CN1313363C - Method for preparing technical grade phosphoric acid, foodstuff grade phosphoric acid and phosphate using wet method and thin phosphoric acid - Google Patents
Method for preparing technical grade phosphoric acid, foodstuff grade phosphoric acid and phosphate using wet method and thin phosphoric acid Download PDFInfo
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- CN1313363C CN1313363C CNB2005100216952A CN200510021695A CN1313363C CN 1313363 C CN1313363 C CN 1313363C CN B2005100216952 A CNB2005100216952 A CN B2005100216952A CN 200510021695 A CN200510021695 A CN 200510021695A CN 1313363 C CN1313363 C CN 1313363C
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Abstract
The present invention relates to a method for preparing industrial-grade phosphoric acid with wet-process diluted phosphoric acid. Processing steps successively comprise pretreatment, secondary desulfurization and defluorination, filtering separation, extraction, deep desulfurization, washing, back extraction and concentration. A method for preparing food-grade phosphoric acid with the wet-process diluted phosphoric acid has difference from the method that pretreatment comprises not only desulfurization, defluorination and decolorization, but also dearsenication and heavy metal removal; after the back extraction, the deep defluorination and the concentration are carried out together. The method for preparing industrial-grade phosphoric acid with the wet-process diluted phosphoric acid successively comprises the following processing steps of pretreatment, secondary desulfurization and defluorination, filtering separation, extraction, deep desulfurization, washing, back extraction, concentration and spray drying or guniting for pelletizing, wherein the extractant used in the back extraction process is a KOH saturated solution or an NH4OH saturated solution. The method can decrease energy consumption and production cost of the product, and fully utilizes China's phosphate ore resource. The same equipment can be used for producing purified phosphoric acid and directly producing various phosphates.
Description
PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and phosphatic method
Technical field
The invention belongs to purifying phosphoric acid and method for production of phosphate salt, particularly a kind of is that raw material, employing solvent extration prepare PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and phosphatic method with the wet method dilute phosphoric acid.
Background technology
The various phosphate product that with the thermal phosphoric acid are raw material production are being brought into play important effect in the national economy every field, are one of main productss of China's foreign exchange earning.But; thermal phosphoric acid is a kind of high energy consumption, high pollution, " four height " with high investment and expensive product; along with the appearance of energy dilemma and the raising of people's environmental protection consciousness; use the profit margin of thermal phosphoric acid production phosphate product more and more littler, a lot of small-sized phosphoric acid saltworks go bankrupt one after another or stops production.Therefore, phosphoric acid by wet process is purified to replace thermal phosphoric acid to produce various phosphoric acid salt goods, become a research direction of world's phosphorous chemical industry high-technology field.
Chinese patent ZL 03117850.2 has introduced and has a kind ofly prepared the method for PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid with phosphoric acid by wet process, and this method is to contain P
2O
550% wet method concentrated phosphoric acid is a raw material, and processing step comprises desulfurization, decolouring, defluorinate pre-treatment, secondary desulfurization, filtering separation, extraction, dark desulfurization, washing, back extraction and concentrated (or concentrated degree of depth defluorinate).Extraction agent is selected tributyl phosphate for use, and thinner is a kerosene.Though this method has successfully been prepared satisfactory PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid, raw material can only be the phosphoric acid by wet process after concentrating, and can not directly use the wet method dilute phosphoric acid.This mainly is because extraction agent tributyl phosphate extraction dilute phosphoric acid poor effect, but tributyl phosphate separating metal positively charged ion effect is fine, therefore, if can add one or more association's extraction agents, strengthen the phosphoric acid extraction rate, add suitable pre-process and post-process operation, then the scope of application of novel process is wider, is more suitable for Chinese phosphate rock resource characteristics.
85%H is bought in industrial grade phosphate production at present usually
3PO
4(61.5%P
2O
5) strong phosphoric acid is raw material, dilute with water during use is then with KOH or NH
4OH neutralization obtains salts solution, to salts solution concentrate, crystallisation by cooling, centrifugation get product.And the pure dilute phosphoric acid that back extraction obtains in the solvent extration purification of wet process phosphoric acid also will dilute after concentrating once more, and energy consumption is bigger, complex operation.
The wet method dilute phosphoric acid compares to the phosphoric acid by wet process after concentrating, P
2O
5Content is low, and water content is big, and foreign matter content is higher.Production practice show that the concentrated power consumption of wet method dilute phosphoric acid is bigger, will contain P
2O
5Wet method dilute phosphoric acid about 30% is condensed into and contains P
2O
5Phosphoric acid by wet process about 50% evaporates 1 ton of water and will consume 1.1～1.2 tons of steam, if raw ore is a collophanite, more can increase spissated difficulty.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, a kind of method for preparing PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and industrial phosphoric acid salt with the wet method dilute phosphoric acid is provided, this kind method is guaranteeing under the product quality premise, the energy consumption and the production cost of product have been reduced, and can utilize China's phosphate rock resource more fully, reduce facility investment.
Technical scheme of the present invention: according to wet method dilute phosphoric acid P
2O
5Content is low, and water content is big, and the foreign matter content height in when extraction percentage extraction characteristics design technology flow process such as low with select processing parameter, with respect to ZL 03117850.2 patent, has been done following improvement.
1, pretreatment process has improved temperature of reaction, has prolonged the reaction times to strengthen impurity-eliminating effect.
2, increased secondary defluorinate operation, with the fluorine content in the further reduction phosphoric acid, the defluorinating agent that the secondary defluorinate adds is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, defluorinating agent is extraordinarily gone into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, 60～80 ℃ of temperature of reaction, 2～5 hours reaction times.
3, the extraction agent that uses of extraction process is the mixture of tributyl phosphate, isopropyl ether and kerosene, can improve the percentage extraction of phosphoric acid, reduces the density and the viscosity of organic phase, makes the two-phase phase-splitting easy.
4, preparation PHOSPHORIC ACID TECH.GRADE, enrichment process adopts forces vacuum concentration equipment, and vacuum tightness is 80～85kpa, to reduce thickening temperature, reduces equipment corrosion.
5, preparation industrial phosphoric acid salt, the extraction agent that the back extraction operation is used is KOH saturated solution or NH
4The OH saturated solution adds by phosphoric acid stoichiometric ratio in the organic phase, and 60 ℃ of initial reaction temperature are delivered to the concentrating unit evaporation concentration to moisture 25～30%, then spraying drying or spray granulating system industrial phosphoric acid salt when temperature rises to 80～100 ℃.
6, the secondary defluorinate adds the precipitation promoter alkyl benzene sulphonate (ABS), and add-on is 0.005～0.01% of a fluorine content, so that fluorine-containing precipitation is separated out fast and helped separating.
7, the washings that uses of washing procedure is purifying phosphoric acid, is added with phosphoric acid quality 0.5～1%NH in the washings
4H
2PO
4, processing parameter: organic phase compares 18～20: 1 with washings, and 50～60 ℃ of temperature, organic phase are external phase, so not only can strengthen washing out micro-SO
4 2-, but also the phosphorus that can remedy in the scavenging process loses.
Provided by the present inventionly prepare the method for PHOSPHORIC ACID TECH.GRADE with the wet method dilute phosphoric acid, processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction successively and concentrates.Pre-treatment is to add sweetening agent, defluorinating agent, discoloring agent in the wet method dilute phosphoric acid, desulfurization, defluorinate, decolouring is placed on an operation carries out, and sweetening agent is a ground phosphate rock, presses SO in the phosphoric acid
4 2-1.1～1.3 of stoichiometric ratio is extraordinarily gone into, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, extraordinarily go into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, discoloring agent is that activated carbon is or/and diatomite, add-on is 0.1～1% of a phosphoric acid quality, 60～100 ℃ of temperature of reaction, 3～6 hours reaction times; The sweetening agent that secondary desulfurization defluorinate operation adds is a lime carbonate or/and calcium oxide, and the add-on of sweetening agent is SO in the phosphoric acid
4 2-1～1.3 times of stoichiometric ratio, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, defluorinating agent is extraordinarily gone into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, 60～80 ℃ of temperature of reaction, 2～5 hours reaction times; The extraction agent that extraction process uses is the mixture of tributyl phosphate, isopropyl ether and kerosene, the volume percent of tributyl phosphate is 50～70%, the volume percent of isopropyl ether is 10～20%, the volume percent of kerosene is 20～40%, the extraction process parameter: organic phase compares 3～6: 1 with water, 50～60 ℃ of temperature, organic phase are external phase; Dark desulfurization process is that the organic phase after the extraction is carried out desulfurization, and the sweetening agent of adding is a barium carbonate or/and hydrated barta, and the sweetening agent add-on is by SO in the organic phase
4 2-Stoichiometric ratio adds, 50～60 ℃ of temperature of reaction, reaction times 10～30min; The extraction agent that the back extraction operation is used is soft water, processing parameter: organic phase compares 6～10: 1 with water, 50～60 ℃ of temperature, and water is an external phase; Enrichment process adopts forces vacuum concentration equipment, and vacuum tightness is 80～85kpa.
The method for preparing food grade phosphoric acid with the wet method dilute phosphoric acid provided by the present invention belongs to a total inventive concept with the above-mentioned method for preparing PHOSPHORIC ACID TECH.GRADE with the wet method dilute phosphoric acid, and processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction and degree of depth defluorinate successively and concentrates.With the above-mentioned difference for preparing the method for PHOSPHORIC ACID TECH.GRADE with the wet method dilute phosphoric acid be the concrete operations of pretreatment process and enrichment process: pre-treatment is to add sweetening agent, defluorinating agent, discoloring agent, dearsenic agent, removing heavy-metal agent in phosphoric acid by wet process, desulfurization, defluorinate, decolouring, dearsenification, removing heavy-metal are placed on an operation to carry out, sweetening agent is a ground phosphate rock, presses SO in the phosphoric acid
4 2-1.1～1.3 of stoichiometric ratio is extraordinarily gone into, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, extraordinarily go into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, discoloring agent is that activated carbon is or/and diatomite, add-on is 0.1～1% of a phosphoric acid quality, dearsenic agent and removing heavy-metal agent are that sodium sulphite is or/and thiophosphoric anhydride, dearsenic agent and removing heavy-metal agent are extraordinarily gone into by 1～1.2 of arsenic in the phosphoric acid and heavy metal content stoichiometric ratio, 60～100 ℃ of temperature of reaction, 3～6 hours reaction times; Degree of depth defluorinate combines with concentrated, carries out under vacuum condition, and vacuum tightness is 88～95kpa, and defluorinating agent is selected active silica for use, and its add-on is extraordinarily gone into by 1.3～2 of fluorine content stoichiometric ratio in the phosphoric acid, 80～90 ℃ of temperature of reaction.
Provided by the present inventionly prepare the method for industrial phosphoric acid salt with the wet method dilute phosphoric acid, processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction successively, concentrates, spraying drying or spray granulating.In the above-mentioned processing step, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization and washing step and the corresponding steps for preparing with the wet method dilute phosphoric acid in the method for PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid are identical, pre-treatment step is identical with the pre-treatment step for preparing in the PHOSPHORIC ACID TECH.GRADE method with the wet method dilute phosphoric acid, and the extraction agent that the back extraction operation is used is KOH saturated solution or NH
4The OH saturated solution; add by phosphoric acid stoichiometric ratio in the organic phase; initial reaction temperature is 60 ℃ (these are thermopositive reaction), is delivered to the concentrating unit evaporation concentration to moisture 20～25% when temperature rises to 80～100 ℃, and spraying drying or spray granulating obtain industrial phosphoric acid salt then.
In above-mentioned three kinds of methods, can add the precipitation promoter alkyl benzene sulphonate (ABS) during secondary defluorinate, the add-on of alkyl benzene sulphonate (ABS) is 0.005～0.01% of a fluorine content.
In above-mentioned three kinds of methods, the washings that washing procedure uses is purifying phosphoric acid, is added with the NH of phosphoric acid quality 0.5～1% in the washings
4H
2PO
4, processing parameter: organic phase compares 18～20: 1 with washings, and 50～60 ℃ of temperature, organic phase are external phase.
The present invention has following beneficial effect:
1, the method for the invention good purification, prepared PHOSPHORIC ACID TECH.GRADE, food grade phosphoric acid and industrial phosphoric acid salt meet national standard fully.
2, owing to use wet method dilute phosphoric acid direct purification to prepare technical grade, food grade phosphoric acid and industrial phosphoric acid salt, with respect to Chinese patent ZL 03117850.2, saved concentration process from dilute phosphoric acid to strong phosphoric acid, thereby can reduce energy consumption and production costs that (one production line is by 50,000 tons/year, can reduce steam consumption is 1.5 * 50,000=7.5 ten thousand tons/year, if steam expense per ton is 80 yuan/ton, then can save ten thousand yuan of 80 * 7.5=600).
3, there are a large amount of collophanites in China, the ore dressing difficulty, adopt method provided by the present invention to prepare technical grade, food grade phosphoric acid and industrial phosphoric acid salt, needn't carry out ore dressing, can reduce the investment of preparation equipment, further reduce cost (price of concentrate double about), make full use of Mineral Resources in China than raw ore.
4, increase the secondary defluorinate, guaranteed the defluorination effect of diluted acid.Add the precipitation promoter alkyl benzene sulphonate (ABS) during secondary defluorinate, be convenient to fluorine-containing precipitation and separate out fast and help separating.
5, be extraction agent with tributyl phosphate and isopropyl ether, with kerosene is thinner, has reduced the density and the viscosity of organic phase during extraction, and the two-phase phase-splitting is easy, improved the percentage extraction of dilute phosphoric acid, extraction agent is dissolved in phosphoric acid hardly, and raffinate is carried organic phase secretly and can be ignored, so raffinate can reclaim extraction agent without rectifying, be directly used in the fertilizer manufacturing, simplify flow process, reduced energy consumption, saved cost.
6, in washing process, in washings, add an amount of NH
4H
2PO
4Solution not only can strengthen washing out micro-SO
4 2-Effect, but also the phosphorus that can remedy in the scavenging process loses.
7, whole technology has been considered to combine with phosphate production, and promptly fertile, salt binding are all sent to composting with extract remainder; Can painstakingly not pursue percentage extraction in the technological process, and be target with maximum phosphorus yield, this technology phosphorus yield can reach more than 99%.
8, on same set of device, both can produce purifying phosphoric acid, but the also multiple phosphoric acid salt of direct production helps reducing facility investment, the handiness that enhancing equipment uses.
Description of drawings
Fig. 1 is a kind of process flow sheet for preparing PHOSPHORIC ACID TECH.GRADE with the wet method dilute phosphoric acid provided by the present invention;
Fig. 2 is a kind of process flow sheet for preparing food grade phosphoric acid with the wet method dilute phosphoric acid provided by the present invention;
Fig. 3 is a kind of process flow sheet for preparing industrial phosphoric acid salt with the wet method dilute phosphoric acid provided by the present invention.
Embodiment
Embodiment 1: the preparation PHOSPHORIC ACID TECH.GRADE
In the present embodiment, raw materials used wet method dilute phosphoric acid composed as follows:
P
2O
5SO
4 2-F Fe As heavy metal (in Pb) colourity
28.80％ 2.19％ 1.68％ 0.71％ 0.0014％ 0.0025％ ＞300
Serialization is produced, and processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction and concentrated as shown in Figure 1 successively.
(1) pre-treatment
Pre-treatment is carried out in pretreatment tank, and sweetening agent is selected smart phosphorus ore for use, presses SO in the phosphoric acid
4 2-1.2 of stoichiometric ratio is extraordinarily gone into; Defluorinating agent is selected yellow soda ash and silicon-dioxide for use, and yellow soda ash is extraordinarily gone into by 1.0 of fluorine content stoichiometric ratio in the phosphoric acid, and silicon-dioxide is extraordinarily gone into by 0.3 of fluorine content stoichiometric ratio in the phosphoric acid; Discoloring agent is selected gac and diatomite for use, and add-on is respectively 0.2% of phosphoric acid quality.Temperature of reaction is 60 ℃, and the reaction times is 6 hours.
(2) secondary desulfurization defluorinate
Secondary desulfurization defluorinate is carried out in desulfurization, defluorinate groove, and sweetening agent is selected lime carbonate for use, presses SO in the phosphoric acid
4 2-1.2 of stoichiometric ratio is extraordinarily gone into; Defluorinating agent is selected yellow soda ash and silicon-dioxide for use, yellow soda ash is extraordinarily gone into by 1.0 of fluorine content stoichiometric ratio in the phosphoric acid, silicon-dioxide is extraordinarily gone into by 0.2 of fluorine content stoichiometric ratio in the phosphoric acid, and precipitation agent promotor is alkyl benzene sulphonate (ABS), and the add-on of alkyl benzene sulphonate (ABS) is 0.006% of a fluorine content; Temperature of reaction is 60 ℃, and the reaction times is 5 hours.
(3) filtering separation
Adopt flame filter press to separate the solid impurity of removing in the phosphoric acid.
(4) extraction
Extraction is carried out in extraction tower, and extraction agent is the mixture of tributyl phosphate, isopropyl ether, kerosene, and the percent by volume of tributyl phosphate is 60%, and the volume percent of isopropyl ether is 10%, and the volume percent of kerosene is 30%.Processing parameter: compare 4: 1 of organic phase and water, 50 ℃ of temperature, organic phase are external phase.
(5) dark desulfurization
Dark desulfurization is carried out in desulfurizer, and the sweetening agent barium carbonate is by SO in the organic phase
4 2-Stoichiometric ratio adds, 50 ℃ of temperature of reaction, reaction times 30min.
(6) washing
Washing is carried out in washing tower, and washings is a purifying phosphoric acid, is added with phosphoric acid quality 0.6%NH in the washings
4H
2PO
4, compare 20: 1 of organic phase and washings, 50 ℃ of temperature, organic phase are external phase.
(7) back extraction
Back extraction is carried out in the back extraction tower, and extraction agent is a soft water, compare 6: 1 of organic phase and water, and 60 ℃ of temperature, water is an external phase.
(8) concentrate
Concentrate to adopt and force vacuum concentration equipment, vacuum tightness is 80kpa, promptly is prepared into PHOSPHORIC ACID TECH.GRADE after purification of phosphoric acid that back extraction obtains is concentrated.
Prepared PHOSPHORIC ACID TECH.GRADE in the present embodiment, relevant components contents is as follows:
P
2O
5SO
4 2-F Fe As heavy metal (in Pb) colourity
61.50％ 0.0010％ 0.02％ 0.0020％ 0.0004％ 0.0006％ ＜30
Embodiment 2: the preparation food grade phosphoric acid
In the present embodiment, raw materials used wet method dilute phosphoric acid composed as follows:
P
2O
5SO
4 2-F Fe As heavy metal (in Pb) colourity
28.80％ 2.19％ 1.68％ 0.71％ 0.0014％ 0.0025％ ＞300
Serialization is produced, and processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction and dark defluorinate successively and concentrates as shown in Figure 2.
(1) pre-treatment
Pre-treatment is carried out in pretreatment tank, and sweetening agent is selected smart phosphorus ore for use, presses SO in the phosphoric acid
4 2-1.3 of stoichiometric ratio is extraordinarily gone into; Defluorinating agent is selected salt of wormwood and silicon-dioxide for use, and salt of wormwood is extraordinarily gone into by 1.2 of fluorine content stoichiometric ratio in the phosphoric acid, and silicon-dioxide is extraordinarily gone into by 0.3 of fluorine content stoichiometric ratio in the phosphoric acid; Discoloring agent is selected gac for use, and the gac add-on is 0.8% of a phosphoric acid quality, and sodium sulphite is selected in dearsenic agent and removing heavy-metal agent for use, extraordinarily goes into by 1.1 of the stoichiometric ratio of arsenic in the phosphoric acid and heavy metal content.Temperature of reaction is 90 ℃, and the reaction times is 3 hours.
(2) secondary desulfurization defluorinate
Secondary desulfurization defluorinate is carried out in desulfurization, defluorinate groove, and sweetening agent is selected calcium oxide for use, presses SO in the phosphoric acid
4 2-1.3 of stoichiometric ratio is extraordinarily gone into; Defluorinating agent is selected salt of wormwood and silicon-dioxide for use, salt of wormwood is extraordinarily gone into by 1.2 of fluorine content stoichiometric ratio in the phosphoric acid, silicon-dioxide is extraordinarily gone into by 0.2 of fluorine content stoichiometric ratio in the phosphoric acid, and precipitation promoter is an alkyl benzene sulphonate (ABS), and the add-on of alkyl benzene sulphonate (ABS) is 0.008% of a fluorine content; Temperature of reaction is 80 ℃, and the reaction times is 2 hours.
(3) filtering separation
Adopt flame filter press to separate the solid impurity of removing in the phosphoric acid.
(4) extraction
Extraction is carried out in extraction tower, and extraction agent is the mixture of tributyl phosphate, isopropyl ether, kerosene, and the percent by volume of tributyl phosphate is 60%, and the volume percent of isopropyl ether is 15%, and the volume percent of kerosene is 25%.The extraction process parameter: compare 5: 1 of organic phase and water, 60 ℃ of temperature, organic phase are external phase.
(5) dark desulfurization
Dark desulfurization is carried out in desulfurizer, and the sweetening agent hydrated barta is by SO in the organic phase
4 2-Stoichiometric ratio adds, 60 ℃ of temperature of reaction, reaction times 15min.
(6) washing
Washing is carried out in washing tower, and washings is a purifying phosphoric acid, is added with phosphoric acid quality 0.8%NH in the washings
4H
2PO
4, compare 18: 1 of organic phase and washings, 60 ℃ of temperature, organic phase are external phase.
(7) back extraction
Back extraction is carried out in the back extraction tower, and extraction agent is a soft water, compare 8: 1 of organic phase and water, and 55 ℃ of temperature, water is an external phase.
(9) dark defluorinate is with concentrated
Dark defluorinate and enrichment process carry out under vacuum condition, and vacuum tightness is 93kpa, and equipment used is a rotatory evaporator, and defluorinating agent is selected active silica for use, and its add-on is 1.5 times of fluorine content stoichiometric ratio in the phosphoric acid.Temperature of reaction is 85 ℃, and defluorinate and concentration time are 6 hours.
Prepared food grade phosphoric acid in the present embodiment, relevant components contents is as follows:
P
2O
5SO
4 2-F Fe As heavy metal (in Pb) colourity
61.50％ 0.0010％ 0.001％ 0.0020％ 0.0001％ 0.0001％ ＜20
Embodiment 3: preparation industrial phosphoric acid salt
In the present embodiment, raw materials used wet method dilute phosphoric acid composed as follows:
P
2O
5SO
4 2-F Fe As heavy metal (in Pb) colourity
28.80％ 2.19％ 1.68％ 0.71％ 0.0014％ 0.0025％ ＞300
Serialization is produced, and processing step is followed successively by pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction, concentrated, spraying drying as shown in Figure 3.
(1) pre-treatment
Pre-treatment is carried out in pretreatment tank, and sweetening agent is selected smart phosphorus ore for use, presses SO in the phosphoric acid
4 2-1.1 of stoichiometric ratio is extraordinarily gone into; Defluorinating agent is selected yellow soda ash and silicon-dioxide for use, and yellow soda ash is extraordinarily gone into by 1.0 of fluorine content stoichiometric ratio in the phosphoric acid, and silicon-dioxide is extraordinarily gone into by 0.2 of fluorine content stoichiometric ratio in the phosphoric acid; Discoloring agent is selected diatomite for use, and add-on is 0.6% of a phosphoric acid quality.Temperature of reaction is 80 ℃, and the reaction times is 4 hours.
(2) secondary desulfurization defluorinate
Secondary desulfurization defluorinate is carried out in desulfurization, defluorinate groove, and sweetening agent is selected lime carbonate and calcium oxide for use, and lime carbonate, calcium oxide are pressed SO in the phosphoric acid respectively
4 2-0.6 of stoichiometric ratio is extraordinarily gone into; Defluorinating agent is selected yellow soda ash and silicon-dioxide for use, yellow soda ash is extraordinarily gone into by 1.0 of fluorine content stoichiometric ratio in the phosphoric acid, silicon-dioxide is extraordinarily gone into by 0.3 of fluorine content stoichiometric ratio in the phosphoric acid, and precipitation agent promotor is alkyl benzene sulphonate (ABS), and the add-on of alkyl benzene sulphonate (ABS) is 0.005% of a fluorine content; Temperature of reaction is 70 ℃, and the reaction times is 3.5 hours.
(3) filtering separation
Adopt flame filter press to separate the solid impurity of removing in the phosphoric acid.
(4) extraction
Extraction is carried out in extraction tower, and extraction agent is the mixture of tributyl phosphate, isopropyl ether, kerosene, and the percent by volume of tributyl phosphate is 55%, and the volume percent of isopropyl ether is 18%, and the volume percent of kerosene is 27%.Processing parameter: compare 5: 1 of organic phase and water, 50 ℃ of temperature, organic phase are external phase.
(5) dark desulfurization
Dark desulfurization is carried out in desulfurizer, and the sweetening agent barium carbonate is by SO in the organic phase
4 2-Stoichiometric ratio adds, 50 ℃ of temperature of reaction, reaction times 30min.
(6) washing
Washing is carried out in washing tower, and washings is a purifying phosphoric acid, is added with phosphoric acid quality 0.5%NH in the washings
4H
2PO
4, compare 19: 1 of organic phase and washings, 55 ℃ of temperature, organic phase are external phase.
(7) back extraction, concentrated
The extraction agent that the back extraction operation is used is the KOH saturated solution, stoichiometric ratio by phosphoric acid in the organic phase adds, 60 ℃ of initial reaction temperature (this is thermopositive reaction) are delivered to the concentrating unit evaporation concentration to moisture 20% when salts solution temperature that back extraction goes out rises to about 90 ℃.
(7) spraying drying
Moisture 20% phosphate solution spraying drying is obtained industrial phosphoric acid salt, and spray-dired temperature is 110 ℃.
Prepared industrial phosphoric acid salt in the present embodiment, relevant components contents is as follows:
KH
2PO
4Moisture F Fe As heavy metal (in Pb)
96～98％ ＜3％ 0.02％ ≤0.003％ ≤0.0015％ ≤0.0010％
Claims (6)
1, a kind ofly prepare the method for PHOSPHORIC ACID TECH.GRADE with the wet method dilute phosphoric acid, processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction successively and concentrates;
Pre-treatment is to add sweetening agent, defluorinating agent, discoloring agent in the wet method dilute phosphoric acid, desulfurization, defluorinate, decolouring is placed on an operation carries out, and sweetening agent is a ground phosphate rock, presses SO in the phosphoric acid
4 2-1.1～1.3 of stoichiometric ratio is extraordinarily gone into, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, extraordinarily go into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, discoloring agent is that activated carbon is or/and diatomite, add-on is 0.1～1% of a phosphoric acid quality, 60～100 ℃ of temperature of reaction, 3～6 hours reaction times;
The sweetening agent that secondary desulfurization defluorinate operation adds is a lime carbonate or/and calcium oxide, and the add-on of sweetening agent is the SO in the phosphoric acid
4 2-1～1.3 times of stoichiometric ratio, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, defluorinating agent is extraordinarily gone into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, 60～80 ℃ of temperature of reaction, 2～5 hours reaction times;
The extraction agent that extraction process uses is the mixture of tributyl phosphate, isopropyl ether and kerosene, the volume percent of tributyl phosphate is 50～70%, the volume percent of isopropyl ether is 10～20%, the volume percent of kerosene is 20～40%, the extraction process parameter: organic phase compares 3～6: 1 with water, 50～60 ℃ of temperature, organic phase are external phase;
Dark desulfurization process is that the organic phase after the extraction is carried out desulfurization, and the sweetening agent of adding is a barium carbonate or/and hydrated barta, and the sweetening agent add-on is by SO in the organic phase
4 2-Stoichiometric ratio adds, 50～60 ℃ of temperature of reaction, reaction times 10～30min;
The washings that washing procedure uses is purifying phosphoric acid, is added with the NH of phosphoric acid quality 0.5～1% in the washings
4H
2PO
4, processing parameter: organic phase compares 18～20: 1 with washings, and 50～60 ℃ of temperature, organic phase are external phase;
The extraction agent that the back extraction operation is used is soft water, processing parameter: organic phase compares 6～10: 1 with water, 50～60 ℃ of temperature, and water is an external phase;
Enrichment process adopts forces vacuum concentration equipment, and vacuum tightness is 80～85kpa.
2, according to claim 1ly prepare the method for PHOSPHORIC ACID TECH.GRADE with the wet method dilute phosphoric acid, add the precipitation promoter alkyl benzene sulphonate (ABS) when it is characterized in that secondary desulfurization defluorinate, add-on is 0.005～0.01% of a fluorine content.
3, a kind ofly prepare the method for food grade phosphoric acid with the wet method dilute phosphoric acid, processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction and dark defluorinate successively and concentrates;
Pre-treatment is to add sweetening agent, defluorinating agent, discoloring agent, dearsenic agent, removing heavy-metal agent in phosphoric acid by wet process, desulfurization, defluorinate, decolouring, dearsenification, removing heavy-metal is placed on an operation carries out, and sweetening agent is a ground phosphate rock, presses SO in the phosphoric acid
4 2-1.1～1.3 of stoichiometric ratio is extraordinarily gone into, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, extraordinarily go into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, discoloring agent is that activated carbon is or/and diatomite, add-on is 0.1～1% of a phosphoric acid quality, dearsenic agent and removing heavy-metal agent are that sodium sulphite is or/and thiophosphoric anhydride, dearsenic agent and removing heavy-metal agent are extraordinarily gone into by 1～1.2 of arsenic in the phosphoric acid and heavy metal content stoichiometric ratio, 60～100 ℃ of temperature of reaction, 3～6 hours reaction times;
The sweetening agent that secondary desulfurization defluorinate operation adds is a lime carbonate or/and calcium oxide, and the add-on of sweetening agent is the SO in the phosphoric acid
4 2-1～1.3 times of stoichiometric ratio, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, defluorinating agent is extraordinarily gone into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, 60～80 ℃ of temperature of reaction, 2～5 hours reaction times;
The extraction agent that extraction process uses is the mixture of tributyl phosphate, isopropyl ether and kerosene, the volume percent of tributyl phosphate is 50～70%, the volume percent of isopropyl ether is 10～20%, the volume percent of kerosene is 20～40%, the extraction process parameter: organic phase compares 3～6: 1 with water, 50～60 ℃ of temperature, organic phase are external phase;
Dark desulfurization process is that the organic phase after the extraction is carried out desulfurization, and the sweetening agent of adding is a barium carbonate or/and hydrated barta, and the sweetening agent add-on is by SO in the organic phase
4 2-Stoichiometric ratio adds, 50～60 ℃ of temperature of reaction, reaction times 10～30min;
The washings that washing procedure uses is purifying phosphoric acid, is added with the NH of phosphoric acid quality 0.5～1% in the washings
4H
2PO
4, processing parameter: organic phase compares 18～20: 1 with washings, and 50～60 ℃ of temperature, organic phase are external phase;
The extraction agent that the back extraction operation is used is soft water, processing parameter: organic phase compares 6～10: 1 with water, 50～60 ℃ of temperature, and water is an external phase;
Dark defluorinate is carried out with being concentrated under the vacuum condition, and vacuum tightness is 88～95kpa, and defluorinating agent is selected active silica for use, and its add-on is 1.3～2 times of stoichiometric ratio of fluorine content in the phosphoric acid, 80～90 ℃ of temperature of reaction.
4, according to claim 3ly prepare the method for food grade phosphoric acid with the wet method dilute phosphoric acid, add the precipitation promoter alkyl benzene sulphonate (ABS) when it is characterized in that secondary desulfurization defluorinate, add-on is 0.005～0.01% of a fluorine content.
5, a kind ofly prepare the method for industrial phosphoric acid salt with the wet method dilute phosphoric acid, processing step comprises pre-treatment, secondary desulfurization defluorinate, filtering separation, extraction, dark desulfurization, washing, back extraction successively, concentrates, spraying drying or spray granulating;
Pre-treatment is to add sweetening agent, defluorinating agent, discoloring agent in the wet method dilute phosphoric acid, desulfurization, defluorinate, decolouring is placed on an operation carries out, and sweetening agent is a ground phosphate rock, presses SO in the phosphoric acid
4 2-1.1～1.3 of stoichiometric ratio is extraordinarily gone into, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, extraordinarily go into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, discoloring agent is that activated carbon is or/and diatomite, add-on is 0.1～1% of a phosphoric acid quality, 60～100 ℃ of temperature of reaction, 3～6 hours reaction times;
The sweetening agent that secondary desulfurization defluorinate operation adds is a lime carbonate or/and calcium oxide, and the add-on of sweetening agent is the SO in the phosphoric acid
4 2-1～1.3 times of stoichiometric ratio, defluorinating agent is yellow soda ash and silicon-dioxide or salt of wormwood and silicon-dioxide, defluorinating agent is extraordinarily gone into by 1～1.5 of fluorine content stoichiometric ratio in the phosphoric acid, 60～80 ℃ of temperature of reaction, 2～5 hours reaction times;
The extraction agent that extraction process uses is the mixture of tributyl phosphate, isopropyl ether and kerosene, the volume percent of tributyl phosphate is 50～70%, the volume percent of isopropyl ether is 10～20%, the volume percent of kerosene is 20～40%, the extraction process parameter: organic phase compares 3～6: 1 with water, 50～60 ℃ of temperature, organic phase are external phase;
Dark desulfurization process is that the organic phase after the extraction is carried out desulfurization, and the sweetening agent of adding is a barium carbonate or/and hydrated barta, and the sweetening agent add-on is by SO in the organic phase
4 2-Stoichiometric ratio adds, 50～60 ℃ of temperature of reaction, reaction times 10～30min;
The washings that washing procedure uses is purifying phosphoric acid, is added with the NH of phosphoric acid quality 0.5～1% in the washings
4H
2PO
4, processing parameter: organic phase compares 18～20: 1 with washings, and 50～60 ℃ of temperature, organic phase are external phase;
The extraction agent that the back extraction operation is used is KOH saturated solution or NH
4The OH saturated solution adds by phosphoric acid stoichiometric ratio in the organic phase, and 60 ℃ of initial reaction temperature are delivered to the concentrating unit evaporation concentration to moisture 20～25% when temperature rises to 80～100 ℃, then spraying drying or spray granulating system industrial phosphoric acid salt.
6, according to claim 5ly prepare the method for industrial phosphoric acid salt with the wet method dilute phosphoric acid, add the precipitation promoter alkyl benzene sulphonate (ABS) when it is characterized in that secondary desulfurization defluorinate, add-on is 0.005～0.01% of a fluorine content.
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| CN102791623A (en) * | 2010-03-12 | 2012-11-21 | 科学工业研究委员会 | A process for the preparation of inorganic hydrogels with alkali halides |
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| CN102791623B (en) * | 2010-03-12 | 2015-07-01 | 科学工业研究委员会 | A process for the preparation of inorganic hydrogels with alkali halides |
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