producing process is or/and solid-state phosphorous waste material, or the phosphorous waste material of liquid state is after treatment or/and solid-state phosphorous waste material, described solid-state phosphorous waste material comprises phosphorus-containing waste slag or/and phosphorous by product, the phosphorous waste material of described liquid towards is or/and the processing of solid-state phosphorous waste material includes but not limited to concentration, processed, regulate pH to process, extraction treatment, rectification process, remove not phosphorous raw material, by product, the processing of solvent, described phosphorous waste material includes but not limited to the mother liquor and the waste water that in glyphosate production process, produce, the phosphorous acid by product and the waste water that in acetochlor production process, produce, the phosphorus-containing wastewater producing in acephate production process and by product, the organophosphorus waste liquid producing in Chlorpyrifos 94 production process, the phosphorus-containing waste slag producing in Stam F-34 production process and waste liquid, the phosphorous by product and the waste liquid that in grass ammonium phosphine production process, produce, Provado, chlorimuronethyl, triazophos, Malathion, Trichlorphon, SD-1750, the phosphorous waste material producing in the pesticide producing such as Rogor and acephatemet, phosphorus trichloride, phosphorus oxychloride, phosphoric acid, the phosphorous waste material producing in the phosphorous raw material that the agricultural chemicals such as phosphorous acid and dimethylphosphite is required or the production process of intermediate.
3. method according to claim 1 and 2, it is characterized in that: described phosphorous waste material be in glyphosate or glyphosate intermediate production process, directly produce containing phosphorus waste liquid or after treatment containing phosphorus waste liquid, be preferably at least one in following mother liquor: 1. in process of preparing glyphosate by glycine method, add alkali and reclaim the glyphosate alkaline mother liquor after triethylamine, 2. IDA legal system is for the mother liquor producing in glyphosate process, 3. the mother liquor producing in the intermediate pmida98 preparation process of glyphosate, 4. above-mentioned 1., 2., the 3. mother liquor of three kinds of mother liquors gained after dechloratation salt is processed.
4. according to the treatment process described in claim 1,2 or 3, it is characterized in that: when phosphorous waste material is the phosphorous waste material of liquid state that contains chloride salt, adopt the phosphorous waste material of following step process:
(1) by phosphorous waste material evaporation concentration, filter after being cooled to room temperature, get filter cake, obtain solid salt;
(2) by filtrate dehydration, obtain phosphorous solid materials;
(3) adopt respectively separately following method to process the phosphorous solid materials of the solid salt of step (1) and step (2): solid salt or phosphorous solid materials are added to thermal cracker, making the organic substance thermo-cracking in solid salt or phosphorous solid materials is organic gas, organic gas is introduced to fully burning in combustion unit, after burning gained tail gas quenching, discharge; Solid salt after thermo-cracking or phosphorous solid materials enter carbonizing plant, by high temperature cabonization, be further purified, after solid salt carbonization, obtain high purity chloride salt, obtain high-purity phosphoric acid salt after solid materials carbonization, the gas that carbonization produces is also introduced combustion unit and is fully burnt.
5. according to the treatment process described in any one in claim 1-4, it is characterized in that: thermo-cracking is carried out under oxygen free condition, thermo-cracking temperature is 350-550 ℃; Carbonization is carried out under the existence of oxygen-containing gas, and carbonization temperature is 650-750 ℃; The gas that thermo-cracking and carbonization the produce 2-5s that burns at 900-1100 ℃, discharge after burning gained tail gas quenching to 200 is ℃ following; Gained high purity chloride salt water is made into salt solution, and gained salt solution removes by filter after the trace amounts of phosphorus containing, for chlorine industry by chemical precipitation agent or nanofiltration membrane.
6. treatment process according to claim 5, is characterized in that: the thermo-cracking time is 5-60min, preferably 5-10min; Carbonization time is 10-60min, preferably 10-15min; Oxygen-containing gas is one or more in air, oxygen-rich air and oxygen.
7. according to the treatment process described in any one in claim 1-4, it is characterized in that: described method is also included in before liquid phosphorous waste material dehydration obtains phosphorous solid materials, regulate the step of the ratio of phosphorus and metal ion in liquid phosphorous waste material, or/and the step of the high-purity phosphoric acid salt recrystallization that carbonization is obtained.
8. treatment process according to claim 7, is characterized in that: the phosphoric acid salt purity after recrystallization is more than 98%.
9. treatment process according to claim 7, is characterized in that: the metal ion in the phosphorous waste material of described liquid state is one or more in sodium ion, potassium ion, calcium ion, magnesium ion, cupric ion, aluminum ion, zine ion and tin ion; When the ratio long-pending and phosphorus mole number of metal ion mole number and metal ion price is 3.0-4.5, the high-purity phosphoric acid salt finally obtaining be take orthophosphoric acid salt as main; When the ratio long-pending and phosphorus mole number of metal ion mole number and metal ion price is 1.9-2.2, the high-purity phosphoric acid salt finally obtaining be take pyrophosphate salt as main; When the ratio long-pending and phosphorus mole number of metal ion mole number and metal ion price is 1.5-1.8, the high-purity phosphoric acid salt finally obtaining be take poly-phosphate as main; When the ratio long-pending and phosphorus mole number of metal ion mole number and metal ion price is 0.9-1.2, the high-purity phosphoric acid salt finally obtaining be take metaphosphate as main.
10. according to the treatment process described in any one in claim 1-4, it is characterized in that: the mode of evaporation concentration is single-effect evaporation, multiple-effect evaporation or MVR evaporation; In step (3), 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; Carbonizing plant is rotary kiln, vertical incinerator, horizontal incinerator, box-type furnace, fluidizing furnace, grate incinerator or fluidized bed incinerator, preferably rotary kiln; Combustion unit is the roasting kiln for organic gas burning.
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| CN104761093A (en) * | 2015-03-16 | 2015-07-08 | 浙江新安化工集团股份有限公司 | Treatment method and treatment system of glufosinate-ammonium magnesium-containing waste water |
| CN108059140A (en) * | 2018-01-23 | 2018-05-22 | 浙江新安化工集团股份有限公司 | A kind of method for preparing industry trisodium phosphate using glyphosate production waste material one-step method |
| CN110407387A (en) * | 2019-08-12 | 2019-11-05 | 天津理工大学 | A kind of processing method of saliferous phosphor-containing organic wastewater |
| CN111112286A (en) * | 2019-12-17 | 2020-05-08 | 宁波巨化化工科技有限公司 | Organic waste treatment method |
| CN114105181A (en) * | 2021-09-23 | 2022-03-01 | 浙江巨化技术中心有限公司 | Method for treating waste containing organic phosphorus chlorohydrocarbon |
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| CN103274380A (en) * | 2013-05-08 | 2013-09-04 | 山东潍坊润丰化工有限公司 | Glyphosate mother liquid treatment method and device |
| CN103484125A (en) * | 2013-10-14 | 2014-01-01 | 厦门大学 | Soil improvement agent and improvement method of heavy metal lead-contaminated soil |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104761093A (en) * | 2015-03-16 | 2015-07-08 | 浙江新安化工集团股份有限公司 | Treatment method and treatment system of glufosinate-ammonium magnesium-containing waste water |
| CN108059140A (en) * | 2018-01-23 | 2018-05-22 | 浙江新安化工集团股份有限公司 | A kind of method for preparing industry trisodium phosphate using glyphosate production waste material one-step method |
| CN108059140B (en) * | 2018-01-23 | 2020-02-18 | 浙江新安化工集团股份有限公司 | Method for preparing industrial trisodium phosphate by using glyphosate production waste through one-step method |
| CN110407387A (en) * | 2019-08-12 | 2019-11-05 | 天津理工大学 | A kind of processing method of saliferous phosphor-containing organic wastewater |
| CN111112286A (en) * | 2019-12-17 | 2020-05-08 | 宁波巨化化工科技有限公司 | Organic waste treatment method |
| CN114105181A (en) * | 2021-09-23 | 2022-03-01 | 浙江巨化技术中心有限公司 | Method for treating waste containing organic phosphorus chlorohydrocarbon |
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