CN102616914B - Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby - Google Patents
Treatment method of phosphorus-containing waste from pesticide production and product obtained thereby Download PDFInfo
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Abstract
The invention relates to a treatment method of phosphorus-containing waste liquids from pesticide production. The method comprises: subjecting a phosphorus-containing waste from pesticide production to high-temperature oxidation by contacting the phosphorus-containing waste from pesticide production with an oxygen-containing gas under a temperature of 250DEG C-1200DEG C, and recovering the obtained solid product. By means of the method provided in the invention, the use of expensive reagents can be avoided and no secondary waste that is difficult to treat can be produced. The phosphorus-containing pesticide production waste liquids can be transformed into pyrophosphates, polyphosphates, metaphosphates, orthophosphates, and other substances. These substances can be used for other chemical production so as to realize recycling of the phosphorus element.
Description
Technical field
The present invention relates to a kind of method processing the phosphorous waste material of pesticide producing and the product obtained by the method, more specifically, relate to a kind of by phosphorous for pesticide producing waste material high-temperature oxide treatment, and reclaim the method for phosphor resource, and the product obtained by the method.
Background technology
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.
As chemical dephosphorization method, Chinese patent 200910050066.0 discloses a kind for the treatment of process containing organism P wastewater.Trade effluent containing organophosphorus is removed after suspended substance through sandfiltration pot and is regulated pH by it, through efficiently catalyzing and oxidizing device, add hydrogen peroxide and oxidative degradation is carried out to it, then the organism of difficult degradation is removed by catalytic microelectrolyzer, again through the multi-stage oxidizing process of hydrogen peroxide, add flocculation sediment after lime, form phosphoric acid molysite and calcium precipitation, thus the phosphorus in removing waste water.
Chinese patent 200910308364.5 discloses a kind of method by integrated membrane separation process process glyphosate mother solution, mainly for the treatment of the glyphosphonic acid aqueous mother liquor of producing glyphosate by using glycine gained.It first carries out electrodialysis to glyphosate mother solution, and next carries out nanofiltration process, then carries out reverse-osmosis treated.Final warp concentrates the solution obtained containing more than 5% ammonium glyphosate.The method can reduce steam consumption comparatively significantly.Shortcoming is that the Integrated Films life-span is shorter, cost is higher, and after process, the glyphosate mother solution residuum that obtains is difficult to further process, and need use a large amount of fresh water and produce the weak brine that a large amount of need process further simultaneously, and commercial application difficulty is larger.
Chinese patent 200910073889.5 discloses a kind of recoverying and utilizing method of glyphosate mother solution.Wherein in glyphosphonic acid aqueous mother liquor, add organic solvent, after the block polymers containing phosphorus polymer that removing produces, separate out glyphosate crystal; After reclaiming the organic solvent in filtrate, add alkali and neutralize and remove triethylamine, obtain glyphosate mother solution; Then glyphosate mother solution being concentrated into glyphosate content is more than 10%.The shortcoming of the method is that the organic solvent used not only increases cost and has detrimentally affect to environment, and meanwhile, the mother liquor finally obtained still needs process further to use.
Chinese patent 201010186166.9 discloses a kind of Deepen processing method of glyphosate mother solution, and process method step is: (1) is reclaimed in the glyphosate mother solution of triethylamine at glycine method and added excessive strong acid; (2) glyphosate mother solution that step (1) obtains being concentrated into glyphosate content is 8-10%; (3) filtrate that step (2) obtains to be added in weak base and in glyphosate mother solution after remaining strong acid, for preparing 30% ammonium glyphosate and 41% glyphosate isopropylamine salt water solution.This treatment process mid-early stage the excessive strong acid introduced the later stage need with in alkali and, produce a large amount of salt, thus add secondary treatment of wastes produced difficulty.
Summary of the invention
For overcoming the above-mentioned problems in the prior art, the invention provides and a kind ofly can process the phosphorous waste material of pesticide producing and therefrom reclaim the method for phosphorus.
Described method comprises, and is oxidized by phosphorous for pesticide producing waste material high-temperature at the temperature of 250 DEG C-1200 DEG C by making the phosphorous waste material of described pesticide producing contact with oxygen-containing gas, then reclaims gained solid product.
By method of the present invention, the phosphoric in the phosphorous waste material of pesticide producing can be changed to positive phosphoric acid salt, pyrophosphate salt, poly-phosphate or metaphosphate, and/or its mixture.This product for industrial and agricultural production directly or after simple separation is purified, can realize the abundant recycling of phosphoric, not only obviously reduces the processing cost of described waste material, and substantially do not produce secondary slugs while process waste material.
Therefore, the present invention also provide on the other hand by aforesaid method obtain based on orthophosphoric acid salt, pyrophosphate salt, poly-phosphate or metaphosphate, or be the product of its mixture.
Embodiment
The method of the phosphorous waste material of process pesticide producing of the present invention comprises, and is oxidized by phosphorous for pesticide producing waste material high-temperature at the temperature of 250 DEG C-1200 DEG C by making the phosphorous waste material of described pesticide producing contact with oxygen-containing gas, then reclaims gained solid product.
The phosphorous waste material of described pesticide producing refers to the phosphorous waste material or by product that produce in various pesticide producing process and in intermediate production process, such as waste water, solid waste or solid-liquid mixtures waste material etc.Such as can be: the mother liquor produced 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, and Provado, chlorimuronethyl, triazophos, the phosphorous waste material produced in the pesticide producing such as Malathion, or phosphorus trichloride, phosphorus oxychloride, phosphorous acid, the waste material produced in the phosphorous raw material used in the pesticide producing such as dimethylphosphite or the production process of intermediate.
The phosphorous waste material produced in the preferred glyphosate production process of the phosphorous waste material of described pesticide producing, more preferably the glyphosate alkaline mother liquor after alkali collection triethylamine is added in process of preparing glyphosate by glycine method, or IDA method glyphosate production glyphosate prepares produced mother liquor or intermediate pmida98 prepares produced mother liquor, or above-mentioned three kinds of mother liquors are respectively through the material of gained after process or its material of gained after treatment after mixing arbitrarily, or two or more mixture any of above-mentioned three kinds of mother liquors and the material of gained after treatment thereof.
Outside dephosphorization, the phosphorous waste material of described pesticide producing can also containing other can high temperature oxidation remove material and/or salt.
Described high temperature oxidation can carry out as follows: passed into by oxygen-containing gas in high-temperature oxidation device, contacts, carry out oxidizing reaction with the phosphorous waste material of described pesticide producing.Wherein, can by passing into high-temperature gas and make to reach temperature required in described high-temperature oxidation device in described high-temperature oxidation device, also can adopt other any known type of heating, direct heating be carried out to high-temperature oxidation device and material as electrically heated or the type of heating such as magnetic field heating or thermal field heating.When using described high-temperature gas, it can pass into high-temperature oxidation device respectively with oxygen-containing gas, or passes into high-temperature oxidation device after mixing with oxygen-containing gas.
Described oxygen-containing gas can be such as air, oxygen or its mixed gas etc.
Described high-temperature oxidation device can be the combination of one or more devices be selected from the reactors such as fixed bed, fluidized-bed, ebullated bed, agitated bed, rotary kiln, preferred fluidized-bed or ebullated bed.
Described high temperature oxidation also can be undertaken by following burning mode: under the condition that oxygen-containing gas injects, make to enter incinerator liquid or gas fuel combustion, by the phosphorous waste material high-temperature oxidation of described pesticide producing entering this device.Burning can use liquid fuel, geseous fuel or by any one or a few solid fuel such as coal, charcoal, timber or will add thermogenetic high-temperature gas by alternate manners such as electrically heated, magnetic field heating or thermal field heating and pass into incinerator, fully to burn simultaneously.
Described incinerator can be the combination of any one or these devices be selected from vertical incinerator, horizontal incinerator, box-type furnace, rotary kiln, grate incinerator, fluidized bed incinerator, fluidizing furnace, is preferably grate incinerator, fluidized bed incinerator, fluidizing furnace, box-type furnace.
Described liquid fuel or geseous fuel can be any known liquid or geseous fuel, such as, the mixture of one or more materials in coal gas, water-gas, Sweet natural gas, liquefied petroleum gas (LPG), lightweight oil, mink cell focus, methyl alcohol, ethanol, methylal or formaldehyde etc.
Liquid waste dispersion state can introduce described high-temperature oxidation device or incinerator, preferably introduces with Sprayable.Solid waste or solid-liquid mixtures waste material can be introduced into described high-temperature oxidation device or incinerator by liquid or gas entrainment introducing or mechanical dispersion.Also phosphorous pesticide producing waste liquid or solid-liquid mixtures waste material first can be carried out drying and/or granulation, then evenly be filled in high-temperature oxidation device or incinerator.Described drying and/or prilling temperature can be 80 ~ 600 DEG C.
Described high temperature oxidation can carry out in a high-temperature oxidation device and/or incinerator, also can carry out in the high-temperature oxidation device of two or more series connection and/or incinerator.When carrying out in the high-temperature oxidation device and/or incinerator of two or more series connection, wherein any one or morely can be described high-temperature oxidation device or for described incinerator.When using incinerator as the first high-temperature oxidation device, preferably connect thereafter one or more incinerator or high-temperature oxidation device, to guarantee that high temperature oxidation fully carries out again.
Described high temperature oxidation can the mode of intermittent type, continous way or semi continuous carry out.
Make the tail gas from high-temperature oxidation device or incinerator enter exhaust treatment system to process.Described exhaust treatment system can be tail gas high-temperature oxidation device, fly-ash collector, residual heat using device, tail gas desulfurizing device, quenching apparatus and/or cleaning apparatus etc.Preferred described vent gas treatment is: make the tail gas from high-temperature oxidation device or incinerator enter tail gas high-temperature oxidation device, such as secondary combustion chamber, high-temperature chamber, oxygenating room etc., thus carry out high temperature oxidation to tail gas.Ash content in the tail gas that fly-ash collector collection tail gas high-temperature oxidation device also can be used to produce, is preferably back to described high-temperature oxidation device by this ash content subsequently or incinerator carries out high temperature oxidation further.Interchanger can be entered from the tail gas of fly-ash collector discharge and carry out energy recovery, as entered waste heat boiler to produce steam; Gac and slaked lime and fly-ash separator finally can be used to process the tail gas after energy recovery.
Preferably waste material high-temperature is oxidizing to it and is all converted into white or pale solid.This solid phase prod main component is one or more in orthophosphoric acid salt, poly-phosphate, pyrophosphate salt, metaphosphate.Also other inorganic salts, such as sodium-chlor, Repone K, calcium chloride, magnesium chloride, cupric chloride, aluminum chloride, zinc chloride, tin chloride, sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, copper sulfate, Tai-Ace S 150, zinc sulfate, tin sulphate etc. may be contained in product.
The total content of described orthophosphoric acid salt, poly-phosphate, pyrophosphate salt, metaphosphate or its mixture can account for 25 ~ 99.9% of the weight of described solid phase prod, and preferably 50 ~ 99%, more preferably 70 ~ 99%.Described orthophosphoric acid salt, poly-phosphate, pyrophosphate salt, metaphosphate can be one or more of sodium salt, sylvite, calcium salt, magnesium salts, mantoquita, aluminium salt, zinc salt, pink salt etc.Described poly-phosphate can be tri-polyphosphate or other poly-phosphate and composition thereof.Described metaphosphate can be trimetaphosphate, tetrametaphosphate or hexametaphosphate and composition thereof.
In the present invention, content represents with weight percent, unless otherwise noted.
Orthophosphoric acid salt in the present invention also known as phosphoric acid salt, as sodium phosphate.
Method of the present invention carries out pre-treatment to the phosphorous waste material of pesticide producing before also can being included in described high temperature oxidation.
Described pre-treatment comprises the content reducing other inorganic salt and/or the content improving phosphorus in described waste material.Negatively charged ion in phosphorous for pesticide producing waste material, such as chloride ion content be reduced to less than 5 % by weight preferably by pre-treatment, sulfate ion is reduced to less than 13 % by weight, nitrate ion is reduced to less than 9 % by weight.
Described pretreated method can be one in oxidation, concentrated, precipitation, filtration treatment mode or its combination.
The effect of described oxidation mainly makes the longer organic molecule of chain length be converted into the shorter organic molecule of chain length, when combinationally using with concentration technology, can effectively make liquid viscosity reduce, and concentration rate improves, and makes to be more prone to during concentrated removing inorganic salt.
Described oxidation is by gas sparging or add oxygenant, or the two makes for realizing simultaneously.
The described gas for bubbling can be air or oxygen or any other oxidizing gas.
Described oxygenant can be hydrogen peroxide, hydrogen peroxide/ozone, Fenton reagent, dioxide peroxide, sodium chlorate, potassium permanganate, gac, platinum carbon, palladium carbon and other known oxygen agents.
Described concentrating can improve phosphorus element content, reduces moisture content and/or other salt content except phosphoric acid salt, thus reduces the energy consumption in subsequent disposal, and the product purity that subsequent disposal is obtained is higher.Concentrate and undertaken by such as evaporation or other suitable method.If employing evaporation concentration, then can be that single-action is concentrated, Multi-effect concentration or heat pump techniques concentrate.
Concentrate and also undertaken by membrane separating method, the phosphorus content obtained by membrane sepn is higher and other inorganic salt contents are lower solution (rich phosphorus solution) carries out high temperature oxidation process according to the method described above.
Described film is any known micro-filtration and ultra-filtration membrane that can reach described concentrated effect, as permeable membrane, ionic membrane, ultra-filtration membrane, reverse osmosis membrane, vacuum tunica fibrosa, nanofiltration membrane, millipore filter etc.
Described precipitin reaction mainly adopts the metal ions such as calcium, magnesium, copper, tin the organophosphorus in waste material or inorganic phosphorus to be precipitated, and then carries out above-mentioned high temperature oxidation process to precipitated solid.
Described solid or liquid-solid material, if separate out or dissolve in the solid of conventional acid, alkali (example hydrochloric acid, liquid caustic soda) because of satiety, need first to dissolve before carrying out above-mentioned pre-treatment.
The present invention also provide by aforesaid method obtain based on orthophosphoric acid salt, pyrophosphate salt, poly-phosphate or metaphosphate, or be the product of its mixture.
As needed to produce based on a kind of product in orthophosphoric acid salt, pyrophosphate salt, poly-phosphate or metaphosphate, the ratio of phosphorus and metal ion in described waste material can be adjusted before high temperature oxidation.As used simultaneously, this process and above-mentioned pretreated order are also unrestricted; Preferably first after pre-treatment, then adjust the ratio of phosphorus and metal ion in described waste material.
The ratio of described phosphoric and metal ion adjusts by the material and/or phosphorus containg substances adding metal ion in the phosphorous waste material of pesticide producing.
Described metal ion can be one or more in sodium ion, potassium ion, calcium ion, magnesium ion, cupric ion, aluminum ion, zine ion, tin ion.
Described phosphorus containg substances can be one or more in phosphoric acid, phosphorous acid, phosphoric acid salt, phosphite.
Described phosphoric acid salt and phosphite are preferably sylvite, sodium salt, calcium salt and/or magnesium salts.
According to the ratio of phosphoric in waste material and metal ion, can obtain different from the product of orthophosphoric acid salt, poly-phosphate, pyrophosphate salt or metaphosphate after high temperature oxidation.
In the certain preferred embodiments of the inventive method,
Make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 2.4 and lower than 5.0, thus makes in the solid product of formation based on orthophosphoric acid salt;
Make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 2.0 and lower than 2.4, thus makes in the solid product of formation based on pyrophosphate salt;
Make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 1.2 and lower than 1.6, thus makes in the solid product of formation based on poly-phosphate; Or
Make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 0.8 and lower than 1.2, thus makes in the solid product of formation based on metaphosphate.
In the present invention, statement " based on substance A " represents that in the product formed, substance A content is the highest, and such as " based on orthophosphoric acid salt ", means that in product, orthophosphoric acid salt content is the highest.This content is preferably higher than 50%, more preferably more than 70%, most preferably more than 80%, especially preferred more than 85%.The product that content is the highest in the solid product formed is also referred to as principal product.
In the inventive method, also by adjustment (metal ion * metal ion price): the ratio of phosphorus mole number also controls high temperature oxidation temperature to obtain required principal product.
In a preferred embodiment of the inventive method, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 2.4 ~ 5.0 scopes, preferably in 2.5 ~ 5.0 scopes, and control high temperature oxidation temperature is 400-1200 DEG C, be preferably 600-1200 DEG C, thus make in the solid product of formation based on orthophosphoric acid salt.
In another preferred embodiment of the inventive method, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.6 ~ 2.4 scopes, preferably in 1.7 ~ 2.4 scopes, more preferably in 1.7 ~ 2.3 scopes, and control high temperature oxidation temperature is 600-1200 DEG C, be preferably 600-900 DEG C, thus make in the solid product of formation based on pyrophosphate salt.
In another preferred embodiment of the inventive method, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.2 ~ 2.0 scopes, preferably in 1.2 ~ 1.9 scopes, more preferably in 1.3 ~ 1.9 scopes, and control high temperature oxidation temperature is 250-600 DEG C, preferred 300-550 DEG C, thus make in the solid product of formation based on poly-phosphate.
In another preferred embodiment of the inventive method, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 0.8 ~ 1.2 scope, preferably in 0.9 ~ 1.2 scope, more preferably in 0.9 ~ 1.1 scope, and control high temperature oxidation temperature is 400-900 DEG C, be preferably 500-900 DEG C, thus make in the solid product of formation based on metaphosphate.
The preferred high temperature oxidation time is not less than 15 minutes.
It is noted that above various ratio range just cited by a certain principal product and high temperature oxidation temperature range can arbitrary combination, the embodiment obtained is content of the present invention.
Also be pointed out that, in the present invention, " high temperature oxidation temperature " refers to the temperature of the high temperature oxidation of terminal stage, and such as, when high temperature oxidation carries out in the high-temperature oxidation device that two or more are connected and/or incinerator, " high temperature oxidation temperature " refers to the temperature in last device." high temperature oxidation time " refers to the overall average residence time of reactant in the high-temperature oxidation device of one or more series connection.
The solid product of high temperature oxidation gained can be directly used in work, agriculture production or other purposes after crushed, also can further separation and purification as required, such as, obtain the higher product of purity by recrystallization.
Further illustrate the present invention by the following examples.
Embodiment 1:
By produce in glyphosate production process phosphorous 3% waste liquid at temperature 140-160 DEG C, under the condition of more than pressure 0.6MPa, pass into air and carry out 8h oxidizing reaction, then evaporation concentration, again after filtration except the NaCl decrystallized out, obtain phosphorous 12%, chloride ion-containing 4.0%, dense containing phosphorus waste liquid containing Na ion 17% (mass percent).
Add solid sodium hydroxide to through above-mentioned pretreated dense containing in phosphorus waste liquid, make sodium mole number: phosphorus mole number=2.8.Then be injected to gained waste liquid as in the fluidized bed incinerator of incinerator, spray into natural gas igniting simultaneously, and pass into air, control incineration temperature is 800-1000 DEG C, and mean residence time is 15min.The white solid thing of sodium phosphate content about 90% is obtained at fluidized combustion furnace bottom.Incineration tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after ash content through fly-ash collector, and the ash content of collection is circulated in described fluidized bed incinerator and burns further.
Embodiment 2
By produce in glyphosate production process phosphorous 1.0% the direct evaporation concentration of waste liquid, more after filtration except the NaCl decrystallized out, obtain phosphorous 5%, chloride ion-containing 5.0%, dense containing phosphorus waste liquid containing Na ion 8% (mass percent).
Add sodium hydroxide to through above-mentioned pretreated dense containing in phosphorus waste liquid, make sodium mole number: phosphorus mole number=1.9.Then be injected to gained waste liquid as in the grate incinerator of incinerator, spray into water-gas simultaneously and light, and pass into oxygen, control incineration temperature is 400-500 DEG C, and the mean residence time on fire grate is more than 15min.The white solid thing containing about 92% tripoly phosphate sodium STPP is obtained at bottom of incinerator.Incineration tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after ash content through fly-ash collector, and the ash content of collection is circulated in described fluidized bed incinerator and burns further.
Embodiment 3
By produce in glyphosate production process phosphorous 3.0% the direct evaporation concentration of waste liquid, more after filtration except the NaCl decrystallized out, obtain phosphorous 6%, chloride ion-containing 4.0%, dense containing phosphorus waste liquid containing Na ion 8% (mass percent).
Add SODIUM PHOSPHATE, MONOBASIC to through above-mentioned pretreated dense containing in phosphorus waste liquid, make sodium mole number: phosphorus mole number=1.2.Then be injected to gained waste liquid as in the rotary kiln of incinerator, spray into natural gas igniting simultaneously, and pass into air, control incineration temperature is 250-500 DEG C, obtains dark gray powder shape solid.Be loaded as the fixed bed of high-temperature oxidation device, passed into air, at 250-500 DEG C of high temperature oxidation, ensured that mean residence time is at more than 15min, obtains the tripoly phosphate sodium STPP white solid thing that main component is about 73%.Incineration tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after ash content through fly-ash collector, and the ash content of collection is circulated in described fluidized bed incinerator and burns further.
Embodiment 4:
By produce in glyphosate production process phosphorous 3% waste liquid, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant sodium chlorate oxidation 2h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 11%, chloride ion-containing 2.5%, dense containing phosphorus waste liquid containing Na ion 15% (mass percent).
Add phosphoric acid to through above-mentioned pretreated dense containing in phosphorus waste liquid, make sodium mole number: phosphorus mole number=1.2.Then be injected to gained waste liquid as in the fluidized bed incinerator of incinerator, spray into natural gas igniting simultaneously, and pass into air, control incineration temperature is 600-700 DEG C, and mean residence time is 30min.The white solid thing containing about 80% Trisodium trimetaphosphate is obtained at bottom of incinerator.
Embodiment 5:
By produce in glyphosate production process phosphorous 1.5% waste liquid, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant sodium chlorate oxidation 1h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 10%, chloride ion-containing 3%, dense containing phosphorus waste liquid containing Na ion 13% (mass percent).
Phosphoric acid is added containing in phosphorus waste liquid to through the dense of above-mentioned process, regulate sodium mole number: phosphorus mole number=1.0, then waste liquid is injected to the fluidized bed incinerator as incinerator, incineration temperature is 600-800 DEG C, obtain pulverous solid of grey black, then it is delivered to together with the powder reclaimed from tail gas the fluidized-bed as high-temperature oxidation device, at 400-500 DEG C of high temperature oxidation, ensure that mean residence time is at more than 15min, obtains the Trisodium trimetaphosphate white solid thing that main component is about 90%.
Embodiment 6:
By produce in glyphosate production process phosphorous 2.5% waste liquid, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant sodium chlorate oxidation 1h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 12%, chloride ion-containing 3%, dense containing phosphorus waste liquid containing Na ion 16% (mass percent).
Phosphoric acid is added to through pretreated dense containing in phosphorus waste liquid, regulate sodium mole number: phosphorus mole number=0.8, then waste liquid is injected to the box-type furnace as incinerator, incineration temperature is 800-900 DEG C, obtain pulverous solid of grey black, then it is delivered to together with the powder reclaimed from tail gas the fluidizing furnace as high-temperature oxidation device, at 700-800 DEG C of high temperature oxidation, ensure that mean residence time is at more than 15min, obtains the Sodium hexametaphosphate 99 white solid thing that main component is about 80%.
Embodiment 7:
Add copper sulfate in the waste liquid of produce in glyphosate production process phosphorous 1.0%, make it to generate precipitation, obtain the mantoquita of corresponding organophosphorus and phosphorous acid mantoquita and phosphoric acid mantoquita solid.Solid salt described in filtering separation, makes by adding phosphoric acid (the metal molar number * metal ion price) of gained solid mixture: phosphorus mole number=1.8.Then gained solid is filled into the fluidized bed incinerator as incinerator, sprays into natural gas igniting simultaneously, and pass into air, control incineration temperature is 450-550 DEG C, and mean residence time is 25min, obtains the white solid thing containing about 70% tripolyphosphate copper.By product recrystallization purifying.Incineration tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after ash content through fly-ash collector, and the ash content of collection is circulated in described fluidized bed incinerator and burns further.
Embodiment 8:
By produce in glyphosate production process phosphorous 3% waste liquid, at temperature 50-60 DEG C, under the condition of normal pressure, add oxidant hydrogen peroxide/ozone fully oxidized reaction 6h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 12%, chloride ion-containing 3%, dense containing phosphorus waste liquid containing Na ion 17% (mass percent).
Add solid phosphoric acid to through above-mentioned pretreated dense containing in phosphorus waste liquid, make sodium mole number: phosphorus mole number=0.9.Then gained waste liquid is injected to the grate incinerator as incinerator, sprays into lightweight oil simultaneously and light, and pass into air, control incineration temperature is 800-900 DEG C, and mean residence time is 30min.Obtain the white solid thing containing about 90% sodium-metaphosphate.
Embodiment 9:
By produce in glyphosate production process phosphorous 2.5% waste liquid, spray into incinerator fluidized bed incinerator, spray into natural gas igniting, and pass into air, control incineration temperature is 500-700 DEG C, ensure that mean residence time is at more than 15min, obtain the white solid thing of the Trisodium trimetaphosphate containing about 50%, all the other materials are other phosphoric acid salt materials.Tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after ash content through fly-ash collector, and the ash content of collection is circulated in described fluidized bed incinerator and burns further.
Embodiment 10:
The waste liquid of produce in pmida98 production process phosphorous 2% is carried out drying, obtain solidliquid mixture, it is introduced into fluidizing furnace as incinerator by entrained air, spray into natural gas igniting, control incineration temperature is 500-700 DEG C, ensure that mean residence time is at more than 15min, obtain the white solid thing of the Sodium hexametaphosphate 99 of content about 60%, all the other materials are other phosphoric acid salt materials.This solid product purifying is obtained the Sodium hexametaphosphate 99 of content 98.5%.
Embodiment 11
By in glyphosate production process phosphorous 2.5% waste liquid, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant sodium chlorate oxidation 1h, then concentrate, except the NaCl decrystallized, obtain phosphorous 12%, chloride ion-containing 3%, dense containing phosphorus waste liquid containing Na ion 16% (mass percent).
Pretreatedly densely sodium mole number is made containing adding sodium hydroxide in phosphorus waste liquid: phosphorus mole number=4.0 to through above-mentioned.Then gained waste liquid is sprayed into vertical incinerator, and spray into natural gas igniting, pass into air simultaneously, control incineration temperature is 900-1200 DEG C.Solids is obtained at bottom of incinerator, this solids is entered grate incinerator by entrained air be oxidized further, control temperature is 600-800 DEG C, ensures that mean residence time on fire grate is at more than 15min, finally obtains the white solid thing containing about 85% sodium phosphate.
Embodiment 12
Phosphorus waste liquid (main component is sodium phosphite) is contained by what produce in acetochlor production process, at temperature 20-30 DEG C, under the condition of normal pressure, add oxidant hydrogen peroxide/ozone oxidation 3h, then concentrate, removing NaCl, obtains phosphorous 10%, chloride ion-containing 2.5%, dense containing phosphorus waste liquid containing Na ion 17% (mass percent).
Pretreatedly densely sodium mole number is made containing adding phosphoric acid in phosphorus waste liquid: phosphorus mole number=2.1 to through above-mentioned.Then gained waste liquid is sprayed into vertical incinerator, and spray into natural gas igniting, pass into air simultaneously, control incineration temperature is 700-800 DEG C.Solids is obtained at bottom of incinerator, this solids is entered grate incinerator by entrained air be oxidized further, control temperature is 600-700 DEG C, ensures that mean residence time on fire grate is at more than 15min, finally obtains the pale solid thing containing about 85% trisodium phosphate.
Embodiment 13
By produce in Chlorpyrifos 94 production process phosphorous 2.4% waste liquid, at temperature 40-50 DEG C, under the condition of normal pressure, add oxidant hydrogen peroxide/ozone oxidation 6h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 12%, chloride ion-containing 3%, dense containing phosphorus waste liquid containing Na ion 17% (mass percent).
Pretreatedly densely sodium mole number is made containing adding sodium hydroxide in phosphorus waste liquid: phosphorus mole number=2.4 to through above-mentioned.Then gained waste liquid is sprayed into the fluidized-bed I as high-temperature oxidation device, and pass into oxygen, controlling high temperature oxidation temperature is 800-900 DEG C, ensures that mean residence time is at more than 3min.Under the effect of high gas velocity, take high temperature oxidation gained solid product out of fluidized-bed I, through cyclonic separation laggard enter fluidized-bed II.Controlling high temperature oxidation temperature is 600-700 DEG C, and mean residence time is 20min, obtains the white solid thing containing about 90% trisodium phosphate after being oxidized further.Fluidized-bed tail gas collects tail gas high temperature oxidation solid product through fly-ash collector, and is looped back in described fluidized-bed II by this solid product.
Embodiment 14
By produce in glyphosate production process phosphorous 3% waste liquid, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant Chlorine Dioxide Oxidation 3h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 11.5%, chloride ion-containing 2%, dense containing phosphorus waste liquid containing Na ion 15% (mass percent).
Pretreatedly densely sodium mole number is made containing adding sodium hydroxide in phosphorus waste liquid: phosphorus mole number=2.7 to through above-mentioned.Then gained waste liquid is sprayed into vertical incinerator, and spray into natural gas igniting, pass into air simultaneously, control incineration temperature is 900-1200 DEG C.Solids is obtained at bottom of incinerator, this solids is evenly loaded grate incinerator be oxidized further, control temperature is 700-900 DEG C, ensures that mean residence time on fire grate is at more than 15min, finally obtains the white solid thing containing about 82% sodium phosphate.
Embodiment 15
By produce in pmida98 production process phosphorous 2% waste liquid, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant sodium chlorate oxidation 2h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 12%, chloride ion-containing 2%, dense containing phosphorus waste liquid containing Na ion 15% (mass percent).
Pretreatedly densely sodium mole number is made containing adding sodium hydroxide in phosphorus waste liquid: phosphorus mole number=2.1 to through above-mentioned.Then gained waste liquid is sprayed into the fluidized-bed I as high-temperature oxidation device, pass into air, controlling high temperature oxidation temperature is 800-1000 DEG C, ensures that mean residence time is at more than 3min.Gained solid product takes fluidized-bed I out of under the effect of high gas velocity, after cyclonic separation, this solid product enters fluidized-bed II, pass into air, controlling high temperature oxidation temperature is 600-700 DEG C, ensure that mean residence time is at more than 15min, obtains the white solid thing containing about 95% trisodium phosphate after being oxidized further.Fluidized-bed tail gas collects the high temperature oxidation solid product carried secretly through fly-ash collector, and this solid product is circulated to further high temperature oxidation in described fluidized-bed II.The tail gas of being discharged by fly-ash collector discharges after waste heat boiler, desulfurizing device and sack cleaner.
Embodiment 16
Add calcium oxide in the waste liquid of produce in glyphosate production process phosphorous 1.0%, make it to generate precipitation, be mainly the calcium salt of corresponding organophosphorus and phosphorous acid calcium salt and calcium phosphate salt solid, and carry out solid-liquid separation.Regulate with calcium oxide again (the calcium mole number * 2) that make gained solid: phosphorus mole number=1.65, mix rear loading high-temperature oxidation device fluidized-bed, pass into air and controlled oxidization temperature is 800-900 DEG C, mean residence time is 20min, finally obtains the solids containing about 90% Calcium Pyrophosphate.
Embodiment 17
Add calcium oxide in the waste liquid of produce in glyphosate production process phosphorous 1.0%, make it to generate precipitation, be mainly the calcium salt of corresponding organophosphorus and phosphorous acid calcium salt and calcium phosphate salt solid, and carry out solid-liquid separation.Regulate with phosphoric acid again (the calcium mole number * 2) that make gained solid: phosphorus mole number=1.6, mix rear loading high-temperature oxidation device fluidized-bed, pass into air and controlled oxidization temperature is 450-550 DEG C, ensure that mean residence time is at more than 15min, finally obtains the solids containing about 85% tripolyphosphate calcium.
Embodiment 18
Add calcium oxide in the waste liquid of produce in glyphosate production process phosphorous 2.0%, make it to generate precipitation, be mainly the calcium salt of corresponding organophosphorus and phosphorous acid calcium salt and calcium phosphate salt solid, and carry out solid-liquid separation.Regulate with calcium oxide again (the calcium mole number * 2) that make gained solid: phosphorus mole number=3.2, horizontal incinerator is entered by entrained air after mixing, and spray into natural gas igniting, burn, controlled oxidization temperature is 800-1200 DEG C, ensure that mean residence time is at more than 15min, finally obtains the pale solid thing containing about 80% calcium phosphate.Successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after the flying dust that tail gas is carried secretly out by cyclone collection, the flying dust of collection loops back in described horizontal incinerator and burns further.
Embodiment 19
Add copper sulfate in the waste liquid of produce in glyphosate production process phosphorous 1.0%, make it to generate precipitation, be mainly the mantoquita of corresponding organophosphorus and phosphorous acid mantoquita and phosphoric acid mantoquita solid, and carry out solid-liquid separation.Regulate with copper hydroxide again (the copper mole number * 2) that make gained solid: phosphorus mole number=2.0, mix rear loading high-temperature oxidation device fluidized-bed, pass into air and controlled oxidization temperature is 700-900 DEG C, ensure that mean residence time is at more than 15min, finally obtains the cupric pyrophosphate containing about 90%.Successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after the flying dust that tail gas is carried secretly out by cyclone collection, the flying dust of collection loops back in described fluidized-bed.
Embodiment 20
By the solid waste produced in Stam F-34 production process, sodium mole number is regulated: phosphorus mole number=1.7 with phosphorous acid, mix rear loading high-temperature oxidation device fluidized-bed, pass into air and controlled oxidization temperature is 400-500 DEG C, mean residence time is 35min, finally obtains the white solid thing containing about 95% tripoly phosphate sodium STPP.Successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after the flying dust that tail gas is carried secretly out by cyclone collection, the flying dust of collection loops back in described fluidized-bed.
Embodiment 21
Add magnesium chloride in the waste water produced in acephate production process, make it to generate precipitation, obtain corresponding phosphorous acid magnesium salts, and carry out solid-liquid separation.Regulate with magnesium oxide again and make (magnesium mole number * 2): phosphorus mole number=2.0, mix rear loading high-temperature oxidation device ebullated bed and carry out oxidizing reaction, pass into air and controlled oxidization temperature is 800-900 DEG C, ensure that mean residence time is at more than 15min, finally obtains the solids containing about 92% magnesium pyrophosphate.Successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after the flying dust that tail gas is carried secretly out by cyclone collection, the flying dust of collection loops back in described ebullated bed.
Embodiment 22
Add tin protochloride in the waste water produced in Provado production process, make it to generate precipitation, obtain corresponding phosphorous acid tin salt, and carry out solid-liquid separation.Regulate with tin protoxide again and make (tin mole number * 2): phosphorus mole number=2.0, enter high-temperature oxidation device fluidized-bed after mixing and carry out oxidizing reaction, controlled oxidization temperature is 700-800 DEG C, ensure that mean residence time is at more than 15min, finally obtains the stannous pyrophosphate containing about 95%.The flying dust that tail gas is carried secretly out by cyclone collection turns back to fluidized-bed, then through waste heat boiler, desulfurizing device and sack cleaner, discharges after reaching exhaust emission standard.
Embodiment 23
Waste liquid (adopting potassium hydroxide to reclaim the alkaline waste liquor after triethylamine) by produce in glyphosate production process phosphorous 2%, temperature 80-100 DEG C, under the condition of normal pressure, add oxidant potassium permanganate oxidation 2h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 9%, chloride ion-containing 3.5%, dense containing phosphorus waste liquid containing potassium ion 24% (mass percent).
Add potassium hydroxide to through above-mentioned pretreated dense containing in phosphorus waste liquid, make potassium mole number: phosphorus mole number=2.2.Then gained waste liquid is sprayed into vertical incinerator, and spray into natural gas igniting, pass into air simultaneously, control incineration temperature is 700-800 DEG C.Obtain solids at bottom of incinerator, this solids is loaded box-type furnace and is oxidized further, pass into air and control temperature is 600-700 DEG C, ensure that mean residence time is at more than 15min, finally obtains the pale solid thing containing about 90% potassium pyrophosphate.Incineration tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected after tail gas high temperature oxidation solid product through fly-ash collector, remaining tail gas is through waste heat boiler, desulfurizing device and sack cleaner, discharge after reaching exhaust emission standard, the solid product of collection is then circulated in described box incinerator and burns further.
Embodiment 24
By produce in glyphosate production process phosphorous 3% waste liquid at temperature 140-160 DEG C, under the condition of more than pressure 0.6MPa, pass into air and carry out 8h oxidizing reaction, then evaporation concentration, again after filtration except the NaCl decrystallized out, obtain phosphorous 12%, chloride ion-containing 4.0%, dense containing phosphorus waste liquid containing Na ion 17% (mass percent).
Pretreatedly densely sodium mole number is made containing adding phosphoric acid in phosphorus waste liquid: phosphorus mole number=1.7 to through above-mentioned.Then gained waste liquid is sprayed into vertical incinerator, and spray into natural gas igniting, pass into air simultaneously, control incineration temperature is 600-800 DEG C.Solids is obtained at bottom of incinerator, this solids is entered grate incinerator by entrained air be oxidized further, control temperature is 300-500 DEG C, ensures that mean residence time on fire grate is at more than 15min, finally obtains the pale solid thing containing about 92% tripoly phosphate sodium STPP.
Embodiment 25
Waste liquid (adopting potassium hydroxide to reclaim the alkaline waste liquor after triethylamine) by produce in glyphosate production process phosphorous 2%, temperature 80-100 DEG C, under the condition of normal pressure, add oxidant potassium permanganate oxidation 2h, then concentrate, except the NaCl decrystallized out, obtain phosphorous 9%, chloride ion-containing 3.5%, dense containing phosphorus waste liquid containing potassium ion 24% (mass percent)
Phosphoric acid is used to regulate potassium mole number: phosphorus mole number=1.8, oven dry granulation is carried out at temperature 300-400 DEG C, obtain SOLID ORGANIC sodium phosphate salt, then enter high-temperature oxidation device fluidized-bed and carry out oxidizing reaction, controlled oxidization temperature is 400-500 DEG C, ensure that mean residence time is at more than 15min, finally obtains the tripoly phosphate sodium STPP containing about 88%.Successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after the flying dust that tail gas is carried secretly out by cyclone collection, the flying dust of collection loops back in described fluidized-bed.
Embodiment 26
By in glyphosate production process phosphorous 2% waste liquid, hydrochloric acid is used to regulate pH value to be 0.5, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant sodium chlorate oxidation 2h, then concentrate, removing NaCl, obtain phosphorous 11%, chloride ion-containing 2.5%, pretreated dense containing phosphorus waste liquid containing Na ion 15% (mass percent).
Pretreatedly densely sodium mole number is made containing adding sodium hydroxide in phosphorus waste liquid: phosphorus mole number=2.1 to through above-mentioned.Then gained waste liquid is sprayed into vertical incinerator, control incineration temperature is 700-900 DEG C.Obtain solids at bottom of incinerator, solids enters grate incinerator and is oxidized further, and control temperature is 600-800 DEG C, ensures that mean residence time on fire grate is at more than 15min, finally obtains the pale solid thing containing about 92% trisodium phosphate.Incineration tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after ash content through fly-ash collector, and the ash content of collection is circulated in described grate incinerator and burns further.
Embodiment 27
Using in glyphosate production process (utilizing sulfuric acid in glyphosate synthesis process as hydrolysis reaction catalyzer) phosphorous 2% waste liquid, sulfuric acid is used to regulate pH value to be 0.5, at temperature 80-100 DEG C, under the condition of normal pressure, add oxygenant Chlorine Dioxide Oxidation 3h, then concentrate, desalination, obtain phosphorous 11.5%, sulphate-containing ion 2%, pretreated dense containing phosphorus waste liquid containing Na ion 13% (mass percent).
Pretreatedly densely sodium mole number is made containing adding sodium hydroxide in phosphorus waste liquid: phosphorus mole number=2.2 to through above-mentioned.Then gained waste liquid is sprayed into vertical incinerator, control incineration temperature is 700-900 DEG C.Obtain solids at bottom of incinerator, solids enters grate incinerator and is oxidized further, and control temperature is 600-800 DEG C, ensures that mean residence time on fire grate is at more than 15min, finally obtains the pale solid thing containing about 72% trisodium phosphate.Incineration tail gas passes into the secondary combustion chamber as tail gas high-temperature oxidation device, the tail gas that secondary combustion chamber produces is collected successively by discharging after waste heat boiler, desulfurizing device and sack cleaner after ash content through fly-ash collector, and the ash content of collection is circulated in described grate incinerator and burns further.
Below be only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (50)
1. one kind processes the method for the phosphorous waste material of pesticide producing, by making the phosphorous waste material of described pesticide producing contact with oxygen-containing gas, phosphorous for pesticide producing waste material high-temperature is oxidized under being included in the temperature of 250 DEG C-1200 DEG C, and reclaim gained solid product, described high temperature oxidation proceeds to described solid product for white or pale solid, the phosphorous waste material of described pesticide producing is the mother liquor that produces in glyphosate 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 phosphorous by product produced in grass ammonium phosphine production process and waste liquid, or triazophos, the phosphorous waste material produced in Malathion pesticide producing, before described method is also included in and carries out described high temperature oxidation, phosphorous for pesticide producing waste material is carried out pre-treatment to reduce the step of the content of other not inorganic phosphor-contained salt, and described pre-treatment comprises oxidation, concentrated, precipitation, one in filtration treatment mode or its combination.
2. method according to claim 1, it is characterized in that, the mother liquor produced in described glyphosate production process and waste water are the glyphosate alkaline mother liquor after adding alkali collection triethylamine in process of preparing glyphosate by glycine method, or IDA method glyphosate production glyphosate prepares produced mother liquor or intermediate pmida98 prepares produced mother liquor, or above-mentioned three kinds of mother liquors are respectively through the material of gained after process or its material of gained after treatment after mixing arbitrarily, or two or more mixture any of above-mentioned three kinds of mother liquors and the material of gained after treatment thereof.
3. method according to claim 1, is characterized in that, described oxygen-containing gas is air, oxygen or its mixed gas.
4. method according to claim 1, is characterized in that, described high temperature oxidation carries out in incinerator.
5. method according to claim 4, is characterized in that, under the condition that oxygen-containing gas injects, make the liquid or the gas fuel combustion that enter incinerator, by the phosphorous waste material high-temperature oxidation of described pesticide producing entering this device.
6. method according to claim 5, is characterized in that, described incinerator is selected from the combination of any one or these devices in vertical incinerator, horizontal incinerator, box-type furnace, rotary kiln, grate incinerator, fluidized bed incinerator, fluidizing furnace.
7. method according to claim 1, is characterized in that, described high temperature oxidation carries out in high-temperature oxidation device, and described high-temperature oxidation device is selected from the combination of a kind of or these devices in fixed bed, fluidized-bed, ebullated bed, agitated bed and rotary kiln.
8. method according to claim 7, described high-temperature oxidation device is fluidized-bed or ebullated bed.
9. the method described in claim 4 or 7, is characterized in that, liquid waste introduces described high-temperature oxidation device or incinerator with dispersion state; Solid waste or solid-liquid mixtures waste material are introduced into described high-temperature oxidation device or incinerator by liquid entrainment or gas entrainment introducing or mechanical dispersion; Or evenly add high-temperature oxidation device or incinerator after phosphorous pesticide producing waste liquid or solid-liquid mixtures waste material are first carried out drying and/or granulation; Or described phosphorous pesticide producing solid waste is evenly filled into high-temperature oxidation device or incinerator.
10. method according to claim 9, is characterized in that, liquid waste enters described high-temperature oxidation device or incinerator with Sprayable.
11. methods according to claim 1, is characterized in that, described high temperature oxidation carries out in the high-temperature oxidation device and/or incinerator of one or more series connection.
12. methods according to claim 11, is characterized in that, the high temperature oxidation time is at more than 15min.
13. methods according to claim 11, is characterized in that when using incinerator as the first high-temperature oxidation device, connect thereafter one or more incinerator or high-temperature oxidation device again.
14. methods according to claim 5, it is characterized in that, described liquid fuel or geseous fuel are the mixtures of one or more materials in coal gas, water-gas, Sweet natural gas, liquefied petroleum gas (LPG), lightweight oil, mink cell focus, methyl alcohol, ethanol, methylal or formaldehyde.
Method described in 15. claims 4 or 7, is characterized in that, makes the tail gas from high-temperature oxidation device or incinerator enter tail gas high-temperature oxidation device and carries out tail gas high temperature oxidation.
16. methods according to claim 15, is characterized in that, the ash content in the tail gas using fly-ash collector collection tail gas high-temperature oxidation device to produce, is back to described high-temperature oxidation device by this ash content subsequently or incinerator carries out high temperature oxidation further.
17. methods according to claim 1, is characterized in that, the chloride ion content in phosphorous pesticide producing waste liquid is reduced to less than 5 % by weight, sulfate ion is reduced to less than 13 % by weight, nitrate ion is reduced to less than 9 % by weight by pre-treatment.
18. methods according to claim 1, is characterized in that, described oxide treatment is by by gas sparging or add oxygenant and carry out, and the gas for bubbling is air or oxygen or any other oxidizing gas; Described oxygenant is hydrogen peroxide, hydrogen peroxide/ozone, Fenton reagent, dioxide peroxide, sodium chlorate, potassium permanganate, palladium carbon, platinum carbon or other known oxygen agents.
19. methods according to claim 1, is characterized in that, described method adjusts the ratio of phosphorus and metal ion in described waste material before being also included in high temperature oxidation.
20. methods according to claim 19, is characterized in that, the step adjusting the ratio of phosphorus and metal ion in described waste material is carried out after the pre-treatment.
21. methods according to claim 19, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 2.4 and lower than 5.0, thus makes in the solid product of formation based on orthophosphoric acid salt.
22. methods according to claim 19, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 2.0 and lower than 2.4, thus makes in the solid product of formation based on pyrophosphate salt.
23. methods according to claim 19, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 1.2 and lower than 1.6, thus makes in the solid product of formation based on poly-phosphate.
24. methods according to claim 19, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number higher than 0.8 and lower than 1.2, thus makes in the solid product of formation based on metaphosphate.
25. methods according to claim 19, it is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 2.4 ~ 5.0 scopes, and control high temperature oxidation temperature is 400-1200 DEG C, thus makes in the solid product of formation based on orthophosphoric acid salt.
26. methods according to claim 25, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 2.5 ~ 5.0 scopes.
27. methods according to claim 25, is characterized in that, controlling high temperature oxidation temperature is 600-1200 DEG C.
28. methods according to claim 19, it is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.6 ~ 2.4 scopes, and control high temperature oxidation temperature is 600-1200 DEG C, thus makes in the solid product of formation based on pyrophosphate salt.
29. methods according to claim 28, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.7 ~ 2.4 scopes.
30. methods according to claim 28, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.7 ~ 2.3 scopes.
31. methods according to claim 28, is characterized in that controlling high temperature oxidation temperature is 700-1200 DEG C.
32. methods according to claim 19, it is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.2 ~ 2.0 scopes, and control high temperature oxidation temperature is 250-600 DEG C, thus makes in the solid product of formation based on poly-phosphate.
33. methods according to claim 32, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.2 ~ 1.9 scopes.
34. methods according to claim 32, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 1.3 ~ 1.9 scopes.
35. methods according to claim 32, is characterized in that, controlling high temperature oxidation temperature is 300-550 DEG C.
36. methods according to claim 19, it is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 0.8 ~ 1.2 scope, and control high temperature oxidation temperature is 400-900 DEG C, thus makes in the solid product of formation based on metaphosphate.
37. methods according to claim 36, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 0.9 ~ 1.2 scope.
38. methods according to claim 36, is characterized in that, make (metal ion * metal ion price): the ratio of phosphorus mole number is in 0.9 ~ 1.1 scope.
39. methods according to claim 36, is characterized in that, controlling high temperature oxidation temperature is 500-900 DEG C.
Method according to any one of 40. claim 19-36, is characterized in that, also comprises described solid product recrystallization with the step of purified product.
41. methods according to any one of claim 1-19 and 40 obtain based on orthophosphoric acid salt, pyrophosphate salt, poly-phosphate or metaphosphate, or be the product of its mixture.
42. products according to claim 41, is characterized in that, described orthophosphoric acid salt, pyrophosphate salt, poly-phosphate or metaphosphate are the mixture of one or more in sodium salt, sylvite, calcium salt, magnesium salts, mantoquita, aluminium salt, zinc salt and pink salt.
The product based on orthophosphoric acid salt that 43. methods according to any one of claim 21 or 25-27 obtain.
44. products according to claim 43, is characterized in that, described orthophosphoric acid salt is the mixture of one or more in sodium salt, sylvite, calcium salt, magnesium salts, mantoquita, aluminium salt, zinc salt and pink salt.
The product based on pyrophosphate salt that 45. methods according to any one of claim 22 or 28-31 obtain.
46. products according to claim 45, is characterized in that, described pyrophosphate salt is the mixture of one or more in sodium salt, sylvite, calcium salt, magnesium salts, mantoquita, aluminium salt, zinc salt and pink salt.
The product based on poly-phosphate that 47. methods according to any one of claim 23 or 32-35 obtain.
48. products according to claim 47, is characterized in that, described poly-phosphate is the mixture of one or more in sodium salt, sylvite, calcium salt, magnesium salts, mantoquita, aluminium salt, zinc salt and pink salt.
The product based on metaphosphate that 49. methods according to any one of claim 24 or 36-39 obtain.
50. products according to claim 49, is characterized in that, described metaphosphate is the mixture of one or more in sodium salt, sylvite, calcium salt, magnesium salts, mantoquita, aluminium salt, zinc salt and pink salt.
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| CN1208717A (en) * | 1997-08-05 | 1999-02-24 | 味之素株式会社 | Process for producing alkali metal polyphosphates |
| CN1384051A (en) * | 2001-04-28 | 2002-12-11 | 单光渝 | Prepn of feed-level tricalcium phosphate with phosphorus-containg waste liquid |
| CN101058415A (en) * | 2007-06-06 | 2007-10-24 | 南开大学 | Method of preparing feedstuff-stage tricalcium phosphate from industrial production sodium hypophosphite waste slag |
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| CN102620300A (en) | 2012-08-01 |
| CN102620300B (en) | 2014-12-31 |
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