CN106044730B - Utilize the method for high-grade phosphorus ore production phosphoric acid by wet process - Google Patents
Utilize the method for high-grade phosphorus ore production phosphoric acid by wet process Download PDFInfo
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- CN106044730B CN106044730B CN201610392154.9A CN201610392154A CN106044730B CN 106044730 B CN106044730 B CN 106044730B CN 201610392154 A CN201610392154 A CN 201610392154A CN 106044730 B CN106044730 B CN 106044730B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
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- C—CHEMISTRY; METALLURGY
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F11/46—Sulfates
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Abstract
The invention discloses a kind of methods using high-grade phosphorus ore production phosphoric acid by wet process, belong to phosphorous chemical industry manufacture field, and this method is using two-step reaction, countercurrent washing flow, produces high-concentration phosphoric acid and technical grade gypsum by high-grade phosphorus ore, comprises the following steps：It pressurizes acidolysis reaction step, acid hydrolysate separation circuit, clear liquid sink calcium reaction process and cleaning solution recycles process.P elements in high-grade phosphorus ore can be produced into the phosphoric acid of high concentration simultaneously by the method for the present invention, additionally it is possible to the calcium constituent in phosphorus ore be produced into technical grade gypsum, the valueization for reaching energy saving purpose and calcium constituent utilizes.
Description
Technical field
The present invention relates to technical field of phosphorous chemical industry, and in particular to utilizes the method for high-grade phosphorus ore production phosphoric acid by wet process.
Background technology
Wet Processes of Phosphoric Acid is with the process of inorganic acid (mainly sulfuric acid) decomposing phosphate rock manufacture phosphoric acid, i.e., with sulfuric acid and phosphorus
Ore deposit reaction generation crystal of calcium sulfate and phosphoric acid solution, then solid-liquor separation is carried out, obtain phosphoric acid.Wherein inorganic acid can also be nitric acid
And hydrochloric acid.The defects of Wet Processes of Phosphoric Acid is difficult to overcome there are some, since processing technology is extensive, the objectionable impurities in ore is big
Part enters in phosphoric acid.Particularly fluorine element, once into liquid phase, it will be difficult to it separates.More seriously, generate substantial amounts of
Ardealite waste material causes serious pollution and waste.
Wet Processes of Phosphoric Acid process is improved by scholar's research, reaction is carried out in two steps, used first
Phosphoric acid leaches decomposing phosphate rock stone, secondly provides suitable crystallization condition, reduces the impurity content in by-product ardealite.Phosphorus at present
Sour decomposing phosphate rock has application foundation in two water law phosphoric acid and slurry process coarse whiting technique,
Chinese patent application CN102001636B discloses a kind of utilization wide concentration phosphoric acid of mid low grade phosphate rock wet production
With the method for clean plaster, in the acid decomposed by phosphoric acid phosphorus ore process of this method, acidolysis reaction temperature is less than 105 DEG C, so as to cause
Phosphorite stope reaction is incomplete, meanwhile, since reactivity is relatively low, phosphorus ore also decomposes not mid low grade phosphate rock in Phosphoric Acid
Completely, the complete phosphorus ore of unreacted still needs is decomposed again with sulfuric acid, using mid low grade phosphate rock, since impurity contains in phosphorus ore
Amount is high, and reacting slurry viscosity is very big, and solid phase is precipitated in feed liquid and blocks filter plant, the separation of the complete phosphorus ore of unreacted and liquid phase
It is an industrialization technology problem, substantially without industrialized possibility.There are phosphorus ore reaction recrement and gypsum for the above method simultaneously
Separation it is difficult, the problem of gypsum impurity content of production is high.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency in the presence of the prior art, high-grade phosphorus ore production wet method is utilized
The method of phosphoric acid.This method directly produces high-concentration phosphoric acid by controlling the process conditions of phosphorus ore acid hydrolysis using high-grade phosphorus ore,
And by-product high quality industrial gypsum, enabling high-grade phosphorus ore, preferably valueization utilizes.
In order to realize foregoing invention purpose, the present invention provides following technical schemes：
Using the method for high-grade phosphorus ore production phosphoric acid by wet process, comprise the following steps：
Phosphate ore pulp and phosphoric acid are added in acidolysis reaction equipment by S1,0.2~0.5MPa are forced into, at 105~200 DEG C
1~5h of reaction obtains acidolysis slurries, and the acidolysis slurries are carried out isolated clear liquid and solid phase；
S2 adds in sulfuric acid into the clear liquid, is reacted at 50~100 DEG C, precipitated and separated, isolated P2O5Content is
More than 36% phosphoric acid and semi-finished product technical grade gypsum；
By the solid phase after sulfuric acid washing separates, cleaning solution enters step S1 and recycles S3；By described half into
Product technical grade gypsum is washed with water to obtain technical grade gypsum and gypsum washing lotion, and the gypsum washing lotion enters step S1 and recycles.
Method provided by the invention is using two-step reaction, countercurrent washing flow, and high concentration phosphorus are produced by high-grade phosphorus ore
Acid and technical grade gypsum.The reaction rate of phosphoric acid phosphate rock-sulfuric acid can be rapid unlike second step crystallization reaction in above-mentioned steps
It completes, and subsequently obtains the quality of technical grade gypsum and the effect of high-concentration phosphoric acid is realized by acid decomposed by phosphoric acid phosphorus ore.It is logical
The mode of reaction temperature is overpressurized and improved, acidolysis reaction rate and conversion ratio can be greatlyd improve, carries out acidolysis reaction
It is more thorough, it is difficult so as to greatly alleviate the separation of clear liquid and solid phase after acidolysis reaction, avoid causing reaction slurry
Fluid viscosity is very big, and solid phase is precipitated in feed liquid and blocks filter plant.Applicant has found by substantial amounts of experimental study, in reaction pressure
For 0.2~0.5MPa, when reaction temperature is 105~200 DEG C, compared with the prior art acidolysis reaction rate can improve 40~
50%, while the conversion ratio of phosphorus ore can reach more than 97%.
Further, the moisture of phosphate ore pulp is 1~20wt% in step S1, P in phosphorus ore2O5Content for 30~
38wt%, content of MgO are 0.1~1.0wt%, Al2O3And Fe2O3Content and for 0.1~1.5wt%.
The high-grade phosphorus ore selected in said program can ensure the reactivity of acidolysis reaction, impurity content in phosphorus ore
Low, acidolysis reaction slurry viscosity is moderate, and filter plant is not easy to plug in feed liquid, can realize very well the complete phosphorus ore of unreacted and
The separation of liquid phase, achievees the purpose that industrialized production.
Further, in step S1 phosphoric acid used in acidolysis reaction P2O5Content is more than 36wt%.
Further, equipment used in being centrifuged in step S2 is cyclone separator or Horizontal helical type centrifuge.
Select said program in centrifugal separation equipment be because the equipment in the solid-liquid separation step of acidolysis slurries not
Easily block filter plant.
Further, the concentration of sulfuric acid is 5~55wt% used in pickling separation in step S3.
Further, cleaning solution and gypsum washing lotion enter step and heating concentration are further included before S1 is recycled in step S3
Step.
Further, P in the washing lotion after above-mentioned heating concentration2O5Content is more than 36wt%, concentrate the temperature of washing lotion for 90~
100℃。
Concentration washing lotion in the temperature range can realize that acid hemolysis process heat is put down after acidolysis reaction equipment of pressurizeing is entered
Weighing apparatus, and as P in concentration washing lotion2O5When content is less than 36wt%, the resolution ratio of acidolysis reaction is poor.
Compared with prior art, beneficial effects of the present invention：
Method provided by the invention using high-grade phosphorus ore production phosphoric acid by wet process in the step of phosphate rock-sulfuric acid, passes through
Pressurization and the mode for improving reaction temperature, drastically increase reaction rate and conversion ratio, acidolysis reaction are made to carry out more thorough
Bottom, compared with the prior art acidolysis reaction rate can improve 40~50%, while the conversion ratio of phosphorus ore can reach more than 97%, from
And can greatly alleviate the separation difficulty of clear liquid and solid phase after acidolysis reaction, it avoids causing reacting slurry viscosity very big, expect
Solid phase is precipitated in liquid and blocks filter plant.Simultaneously because improve the quality that acidolysis process improves white cream obtained by follow-up heavy calcium.
It is high using high-grade phosphorus ore wet production using high-concentration wet process phosphoric acid proposed by the present invention and industrial gypsum coproduction technology
Concentration phosphoric acid and industrial gypsum have extraordinary economic benefit.Produce 1 ton of P2O5Phosphoric acid, can with 3.2 tons of industrial gypsums of output,
While reducing by 3.2 tons of gypsum stacking pressure, 320 yuan of gypsum income from sales can also be realized.
Description of the drawings
Fig. 1 is the process flow chart of the present invention that phosphoric acid by wet process method is produced using high-grade phosphorus ore.
Fig. 2 is the process flow chart of the embodiment of the present invention 1.
Specific embodiment
With reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
The technological process of the present embodiment is as shown in Figure 2.The P of certain phosphorus ore2O5Grade is 31wt%, and content of MgO is in phosphorus ore
0.5wt%, Al in phosphorus ore2O3+Fe2O3The sum of content is 1wt%, phosphorus ore is worn into ore pulp, with Horizontal helical type centrifuge ore pulp water
The separation heart is separated to 16wt%.The P that concentration is come2O5Phosphate ore pulp of 95 DEG C of phosphoric acid with moisture content 16wt% that content is 37wt%
Acidolysis reaction, 1000 parts of the butt phosphorus ore of addition are carried out in compressive reaction slot R1, acidolysis reaction operating condition is：Temperature is
117 DEG C, reaction pressure 0.3MPa, when the reaction time 2 is small.The acidolysis slurry reacted enters separator F1, carries out separation of solid and liquid,
Obtained solid slag carries out water-washing process in washer R2, obtains phosphorous 1000 parts of wash water, wherein P2O5100 parts of content, obtains
Clear liquid adds in sulfuric acid and carries out heavy calcium reaction into heavy calcium slot C1, and after fully heavy calcium reaction, reaction slurry is through F2 points of vacuum filter
White industrial gypsum and concentrated phosphoric acid are separated out, clean gypsum and phosphorous washings are obtained after the washing of white industrial gypsum, through dry
It is dry to obtain clean 650~750 parts of industrial gypsum, while obtain P2O5Concentration be 40% 550~570 parts of phosphoric acid, phosphorous acid washing water
It after mixing, is concentrated into inspissator C2,95 DEG C of concentrates return to compressive reaction slot R1 as recycled phosphoric acid.
Embodiment 2
The technological process of the present embodiment is as shown in Figure 2.The P of certain phosphorus ore2O5Grade is 36wt%, and content of MgO is in phosphorus ore
0.4wt%, Al in phosphorus ore2O3And Fe2O3Content summation for 0.9wt%, phosphorus ore is worn into ore pulp, with Horizontal helical type centrifuge handle
Ore pulp moisture is centrifuged to 12%.Contain P what concentration came2O5For the phosphorus ore of the 90 DEG C of phosphoric acid and moisture content 16wt% of 37wt%
Slurry carries out acidolysis reaction, 1000 parts of the butt phosphorus ore of addition in compressive reaction slot R1, and acidolysis reaction operating condition is：Temperature is
105 DEG C, reaction pressure 0.2MPa, when the reaction time is 3 small.The acidolysis slurry reacted enters separator F1, carries out solid-liquid point
From obtained slag carries out water-washing process in washer R2, obtains phosphorous 1000 parts of wash water, wherein P2O5100 parts of content, obtains
Clear liquid adds in sulfuric acid and carries out heavy calcium reaction into heavy calcium slot C1, and after fully heavy calcium reaction, reaction slurry is through F2 points of vacuum filter
White industrial gypsum and concentrated phosphoric acid are separated out, clean gypsum and phosphorous washings are obtained after the washing of white industrial gypsum, through dry
It is dry to obtain clean 650~750 parts of industrial gypsum, while obtain P2O5Concentration be 42% 550~570 parts of phosphoric acid, phosphorous acid washing water
It after mixing, is concentrated into inspissator C2,90 DEG C of concentrates return to compressive reaction slot R1 as recycled phosphoric acid.
Embodiment 3
The technological process of the present embodiment is as shown in Figure 2.The P of certain phosphorus ore2O5Grade is 33%, and content of MgO is in phosphorus ore
0.6wt%, Al in phosphorus ore2O3+Fe2O3The sum of content is 1wt%, phosphorus ore is worn into ore pulp, with Horizontal helical type centrifuge ore pulp water
The separation heart is separated to 2wt%.Contain P what concentration came2O5Phosphate ore pulp for the 95 DEG C of phosphoric acid and moisture content 2wt% of 37wt% is adding
The interior progress acidolysis reactions of reactive tank R1,1000 parts of the butt phosphorus ore of addition are pressed, acidolysis reaction operating condition is：Temperature is 140 DEG C,
Reaction pressure 0.3MPa, when the reaction time 5 is small.The acidolysis slurry reacted enters separator F1, carries out separation of solid and liquid, obtains
Slag carries out water-washing process in washer R2, obtains phosphorous 1000 parts of wash water, wherein P2O5100 parts of content, obtained clear liquid enter heavy
Calcium slot C1 adds in sulfuric acid and carries out heavy calcium reaction, and after fully heavy calcium reaction, reaction slurry isolates white work through vacuum filter F2
Industry gypsum and concentrated phosphoric acid obtain clean gypsum and phosphorous washings after the washing of white industrial gypsum, clean through being dried to obtain
650~750 parts of industrial gypsum, while obtain P2O5Concentration is 42% 550~570 parts of phosphoric acid, after phosphorous acid washing water mixing,
It is concentrated into inspissator C2,95 DEG C of concentrates return to compressive reaction slot R1 as recycled phosphoric acid.
Embodiment 4
The technological process of the present embodiment is as shown in Figure 2.The P of certain phosphorus ore2O5Grade is 32wt%, and content of MgO is in phosphorus ore
0.8wt%, Al in phosphorus ore2O3+Fe2O3The sum of content is 0.5wt%, phosphorus ore is worn into ore pulp, with Horizontal helical type centrifuge ore pulp
Moisture is centrifuged to 18wt%.The P that concentration is come2O5Phosphorus ore of 98 DEG C of phosphoric acid with moisture content 18wt% that content is 37wt%
Slurry carries out acidolysis reaction, 1000 parts of the butt phosphorus ore of addition in compressive reaction slot R1, and acidolysis reaction operating condition is：Temperature is
110 DEG C, reaction pressure 0.3MPa, when the reaction time 2 is small.The acidolysis slurry reacted enters separator F1, carries out separation of solid and liquid,
Obtained solid slag carries out water-washing process in washer R2, obtains phosphorous 1000 parts of wash water, wherein P2O5100 parts of content, obtains
Clear liquid adds in sulfuric acid and carries out heavy calcium reaction into heavy calcium slot C1, and after fully heavy calcium reaction, reaction slurry is through F2 points of vacuum filter
White industrial gypsum and concentrated phosphoric acid are separated out, clean gypsum and phosphorous washings are obtained after the washing of white industrial gypsum, through dry
It is dry to obtain clean 650~750 parts of industrial gypsum, while obtain P2O5Concentration be 43% 550~570 parts of phosphoric acid, phosphorous acid washing water
It after mixing, is concentrated into inspissator C2,98 DEG C of concentrates return to compressive reaction slot R1 as recycled phosphoric acid.
Comparative example 1
The technological process of the present embodiment is as shown in Figure 2.The P of certain phosphorus ore2O5Grade is 31wt%, and content of MgO is in phosphorus ore
0.5wt%, Al in phosphorus ore2O3+Fe2O3The sum of content is 1wt%, phosphorus ore is worn into ore pulp, with Horizontal helical type centrifuge ore pulp water
The separation heart is separated to 16wt%.The P that concentration is come2O5Phosphate ore pulp of 95 DEG C of phosphoric acid with moisture content 16wt% that content is 37wt%
Acidolysis reaction, 1000 parts of the butt phosphorus ore of addition are carried out in compressive reaction slot R1, acidolysis reaction operating condition is：Temperature is
117 DEG C, reaction pressure is normal pressure, when the reaction time is 2 small.The acidolysis slurry reacted enters separator F1, carries out solid-liquid point
From obtained solid slag carries out water-washing process in washer R2, obtains phosphorous 1000 parts of wash water, wherein P2O5100 parts of content, obtains
The clear liquid arrived adds in sulfuric acid and carries out heavy calcium reaction, after fully heavy calcium reaction, reaction slurry is through vacuum filter into heavy calcium slot C1
F2 isolates white industrial gypsum and concentrated phosphoric acid, and clean gypsum and phosphorous washings are obtained after the washing of white industrial gypsum,
Through being dried to obtain clean 650~750 parts of industrial gypsum, while 550~570 parts of phosphoric acid is obtained, after phosphorous acid washing water mixing, into
Enter inspissator C2 concentrations, 95 DEG C of concentrates return to compressive reaction slot R1 as recycled phosphoric acid.
Comparative example 2
The technological process of the present embodiment is as shown in Figure 2.The P of certain phosphorus ore2O5Grade is 31wt%, and content of MgO is in phosphorus ore
0.5wt%, Al in phosphorus ore2O3+Fe2O3The sum of content is 1wt%, phosphorus ore is worn into ore pulp, with Horizontal helical type centrifuge ore pulp water
The separation heart is separated to 25wt%.The P that concentration is come2O5Phosphate ore pulp of 80 DEG C of phosphoric acid with moisture content 25wt% that content is 30wt%
Acidolysis reaction, 1000 parts of the butt phosphorus ore of addition are carried out in compressive reaction slot R1, acidolysis reaction operating condition is：Temperature is 95
DEG C, reaction pressure 0.1MPa, when the reaction time 1.5 is small.The acidolysis slurry reacted enters separator F1, carries out separation of solid and liquid,
Obtained solid slag carries out water-washing process in washer R2, obtains phosphorous 1000 parts of wash water, wherein P2O5100 parts of content, obtains
Clear liquid adds in sulfuric acid and carries out heavy calcium reaction into heavy calcium slot C1, and after fully heavy calcium reaction, reaction slurry is through F2 points of vacuum filter
White industrial gypsum and concentrated phosphoric acid are separated out, clean gypsum and phosphorous washings are obtained after the washing of white industrial gypsum, through dry
It is dry to obtain clean 650~750 parts of industrial gypsum, while 550~570 parts of phosphoric acid is obtained, after phosphorous acid washing water mixing, entrance is dense
Contracting device C2 is concentrated, and 80 DEG C of concentrates return to compressive reaction slot R1 as recycled phosphoric acid.
By the concentration of the embodiment 1-4 and comparative example 1-2 phosphoric acid prepared, the content of industrial gypsum, the conversion of phosphorus ore acid hydrolysis
Rate and four aspect of acidolysis reaction time compare and analyze, as a result as shown in following table one：
As can be seen from the above table, in the embodiment 1-4 in technical solution of the present invention wet method phosphorus is produced using high-grade phosphorus ore
The method of acid, in first step acidolysis reaction, the conversion ratio of phosphorus ore reaches more than 97.5%, while the acidolysis reaction time is also big
It is big to shorten, it can be completed in 120~210min, while the concentration of the phosphoric acid by wet process prepared is in more than 39wt%, by-product work
CaSO in industry gypsum4·1/2H2O and CaSO4·2H2The total content of O reaches more than 70wt%, can direct plunge into use.And
In the preparation method for reviewing comparative example 1 and comparative example 2, the reaction time consumption of phosphate rock-sulfuric acid is in 360~480min, and final conversion
Rate only has 80%, and there are undecomposed in below 51wt%, gypsum for the content of principal product in the industrial gypsum of two-step reaction output
Phosphorus ore, the plurality of impurities such as fluoride, poor-performing, it is impossible to come into operation.
Claims (6)
1. utilize the method for high-grade phosphorus ore production phosphoric acid by wet process, which is characterized in that comprise the following steps：
Phosphate ore pulp and phosphoric acid are added in acidolysis reaction equipment by S1, are forced into 0.2~0.5MPa, anti-at 110~200 DEG C
1~5h is answered to obtain acidolysis slurries, the acidolysis slurries are subjected to isolated clear liquid and solid phase；The moisture of the phosphate ore pulp contains
It measures as 1~20wt%, P in phosphorus ore2O5Content is 30~38wt%, and content of MgO is 0.1~1.0wt%, Al2O3And Fe2O3Content and
For 0.1~1.5wt%；
S2 adds in sulfuric acid into the clear liquid, is reacted at 50~100 DEG C, precipitated and separated, isolated P2O5Content is 36%
Above phosphoric acid and semi-finished product technical grade gypsum；
By the solid phase after sulfuric acid washing separates, cleaning solution enters step S1 and recycles S3；By the semi-finished product work
Industry grade gypsum is washed with water to obtain technical grade gypsum and gypsum washing lotion, and the gypsum washing lotion enters step S1 and recycles.
2. the method according to claim 1 using high-grade phosphorus ore production phosphoric acid by wet process, which is characterized in that the step
Phosphoric acid P used in acidolysis reaction in S12O5Content is more than 36wt%.
3. the method according to claim 1 using high-grade phosphorus ore production phosphoric acid by wet process, which is characterized in that the step
Equipment used in being centrifuged in S1 is cyclone separator or Horizontal helical type centrifuge.
4. the method according to claim 1 using high-grade phosphorus ore production phosphoric acid by wet process, which is characterized in that the step
Sulfuric acid concentration described in S3 is 5~55wt%.
5. the method according to claim 1 using high-grade phosphorus ore production phosphoric acid by wet process, which is characterized in that the step
Cleaning solution described in S3 and the gypsum washing lotion enter step the step of heating concentration is further included before S1 is recycled.
6. the method according to claim 5 using high-grade phosphorus ore production phosphoric acid by wet process, which is characterized in that heating concentration
P in washing lotion afterwards2O5Content is more than 36wt%, and the temperature for concentrating washing lotion is 90~100 DEG C.
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| CN107619061A (en) * | 2017-10-28 | 2018-01-23 | 湖北省绿盛坤环保科技有限公司 | A kind of method that synthetic gypsum is produced using phosphoric acid as transition vector |
| CN109292744B (en) * | 2018-09-04 | 2020-03-17 | 安徽六国化工股份有限公司 | Method for producing wet-process phosphoric acid and α semi-hydrated phosphogypsum from medium-grade phosphate ore |
| CN109628239A (en) * | 2018-12-17 | 2019-04-16 | 武汉飞博乐环保工程有限公司 | Produce method, ceramic cleaning agent and its production method of ceramic cleaning agent coproduction ultrawhite ardealite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1792776A (en) * | 2005-12-23 | 2006-06-28 | 中国石化集团南京设计院 | Process for producing wet method phosphoric acid by medium low grade phosphorus mine |
| CN102001636A (en) * | 2010-09-26 | 2011-04-06 | 四川大学 | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process |
| CN103213964A (en) * | 2013-05-17 | 2013-07-24 | 成都川科化工有限公司 | Method for producing wet-process phosphoric acid by utilizing low-grade phosphorite |
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| BE1015013A3 (en) * | 2002-06-28 | 2004-08-03 | Ecophos | Process phosphoric acid production and / or salt thereof and products obtained. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792776A (en) * | 2005-12-23 | 2006-06-28 | 中国石化集团南京设计院 | Process for producing wet method phosphoric acid by medium low grade phosphorus mine |
| CN102001636A (en) * | 2010-09-26 | 2011-04-06 | 四川大学 | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process |
| CN103213964A (en) * | 2013-05-17 | 2013-07-24 | 成都川科化工有限公司 | Method for producing wet-process phosphoric acid by utilizing low-grade phosphorite |
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