CN103496729A - Method for improving by-product phosphogypsum quality during phosphoric acid production process - Google Patents

Method for improving by-product phosphogypsum quality during phosphoric acid production process Download PDF

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CN103496729A
CN103496729A CN201310395847.XA CN201310395847A CN103496729A CN 103496729 A CN103496729 A CN 103496729A CN 201310395847 A CN201310395847 A CN 201310395847A CN 103496729 A CN103496729 A CN 103496729A
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phosphoric acid
phosphogypsum
extraction
filtrate
sulfuric acid
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CN103496729B (en
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张文胜
吴健
金先煜
陈开翔
但永东
梁强立
罗雅超
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GUIZHOU JINLIN CHEMICAL Co Ltd
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Abstract

The invention discloses a method for improving the by-product phosphogypsum quality during a phosphoric acid production process. The method comprises the steps that: (1) phosphoric acid is subjected to a reaction with phosphate concentrate; filtering is carried out, such that a filtrate containing calcium dihydrogen phosphate, calcium hydrogen phosphate, and phosphoric acid is obtained; and the filtrate is delivered to an extraction tank; (2) the filtrate is subjected to an extraction reaction in the extraction tank by using sulfuric acid with calcium dihydrogen phosphate and calcium hydrogen phosphate, and an obtained extract liquid is dilute phosphoric acid containing phosphogypsum; during the process, through analyzing filtrate calcium content, sulfuric acid theoretical dose is calculated according to a phosphoric acid extraction reaction formula, and sulfuric acid addition amount is determined; and (3) the extraction liquid is filtered by using a filtering machine, such that dilute phosphoric acid and phosphogypsum comprising 97% of dehydrate are obtained. In the phosphogypsum provided by the invention, dihydrate gypsum content is greatly higher than that of prior art, phosphorus content is substantially reduced, and phosphogypsum quality is greatly improved. Therefore, good raw material is provided for downstream phosphogypsum construction material manufacturing, and a basis is provided for sufficient utilization of phosphogypsum. The method is suitable for wet-method phosphoric acid production enterprises intending to utilize phosphogypsum.

Description

Improve the method for by-product phosphogypsum quality in production process of phosphoric acid
Technical field
The present invention relates to phosphoric acid, in particular to the phosphogypsum of by-product in phosphoric acid production.
Technical background
As everyone knows, phosphogypsum is the waste residue produced in phosphoric acid and Phosphate Fertilizer Industry production process, and 1 ton of phosphoric acid by wet process of every production is discharged approximately 4~6 tons, gypsum, approximately 200,000,000 tons of the phosphogypsum slags of the annual discharge in the whole world at present, and China is emitted on more than 5,000 ten thousand tons every year.The phosphogypsum that countries in the world produce while producing phosphoric acid is many to be stacked as waste, and this needs the land occupation resource, and the phosphogypsum of stacking fluorine and phosphorus wherein after rain will leach with rainwater, enters soil or rivers, causes surface water and groundwater pollution.Therefore how people utilize phosphogypsum, changing waste into valuable in research in recent years.
In Chinese patent database, the application part of relevant phosphogypsum utilization has reached hundreds of, and the overwhelming majority is the technical scheme of exploitation in nearest 10 years.For example No. 200510040512.1 " utilizing the working method of producing building powdered gypsum by using phosphogypsum ", number 200610054521.0 " phosphogypsum high-strength wall brick and production method thereof ", number 200710051599.1 " a kind of method of utilizing residue phosphogypsum to prepare wollastonite and sulfuric acid ", number 200810046201.X " a kind of modified ardealite setting retarder for cement and preparation method thereof ", number 200910016318.8 " utilizing phosphogypsum and the plaster of paris to produce the technique of Thistle board ", number 201010100554.0 " tomato yield increasing agent of phosphogypsum and its preparation method and application ", number 201110449184.6 " a kind of phosphogypsum prepares the method for sulfuric acid and cement ", number 201210167278.9 " production method of phosphogypsum calcium carbide processed " and No. 201310003598.5 " the environment-friendly light partition plates that utilize the waste phosphogypsum to produce " etc.The utilization of this explanation phosphogypsum has become people's question of common concern.At present, the phosphogypsum utilization ratio of China is in 10% left and right.
One of difficult problem of phosphogypsum utilization is the needs that quality can not meet goods, and in phosphogypsum, two water thing content are only 90%, are difficult to enlarge it and utilize scope.And there is no at present the patent application that improves the phosphogypsum quality, also have no the report of relevant new technology.
Summary of the invention
The object of the present invention is to provide a kind of method that improves by-product phosphogypsum quality in production process of phosphoric acid, so that the phosphogypsum resource utilization, thereby can be fully used.
In the raising production process of phosphoric acid that the contriver provides, the method for by-product phosphogypsum quality comprises:
(1) set up pretreatment process in the Wet-process Phosphoric Acid Production flow process: first with phosphoric acid, with the phosphorus concentrate, react, filter afterwards, the filtrate of containing monocalcium phosphate, secondary calcium phosphate, phosphoric acid obtained is for the production of phosphoric acid; In this operation, control phosphoric acid and phosphorus concentrate liquid-solid ratio are 4: 1~8: 1, control 3~4 hours reaction times, control 35 ℃~80 ℃ of temperature;
(2) filtrate is carried out extractive reaction with sulfuric acid and monocalcium phosphate, secondary calcium phosphate, and the extraction liquid obtained is the dilute phosphoric acid that contains phosphogypsum; By analyzing the filtrate calcium contents, calculate the theoretical consumption of sulfuric acid according to the reaction formula of phosphoric acid extraction in this operation, then determine the sulfuric acid amount added; The extraction control temperature, at 35 ℃~80 ℃, is controlled 3~4 hours reaction times;
(3) extraction liquid filters with filter, obtains dilute phosphoric acid and phosphogypsum, and phosphogypsum washs with clear water, and the phosphogypsum obtained is containing two water things 97%.
Above-mentioned steps (1) in, the dilute phosphoric acid of the massfraction of described phosphoric acid (take Vanadium Pentoxide in FLAKES) as 23%~24%, the grade of the described phosphorus concentrate massfraction of Vanadium Pentoxide in FLAKES (take) is 32%; The described sulfuric acid amount added is theoretical consumption 0.9~1.1 times; Described phosphoric acid reacts in reactive tank or extraction tank and carries out with the phosphorus concentrate.
Above-mentioned steps (2) in, the massfraction of described sulfuric acid is 98%; The reaction formula of described phosphoric acid extraction is: Ca 2++ SO 4 2-=CaSO 4.
Above-mentioned steps (3) in, described filter is plate and frame(type)filter press or vacuum band-type filter machine.
In the phosphogypsum that the inventive method is produced, dihydrate gypsum content can reach 97%, far above 90% of conventional art, phosphorus content significantly reduces, and quality is greatly improved, for phosphogypsum building materials processed in downstream provide raw material preferably, for phosphogypsum is taken full advantage of and lays the foundation.Be applicable to plan the Wet-process Phosphoric Acid Production enterprise of phosphogypsum processing and utilization.
embodiment
embodiment:
Guizhou brocade unicorn chemical industry limited liability company has built the industrialized unit of processing 10,000 tons of phosphorus concentrate by-product phosphogypsums a year, and its technical process is as follows:
At first, the phosphorus concentrate measures by charging belt, and enters reactive tank together with under meter metering phosphoric acid, control phosphoric acid and phosphorus concentrate liquid-solid ratio 8: 1,35 ℃ of 4 hours lower reaction times of temperature, reaction slurry enters plate and frame(type)filter press, and filter residue is shifted out, and filtrate enters the 2nd reactive tank.
[0013] after filtrate sampling analysis calcium contents, according to the reaction formula Ca of phosphoric acid extraction 2++ SO 4 2-=CaSO 4calculate the theoretical consumption of sulfuric acid, again according to 0.9~1.1 times of definite sulfuric acid consumption of theoretical amount, carry out extractive reaction with sulfuric acid and phosphorus ore, monocalcium phosphate, secondary calcium phosphate at the 2nd reactive tank, in the 4 hours reaction times under 60 ℃ ± 10 ℃ conditions, the extraction liquid obtained is the dilute phosphoric acid that contains phosphogypsum;
Extraction liquid filters by plate and frame(type)filter press, obtains dilute phosphoric acid and phosphogypsum, and phosphogypsum washs with clear water, and the phosphogypsum obtained is containing two water things 97%.Content analysis result to phosphogypsum (butt) is as follows:
Figure 515530DEST_PATH_GDA0000400237020000031
The phosphogypsum of producing can be for the manufacture of multiple plasterings such as Thistle board, gypsum block, plasterboards.

Claims (4)

1. the method for by-product phosphogypsum quality in raising production process of phosphoric acid, its feature comprises:
(1) set up pretreatment process in the Wet-process Phosphoric Acid Production flow process: first with phosphoric acid, with the phosphorus concentrate, react, filter afterwards, the filtrate of containing monocalcium phosphate, secondary calcium phosphate, phosphoric acid obtained is for the production of phosphoric acid; In this operation, control phosphoric acid and phosphorus concentrate liquid-solid ratio are 4: 1~8: 1, control 3~4 hours reaction times, control 35 ℃~80 ℃ of temperature;
(2) filtrate is carried out extractive reaction with sulfuric acid and phosphorus ore, monocalcium phosphate, secondary calcium phosphate, and the extraction liquid obtained is the dilute phosphoric acid that contains phosphogypsum; By analyzing the filtrate calcium contents, calculate the theoretical consumption of sulfuric acid according to the reaction formula of phosphoric acid extraction in this operation, then determine the sulfuric acid amount added; The extraction control temperature, at 35 ℃~80 ℃, is controlled 3~4 hours reaction times;
(3) extraction liquid filters with filter, obtains dilute phosphoric acid and phosphogypsum, and phosphogypsum washs with clear water, and the phosphogypsum obtained is containing two water things 97%.
2. the method for claim 1, is characterized in that step (1), and described phosphoric acid be take the dilute phosphoric acid that the massfraction of Vanadium Pentoxide in FLAKES is 23%~24%, and it is 32% that described phosphorus concentrate be take the grade of massfraction of Vanadium Pentoxide in FLAKES; The described sulfuric acid amount added is theoretical consumption 0.9~1.1 times; Described phosphoric acid reacts in reactive tank or extraction tank and carries out with the phosphorus concentrate.
3. the method for claim 1, is characterized in that step (2), and the massfraction of described sulfuric acid is 98%; The reaction formula of described phosphoric acid extraction is: Ca 2++ SO 4 2-=CaSO 4.
4. the method for claim 1, is characterized in that step (3), and described filter is plate and frame(type)filter press or vacuum band-type filter machine.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104401959A (en) * 2014-10-13 2015-03-11 云南红富化肥有限公司 Method for filtering phosphogypsum with dilute phosphoric acid for circulating washing
CN105948009A (en) * 2016-04-28 2016-09-21 昆明川金诺化工股份有限公司 Energy-saving semihydrate-dihydrate wet-process phosphoric acid and white gypsum coproduction method
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
CN109896509A (en) * 2019-04-22 2019-06-18 武汉工程大学 A method of phosphoric acid by wet process extraction reaction is strengthened in pretreatment
CN113072046A (en) * 2021-04-09 2021-07-06 郑州大学 Method for removing impurities and improving whiteness of phosphogypsum through flotation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627485A (en) * 1968-11-05 1971-12-14 Nippon Kokan Kk Method of producing calcium sulfate dihydrate
GB2039269A (en) * 1979-01-12 1980-08-06 Charbonnages Ste Chimique Phosphogypsum
CN103213960A (en) * 2013-05-17 2013-07-24 成都川科化工有限公司 Method for producing phosphoric acid by decomposing low-grade phosphate rock with wet-process phosphoric acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627485A (en) * 1968-11-05 1971-12-14 Nippon Kokan Kk Method of producing calcium sulfate dihydrate
GB2039269A (en) * 1979-01-12 1980-08-06 Charbonnages Ste Chimique Phosphogypsum
CN103213960A (en) * 2013-05-17 2013-07-24 成都川科化工有限公司 Method for producing phosphoric acid by decomposing low-grade phosphate rock with wet-process phosphoric acid

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104401959A (en) * 2014-10-13 2015-03-11 云南红富化肥有限公司 Method for filtering phosphogypsum with dilute phosphoric acid for circulating washing
CN104401959B (en) * 2014-10-13 2016-06-22 云南红富化肥有限公司 A kind of method filtering ardealite employing light phosphoric acid circulation washing
CN105948009A (en) * 2016-04-28 2016-09-21 昆明川金诺化工股份有限公司 Energy-saving semihydrate-dihydrate wet-process phosphoric acid and white gypsum coproduction method
CN105948009B (en) * 2016-04-28 2017-09-29 昆明川金诺化工股份有限公司 A kind of method for saving the half white gypsum of water dihydrate wet phosphoric acid coproduction
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
CN109896509A (en) * 2019-04-22 2019-06-18 武汉工程大学 A method of phosphoric acid by wet process extraction reaction is strengthened in pretreatment
CN113072046A (en) * 2021-04-09 2021-07-06 郑州大学 Method for removing impurities and improving whiteness of phosphogypsum through flotation method

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