CN101774556B - Method for preparing industrial grade and food grade phosphoric acid by decomposing low grade phosphate rocks with hydrochloric acid - Google Patents
Method for preparing industrial grade and food grade phosphoric acid by decomposing low grade phosphate rocks with hydrochloric acid Download PDFInfo
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Abstract
The invention relates to a method for preparing industrial grade and food grade phosphoric acid by decomposing low grade phosphate rocks with hydrochloric acid. The method comprises the following processing steps: (1) decomposing phosphate rock powder with hydrochloric acid; (2) extracting to remove iron; (3) preparing dilute phosphoric acid; (4) preparing industrial grade phosphoric acid; and (5) preparing food grade phosphoric acid. Food grade phosphoric acid can be prepared only by adding deep defluorination process on the basis of the preparation steps of industrial grade phosphoric acid. The deep defluorination process adopts vacuum steam stripping process and the processing conditions are as follows: the vacuum degree is 0.075-0.090Mpa, and the temperature is 95-110 DEG C. Industrial grade phosphoric acid prepared by the method of the invention meets the super grade or first-class product standards of GB/T 2091-2008; and food grade phosphoric acid meets the standards of GB 3149-2004.
Description
Technical field
The invention belongs to the preparation field of PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid, particularly a kind of hydrochloric acid decomposing medium and low grade prepares the method for PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid.
Background technology
It is raw material that the preparation of PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid can be adopted thermal phosphoric acid, and also can adopt phosphoric acid by wet process is raw material.Because thermal phosphoric acid production is to phosphorus ore grade requirement height, the energy consumption height, thereby come production PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid more and more to be subjected to people's attention with phosphoric acid by wet process.Both at home and abroad the solvent extration Research on Purification of Wet Phosphoric Acid was never stopped, and obtained very big progress, but the research of this respect many be feedstock production PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid (as ZL03117850.2 and ZL200510021695.2) with the sulfuric acid process phosphoric acid by wet process.With the sulfuric acid process phosphoric acid by wet process is that the problem that feedstock production PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid exist is: produce a large amount of phosphogypsums and pile up, recycle comparatively difficulty.The sulphur inadequate resource of China in addition, sulfuric acid is in short supply, and China's mid low grade phosphate rock resource is more, and a lot of enterprises by-product hydrochloric acid is arranged, hydrochloric acid is more than needed, and is cheap.Therefore, with salt acid substitution sulfuric acid decomposing medium and low grade, adopt solvent extration purification preparation PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid to have realistic meaning.
Chinese patent ZL 200510019049.2 discloses a kind of method of hydrochloric acid decomposing medium and low grade process industry phosphoric acid, this method is with decomposing phosphate rock by chlorhydric acid, prepare calcium chlorophosphate, with hydrochloric acid making beating dissolving,, concentrate then with the tributyl phosphate extraction, again with tributyl phosphate and isopropyl ether extraction, reconcentration, 85% PHOSPHORIC ACID TECH.GRADE is made in decolouring.But this method has the following disadvantages: 1. finish the first step with preparation calcium chlorophosphate crystal and purify, because the calcium chlorophosphate crystallization velocity is very slow, for example under 20～22 ℃, HCl content is about at 12% o'clock in the solution, contains 9.4%P
2O
5Decomposed solution in P
2O
5Dropping to the needed time of 4% left and right sides is 210 minutes (seeing " research of decomposing phosphate rock by chlorhydric acid circulation process ", author Wang Changhui, Yao Dingwen, chemical fertilizer industry,, the 5th phase, 14～17 pages in 1988), and this just needs very big crystallizer, and facility investment increases; Calcium chlorophosphate is that powdery is carefully brilliant, causes dust removal rate not high easily, and filtration difficulty improves equipment requirements; Ca in the calcium chlorophosphate making beating liquid
2+Content is far below Ca in the acid hydrolysis solution
2+Content influences next step extraction efficiency to phosphoric acid, causes percentage extraction to descend.2. with the tributyl phosphate phosphoric acid extraction, foreign ions such as separating calcium, iron, through washing, back extraction was finished for second step and is purified, but in the phosphoric acid solution in the presence of the hydrochloric acid, Fe
3+With Cl
-The title complex that forms is easy to preferentially be extracted by tributyl phosphate, even also be difficult to reach separation fully through washing; And these method employing washing water second time and raffinate water wash organic phase as washing lotion, and phosphoric acid concentration is higher in the washing lotion, and viscosity is bigger, can cause washing effect relatively poor, finally causes Fe in the finished product phosphoric acid
3+Content is higher, influences the colourity and the quality of product.With regard to the PHOSPHORIC ACID TECH.GRADE that this patent working example is produced, iron level can only reach GB/T 2091-2003 salable product index.3. flash-point, the boiling point of the extraction second time composition isopropyl ether in the extraction agent that uses are all very low, need extraction at low temperatures, and high volatility, and be extremely inflammable, can form explosive mixture with air, and chance naked light, high heat energy cause combustion explosion, and danger is bigger.4. need through twice solvent extraction, twice concentrated, and because extraction temperature is at 0 ℃～10 ℃ for the second time, the phosphoric acid after concentrating for the first time also needs cooling to extract again, has increased energy consumption.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of hydrochloric acid decomposing medium and low grade to prepare the method for PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid, this method can not only obtain high-quality PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid, and the time that can simplify technology, the whole flow process of shortening, cut down the consumption of energy and cost.
Hydrochloric acid decomposing medium and low grade of the present invention prepares the method for PHOSPHORIC ACID TECH.GRADE, and processing step is as follows successively:
(1) hydrochloric acidolysis ground phosphate rock
Hydrochloric acidolysis mid low grade phosphate rock powder with mass concentration 15%～26%, described hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 95%～105% of required hydrochloric acid theoretical amount, during acidolysis, ground phosphate rock is added in the hydrochloric acid, under agitation react in room temperature (indoor natural temperature), normal pressure, reaction times was at least 30 minutes, and reaction finishes the back and adds the flocculation agent flocculation sediment, obtains acid hydrolysis solution through solid-liquid separation then;
(2) extraction deironing
Step (1) acid hydrolysis solution that obtains is carried out counter-current extraction, the volume ratio of acid hydrolysis solution and extraction agent=2～4: 1,20 ℃～40 ℃ of extraction temperature, the raffinate water that obtains is the deironing raw phosphoric acid,
Described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, and the percent by volume of tributyl phosphate is 5%～15%, and the n-Octanol percent by volume is 10%～35%, and the percent by volume of kerosene is 50%～85%;
(3) preparation dilute phosphoric acid
Step (2) the deironing raw phosphoric acid that obtains is carried out counter-current extraction, then extracted organic phase that counter-current extraction obtains is carried out twice washing, the extracted organic phase after will washing is again carried out countercurrent reextraction and is promptly obtained the purification dilute phosphoric acid,
During counter-current extraction, the volume ratio of deironing raw phosphoric acid and extraction agent=1: 2～5,20 ℃～40 ℃ of extraction temperature, described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, the percent by volume of tributyl phosphate is 70%～90%, the n-Octanol percent by volume is 5%～15%, and the percent by volume of kerosene is 5%～15%
During countercurrent reextraction, the volume ratio of soft water and extracted organic phase=1: 3～6,50 ℃～65 ℃ of back extraction temperature;
(4) preparation PHOSPHORIC ACID TECH.GRADE
Step (3) obtained purify steps in sequence that dilute phosphoric acid is prepared into PHOSPHORIC ACID TECH.GRADE for concentrating, dearsenification removing heavy-metal, decolouring, filtration, decolouring deeply and regulate concentration.
In order better to realize goal of the invention, for above-mentioned each processing step also preferred following technical scheme:
(1) in the hydrochloric acidolysis ground phosphate rock step, the particle diameter of described ground phosphate rock≤1165 μ m, described flocculation agent is the polyacrylamide solution of mass concentration 0.05%～0.3%, the add-on of flocculation agent is 0.2%～2.5% of an acidolysis reaction slip volume, and the molecular weight of described polyacrylamide is at least 3,000,000 dalton.
(2) extracted organic phase of extraction deironing step generation is carried out countercurrent reextraction with the dilute hydrochloric acid of mass concentration 5%～10%, the volume ratio of described dilute hydrochloric acid and described extracted organic phase=0.5～2: 1,30 ℃～50 ℃ of back extraction temperature, the strip aqueous that produces is used to prepare hydrochloric acid, and the back extraction organic phase circulation of generation is used to extract deironing;
(3) in the preparation dilute phosphoric acid step, countercurrent washing is adopted in twice washing of described extracted organic phase, operate as follows: the wash temperature of washing is 35 ℃～50 ℃ for the first time, the volume ratio of water and extracted organic phase=0.05～0.1: 1, it is formulated that described water adds sulfuric acid by the elutant of washing for the second time, the vitriolic add-on is: required vitriolic theoretical amount when calcium ion in the extracted organic phase and sulfuric acid complete reaction, and the elutant of washing is used to prepare hydrochloric acid for the first time; The wash temperature of washing is 35 ℃～50 ℃ for the second time, volume ratio=0.05～0.1 of soft water and the extracted organic phase behind once washing: 1.
(4) in the preparation dilute phosphoric acid step, raffinate water and milk of lime that extraction produces carry out neutralization reaction, reaction slurry is through solid-liquid separation, the institute's filter cake that obtains soft water countercurrent washing, fertilely in vain dry, the elutant that described countercurrent washing produces is incorporated in the water that the thickening-purification technology dilute phosphoric acid is produced in the preparation PHOSPHORIC ACID TECH.GRADE step, institute's obtain filtrate is through evaporation concentration, the dry calcium chloride that gets, described neutralization reaction pH value is controlled at 8.0～9.0,50 ℃～60 ℃ of temperature of reaction, in 30 minutes～90 minutes reaction times, the water that described evaporation concentration produces is used to prepare the residue of hydrochloric acid or the generation of washing hydrochloric acid phosphate rock-sulfuric acid powder step.
(5) in the preparation PHOSPHORIC ACID TECH.GRADE step, described concentrating is the purification dilute phosphoric acid to be concentrated into contain P
2O
5Be 61%～66%; Described dearsenification removing heavy-metal is the thiophosphoric anhydride solution that under agitation adds mass concentration 2%～4% in concentrated phosphoric acid, the add-on of described thiophosphoric anhydride solution is: during sulfonium ion complete reaction in the arsenic in the concentrated phosphoric acid, the plumbous and thiophosphoric anhydride solution 150%～300% of required thiophosphoric anhydride solution theory amount, 65 ℃～85 ℃ of temperature of reaction, the reaction times was at least 45 minutes; Described decolouring is under agitation to add activated carbon in concentrated phosphoric acid, and the activated carbon add-on is 20～50 gram/kilogram concentrated phosphoric acids, 65 ℃～85 ℃ of bleaching temperatures, and the time was at least 45 minutes; Described dark decolouring is the hydrogen peroxide that under agitation adds mass concentration 30% in decolouring phosphoric acid, and the add-on of described hydrogen peroxide is 20～40 a gram/kilograms decolouring phosphoric acid, 65 ℃～85 ℃ of dark bleaching temperatures, and the time was at least 45 minutes.
(6) in the preparation dilute phosphoric acid step, the extracted organic phase after the washing is carried out the extraction that back extraction organic phase that countercurrent reextraction produces is used for the deironing raw phosphoric acid; In the preparation PHOSPHORIC ACID TECH.GRADE step, the phosphoric acid after the decolouring is filtered the filter cake that obtains wash with soft water, its elutant is incorporated the purification dilute phosphoric acid into.
Method and the above-mentioned method for preparing PHOSPHORIC ACID TECH.GRADE that hydrochloric acid decomposing medium and low grade of the present invention prepares food grade phosphoric acid belong to a total inventive concept, and processing step is as follows successively:
(1) hydrochloric acidolysis ground phosphate rock
(2) extraction deironing
(3) preparation dilute phosphoric acid
(4) preparation food grade phosphoric acid
In the processing step (1) (2) (3), hydrochloric acidolysis ground phosphate rock, extraction deironing and raw materials used, the technological operation of preparation dilute phosphoric acid, processing parameter are all identical with the corresponding processing step for preparing PHOSPHORIC ACID TECH.GRADE, processing step (4) preparation food grade phosphoric acid only is to have increased " dark defluorinate " on the basis of above-mentioned preparation PHOSPHORIC ACID TECH.GRADE step, be about to step (3) obtain purify steps in sequence that dilute phosphoric acid is prepared into food grade phosphoric acid for concentrate, dearsenification removing heavy-metal, decolouring, filtration, dark decolouring, dark defluorinate and adjusting concentration.The vacuum and steam vaporizing extract process is adopted in described dark defluorinate, and processing condition are: vacuum tightness 0.075Mpa～0.090Mpa, 95 ℃～110 ℃ of temperature.
Hydrochloric acid decomposing medium and low grade of the present invention prepares the method for food grade phosphoric acid, has also adopted the above-mentioned method institute optimized technical scheme for preparing PHOSPHORIC ACID TECH.GRADE.
The present invention has following beneficial effect:
1, compared with prior art, the method of the invention provides a kind of technical scheme of different designs for the production of PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid, not only available mid low grade phosphate rock manufacture level phosphoric acid and food grade phosphoric acid, and the time that can simplify technology, the whole flow process of shortening, cut down the consumption of energy and cost.
2, adopt the PHOSPHORIC ACID TECH.GRADE of the method for the invention preparation to meet premium grads standard or the acceptable end product standard that GB/T 2091-2008 stipulates; Food grade phosphoric acid meets GB 3149-2004 specified standards (concrete data are seen embodiment).
3, before phosphoric acid extraction, remove iron ion in the acid hydrolysis solution in advance, obtain the deironing raw phosphoric acid, guaranteed that the iron level of the finished product is up to state standards.
4, extract the deironing step owing to selected the extraction agent of tributyl phosphate, n-Octanol and kerosene composition, thereby good iron removal effect.
5, the extraction agent of forming with tributyl phosphate, n-Octanol and kerosene comes phosphoric acid extraction, the extraction conditions gentleness, and the extraction efficiency height, and extraction agent is water insoluble, need not reclaim solvent, can shorten flow process, reduces energy consumption.
6, the raffinate water behind the extraction deironing raw phosphoric acid neutralizes with milk of lime, has fully reclaimed P
2O
5
7, the calcium chloride of by-product is the extremely wide Chemicals of a kind of purposes, can be used to produce multi-purpose siccative, refrigeration agent, building anti-freezing agent, road surface dust-collecting agent, empty harbour antifogging agent, fabric fireproofing agent and some calcium salt.
8, on same set of device, but both manufacture level phosphoric acid can be produced food grade phosphoric acid again, helps reducing facility investment, the handiness that enhancing equipment uses.
Description of drawings
Fig. 1 is a kind of process flow sheet that hydrochloric acid decomposing medium and low grade of the present invention prepares the method for technical grade and food grade phosphoric acid;
Fig. 2 is another process flow sheet that hydrochloric acid decomposing medium and low grade of the present invention prepares the method for technical grade and food grade phosphoric acid, compare with the described technical process of Fig. 1, raffinate water, elutant, the recycling that concentrates the water that produces and main line technical process behind the extraction deironing raw phosphoric acid are organically combined.
Embodiment
The method of the invention is described further by embodiment below in conjunction with accompanying drawing.Data among the following embodiment are that laboratory lab scale serialization operation, system reach the data after stablizing.Used mid low grade phosphate rock powder footpath≤1165 μ m among the following embodiment, its composition (mass percent, %) as following table:
Embodiment 1
Present embodiment prepares PHOSPHORIC ACID TECH.GRADE and food grade phosphoric acid with mid low grade phosphate rock, and processing step is seen Fig. 1, and is as follows successively:
(1) hydrochloric acidolysis ground phosphate rock
The acidolysis of ground phosphate rock is carried out in the acidolysis groove, and the hydrochloric acid mass concentration is 21%, and the hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 100% of required hydrochloric acid theoretical amount; At first hydrochloric acid is added in the acidolysis groove, then ground phosphate rock is added in the hydrochloric acid, under agitation react in room temperature (25 ℃), normal pressure, 45 minutes reaction times, it is that mass concentration that 3,000,000 daltonian polyacrylamides are prepared is that 0.15% polyacrylamide solution carries out flocculation sediment that reaction finishes that the back adds with molecular weight, the add-on of described polyacrylamide solution is 1.5% of an acidolysis reaction slip volume, obtains acid hydrolysis solution through vacuum filtration then.
(2) extraction deironing
Step (1) acid hydrolysis solution that obtains is carried out the extraction of 5 stage countercurrents, the volume ratio of acid hydrolysis solution and extraction agent=3: 1,25 ℃ of extraction temperature, 25 minutes residence time of extraction, obtain raffinate water and extracted organic phase, the raffinate water that obtains is the deironing raw phosphoric acid; Described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, and the percent by volume of tributyl phosphate is 10%, and the n-Octanol percent by volume is 20%, and the percent by volume of kerosene is 70%;
With obtaining extracted organic phase mass concentration is that 7% dilute hydrochloric acid carries out 4 stage countercurrent back extractions, the volume ratio of described dilute hydrochloric acid and extracted organic phase=1: 1,40 ℃ of back extraction temperature, 20 minutes back extraction residence time, the strip aqueous that back extraction produces is used to prepare hydrochloric acid, and the back extraction organic phase circulation of generation is used to extract deironing.
(3) preparation of dilute phosphoric acid
Step (2) the deironing raw phosphoric acid that obtains is carried out the extraction of 5 stage countercurrents, the volume ratio of deironing raw phosphoric acid and extraction agent=1: 3,30 ℃ of extraction temperature, 25 minutes residence time of extraction, obtain raffinate water and extracted organic phase (after testing, the content of calcium ion is 0.0884% in the extracted organic phase), described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, the percent by volume of tributyl phosphate is 80%, and the n-Octanol percent by volume is 10%, and the percent by volume of kerosene is 10%;
Obtaining extracted organic phase is carried out twice washing; The washing of 5 stage countercurrents is adopted in washing for the first time, the volume ratio of water and extracted organic phase=0.075: 1,45 ℃ of wash temperatures, 25 minutes residence time of washing, it is formulated that described water adds sulfuric acid by the elutant of washing for the second time, the vitriolic add-on is: required vitriolic theoretical amount when calcium ion in the extracted organic phase and sulfuric acid complete reaction, and the elutant of washing is used to prepare hydrochloric acid for the first time; Washing is for the second time carried out the washing of 5 stage countercurrents with soft water, soft water with through the volume ratio of the extracted organic phase of once washing=0.075: 1,45 ℃ of wash temperatures, 25 minutes residence time of washing;
Extracted organic phase that will be after secondary washing is carried out 4 stage countercurrent back extractions with soft water and is obtained and purify dilute phosphoric acid and back extraction organic phase, soft water with through the volume ratio of the extracted organic phase of secondary washing=1: 5,60 ℃ of back extraction temperature, 20 minutes back extraction residence time, described back extraction organic phase circulation is used for the extraction of deironing raw phosphoric acid.
(4) preparation of PHOSPHORIC ACID TECH.GRADE
Step (3) obtained purify steps in sequence that dilute phosphoric acid is prepared into PHOSPHORIC ACID TECH.GRADE for concentrating, dearsenification removing heavy-metal, decolouring, filtration, decolouring deeply and regulate concentration;
Described concentrate is step (3) to be obtained the purification dilute phosphoric acid be concentrated into and contain P
2O
5Be 64% (after testing, arsenic content is 0.0006% in the concentrated phosphoric acid, lead content is 0.0013%);
Described dearsenification removing heavy-metal is the thiophosphoric anhydride solution that under agitation adds mass concentration 3% in concentrated phosphoric acid, described thiophosphoric anhydride solution add-on is: during sulfonium ion complete reaction in the arsenic in the concentrated phosphoric acid, the plumbous and thiophosphoric anhydride solution 200% of required thiophosphoric anhydride solution theory amount, 75 ℃ of temperature of reaction, 60 minutes reaction times;
Described decolouring is under agitation to add activated carbon in the concentrated phosphoric acid behind the dearsenification removing heavy-metal, and the activated carbon add-on is 35 gram/kilogram concentrated phosphoric acids, 75 ℃ of bleaching temperatures, and 60 minutes time, after reaction finished, vacuum filtration obtained the phosphoric acid that decolours;
Described dark decolouring is the hydrogen peroxide that under agitation adds mass concentration 30% in decolouring phosphoric acid, and the add-on of described hydrogen peroxide is 30 a gram/kilograms decolouring phosphoric acid, 75 ℃ of dark bleaching temperatures, 60 minutes time.
After dark decolouring finishes, the dark decolouring phosphoric acid that accounts for total amount 50% is regulated concentration obtain 85% PHOSPHORIC ACID TECH.GRADE.
(5) preparation of food grade phosphoric acid
Adopt the vacuum and steam vaporizing extract process to carry out dark defluorinate the dark decolouring phosphoric acid that accounts for total amount 50% after the dark decolouring in the step (4), the stripping condition is: vacuum tightness 0.075Mpa, 95 ℃ of temperature.After stripping finishes, regulate concentration and promptly obtain 85% food grade phosphoric acid.
The PHOSPHORIC ACID TECH.GRADE that present embodiment is prepared, about components contents (mass percent) and colourity see the following form:
The food grade phosphoric acid that present embodiment is prepared, about components contents (mass percent) and colourity see the following form:
Data from table as can be seen, the prepared PHOSPHORIC ACID TECH.GRADE of present embodiment meets the premium grads standard of GB/T 2091-2008 regulation, the prepared food grade phosphoric acid of present embodiment meets GB 3149-2004 specified standards.
Embodiment 2
Present embodiment prepares PHOSPHORIC ACID TECH.GRADE with mid low grade phosphate rock, and processing step is seen Fig. 2, and is as follows successively:
(1) hydrochloric acidolysis ground phosphate rock
The acidolysis of ground phosphate rock is carried out in the acidolysis groove, and the hydrochloric acid mass concentration is 15%, and the hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 105% of required hydrochloric acid theoretical amount; At first hydrochloric acid is added in the acidolysis groove, then ground phosphate rock is added in the hydrochloric acid, under agitation react in room temperature (20 ℃), normal pressure, 30 minutes reaction times, it is that mass concentration that 3,000,000 daltonian polyacrylamides are prepared is that 0.05% polyacrylamide solution carries out flocculation sediment that reaction finishes that the back adds with molecular weight, the add-on of described polyacrylamide solution is 2.5% of an acidolysis reaction slip volume, obtain acid hydrolysis solution and residue through vacuum filtration then, residue is washed, and its elutant is returned the acidolysis that the acidolysis groove is used for ground phosphate rock.
(2) extraction deironing
Step (1) acid hydrolysis solution that obtains is carried out the extraction of 6 stage countercurrents, the volume ratio of acid hydrolysis solution and extraction agent=2: 1,20 ℃ of extraction temperature, 30 minutes residence time of extraction, obtain raffinate water and extracted organic phase, the raffinate water that obtains is the deironing raw phosphoric acid; Described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, and the percent by volume of tributyl phosphate is 5%, and the n-Octanol percent by volume is 10%, and the percent by volume of kerosene is 85%;
With obtaining extracted organic phase mass concentration is that 10% dilute hydrochloric acid carries out 3 stage countercurrent back extractions, the volume ratio of described dilute hydrochloric acid and extracted organic phase=2: 1,30 ℃ of back extraction temperature, 15 minutes back extraction residence time, the strip aqueous that back extraction produces is used to prepare hydrochloric acid, and the back extraction organic phase circulation of generation is used to extract deironing.
(3) preparation of dilute phosphoric acid
Step (2) the deironing raw phosphoric acid that obtains is carried out the extraction of 7 stage countercurrents, the volume ratio of deironing raw phosphoric acid and extraction agent=1: 2,20 ℃ of extraction temperature, 35 minutes residence time of extraction, obtain raffinate water and extracted organic phase (after testing, the content of calcium ion is 0.1047% in the extracted organic phase), described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, the percent by volume of tributyl phosphate is 90%, and the n-Octanol percent by volume is 5%, and the percent by volume of kerosene is 5%;
Obtaining extracted organic phase is carried out twice washing; The washing of 3 stage countercurrents is adopted in washing for the first time, the volume ratio of water and extracted organic phase=0.1: 1,35 ℃ of wash temperatures, 15 minutes residence time of washing, it is formulated that described water adds sulfuric acid by the elutant of washing for the second time, the vitriolic add-on is: required vitriolic theoretical amount when calcium ion in the extracted organic phase and sulfuric acid complete reaction, and the elutant of washing is used to prepare hydrochloric acid for the first time; Washing is for the second time carried out the washing of 3 stage countercurrents with soft water, soft water with through the volume ratio of the extracted organic phase of once washing=0.1: 1,35 ℃ of wash temperatures, 15 minutes residence time of washing;
Extracted organic phase that will be after secondary washing is carried out 6 stage countercurrent back extractions with soft water and is obtained and purify dilute phosphoric acid and back extraction organic phase, soft water with through the volume ratio of the extracted organic phase of secondary washing=1: 6,50 ℃ of back extraction temperature, 30 minutes back extraction residence time, described back extraction organic phase is used for the extraction of deironing raw phosphoric acid;
Under agitation obtaining raffinate water and milk of lime are carried out neutralization reaction, the pH value of described neutralization reaction is controlled at 9.0,55 ℃ of temperature of reaction, 45 minutes reaction times, reaction finishes final vacuum and filters, the institute's filter cake that obtains soft water countercurrent washing, fertilely in vain dry, the elutant that countercurrent washing produces is incorporated in the water that the thickening-purification technology dilute phosphoric acid is produced in the preparation PHOSPHORIC ACID TECH.GRADE step, institute's obtain filtrate is through evaporation concentration, the dry calcium chloride that gets, and the water that evaporation concentration produces is used to prepare the residue of hydrochloric acid or the generation of washing hydrochloric acid phosphate rock-sulfuric acid powder step.
(4) preparation of PHOSPHORIC ACID TECH.GRADE
Step (3) obtained purify steps in sequence that dilute phosphoric acid is prepared into PHOSPHORIC ACID TECH.GRADE for concentrating, dearsenification removing heavy-metal, decolouring, filtration, decolouring deeply and regulate concentration;
Described concentrate is step (3) to be obtained the purification dilute phosphoric acid be concentrated into and contain P
2O
5Be 61% (after testing, arsenic content is 0.0007% in the concentrated phosphoric acid, lead content is 0.0015%);
Described dearsenification removing heavy-metal is the thiophosphoric anhydride solution that under agitation adds mass concentration 2% in concentrated phosphoric acid, described thiophosphoric anhydride solution add-on is: during sulfonium ion complete reaction in the arsenic in the concentrated phosphoric acid, the plumbous and thiophosphoric anhydride solution 150% of required thiophosphoric anhydride solution theory amount, 65 ℃ of temperature of reaction, 45 minutes reaction times;
Described decolouring is under agitation to add activated carbon in the concentrated phosphoric acid behind the dearsenification removing heavy-metal, the activated carbon add-on is 20 gram/kilogram concentrated phosphoric acids, 65 ℃ of bleaching temperatures, 45 minutes time, reaction finishes final vacuum and filters, obtain decolouring phosphoric acid and filter cake, the filter cake that obtains washs with soft water, and its elutant is incorporated the purification dilute phosphoric acid into;
Described dark decolouring is the hydrogen peroxide that under agitation adds mass concentration 30% in decolouring phosphoric acid, and the add-on of described hydrogen peroxide is 20 a gram/kilograms decolouring phosphoric acid, 65 ℃ of dark bleaching temperatures, 45 minutes time.
After dark decolouring finished, the phosphoric acid that will decolour was deeply regulated concentration and is promptly obtained 85% PHOSPHORIC ACID TECH.GRADE.
The PHOSPHORIC ACID TECH.GRADE that present embodiment is prepared, about components contents (mass percent) and colourity see the following form:
Data from table as can be seen, the prepared PHOSPHORIC ACID TECH.GRADE of present embodiment meets the acceptable end product standard of GB/T 2091-2008 regulation.
Embodiment 3
Present embodiment prepares food grade phosphoric acid with mid low grade phosphate rock, and processing step is seen Fig. 2, and is as follows successively:
(1) hydrochloric acidolysis ground phosphate rock
The acidolysis of ground phosphate rock is carried out in the acidolysis groove, and the hydrochloric acid mass concentration is 26%, and the hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 95% of required hydrochloric acid theoretical amount; At first hydrochloric acid is added in the acidolysis groove, then ground phosphate rock is added in the hydrochloric acid, under agitation react in room temperature (28 ℃), normal pressure, 60 minutes reaction times, it is that mass concentration that 3,000,000 daltonian polyacrylamides are prepared is that 0.3% polyacrylamide solution carries out flocculation sediment that reaction finishes that the back adds with molecular weight, the add-on of described polyacrylamide solution is 0.2% of an acidolysis reaction slip volume, obtain acid hydrolysis solution and residue through vacuum filtration then, residue is washed, and its elutant is returned the acidolysis that the acidolysis groove is used for ground phosphate rock.
(2) extraction deironing
Step (1) acid hydrolysis solution that obtains is carried out the extraction of 4 stage countercurrents, the volume ratio of acid hydrolysis solution and extraction agent=4: 1,40 ℃ of extraction temperature, 20 minutes residence time of extraction, obtain raffinate water and extracted organic phase, the raffinate water that obtains is the deironing raw phosphoric acid; Described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, and the percent by volume of tributyl phosphate is 15%, and the n-Octanol percent by volume is 35%, and the percent by volume of kerosene is 50%;
With obtaining extracted organic phase mass concentration is that 5% dilute hydrochloric acid carries out 5 stage countercurrent back extractions, the volume ratio of described dilute hydrochloric acid and extracted organic phase=0.5: 1,50 ℃ of back extraction temperature, 25 minutes back extraction residence time, the strip aqueous that back extraction produces is used to prepare hydrochloric acid, and the back extraction organic phase circulation of generation is used to extract deironing.
(3) preparation of dilute phosphoric acid
Step (2) the deironing raw phosphoric acid that obtains is carried out the extraction of 3 stage countercurrents, the volume ratio of deironing raw phosphoric acid and extraction agent=1: 5,40 ℃ of extraction temperature, 15 minutes residence time of extraction, obtain raffinate water and extracted organic phase (after testing, the content of calcium ion is 0.0682% in the extracted organic phase), described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, the percent by volume of tributyl phosphate is 70%, and the n-Octanol percent by volume is 15%, and the percent by volume of kerosene is 15%;
Obtaining extracted organic phase is carried out twice washing; The washing of 7 stage countercurrents is adopted in washing for the first time, the volume ratio of water and extracted organic phase=0.05: 1,50 ℃ of wash temperatures, 35 minutes residence time of washing, it is formulated that described water adds sulfuric acid by the elutant of washing for the second time, the vitriolic add-on is: required vitriolic theoretical amount when calcium ion in the extracted organic phase and sulfuric acid complete reaction, and the elutant of washing is used to prepare hydrochloric acid for the first time; Washing is for the second time carried out the washing of 7 stage countercurrents with soft water, soft water with through the volume ratio of the extracted organic phase of once washing=0.05: 1,50 ℃ of wash temperatures, 35 minutes residence time of washing;
Extracted organic phase that will be after secondary washing is carried out 3 stage countercurrent back extractions with soft water and is obtained and purify dilute phosphoric acid and back extraction organic phase, soft water with through the volume ratio of the extracted organic phase of secondary washing=1: 3,65 ℃ of back extraction temperature, 15 minutes back extraction residence time, described back extraction organic phase is used for the extraction of deironing raw phosphoric acid;
Under agitation obtaining raffinate water and milk of lime are carried out neutralization reaction, the pH value of described neutralization reaction is controlled at 8.5,50 ℃ of temperature of reaction, 60 minutes reaction times, reaction finishes final vacuum and filters, the institute's filter cake that obtains soft water countercurrent washing, fertilely in vain dry, the elutant that countercurrent washing produces is incorporated in the water that the thickening-purification technology dilute phosphoric acid is produced in the preparation food grade phosphoric acid step, institute's obtain filtrate is through evaporation concentration, the dry calcium chloride that gets, and the water that evaporation concentration produces is used to prepare the residue of hydrochloric acid or the generation of washing hydrochloric acid phosphate rock-sulfuric acid powder step.
(4) preparation of food grade phosphoric acid
With step (3) obtain purify steps in sequence that dilute phosphoric acid is prepared into food grade phosphoric acid for concentrate, dearsenification removing heavy-metal, decolouring, filtration, dark decolouring, dark defluorinate and regulate concentration;
Described concentrate is step (3) to be obtained the purification dilute phosphoric acid be concentrated into and contain P
2O
5Be 66% (after testing, arsenic content is 0.0006% in the concentrated phosphoric acid, lead content is 0.0011%);
Described dearsenification removing heavy-metal is the thiophosphoric anhydride solution that under agitation adds mass concentration 4% in concentrated phosphoric acid, described thiophosphoric anhydride solution add-on is: during sulfonium ion complete reaction in the arsenic in the concentrated phosphoric acid, the plumbous and thiophosphoric anhydride solution 300% of required thiophosphoric anhydride solution theory amount, 85 ℃ of temperature of reaction, 90 minutes reaction times;
Described decolouring is under agitation to add activated carbon in the concentrated phosphoric acid behind the dearsenification removing heavy-metal, the activated carbon add-on is 50 gram/kilogram concentrated phosphoric acids, 85 ℃ of bleaching temperatures, 90 minutes time, reaction finishes final vacuum and filters, obtain decolouring phosphoric acid and filter cake, the filter cake that obtains washs with soft water, and its elutant is incorporated the purification dilute phosphoric acid into;
Described dark decolouring is the hydrogen peroxide that under agitation adds mass concentration 30% in decolouring phosphoric acid, and the add-on of described hydrogen peroxide is 40 a gram/kilograms decolouring phosphoric acid, 85 ℃ of dark bleaching temperatures, 90 minutes time.
The vacuum and steam vaporizing extract process is adopted in described dark defluorinate, and the stripping condition is: vacuum tightness 0.090Mpa, 110 ℃ of temperature.After stripping finishes, regulate concentration and promptly obtain 85% food grade phosphoric acid.
The food grade phosphoric acid that present embodiment is prepared, about components contents (mass percent) and colourity see the following form:
From the table data as can be seen, the prepared food grade phosphoric acid of present embodiment meets GB 3149-2004 specified standards.
Claims (10)
1. a hydrochloric acid decomposing medium and low grade prepares the method for PHOSPHORIC ACID TECH.GRADE, it is characterized in that processing step is as follows successively:
(1) hydrochloric acidolysis ground phosphate rock
Hydrochloric acidolysis mid low grade phosphate rock powder with mass concentration 15%～26%, described hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 95%～105% of required hydrochloric acid theoretical amount, during acidolysis, ground phosphate rock is added in the hydrochloric acid, under agitation in room temperature, normal pressure reacts, reaction times was at least 30 minutes, reaction finishes the back and adds the flocculation agent flocculation sediment, obtain acid hydrolysis solution through solid-liquid separation then, described flocculation agent is the polyacrylamide solution of mass concentration 0.05%～0.3%, the add-on of flocculation agent is 0.2%～2.5% of an acidolysis reaction slip volume, and the molecular weight of described polyacrylamide is at least 3,000,000 dalton;
(2) extraction deironing
Step (1) acid hydrolysis solution that obtains is carried out counter-current extraction, the volume ratio of acid hydrolysis solution and extraction agent=2～4: 1,20 ℃～40 ℃ of extraction temperature, the raffinate water that obtains is the deironing raw phosphoric acid,
Described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, and the percent by volume of tributyl phosphate is 5%～15%, and the n-Octanol percent by volume is 10%～35%, and the percent by volume of kerosene is 50%～85%;
(3) preparation dilute phosphoric acid
Step (2) the deironing raw phosphoric acid that obtains is carried out counter-current extraction, then extracted organic phase that counter-current extraction obtains is carried out twice washing, the extracted organic phase after will washing is again carried out countercurrent reextraction and is promptly obtained the purification dilute phosphoric acid,
During counter-current extraction, the volume ratio of deironing raw phosphoric acid and extraction agent=1: 2～5,20 ℃～40 ℃ of extraction temperature, described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, the percent by volume of tributyl phosphate is 70%～90%, the n-Octanol percent by volume is 5%～15%, and the percent by volume of kerosene is 5%～15%
During countercurrent reextraction, the volume ratio of soft water and extracted organic phase=1: 3～6,50 ℃～65 ℃ of back extraction temperature;
(4) preparation PHOSPHORIC ACID TECH.GRADE
Step (3) obtained purify steps in sequence that dilute phosphoric acid is prepared into PHOSPHORIC ACID TECH.GRADE for concentrating, dearsenification removing heavy-metal, decolouring, filtration, decolouring deeply and regulate concentration.
2. prepare the method for PHOSPHORIC ACID TECH.GRADE according to the described hydrochloric acid decomposing medium and low grade of claim 1, it is characterized in that:
(1) in the hydrochloric acidolysis ground phosphate rock step, the particle diameter of described ground phosphate rock≤1165 μ m;
(2) in the preparation PHOSPHORIC ACID TECH.GRADE step, described concentrating is the purification dilute phosphoric acid to be concentrated into contain P
2O
5Be 61%～66%; Described dearsenification removing heavy-metal is the thiophosphoric anhydride solution that under agitation adds mass concentration 2%～4% in concentrated phosphoric acid, the add-on of described thiophosphoric anhydride solution is: during sulfonium ion complete reaction in the arsenic in the concentrated phosphoric acid, the plumbous and thiophosphoric anhydride solution 150%～300% of required thiophosphoric anhydride solution theory amount, 65 ℃～85 ℃ of temperature of reaction, the reaction times was at least 45 minutes; Described decolouring is under agitation to add activated carbon in concentrated phosphoric acid, and described activated carbon add-on is 20～50 gram/kilogram concentrated phosphoric acids, 65 ℃～85 ℃ of bleaching temperatures, and the time was at least 45 minutes; Described dark decolouring is the hydrogen peroxide that under agitation adds mass concentration 30% in decolouring phosphoric acid, and the add-on of described hydrogen peroxide is 20～40 a gram/kilograms decolouring phosphoric acid, 65 ℃～85 ℃ of dark bleaching temperatures, and the time was at least 45 minutes.
3. prepare the method for PHOSPHORIC ACID TECH.GRADE according to claim 1 or 2 described hydrochloric acid decomposing medium and low grade, it is characterized in that preparing in the dilute phosphoric acid step, countercurrent washing is adopted in twice washing of described extracted organic phase, operates as follows:
The wash temperature of washing is 35 ℃～50 ℃ for the first time, the volume ratio of water and extracted organic phase=0.05～0.1: 1, it is formulated that described water adds sulfuric acid by the elutant of washing for the second time, the vitriolic add-on is: required vitriolic theoretical amount when calcium ion in the extracted organic phase and sulfuric acid complete reaction, and the elutant of washing is used to prepare hydrochloric acid for the first time;
The wash temperature of washing is 35 ℃～50 ℃ for the second time, volume ratio=0.05～0.1 of soft water and the extracted organic phase behind once washing: 1.
4. prepare the method for PHOSPHORIC ACID TECH.GRADE according to claim 1 or 2 described hydrochloric acid decomposing medium and low grade, it is characterized in that:
(1) extracted organic phase of extraction deironing step generation is carried out countercurrent reextraction with the dilute hydrochloric acid of mass concentration 5%～10%, the volume ratio of described dilute hydrochloric acid and described extracted organic phase=0.5～2: 1,30 ℃～50 ℃ of back extraction temperature, strip aqueous is used to prepare hydrochloric acid, and the circulation of back extraction organic phase is used to extract deironing;
(2) in the preparation dilute phosphoric acid step, raffinate water and milk of lime that extraction produces carry out neutralization reaction, reaction slurry is through solid-liquid separation, the institute's filter cake that obtains soft water countercurrent washing, fertilely in vain dry, institute's obtain filtrate is through evaporation concentration, the dry calcium chloride that gets, described neutralization reaction pH value is controlled at 8.0～9.0,50 ℃～60 ℃ of temperature of reaction, 30 minutes～90 minutes reaction times.
5. prepare the method for PHOSPHORIC ACID TECH.GRADE according to the described hydrochloric acid decomposing medium and low grade of claim 3, it is characterized in that:
(1) extracted organic phase of extraction deironing step generation is carried out countercurrent reextraction with the dilute hydrochloric acid of mass concentration 5%～10%, the volume ratio of described dilute hydrochloric acid and described extracted organic phase=0.5～2: 1,30 ℃～50 ℃ of back extraction temperature, strip aqueous is used to prepare hydrochloric acid, and the circulation of back extraction organic phase is used to extract deironing;
(2) in the preparation dilute phosphoric acid step, raffinate water and milk of lime that extraction produces carry out neutralization reaction, reaction slurry is through solid-liquid separation, the institute's filter cake that obtains soft water countercurrent washing, fertilely in vain dry, institute's obtain filtrate is through evaporation concentration, the dry calcium chloride that gets, described neutralization reaction pH value is controlled at 8.0～9.0,50 ℃～60 ℃ of temperature of reaction, 30 minutes～90 minutes reaction times.
6. a hydrochloric acid decomposing medium and low grade prepares the method for food grade phosphoric acid, it is characterized in that processing step is as follows successively:
(1) hydrochloric acidolysis ground phosphate rock
Hydrochloric acidolysis mid low grade phosphate rock powder with mass concentration 15%～26%, described hydrochloric acid consumption is: when CaO in the ground phosphate rock and hydrochloric acid complete reaction 95%～105% of required hydrochloric acid theoretical amount, during acidolysis, ground phosphate rock is added in the hydrochloric acid, under agitation in room temperature, normal pressure reacts, reaction times was at least 30 minutes, reaction finishes the back and adds the flocculation agent flocculation sediment, obtain acid hydrolysis solution through solid-liquid separation then, described flocculation agent is the polyacrylamide solution of mass concentration 0.05%～0.3%, the add-on of flocculation agent is 0.2%～2.5% of an acidolysis reaction slip volume, and the molecular weight of described polyacrylamide is at least 3,000,000 dalton;
(2) extraction deironing
Step (1) acid hydrolysis solution that obtains is carried out counter-current extraction, the volume ratio of acid hydrolysis solution and extraction agent=2～4: 1,20 ℃～40 ℃ of extraction temperature, the raffinate water that obtains is the deironing raw phosphoric acid,
Described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, and the percent by volume of tributyl phosphate is 5%～15%, and the n-Octanol percent by volume is 10%～35%, and the percent by volume of kerosene is 50%～85%;
(3) preparation dilute phosphoric acid
Step (2) the deironing raw phosphoric acid that obtains is carried out counter-current extraction, then extracted organic phase that counter-current extraction obtains is carried out twice washing, the extracted organic phase after will washing is again carried out countercurrent reextraction and is promptly obtained the purification dilute phosphoric acid,
During counter-current extraction, the volume ratio of deironing raw phosphoric acid and extraction agent=1: 2～5,20 ℃～40 ℃ of extraction temperature, described extraction agent is made up of tributyl phosphate, n-Octanol and kerosene, the percent by volume of tributyl phosphate is 70%～90%, the n-Octanol percent by volume is 5%～15%, and the percent by volume of kerosene is 5%～15%
During countercurrent reextraction, the volume ratio of soft water and extracted organic phase=1: 3～6,50 ℃～65 ℃ of back extraction temperature;
(4) preparation food grade phosphoric acid
With step (3) obtain purify steps in sequence that dilute phosphoric acid is prepared into food grade phosphoric acid for concentrate, dearsenification removing heavy-metal, decolouring, filtration, dark decolouring, dark defluorinate and regulate concentration.
7. prepare the method for food grade phosphoric acid according to the described hydrochloric acid decomposing medium and low grade of claim 6, it is characterized in that:
(1) in the hydrochloric acidolysis ground phosphate rock step, the particle diameter of described ground phosphate rock≤1165 μ m;
(2) in the preparation food grade phosphoric acid step, described concentrating is the purification dilute phosphoric acid to be concentrated into contain P
2O
5Be 61%～66%; Described dearsenification removing heavy-metal is the thiophosphoric anhydride solution that under agitation adds mass concentration 2%～4% in concentrated phosphoric acid, the add-on of described thiophosphoric anhydride solution is: during sulfonium ion complete reaction in the arsenic in the concentrated phosphoric acid, the plumbous and thiophosphoric anhydride solution 150%～300% of required thiophosphoric anhydride solution theory amount, 65 ℃～85 ℃ of temperature of reaction, the reaction times was at least 45 minutes; Described decolouring is under agitation to add activated carbon in concentrated phosphoric acid, and described activated carbon add-on is 20～50 gram/kilogram concentrated phosphoric acids, 65 ℃～85 ℃ of bleaching temperatures, and the time was at least 45 minutes; Described dark decolouring is the hydrogen peroxide that under agitation adds mass concentration 30% in decolouring phosphoric acid, and the add-on of described hydrogen peroxide is 20～40 a gram/kilograms decolouring phosphoric acid, 65 ℃～85 ℃ of dark bleaching temperatures, and the time was at least 45 minutes; The vacuum and steam vaporizing extract process is adopted in described dark defluorinate, and processing condition are: vacuum tightness 0.075Mpa～0.090Mpa, 95 ℃～110 ℃ of temperature.
8. prepare the method for food grade phosphoric acid according to claim 6 or 7 described hydrochloric acid decomposing medium and low grade, it is characterized in that preparing in the dilute phosphoric acid step, countercurrent washing is adopted in twice washing of described extracted organic phase, operates as follows:
The wash temperature of washing is 35 ℃～50 ℃ for the first time, the volume ratio of water and extracted organic phase=0.05～0.1: 1, it is formulated that described water adds sulfuric acid by the elutant of washing for the second time, the vitriolic add-on is: required vitriolic theoretical amount when calcium ion in the extracted organic phase and sulfuric acid complete reaction, and the elutant of washing is used to prepare hydrochloric acid for the first time;
The wash temperature of washing is 35 ℃～50 ℃ for the second time, volume ratio=0.05～0.1 of soft water and the extracted organic phase behind once washing: 1.
9. prepare the method for food grade phosphoric acid according to claim 6 or 7 described hydrochloric acid decomposing medium and low grade, it is characterized in that:
(1) extracted organic phase of extraction deironing step generation is carried out countercurrent reextraction with the dilute hydrochloric acid of mass concentration 5%～10%, the volume ratio of described dilute hydrochloric acid and described extracted organic phase=0.5～2: 1,30 ℃～50 ℃ of back extraction temperature, strip aqueous is used to prepare hydrochloric acid, and the circulation of back extraction organic phase is used to extract deironing;
(2) in the preparation dilute phosphoric acid step, raffinate water and milk of lime that extraction produces carry out neutralization reaction, reaction slurry is through solid-liquid separation, the institute's filter cake that obtains soft water countercurrent washing, fertilely in vain dry, institute's obtain filtrate is through evaporation concentration, the dry calcium chloride that gets, described neutralization reaction pH value is controlled at 8.0～9.0,50 ℃～60 ℃ of temperature of reaction, 30 minutes～90 minutes reaction times.
10. described according to Claim 8 hydrochloric acid decomposing medium and low grade prepares the method for food grade phosphoric acid, it is characterized in that:
(1) extracted organic phase of extraction deironing step generation is carried out countercurrent reextraction with the dilute hydrochloric acid of mass concentration 5%～10%, the volume ratio of described dilute hydrochloric acid and described extracted organic phase=0.5～2: 1,30 ℃～50 ℃ of back extraction temperature, strip aqueous is used to prepare hydrochloric acid, and the circulation of back extraction organic phase is used to extract deironing;
(2) in the preparation dilute phosphoric acid step, raffinate water and milk of lime that extraction produces carry out neutralization reaction, reaction slurry is through solid-liquid separation, the institute's filter cake that obtains soft water countercurrent washing, fertilely in vain dry, institute's obtain filtrate is through evaporation concentration, the dry calcium chloride that gets, described neutralization reaction pH value is controlled at 8.0～9.0,50 ℃～60 ℃ of temperature of reaction, 30 minutes～90 minutes reaction times.
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| CN102515134B (en) * | 2011-12-23 | 2014-04-16 | 凯恩德利(北京)科贸有限公司 | Production technology of food-grade phosphoric acid with hydrochloric acid method |
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| CN108557791A (en) * | 2018-06-08 | 2018-09-21 | 武汉工程大学 | The method for preparing calcium dihydrogen phosphate using low-grade phosphate ore |
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