CN103771378A - Method for reversely extracting and co-production of industrial-grade phosphate by using phosphate mother liquor for wet-method purification phosphoric acid - Google Patents
Method for reversely extracting and co-production of industrial-grade phosphate by using phosphate mother liquor for wet-method purification phosphoric acid Download PDFInfo
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- CN103771378A CN103771378A CN201310690776.6A CN201310690776A CN103771378A CN 103771378 A CN103771378 A CN 103771378A CN 201310690776 A CN201310690776 A CN 201310690776A CN 103771378 A CN103771378 A CN 103771378A
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Abstract
The invention discloses a method for reversely extracting and co-production of industrial-grade phosphate by using phosphate mother liquor for wet-method purification phosphoric acid, which is capable of lowering the production cost. The method comprises the following steps of a, adding a defluorination agent, an adsorbent and oxidizing agent in wet-method purification phosphoric acid for defluorination and decolorization; b, extracting phosphoric acid with an extraction agent, adding inorganic acid in the middle of an extraction tower; c, desulfurating and washing; d, reversely extracting with industrial-grade phosphate mother liquor; e, finely tuning slurry; f, feeding the finely tuned phosphate slurry into a crystallizer for crystallizing, then carrying out solid-liquid separation and drying to obtain product industrial-grade phosphate, wherein the slurry obtained from solid-liquid separation is industrial-grade phosphate mother liquor which is subjected to pH value adjustment and returned to step d for use. Reverse extraction is carried out by cooled and crystallized industrial-grade phosphate mother liquor, the reverse extraction effect is good, the step of evaporation is avoided, desulphurization and washing are carried out simultaneously, the procedures are simplified, and the production cost is saved. A new preparation method of the industrial-grade phosphate is provided.
Description
Technical field
The invention belongs to phosphorus chemistry industrial circle, be specifically related to a kind of method of the Wet Phosphoric Acid Market reducing production costs phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate.
Background technology
It is raw material that domestic and international manufacture level phosphoric acid salt adopts thermal phosphoric acid more, but not only cost is high but also energy consumption is more because thermal phosphoric acid is produced, and requires under the trend of energy-saving and emission-reduction in the current whole world, and it is an inevitable trend that Wet Phosphoric Acid Market substitutes thermal phosphoric acid; And in industry, use purifying phosphoric acid manufacture level phosphoric acid salt still to need the purifying phosphoric acid of producing to concentrate at present, desulfurization decolouring etc.
The patent that China produces Wet Phosphoric Acid Market has: a kind of " method of extracting and purifying wet-process phosphorous acid to produce industrial-grade phosphorous acid " that application number is 201010212175.0, this flow process is to contain 40-58%P
2o
5phosphoric acid by wet process be raw material pass through decolouring, extraction, washing, back extraction, desulfurization, concentration defluorinating, adopt pure water to carry out back extraction, its weak point: (1) is used pure water to carry out back extraction and obtains rare purifying phosphoric acid, need to concentrate moisture evaporation wherein if continue production phosphate product, be unfavorable for cost; (2) need to set up larger phosphoric acid storage tank and carry out centre saving, have disclosure risk, be unfavorable for cost and environmental protection; (3) purifying phosphoric acid of producing also needs to concentrate, desulfurization etc., and flow process is longer, and equipment investment is many, is unfavorable for controlling.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of the Wet Phosphoric Acid Market reducing production costs phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate.
The technical solution adopted for the present invention to solve the technical problems is: the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market, comprises the steps:
A, defluorinate and decolouring: in Wet Phosphoric Acid Market, add defluorinating agent to carry out defluorinate, then add sorbent material to carry out physical decolorization, filter in backward filtrate and add oxygenant to carry out chemical decolorization;
B, use the phosphoric acid after extraction agent phosphoric acid extraction: step a decolouring to enter extraction tower from top heavy phase import, from bottom, light phase import enters extraction tower to extraction agent, adds mineral acid to extract from extraction tower middle part simultaneously;
C, desulfurization washing: from bottom, light phase import enters washing tower to the organic phase obtaining after step b extraction, and sweetening agent enters washing tower from top heavy phase import and carries out desulfurization washing;
D, mother liquor back extraction: from bottom, light phase import enters back extraction tower to the organic phase after step b desulfurization washing, and industrial grade phosphate mother liquor enters back extraction tower from top heavy phase import and carries out countercurrent reextraction; Obtain industrial grade phosphate slip from tower body bottom;
E, slip accurate adjustment: in the industrial grade phosphate slip obtaining to steps d, add and contain cationic alkaline material adjustment identical with phosphoric acid salt, making slip pH value is 3.6～4;
F, crystallisation by cooling: the phosphoric acid salt slip after accurate adjustment is sent into crystallizer and carry out crystallization, then solid-liquid separation, oven dry obtain product industrial grade phosphate; The filtrate that solid-liquid separation obtains is industrial grade phosphate mother liquor, returns to steps d and use after regulating pH value.
Wherein, in aforesaid method step a, the concentration 52～55% of described Wet Phosphoric Acid Market, the amount that described defluorinating agent adds is 1～1.5 times of theoretical reacting weight, the add-on of sorbent material is 1.5～2.5% of Wet Phosphoric Acid Market weight, and the add-on of oxygenant is 0.5～1% of Wet Phosphoric Acid Market weight.
Wherein, in aforesaid method step a, while carrying out defluorinate and decolouring, the temperature of feed liquid is 65～75 ℃.
Wherein, in aforesaid method step a, described defluorinating agent is for containing sodium salt class and the material that active silica can be provided.
Wherein, in aforesaid method step b, described extraction agent be can slective extraction phosphoric acid organic extractant with can with the mixture of the organic solvent of the fine dilution of dissolving each other of organic extractant, described mineral acid provides hydrionic mineral acid for massfraction is greater than 96% the large limit of can doing, and the add-on of mineral acid is 9～13% of phosphoric acid weight.
Wherein, in aforesaid method step b, the volume ratio of extracted organic phase and water is 6～10 ︰ 1, and extraction temperature is 30～45 ℃.
Wherein, in aforesaid method step c, described sweetening agent is the aqueous solution, the add-on of sweetening agent is theoretical reacting weight 1～1.2 times.
Further, sweetening agent is barium carbonate or bariumchloride.
Wherein, in aforesaid method step c, phase volume ratio 20～30 ︰ 1 of washing organic phase and water, wash temperature is 55～65 ℃.
Wherein, in aforesaid method steps d, described phosphoric acid salt mother liquor is soluble phosphoric acid dihydric salt or hydrophosphate or sodium phosphate salt mother liquor, and proportion is 1.3～1.35, and after adjusting, pH value is 6～8.
Wherein, in aforesaid method steps d, the volume ratio of back extraction organic phase and water is 10～15 ︰ 1, and back extraction temperature is 80～85 ℃.
The invention has the beneficial effects as follows: the present invention adopts the industrial grade phosphate mother liquor after crystallisation by cooling to carry out back extraction, and back extraction is effective, avoided the step of evaporation, saved production cost.Integrated artistic desulfurization of the present invention and washing are carried out simultaneously, have further simplified operation, have reduced equipment, are more conducive to technology controlling and process, have also further saved production cost simultaneously.The processing parameter of optimization of the present invention can improve the effect of extraction, washing, back extraction etc., improves the total rate of recovery of phosphoric acid salt.The present invention, for industrial grade phosphate provides a kind of new preparation method, is suitable for applying at phosphorus chemistry industrial circle.
Accompanying drawing explanation
Fig. 1 is technical process schematic block diagram of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further described.
As shown in Figure 1, the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market of the present invention, comprises the steps:
A, defluorinate and decolouring: in Wet Phosphoric Acid Market, add defluorinating agent to carry out defluorinate, then add sorbent material to carry out physical decolorization, filter in backward filtrate and add oxygenant to carry out chemical decolorization;
B, use the phosphoric acid after extraction agent phosphoric acid extraction: step a decolouring to enter extraction tower from top heavy phase import, from bottom, light phase import enters extraction tower to extraction agent, adds mineral acid to extract from extraction tower middle part simultaneously;
C, desulfurization washing: from bottom, light phase import enters washing tower to the organic phase obtaining after step b extraction, and sweetening agent enters washing tower from top heavy phase import and carries out desulfurization washing;
D, mother liquor back extraction: from bottom, light phase import enters back extraction tower to the organic phase after step b desulfurization washing, and industrial grade phosphate mother liquor enters back extraction tower from top heavy phase import and carries out countercurrent reextraction; Obtain industrial grade phosphate slip from tower body bottom;
E, slip accurate adjustment: in the industrial grade phosphate slip obtaining to steps d, add and contain cationic alkaline material adjustment identical with phosphoric acid salt, making slip pH value is 3.6～4;
F, crystallisation by cooling: the phosphoric acid salt slip after accurate adjustment is sent into crystallizer and carry out crystallization, then solid-liquid separation, oven dry obtain product industrial grade phosphate; The filtrate that solid-liquid separation obtains is industrial grade phosphate mother liquor, returns to steps d and use after regulating pH value.
It will be appreciated by persons skilled in the art that extraction tower, washing tower and back extraction tower that the present invention uses can be the equipment such as tower, groove tank of the satisfied extraction function including rotating disc contactor.
Preferably, for cost-saving on the effect basis realizing better defluorinate decolouring, in aforesaid method step a, the concentration 52～55% of described Wet Phosphoric Acid Market, the amount that described defluorinating agent adds is 1～1.5 times of theoretical reacting weight, the add-on of sorbent material is 1.5～2.5% of Wet Phosphoric Acid Market weight, and the add-on of oxygenant is 0.5～1% of Wet Phosphoric Acid Market weight.Further, described sorbent material is gac.Described oxygenant is hydrogen peroxide.
Preferably, in order to make the better effects if of defluorinate decolouring, in aforesaid method step a, while carrying out defluorinate and decolouring, the temperature of feed liquid is 65～75 ℃.
Preferably, in aforesaid method step a, described defluorinating agent is for containing sodium salt class and the material that active silica can be provided.In order to make defluorination effect better, be preferably sodium carbonate and silicon-dioxide.Sodium carbonate and silicon-dioxide together react with the fluorine in phosphoric acid liquid, generate Sodium Silicofluoride (Na
2siF
6) precipitation, defluorination effect is good.The theoretical amount that defluorinating agent adds is that to make the ratio of molecular weight be Na ︰ Si ︰ F=2 ︰ 1 ︰ 6.
Preferably, in order to make the better effects if of extraction, in aforesaid method step b, described extraction agent be can slective extraction phosphoric acid organic extractant with can with the mixture of the organic solvent of the fine dilution of dissolving each other of organic extractant, described mineral acid provides hydrionic acid solution for massfraction is greater than 96% the large limit of can doing, and the add-on of mineral acid is 9～13% of phosphoric acid weight.Further, described extraction agent is the mixture of butyl phosphate and diluent kerosene, and described mineral acid is the vitriol oil that massfraction is greater than 96%.
Preferably, in order to make the better effects if of extraction, production cost is lower simultaneously, and in aforesaid method step b, the volume ratio of extracted organic phase and water is 6～10 ︰ 1, and extraction temperature is 30～45 ℃.
Preferably, in aforesaid method step c, described sweetening agent is that barium salt (it will be understood by those skilled in the art that, sweetening agent of the present invention is to make sulfate radical reacting generating salt can be good at again the salt separating from organic phase) aqueous solution, 1～1.2 times (barium ion and sulfate ion generate process white) that the add-on of sweetening agent is theoretical reacting weight.Concrete sweetening agent is barium carbonate or bariumchloride.
Further, in aforesaid method step c, phase volume ratio 20～30 ︰ 1 of washing organic phase and water, wash temperature is 55～65 ℃.
Wherein, in aforesaid method steps d, described phosphoric acid salt mother liquor is soluble phosphoric acid dihydric salt or hydrophosphate or sodium phosphate salt mother liquor, and preferred specific gravity is that 1.3～1.35, pH value is 6～8.Further, described phosphoric acid salt mother liquor is potassium primary phosphate or primary ammonium phosphate mother liquor.Described pH value is 6～8 pH values for the phosphoric acid salt mother liquor after adjusting.
Preferably, in order to make the better effects if of back extraction, production cost is lower simultaneously, and in aforesaid method steps d, the volume ratio of back extraction organic phase and water is 10～15 ︰ 1, and back extraction temperature is 80～85 ℃.
Below by embodiment, the specific embodiment of the present invention is described further, but therefore protection scope of the present invention is not limited among embodiment.
Embodiment mono-
The 12ktP of Sichuan Chuan Heng Chemical Co., Ltd
2o
5the meticulous salt device of/a technical grade Wet Phosphoric Acid Market coproduction Wet Phosphoric Acid Market 290t(material object), index is as following table 1:
Table 1
The step of manufacture level potassium primary phosphate is: defluorinate decolouring, extraction, desulfurization washing, mother liquor back extraction, slip accurate adjustment, crystallisation by cooling, centrifugal, drying and packaging.
(1) defluorinate decolouring: enter high temperature concentration systems from the phosphoric acid of wet method system and carry out after concentration defluorinating, through measuring with 5m
3the flow of/h adds decoloring reaction groove, with 166kg/h(phosphoric acid weight 2%) amount add wood powder shaped activated carbon 5.8t, add defluorinating agent 5.7t with the amount of 162kg/h simultaneously, temperature of reaction is 65 ℃-72 ℃, 1 hour successive reaction residence time, adopting filter pressing pump to be transported to plate and frame(type)filter press separates rear acid solution and enters phosphoric acid receiving tank, employing is pumped to phosphoric acid storage tank, simultaneously by be metered into massfraction be 30% hydrogen peroxide 1.45t(phosphoric acid weight 0.5%), be total to obtain defluorinate decolouring phosphoric acid 287t, proportion 1.66, P
2o
5be 52.9%, fluorine is 0.078%, obtains washing active carbon dilute phosphoric acid 7.1t, and washing gained phosphoric acid is containing P
2o
5: 23.5%, return to concentration systems.
(2) extraction: the mixed solvent that preparation contains tributyl phosphate and kerosene, proportion is 0.93, decolouring acid and desulfurization washing phosphoric acid mixing raw material (mixing acid proportion is 1.6), send into extraction tower top heavy phase through pump with 2.25m3/h and add entrance, mixed solvent is from solvent transfer tank, extraction phase is than 8:1, through volume pump with 18m
3/ h enters extraction tower by extraction tower bottom fluid inlet, temperature is 32 ℃-34 ℃, sulfuric acid adds at extraction tower middle part, add-on is 9% of phosphoric acid quality, flow is entering in tower of 0.324t/h, bottom extracting phase enters raffinate receiving tank, is delivered to fertilizer system, and top solvent phase enters desulfurization washing tower after clarified separation section: solvent phase proportion is 0.98t/m
3.
(3) desulfurization washing: from the solvent phase of extraction tower with 20m
3/ h enters washing tower bottom, and the sweetening agent preparing is with SO in solvent phase
4 2-% calculates and is incorporated as 0.8m
3/ h enters from desulfurization washing tower top and carries out adverse current desulfurization washing, temperature is 55 ℃-65 ℃, after desulfurization washing, solvent phase enters back extraction tower underfeed mouth through top clarified separation section, washing tower bottom liquid phase is washing acid, after clarified separation, uses again through being pumped into after phosphoric acid storage tank mixes with decolouring phosphoric acid as extraction feed.
(4) mother liquor back extraction: from the organic phase on desulfurization washing tower top with 20m
3/ h enters back extraction tower bottom, be 8 through adjusting pH value, proportion is 1.35 potassium primary phosphate mother liquor, temperature is 80-85 ℃, deliver to back extraction tower top opening for feed with pump with 1.4m3/h, carry out counter current contact, temperature 80-85 ℃ with solvent phase, after back extraction solvent phase through top settling section separate after enter interchanger lower the temperature processing after recycle, solvent phase proportion is 0.932/m
3, the potassium primary phosphate slip after back extraction enters continuously slip accurate adjustment groove after the settling section of back extraction tower bottom, and pH value is 3, and proportion is 1.44.
(5) slip accurate adjustment: directly enter slip accurate adjustment groove from the potassium dihydrogen slip of back extraction tower, to the liquid potash (KOH) that adds 48% concentration in slip accurate adjustment groove, adjusting slip pH value is 3.8, and proportion is 1.48.Slip after adjusting is carried to crystallisation by cooling groove with pump.
(6) crystallisation by cooling: use industrial circulating water to carry out crystallisation by cooling after entering crystallisation by cooling groove from the slip of accurate adjustment groove, slurry temperature uses whizzer to carry out liquid-solid separation while reaching 40 ℃, liquid phase enters mother liquor transfer tank and carries out recycling after pH value adjustment, solid phase enters fluidized-bed and dries, and is packaged to be PHOSPHORIC ACID TECH.GRADE potassium dihydrogen product.Products obtained therefrom index is as table 2:
Table 2
Accumulative total obtains PHOSPHORIC ACID TECH.GRADE potassium dihydrogen product: 281.5t, P2O5:139.9t, and extraction yield is 95%, and back extraction yield is 99%, and drying yield is 98%.
Embodiment bis-
The 12ktP of Sichuan Chuan Heng Chemical Co., Ltd
2o
5the meticulous salt device of/a technical grade Wet Phosphoric Acid Market coproduction raw material Wet Phosphoric Acid Market 132t(material object), index is as following table 3:
Table 3
The step of manufacture level potassium primary phosphate is: defluorinate decolouring, extraction, desulfurization washing, mother liquor back extraction, slip accurate adjustment, crystallisation by cooling, centrifugal, drying and packaging.
(1) defluorinate decolouring: enter high temperature concentration systems from the phosphoric acid of wet method system and carry out after concentration defluorinating, through measuring with 5m
3the flow of/h adds decoloring reaction groove, with 166kg/h(phosphoric acid weight 2%) amount add wood powder shaped activated carbon 2.64t, add defluorinating agent 2.47t with the amount of 155kg/h simultaneously, temperature of reaction is 65 ℃-72 ℃, 1 hour successive reaction residence time, adopting filter pressing pump to be transported to plate and frame(type)filter press separates rear acid solution and enters phosphoric acid receiving tank, employing is pumped to phosphoric acid storage tank, simultaneously by be metered into massfraction be 30% hydrogen peroxide 0.66t(phosphoric acid weight 0.5%), be total to obtain defluorinate decolouring phosphatase 11 31t, proportion 1.66, P
2o
5be 53.2%, fluorine is 0.071%, obtains washing active carbon dilute phosphoric acid 4.67t, and washing gained phosphoric acid is containing P
2o
5: 23%, return to concentration systems.
(2) extraction: the mixed solvent that preparation contains tributyl phosphate and kerosene, proportion is 0.93, decolouring acid and desulfurization washing phosphoric acid mixing raw material (mixing acid proportion is 1.6), send into extraction tower top heavy phase through pump with 2.25m3/h and add entrance, mixed solvent is from solvent transfer tank, extraction phase is than 8:1, through volume pump with 18m
3/ h enters extraction tower by extraction tower bottom fluid inlet, temperature is 32 ℃-34 ℃, sulfuric acid adds at extraction tower middle part, add-on is 9% of phosphoric acid quality, flow is entering in tower of 0.324t/h, bottom extracting phase enters raffinate receiving tank, is delivered to fertilizer system, and top solvent phase enters desulfurization washing tower after clarified separation section: solvent phase proportion is 0.98t/m
3.
(3) desulfurization washing: from the solvent phase of extraction tower with 20m
3/ h enters washing tower bottom, and the sweetening agent preparing is with SO in solvent phase
4 2-% calculates and is incorporated as 0.7m
3/ h enters from desulfurization washing tower top and carries out adverse current desulfurization washing, temperature is 55 ℃-65 ℃, after desulfurization washing, solvent phase enters back extraction tower underfeed mouth through top clarified separation section, washing tower bottom liquid phase is washing acid, after clarified separation, uses again through being pumped into after phosphoric acid storage tank mixes with decolouring phosphoric acid as extraction feed.
(4) mother liquor back extraction: from the organic phase on desulfurization washing tower top with 20m
3/ h enters back extraction tower bottom, is 6 through adjusting pH value, and proportion is 1.3, and temperature is 80-85 ℃, uses pump with 2m
3/ h delivers to back extraction tower top opening for feed, carries out counter current contact with solvent phase, temperature 80-85 ℃, after back extraction solvent phase through top settling section separate after enter interchanger lower the temperature processing after recycle, solvent phase proportion is 0.93t/m
3, the potassium primary phosphate slip after back extraction enters continuously slip accurate adjustment groove after the settling section of back extraction tower bottom, and pH value is 2.5, and proportion is 1.4.
(5) slip accurate adjustment: directly enter slip accurate adjustment groove from the potassium dihydrogen slip of back extraction tower, to the liquid potash (KOH) that adds 48% concentration in slip accurate adjustment groove, adjusting slip pH value is 4, proportion is that 1.44 slip pumps after adjusting are carried to crystallisation by cooling groove.
(6) crystallisation by cooling: use industrial circulating water to carry out crystallisation by cooling after entering crystallisation by cooling groove from the slip of accurate adjustment groove, slurry temperature uses whizzer to carry out liquid-solid separation while reaching 40 ℃, liquid phase enters mother liquor transfer tank and carries out recycling after pH value adjustment, solid phase enters fluidized-bed and dries, and is packaged to be the product that meets industrial phosphoric acid potassium dihydrogen standard (HG2321-92).Products obtained therefrom index is as table 4:
Table 4
Accumulative total obtains PHOSPHORIC ACID TECH.GRADE potassium dihydrogen product: 130.8t, P
2o
5: 64.9t, extraction yield is 95.5%, and back extraction yield is 99.5%, and drying yield is 98%.
Embodiment tri-
The 12ktP of Sichuan Chuan Heng Chemical Co., Ltd
2o
5the meticulous salt device of/a technical grade Wet Phosphoric Acid Market coproduction raw material Wet Phosphoric Acid Market 215.5t(material object), index is as following table 5:
Table 5
The step of manufacture level monoammonium phosphate is: defluorinate decolouring, extraction, desulfurization washing, mother liquor back extraction, slip accurate adjustment, crystallisation by cooling, centrifugal, drying and packaging.
(1) defluorinate decolouring: enter high temperature concentration systems from the phosphoric acid of wet method system and carry out after concentration defluorinating, through measuring with 5m
3the flow of/h adds decoloring reaction groove, with 163kg/h(phosphoric acid weight 2%) amount add wood powder shaped activated carbon 4.31t, add defluorinating agent 4.23t with the amount of 160kg/h simultaneously, temperature of reaction is 65 ℃-72 ℃, 1 hour successive reaction residence time, adopting filter pressing pump to be transported to plate and frame(type)filter press separates rear acid solution and enters phosphoric acid receiving tank, employing is pumped to phosphoric acid storage tank, simultaneously by be metered into massfraction be 30% hydrogen peroxide 1.07t(phosphoric acid weight 0.5%), be total to obtain defluorinate decolouring phosphoric acid 214t, proportion 1.63, P
2o
5be 52.5%, fluorine is 0.064%, obtains washing active carbon dilute phosphoric acid 6.6t, and washing gained phosphoric acid is containing P
2o
5: 22%, return to concentration systems.
(2) extraction: the mixed solvent that preparation contains tributyl phosphate, proportion is 0.93, decolouring acid and desulfurization washing phosphoric acid mixing raw material (mixing acid proportion is 1.58), through pump with 2.25m
3/ h sends into extraction tower top heavy phase and adds entrance, and mixed solvent is from solvent transfer tank, and extraction phase is than 8:1, through volume pump with 18m
3/ h enters extraction tower by extraction tower bottom fluid inlet, temperature is 32 ℃-34 ℃, sulfuric acid adds at extraction tower middle part, add-on is 9% of phosphoric acid quality, flow is entering in tower of 0.32t/h, bottom extracting phase enters raffinate receiving tank, is delivered to fertilizer system, and top solvent phase enters desulfurization washing tower after clarified separation section: solvent phase proportion is 0.98t/m
3.
(3) desulfurization washing: from the solvent phase of extraction tower with 20m
3/ h enters washing tower bottom, and the sweetening agent preparing is with SO in solvent phase
4 2-% calculates and is incorporated as 0.8m
3/ h enters from desulfurization washing tower top and carries out adverse current desulfurization washing, temperature is 55 ℃-65 ℃, rotating speed is 3m/s, after desulfurization washing, solvent phase enters back extraction tower underfeed mouth through top clarified separation section, washing tower bottom liquid phase is washing acid, after clarified separation, uses again through being pumped into after phosphoric acid storage tank mixes with decolouring phosphoric acid as extraction feed.
(4) mother liquor back extraction: from the organic phase on desulfurization washing tower top with 20m
3/ h enters back extraction tower bottom, is 6 through adjusting pH value, and proportion is 1.3, and temperature is the monoammonium phosphate mother liquor of 80-85 ℃, uses pump with 2m
3/ h delivers to back extraction tower top opening for feed, carries out counter current contact with solvent phase, temperature 80-85 ℃, after back extraction solvent phase through top settling section separate after enter interchanger lower the temperature processing after recycle, solvent phase proportion is 0.93t/m
3, the monoammonium phosphate slip after back extraction enters continuously slip accurate adjustment groove after the settling section of back extraction tower bottom, and pH value is 2.5, and proportion is 1.4.
(5) slip accurate adjustment: directly enter slip accurate adjustment groove from the monoammonium phosphate slip of back extraction tower, to ammonia in slip accurate adjustment groove, adjusting slip pH value is 3.6, proportion is that 1.44 slip pumps after adjusting are carried to crystallisation by cooling groove.
(6) crystallisation by cooling: use industrial circulating water to carry out crystallisation by cooling after entering crystallisation by cooling groove from the slip of accurate adjustment groove, slurry temperature uses whizzer to carry out liquid-solid separation while reaching 40 ℃, liquid phase enters mother liquor transfer tank and carries out recycling after pH value adjustment, solid phase enters fluidized-bed and dries, and is packaged to be industrial grade monoammonium phosphate product.Products obtained therefrom index is as table 6:
Table 6
| P 2O 5% | N% | SO 4 2-% | Water-insoluble % | F% | H 2O% | As% | PH | Main content % |
| 61.26 | 11.88 | 0.00 | 0.27 | 0.004 | 0.30 | 0.0029 | 4.47 | 99.2% |
Accumulative total obtains industrial grade monoammonium phosphate product: 166.6t, P2O5:103.6t, and extraction yield is 95%, and back extraction yield is 99%, and drying yield is 98%.
Embodiment tetra-
The 12ktP of Sichuan Chuan Heng Chemical Co., Ltd
2o
5the meticulous salt device of/a technical grade Wet Phosphoric Acid Market coproduction raw material Wet Phosphoric Acid Market 253.9t(material object), index is as following table 7:
Table 7
The step of manufacture level monoammonium phosphate is: defluorinate decolouring, extraction, desulfurization washing, mother liquor back extraction, slip accurate adjustment, crystallisation by cooling, centrifugal, drying and packaging.
(1) defluorinate decolouring: enter high temperature concentration systems from the phosphoric acid of wet method system and carry out after concentration defluorinating, through measuring with 5m
3the flow of/h adds decoloring reaction groove, with 165kg/h(phosphoric acid weight 2%) amount add wood powder shaped activated carbon 4.31t, add defluorinating agent 5.23t with the amount of 170kg/h simultaneously, temperature of reaction is 65 ℃-72 ℃, 1 hour successive reaction residence time, adopting filter pressing pump to be transported to plate and frame(type)filter press separates rear acid solution and enters phosphoric acid receiving tank, employing is pumped to phosphoric acid storage tank, simultaneously by be metered into massfraction be 30% hydrogen peroxide 1.27t(phosphoric acid weight 0.5%), be total to obtain defluorinate decolouring phosphoric acid 252t, proportion 1.65, P
2o
5be 51.7%, fluorine is 0.097%, obtains washing active carbon dilute phosphoric acid 7.3t, and washing gained phosphoric acid is containing P
2o
5: 23%, return to concentration systems.
(2) extraction: the mixed solvent that preparation contains tributyl phosphate and kerosene, proportion is 0.93, decolouring acid and desulfurization washing phosphoric acid mixing raw material (mixing acid proportion is 1.6), through pump with 2.25m
3/ h sends into extraction tower top heavy phase and adds entrance, and mixed solvent is from solvent transfer tank, and extraction phase is than 8:1, through volume pump with 18m
3/ h enters extraction tower by extraction tower bottom fluid inlet, temperature is 32 ℃-34 ℃, sulfuric acid adds at extraction tower middle part, add-on is 9% of phosphoric acid quality, flow is entering in tower of 0.324t/h, bottom extracting phase enters raffinate receiving tank, is delivered to fertilizer system, and top solvent phase enters desulfurization washing tower after clarified separation section: solvent phase proportion is 0.98t/m
3.
(3) desulfurization washing: from the solvent phase of extraction tower with 20m
3/ h enters washing tower bottom, and the sweetening agent preparing is with SO in solvent phase
4 2-% calculates and is incorporated as 0.7m
3/ h enters from desulfurization washing tower top and carries out adverse current desulfurization washing, temperature is 55 ℃-65 ℃, after desulfurization washing, solvent phase enters back extraction tower underfeed mouth through top clarified separation section, washing tower bottom liquid phase is washing acid, after clarified separation, uses again through being pumped into after phosphoric acid storage tank mixes with decolouring phosphoric acid as extraction feed.
(4) mother liquor back extraction: from the organic phase on desulfurization washing tower top with 20m
3/ h enters back extraction tower bottom, is 8 through adjusting pH value, and proportion is 1.35, and temperature is the monoammonium phosphate mother liquor of 80-85 ℃, uses pump with 1.4m
3/ h delivers to back extraction tower top opening for feed, carries out counter current contact with solvent phase, temperature 80-85 ℃, after back extraction solvent phase through top settling section separate after enter interchanger lower the temperature processing after recycle, solvent phase proportion is 0.93t/m
3, the monoammonium phosphate slip after back extraction enters continuously slip accurate adjustment groove after the settling section of back extraction tower bottom, and pH value is 3, and proportion is 1.44.
(5) slip accurate adjustment: directly enter slip accurate adjustment groove from the monoammonium phosphate slip of back extraction tower, to ammonia in slip accurate adjustment groove, adjusting slip pH value is 4, proportion is that 1.48 slip pumps after adjusting are carried to crystallisation by cooling groove.
(6) crystallisation by cooling: use industrial circulating water to carry out crystallisation by cooling after entering crystallisation by cooling groove from the slip of accurate adjustment groove, slurry temperature uses whizzer to carry out liquid-solid separation while reaching 40 ℃, liquid phase enters mother liquor transfer tank and carries out recycling after pH value adjustment, solid phase enters fluidized-bed and dries, and is packaged to be industrial grade monoammonium phosphate product.Products obtained therefrom index is as table 8:
Table 8
| P 2O 5% | N% | SO 4 2-% | Water-insoluble % | F% | H 2O% | As% | PH | Main content % |
| 61.17 | 11.81 | 0.04 | 0.03 | 0.003 | 0.17 | 0.0028 | 4.52 | 99.1% |
Accumulative total obtains industrial grade monoammonium phosphate product: 191.6t, P2O5:118.8t, and extraction yield is 94%, and back extraction yield is 99%, and drying yield is 98%.
Claims (10)
1. the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market, is characterized in that comprising the steps:
A, defluorinate and decolouring: in Wet Phosphoric Acid Market, add defluorinating agent to carry out defluorinate, then add sorbent material to carry out physical decolorization, filter in backward filtrate and add oxygenant to carry out chemical decolorization;
B, use the phosphoric acid after extraction agent phosphoric acid extraction: step a decolouring to enter extraction tower from top heavy phase import, from bottom, light phase import enters extraction tower to extraction agent, adds mineral acid to extract from extraction tower middle part simultaneously;
C, desulfurization washing: from bottom, light phase import enters washing tower to the organic phase obtaining after step b extraction, and sweetening agent enters washing tower from top heavy phase import and carries out desulfurization washing;
D, mother liquor back extraction: from bottom, light phase import enters back extraction tower to the organic phase after step b desulfurization washing, and industrial grade phosphate mother liquor enters back extraction tower from top heavy phase import and carries out countercurrent reextraction; Obtain industrial grade phosphate slip from tower body bottom;
E, slip accurate adjustment: in the industrial grade phosphate slip obtaining to steps d, add and contain cationic alkaline material adjustment identical with phosphoric acid salt, making slip pH value is 3.6～4;
F, crystallisation by cooling: the phosphoric acid salt slip after accurate adjustment is sent into crystallizer and carry out crystallization, then solid-liquid separation, oven dry obtain product industrial grade phosphate; The filtrate that solid-liquid separation obtains is industrial grade phosphate mother liquor, returns to steps d and use after regulating pH value.
2. the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market according to claim 1, it is characterized in that: in step a, the concentration 52～55% of described Wet Phosphoric Acid Market, the amount that described defluorinating agent adds is 1～1.5 times of theoretical reacting weight, the add-on of sorbent material is 1.5～2.5% of Wet Phosphoric Acid Market weight, and the add-on of oxygenant is 0.5～1% of Wet Phosphoric Acid Market weight.
3. the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market according to claim 1, is characterized in that: in step a, while carrying out defluorinate and decolouring, the temperature of feed liquid is 65～75 ℃.
4. the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market according to claim 1, is characterized in that: in step a, described defluorinating agent is for containing sodium salt class and the material that active silica can be provided.
5. the method with phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate according to the Wet Phosphoric Acid Market described in any one in claim 1 to 4, it is characterized in that: in step b, described extraction agent be can slective extraction phosphoric acid organic extractant with can with the mixture of the organic solvent of the fine dilution of dissolving each other of organic extractant, described mineral acid provides hydrionic acid solution for massfraction is greater than 96% the large limit of can doing, and the add-on of mineral acid is 9～13% of phosphoric acid weight.
6. the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market according to claim 5, is characterized in that: in step b, the volume ratio of extracted organic phase and water is 6～10 ︰ 1, and extraction temperature is 30～45 ℃.
7. the method with phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate according to the Wet Phosphoric Acid Market described in any one in claim 1 to 4, it is characterized in that: in step c, described sweetening agent is the barium salt aqueous solution, the add-on of sweetening agent is theoretical reacting weight 1～1.2 times.
8. the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market according to claim 7, is characterized in that: in step c, and phase volume ratio 20～30 ︰ 1 of washing organic phase and water, wash temperature is 55～65 ℃.
9. the method with phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate according to the Wet Phosphoric Acid Market described in any one in claim 1 to 4, it is characterized in that: in steps d, described phosphoric acid salt mother liquor is soluble phosphoric acid dihydric salt or hydrophosphate or sodium phosphate salt mother liquor, proportion is that 1.3～1.35, pH value is 6～8.
10. the method for phosphoric acid salt mother liquor back extraction coproduction industrial grade phosphate for Wet Phosphoric Acid Market according to claim 9, is characterized in that: in steps d, the volume ratio of back extraction organic phase and water is 10～15 ︰ 1, and back extraction temperature is 80～85 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112875662A (en) * | 2021-03-24 | 2021-06-01 | 中国石油化工股份有限公司 | Method for purifying wet-process phosphoric acid by solvent extraction |
| CN114507781A (en) * | 2022-01-26 | 2022-05-17 | 贵州金瑞新材料有限责任公司 | Use method of composite stripping agent in extraction defluorination purification of manganese sulfate solution |
| CN116119633A (en) * | 2023-03-02 | 2023-05-16 | 瓮福达州化工有限责任公司 | Method for preparing monopotassium phosphate from wet-process phosphoric acid containing extractant |
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| CN201719863U (en) * | 2010-06-29 | 2011-01-26 | 贵州川恒化工有限责任公司 | Wet phosphoric acid extraction and purification device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112875662A (en) * | 2021-03-24 | 2021-06-01 | 中国石油化工股份有限公司 | Method for purifying wet-process phosphoric acid by solvent extraction |
| CN112875662B (en) * | 2021-03-24 | 2023-02-24 | 中国石油化工股份有限公司 | Method for purifying wet-process phosphoric acid by solvent extraction |
| CN114507781A (en) * | 2022-01-26 | 2022-05-17 | 贵州金瑞新材料有限责任公司 | Use method of composite stripping agent in extraction defluorination purification of manganese sulfate solution |
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| CN116119633A (en) * | 2023-03-02 | 2023-05-16 | 瓮福达州化工有限责任公司 | Method for preparing monopotassium phosphate from wet-process phosphoric acid containing extractant |
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