CN103710036B - 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 processing in pesticide producing process the phosphorous waste material produced, more specifically, relate to and a kind of the phosphorous waste material produced in pesticide producing process is carried out the process 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, therefore can produce phosphorus-containing waste slag, phosphorous by product in production process, containing phosphorous waste materials such as phosphorus waste liquids, especially in pesticide producing process, can produce a large amount of phosphorous waste materials.Based on the pressure of resources and environment two aspects, since the end of the nineties in last century, people to begin one's study from phosphorous waste removing and reclaim the technology of phosphorus, and have achieved 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 usually needs to use chemical dephosphorization method to carry out pre-treatment, and high for phosphorus content and containing the material of organophosphorus the phosphor-removing effect of the method is not ideal enough.
Applicant has applied for that in 2012 " a kind for the treatment of process of glyphosate mother solution " by name, application number are the patent of invention of 201210384860.0, this patent comprises the following steps: regulate glyphosate mother solution pH, isolate triethylamine, remaining mother liquor concentrates through multiple-effect evaporation, obtain filter cake, filter cake, by washing removing organism, obtains inorganic salt; Filtrate, through 600-900 DEG C of burning, obtains pyrophosphate salt; This invented technology is simple, achieve the recycling of chlorine in glyphosate mother solution, phosphorus and triethylamine, avoid the wasting of resources and the destruction to environment, to some extent solve a process difficult problem for phosphorous pesticide producing waste liquid, but still there is certain deficiency in this method: 1, the method is only suitable for the process with glyphosate mother solution, does not have universality; 2, the method water is difficult to all organic substance removings in inorganic salt; 3, the flue gas produced in the method filtrate burning process contains toxic gas, and the method only make use of the physics heat of these flue gases, does not process the toxic substance in flue gas, 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 process the phosphorus in waste material, the phosphoric acid salt obtained can also be recycled, and the process strengthened toxic gas, avoid 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: by the solid-state phosphorous waste material of drying or/and the phosphorous solid materials that liquid phosphorous dehydrate waste materials obtains adds in thermal cracker, solid-state organic substance thermo-cracking is made to be organic gas, organic gas is introduced Thorough combustion in combustion unit, discharge after burning gained tail gas quenching; 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 also introduces combustion unit Thorough combustion.
Phosphorous waste material of the present invention can be pesticide material, the phosphorous waste material of liquid state directly produced in pesticide intermediate or pesticide producing process is or/and solid-state phosphorous waste material (such as mother liquor, 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 process of solid-state phosphorous waste material includes but not limited to concentration, processed, regulate pH process, extraction treatment, rectification process, remove not phosphorous raw material, by product, the process of solvent.
Concrete, the phosphorous waste material of the present invention includes but not limited to the mother liquor that produces in glyphosate production process and waste water, the phosphorous acid by product produced in acetochlor production process and waste water, the phosphorus-containing wastewater produced in acephate production process and by product, the organophosphorus waste liquid produced in Chlorpyrifos 94 production process, the phosphorus-containing waste slag produced in Stam F-34 production process and waste liquid, the phosphorous by product produced in grass ammonium phosphine production process and waste liquid, Provado, chlorimuronethyl, triazophos, Malathion, Trichlorphon, SD-1750, the phosphorous waste material produced in the pesticide producing such as Rogor and acephatemet, phosphorus trichloride, phosphorus oxychloride, phosphoric acid, the phosphorous waste material produced in phosphorous raw material needed for the agricultural chemicals such as phosphorous acid and dimethylphosphite or the production process of intermediate.
Preferably, the phosphorous waste material of the present invention be directly produce in glyphosate or glyphosate intermediate production process 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 the glyphosate alkaline mother liquor after alkali collection triethylamine, 2. IDA legal system is for the mother liquor produced in glyphosate process, the mother liquor produced in the intermediate pmida98 preparation process of 3. glyphosate, 4. above-mentioned 1., 2., the mother liquor of 3. three kinds of mother liquors gained after dechloratation Ficus caricaL.
The inventive method proposes for the phosphorous waste material produced in pesticide producing (containing phosphorus waste liquid, phosphorus-containing waste slag, phosphorous by product), and its key is fully reclaimed by the phosphorus in phosphorous waste material.Present method both can be the direct treatment process of phosphorous waste material, also can be a part for phosphorous waste treatment process, namely in order to comprehensively process waste water, composition in waste water is carried out 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 enabling present method again after pre-treatment removes other recyclable compositions, enable additive method after the present invention also can be adopted to remove dephosphorization again and 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 only phosphorous waste water, can aforesaid method be directly adopted to process, if also have other compositions in waste water, the chloride salts etc. such as such as sodium-chlor, will first remove concentrated for chloride salt when processing, further dewatering and recovery phosphorus containing components.
When phosphorous waste material is the phosphorous waste material of liquid state containing 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) filtrate is dewatered, obtain phosphorous solid materials;
(3) following method is adopted to process separately respectively the phosphorous solid materials of the solid salt of step (1) and step (2): solid salt or phosphorous solid materials are added thermal cracker, the organic substance thermo-cracking in solid salt or phosphorous solid materials is made to be organic gas, organic gas is introduced Thorough combustion in combustion unit, discharge after burning gained tail gas quenching; Solid salt after thermo-cracking or phosphorous solid materials enter carbonizing plant, are further purified by high temperature cabonization, obtain high purity chloride salt after solid salt carbonization; Obtain high-purity phosphoric acid salt after solid materials carbonization, the gas that carbonization produces also introduces combustion unit Thorough combustion.
In treatment process of the present invention, be also included in before liquid phosphorous dehydrate waste materials 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 obtained 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, the phosphate mixt obtained can be made based on a certain phosphoric acid salt.
When (metal ion × metal ion price): when the ratio of phosphorus mole number is 3.0-4.5, the phosphoric acid salt finally obtained is based on orthophosphoric acid salt.When (metal ion × metal ion price): when the ratio of phosphorus mole number is 1.9-2.2, the phosphoric acid salt finally obtained is based on pyrophosphate salt.When (metal ion × metal ion price): when the ratio of phosphorus mole number is 1.5-1.8, the phosphoric acid salt finally obtained is based on poly-phosphate.When (metal ion × metal ion price): when the ratio of phosphorus mole number is 0.9-1.2, the phosphoric acid salt finally obtained is based on metaphosphate.
In treatment process of the present invention, also comprise the step that the high-purity phosphoric acid salt recrystallization that carbonization 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.Phosphorus also containing trace in the salt of gained, in order to meet the requirement of chlorine industry, by the salt solution that is made into through method of the prior art, such as, phosphorus in the method such as nanofiltration membrane or chemical reagent precipitation removing salt solution, gained salt solution is used further to chlorine industry, such as ionic membrane salt solution.
In treatment process of the present invention, thermo-cracking is carried out under anaerobic, and thermal 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 treatment process of the present invention, carbonization is carried out in the presence of a gas containing oxygen, 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 treatment process of the present invention, the gas that thermo-cracking and carbonization produce burns 2-5s at 900-1100 DEG C, discharges after burning gained tail gas quenching to 200 is DEG C 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, to carry out dehydration equipment used be the drying plant for the moisture wet feed of drying disclosed in existing field, as spray drying device to carry out drying or liquid phosphorous waste material to solid-state phosphorous waste material.
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, preferred rotary kiln.
In treatment process of the present invention, combustion unit for disclosed in existing field for organic gas burning roasting kiln, such as, for the treatment of the dual firing chamber of flue gas in waste incineration.
Method of the present invention has very strong universality, goes in the process of nearly all phosphorous pesticide waste liquid, waste residue, by product.In order to the phosphorus in waste material is recycled in the form of phosphate, 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 anhydrous, can directly use after phosphorous by product or phosphorus-containing waste slag drying, liquid phosphorous waste material will carry out processed, then water-free phosphorous waste material first removes labile organism by thermo-cracking, again by the organism of the difficult volatilization of carbonization removing, and salify, the gas that thermo-cracking and carbonization produce all enters combustion unit and carries out vent gas treatment, the thorough Non-toxic of tail gas after process, meet emission standard.
Height can well be recycled containing the phosphoric in phosphorus waste liquid by the inventive method, and avoid the use of expensive medicament, 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.Meanwhile, this part salt can also be reclaimed containing during the inorganic salt such as sodium-chlor in waste material simultaneously, obtain highly purified muriate inorganic salt.The muriate that process obtains and phosphoric acid salt can be used for, in other Chemical Manufacture, achieving making full use of of resource.And reluctant secondary refuse can not be produced in whole process, without toxic exhaust emission, meet green, environmental requirement.
Embodiment
Below by specific embodiment, the present invention being further elaborated, it is to be understood that following explanation is only to explain the present invention, its particular content not being limited.
The effect of the thermal cracker that the present invention is used is exactly 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, and adopt the mode of continuously feeding, interrupted discharging, being low hydrocarbon thing by the organic substance decomposing of cleavable in material, is subnormal ambient in stove, and the organic gas produced by organic cracking is drawn.Those skilled in the art can select the arbitrary device meeting above-mentioned requirements disclosed in prior art 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 roasting kiln for organic gas burning disclosed 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 select rotary kiln, vertical incinerator, horizontal incinerator, box-type furnace, fluidizing furnace, grate incinerator or fluidized bed incinerator, is preferably rotary kiln.
embodiment 1
Add the glyphosate alkaline mother liquor of phosphorous 1.2% after alkali collection triethylamine in process of preparing glyphosate by glycine method, through MVR evaporation concentration, after being cooled to 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 in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in 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, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, phosphoric acid salt is wherein removed after nanofiltration membrane, 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, phosphorus solid materials must be rich in, throw in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product that obtains through recrystallization, obtain high-purity phosphoric acid sodium, content 99.0%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 2
Add the glyphosate alkaline mother liquor of phosphorous 1.4% after alkali collection triethylamine in process of preparing glyphosate by glycine method, through MVR evaporation concentration, after being cooled to 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 in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, obtain high comparatively 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, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, phosphoric acid salt is wherein removed after nanofiltration membrane, 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, phosphorus solid materials must be rich in, throw in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product that obtains through recrystallization, obtain high purity magnesium pyrophosphate, content 99.3%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 3
Add the glyphosate alkaline mother liquor of phosphorous 2.0% after alkali collection triethylamine in process of preparing glyphosate by glycine method, through MVR evaporation concentration, after being cooled to 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 in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in 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, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, phosphoric acid salt is wherein removed after nanofiltration membrane, 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, phosphorus solid materials must be rich in, throw in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product that obtains through recrystallization, obtain high purity tripoly phosphate sodium STPP, content 99.6%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 4
Add the glyphosate alkaline mother liquor of phosphorous 2.2% after alkali collection triethylamine in process of preparing glyphosate by glycine method, through MVR evaporation concentration, after being cooled to 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 in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in 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, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, through adding calcium chloride precipitation removing 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 6.8%, add copper hydroxide, make (copper mole number × 2): phosphorus mole number=1.9, spray-dried dehydration, phosphorus solid materials must be rich in, throw in vacuum moving-burden bed reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 15min, by the solid product that obtains through recrystallization, obtain high purity cupric pyrophosphate, content 99.1%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 5
IDA legal system is for the mother liquor produced in glyphosate process, the phosphorous dope after glyphosate is reclaimed through membrane concentration, detect phosphorous 2.1%, add sodium hydroxide, make sodium mole number: phosphorus mole number=1.2, spray-dried dehydration, phosphorus solid materials must be rich in, throw in rotary kiln pyrolysis reactor, under starvation, at 350 DEG C of high temperature pyrolysises, time 60min, the organic gas produced passes in combustion unit, 5s is stopped under 900 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 650 DEG C of high temperature cabonization 60min, by the solid product that obtains through recrystallization, obtain Sodium Trimetaphosphate with High Purity, content 99.1%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 6
IDA legal system is for the mother liquor produced in glyphosate process, the phosphorous dope after glyphosate is reclaimed through membrane concentration, detect phosphorous 2.1%, add tin protoxide, make (tin mole number × 2): phosphorus mole number=1.2, spray-dried dehydration, phosphorus solid materials must be rich in, throw in rotary kiln pyrolysis reactor, under starvation, at 350 DEG C of high temperature pyrolysises, time 60min, the organic gas produced passes in combustion unit, 5s is stopped under 900 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 650 DEG C of high temperature cabonization 60min, by the solid product that obtains through recrystallization, obtain high purity stannous pyrophosphate, content 99.1%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 6
The mother liquor produced in the intermediate pmida98 preparation process of glyphosate, through MVR evaporation concentration, after being cooled to 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 in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C 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, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, phosphoric acid salt is wherein removed after nanofiltration membrane, 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 10.0%, add potassium hydroxide, make potassium mole number: phosphorus mole number=2.0, spray-dried dehydration, phosphorus solid materials 800Kg must be rich in, throw in bubbling fluidization bed bioreactor, under starvation, at 420 DEG C of high temperature pyrolysises, time 45min, the organic gas produced passes in combustion unit, 3.5s is stopped under 1100 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 750 DEG C of high temperature cabonization 10min, by the solid product that obtains through recrystallization, obtain high purity potassium pyrophosphate, content 99.2%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 7
Contain phosphorus waste liquid by what produce in acetochlor production process, through MVR evaporation concentration, after being cooled to room temperature, filter.
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 in tubular type pyrolysis reactor, under starvation, at 350 DEG C of high temperature pyrolysises, time 45min, the organic gas produced passes in combustion unit, 4s is stopped under 1100 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C 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, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, phosphoric acid salt is wherein removed after nanofiltration membrane, 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 10.1%, add phosphoric acid, make sodium mole number: phosphorus mole number=4.5, spray-dried dehydration, phosphorus solid materials 800Kg must be rich in, throw in bubbling fluidization bed bioreactor, under starvation, at 420 DEG C of high temperature pyrolysises, time 45min, the organic gas produced passes in combustion unit, 3.5s is stopped under 1100 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 750 DEG C of high temperature cabonization 10min, by the solid product that obtains through recrystallization, obtain high-purity phosphoric acid sodium, content 98.2%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 8
Phosphorus waste liquid is contained by phosphorous acid production process, add sodium hydroxide, make sodium mole number: phosphorus mole number=1.5, spray-dried dehydration, phosphorus solid materials must be rich in, throw in circulating fluid bed reactor, under starvation, at 550 DEG C of high temperature pyrolysises, time 5min, the organic gas produced passes in combustion unit, 5s is stopped under 1050 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 680 DEG C of high temperature cabonization 20min, obtain high purity trimer acid sodium, content 98.5%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 9
By produce in Chlorpyrifos 94 production process phosphorous 2.5% waste liquid, through three-effect evaporation and condensation, after being cooled to room temperature, filter.
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 in tubular type pyrolysis reactor, under starvation, at 380 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C 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, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.Get the higher degree salt 300Kg of above-mentioned high temperature cabonization gained, be made into 1000L salt solution, phosphoric acid salt is wherein removed after nanofiltration membrane, 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 10.2%, add sodium hydroxide, make sodium mole number: phosphorus mole number=0.9, spray-dried dehydration, phosphorus solid materials must be rich in, throw in ablation reactor, under starvation, at 480 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 5s is stopped under 1050 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 38min, by the solid product that obtains through recrystallization, obtain Sodium Trimetaphosphate with High Purity, content 98.2%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 10
By the solid waste produced in Stam F-34 production process, be broken for the particle that particle diameter is 30-2000 μm, sodium mole number is regulated: phosphorus mole number=1.8 with phosphorous acid, after mixing, spray-dried dehydration, phosphorus solid materials must be rich in, throw in rotating cone reactor, under starvation, at 400 DEG C of high temperature pyrolysises, time 30min, the organic gas produced passes in combustion unit, 3.5s is stopped under 1000 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 700 DEG C of high temperature cabonization 38min, by the solid product that obtains through recrystallization, obtain high purity tripoly phosphate sodium STPP, content 98.4%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
embodiment 11
By the phosphorous solid waste produced in phosphate production, be broken for the particle that particle diameter is 30-2000 μm, sodium hydroxide is used to regulate sodium mole number: phosphorus mole number is=3.0, spray-dried dehydration, phosphorus solid materials must be rich in, throw in circle transmission bed bioreactor, under starvation, at 500 DEG C of high temperature pyrolysises, time 10min, the organic gas produced passes in combustion unit, 2.5s is stopped under 1100 DEG C of high temperature, remaining solid is thrown in rotary kiln, under logical oxygen, at 720 DEG C of high temperature cabonization 15min, by the solid product that obtains through recrystallization, obtain high-purity phosphoric acid sodium, content 98.1%, the gas that carbonization produces also passes in combustion chamber, at high temperature Thorough combustion together with the organic gas of thermo-cracking, discharge after the tail gas quenching to 200 DEG C produced is following.
Claims (16)
1. the treatment process of phosphorous waste material in a pesticide producing, it is characterized in that step comprises: by the solid-state phosphorous waste material of drying or/and the phosphorous solid materials that liquid phosphorous dehydrate waste materials obtains adds in thermal cracker, solid-state organic substance thermo-cracking is made to be organic gas, organic gas is introduced Thorough combustion in combustion unit, discharge after burning gained tail gas quenching; 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 also introduces combustion unit Thorough combustion;
Thermo-cracking is carried out under anaerobic, and carbonization is carried out in the presence of a gas containing oxygen.
2. treatment process according to claim 1, it is characterized in that: described phosphorous waste material refers to the phosphorous waste material of liquid state of directly generation in pesticide material, pesticide intermediate or pesticide producing process 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.
3. treatment process according to claim 2, is characterized in that: described solid-state phosphorous waste material comprises phosphorus-containing waste slag or/and phosphorous by product.
4. treatment process according to claim 2, is characterized in that: the phosphorous waste material of described liquid towards is or/and the process of solid-state phosphorous waste material comprises concentration, processed, regulate pH process, extraction treatment, rectification process, removes the process of not phosphorous raw material, by product, solvent.
5. treatment process according to claim 2, it is characterized in that: described phosphorous waste material comprises the mother liquor and waste water that produce in glyphosate production process, the phosphorous acid by product produced in acetochlor production process and waste water, the phosphorus-containing wastewater produced in acephate production process and by product, the organophosphorus waste liquid produced in Chlorpyrifos 94 production process, the phosphorus-containing waste slag produced in Stam F-34 production process and waste liquid, the phosphorous by product produced in grass ammonium phosphine production process and waste liquid, Provado, chlorimuronethyl, triazophos, Malathion, Trichlorphon, SD-1750, the phosphorous waste material that Rogor and methamidophos pesticide produce in producing, phosphorus trichloride, phosphorus oxychloride, phosphoric acid, the phosphorous waste material produced in the production process of phosphorous acid and the phosphorous raw material needed for dimethylphosphite agricultural chemicals or intermediate.
6. method according to claim 1 and 2, is characterized in that: described phosphorous waste material be directly produce in glyphosate or glyphosate intermediate production process containing phosphorus waste liquid or after treatment containing phosphorus waste liquid.
7. method according to claim 6, it is characterized in that: described phosphorous waste material is at least one in following mother liquor: 1. add the glyphosate alkaline mother liquor after alkali collection triethylamine in process of preparing glyphosate by glycine method, 2. IDA legal system is for the mother liquor produced in glyphosate process, the mother liquor produced in the intermediate pmida98 preparation process of 3. glyphosate, 4. above-mentioned 1., 2., the mother liquor of 3. three kinds of mother liquors gained after dechloratation Ficus caricaL.
8. the treatment process according to any one of claim 1-5, is characterized in that: when phosphorous waste material is the phosphorous waste material of liquid state containing 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) filtrate is dewatered, obtain phosphorous solid materials;
(3) following method is adopted to process separately respectively the phosphorous solid materials of the solid salt of step (1) and step (2): solid salt or phosphorous solid materials are added thermal cracker, the organic substance thermo-cracking in solid salt or phosphorous solid materials is made to be organic gas, organic gas is introduced Thorough combustion in combustion unit, discharge after burning gained tail gas quenching; Solid salt after thermo-cracking or phosphorous solid materials enter carbonizing plant, be further purified by high temperature cabonization, obtain high purity chloride salt after solid salt carbonization, obtain high-purity phosphoric acid salt after solid materials carbonization, the gas that carbonization produces also introduces combustion unit Thorough combustion.
9. the treatment process according to any one of claim 1-5, is characterized in that: thermal cracking temperature is 350-550 DEG C; Carbonization temperature is 650-750 DEG C; The gas that thermo-cracking and carbonization produce burns 2-5s at 900-1100 DEG C, discharges after burning gained tail gas quenching to 200 is DEG C following; Gained high purity chloride salt water is made into salt solution, after gained salt solution chemical precipitation agent or nanofiltration membrane remove the trace amounts of phosphorus contained, for chlorine industry.
10. treatment process according to claim 9, is characterized in that: the thermo-cracking time is 5-60min; Carbonization time is 10-60min; Oxygen-containing gas is one or more in air, oxygen-rich air and oxygen.
11. treatment processs according to claim 10, is characterized in that: the thermo-cracking time is 5-10min; Carbonization time is 10-15min.
12. treatment processs according to any one of claim 1-5, it is characterized in that: described method is also included in before liquid phosphorous dehydrate waste materials 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 high-purity phosphoric acid salt recrystallization carbonization obtained.
13. treatment processs according to claim 12, is characterized in that: the phosphoric acid salt purity after recrystallization is more than 98%.
14. treatment processs according to claim 12, 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 metal ion and metal ion price long-pending is 3.0-4.5 with the ratio of phosphorus mole number, the high-purity phosphoric acid salt finally obtained is based on orthophosphoric acid salt; When metal ion and metal ion price long-pending is 1.9-2.2 with the ratio of phosphorus mole number, the high-purity phosphoric acid salt finally obtained is based on pyrophosphate salt; When metal ion and metal ion price long-pending is 1.5-1.8 with the ratio of phosphorus mole number, the high-purity phosphoric acid salt finally obtained is based on poly-phosphate; When metal ion and metal ion price long-pending is 0.9-1.2 with the ratio of phosphorus mole number, the high-purity phosphoric acid salt finally obtained is based on metaphosphate.
15. treatment processs according to claim 8, 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; Combustion unit is the roasting kiln for organic gas burning.
16. treatment processs according to claim 15, is characterized in that: carbonizing plant is rotary kiln.
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| 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 |
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