CN103496729B - Improve the method for by-product phosphogypsum quality in production process of phosphoric acid - Google Patents
Improve the method for by-product phosphogypsum quality in production process of phosphoric acid Download PDFInfo
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- CN103496729B CN103496729B CN201310395847.XA CN201310395847A CN103496729B CN 103496729 B CN103496729 B CN 103496729B CN 201310395847 A CN201310395847 A CN 201310395847A CN 103496729 B CN103496729 B CN 103496729B
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Abstract
The invention discloses a kind of method improving by-product phosphogypsum quality in production process of phosphoric acid, the method comprises: (1) first react with phosphoric acid and phosphorus concentrate, filter afterwards, and the filtrate containing monocalcium phosphate, secondary calcium phosphate, phosphoric acid obtained delivers to extraction tank; (2) filtrate sulfuric acid and monocalcium phosphate, secondary calcium phosphate carry out extractive reaction in extraction tank, and the extraction liquid obtained is the dilute phosphoric acid containing phosphogypsum; By analyzing filtrate calcium contents in this operation, calculate the theoretical amount of sulfuric acid according to the reaction formula of phosphoric acid extraction, then determine the sulfuric acid amount that adds; (3) extraction liquid filter filters, and obtains dilute phosphoric acid and the phosphogypsum containing two water things 97%.In the phosphogypsum that the inventive method is produced, dihydrate gypsum content is far above conventional art, and phosphorus content significantly reduces, and quality is greatly improved, and for downstream phosphogypsum building materials provide good raw material, lays the foundation for being made full use of by phosphogypsum.Be applicable to the Wet-process Phosphoric Acid Production enterprise planning phosphogypsum processing and utilization.
Description
Technical field
The present invention relates to phosphoric acid, 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 often produce 1 ton of phosphoric acid by wet process and discharge about 4 ~ 6 tons, gypsum, phosphogypsum slag about 200,000,000 tons is discharged in the current whole world every year, and China is emitted on more than 5,000 ten thousand tons every year.When countries in the world produce phosphoric acid, the phosphogypsum that produces is many stacks as waste, and this needs land occupation resource, and the phosphogypsum stacked fluorine wherein and phosphorus after rain will leach with rainwater, enter soil or rivers, cause 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 that relevant phosphogypsum utilizes nearly hundreds of, and the overwhelming majority is the technical scheme of exploitation in nearest 10 years.Such as 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 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 ", No. 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 ", No. 201110449184.6 " method of sulfuric acid and cement prepared by a kind of phosphogypsum ", No. 201210167278.9 " production methods of calcium carbide from ardealite " and No. 201310003598.5 " utilizing the Environment-friendlylight light partition board that waste ardealite is produced " etc.This illustrates that the utilization of phosphogypsum has become people's question of common concern.At present, the phosphogypsum utilization ratio of China is about 10%.
One of difficult problem that phosphogypsum utilizes is the needs that quality can not meet goods, and in phosphogypsum, two water thing content are only 90%, are difficult to expand it and utilize scope.And there is no the patent application improving phosphogypsum quality at present, 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 improving by-product phosphogypsum quality in production process of phosphoric acid, to make phosphogypsum resource utilization, thus can be fully used.
In the raising production process of phosphoric acid that contriver provides, the method for by-product phosphogypsum quality comprises:
(1) in Wet-process Phosphoric Acid Production flow process, set up pretreatment process: namely first react with phosphoric acid and phosphorus concentrate, filter afterwards, the filtrate containing monocalcium phosphate, secondary calcium phosphate, phosphoric acid obtained is for the production of phosphoric acid; Control phosphoric acid in this operation and phosphorus concentrate liquid-solid ratio is 4: 1 ~ 8: 1, control 3 ~ 4 hours reaction times, control temperature 35 DEG C ~ 80 DEG C;
(2) filtrate sulfuric acid and monocalcium phosphate, secondary calcium phosphate carry out extractive reaction, and the extraction liquid obtained is the dilute phosphoric acid containing phosphogypsum; By analyzing filtrate calcium contents in this operation, calculate the theoretical amount of sulfuric acid according to the reaction formula of phosphoric acid extraction, then determine the sulfuric acid amount that adds; Extraction control temperature, at 35 DEG C ~ 80 DEG C, controls 3 ~ 4 hours reaction times;
(3) extraction liquid filter filters, and obtains dilute phosphoric acid and phosphogypsum, and phosphogypsum clear water washs, and the phosphogypsum obtained is containing two water things 97%.
Above-mentioned steps (1) in, the massfraction (in Vanadium Pentoxide in FLAKES) of described phosphoric acid is the dilute phosphoric acid of 23% ~ 24%, and the grade (massfraction in Vanadium Pentoxide in FLAKES) of described phosphorus concentrate is 32%; The described sulfuric acid amount added is 0.9 ~ 1.1 times of theoretical amount; Described phosphoric acid and phosphorus concentrate react and carry out in reactive tank or extraction tank.
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 downstream phosphogypsum building materials provide good raw material, lay the foundation for phosphogypsum is made full use of.Be applicable to the Wet-process Phosphoric Acid Production enterprise planning phosphogypsum processing and utilization.
Embodiment
Embodiment:
Guizhou Jin Lin chemical industry limited liability company has built the industrialized unit processing 10,000 tons of phosphorus concentrate by-product phosphogypsums a year, and its technical process is as follows:
First, phosphorus concentrate is measured by charging belt, with under meter metering phosphoric acid together with enter reactive tank, control the 4 hours reaction times at phosphoric acid and phosphorus concentrate liquid-solid ratio 8: 1, temperature 35 DEG C, reaction slurry enters plate and frame(type)filter press, is shifted out by filter residue, and filtrate enters the 2nd reactive tank.
After filtrate sampling analysis calcium contents, according to the reaction formula Ca of phosphoric acid extraction
2++ SO
4 2-=CaSO
4calculate the theoretical amount of sulfuric acid, sulfuric acid dosage is determined again according to 0.9 ~ 1.1 times of theoretical amount, extractive reaction is carried out at the 2nd reactive tank with the phosphorus ore in sulfuric acid and filtrate, monocalcium phosphate, secondary calcium phosphate, in the 4 hours reaction times under 60 DEG C ± 10 DEG C conditions, the extraction liquid obtained is the dilute phosphoric acid containing phosphogypsum;
Extraction liquid is filtered by plate and frame(type)filter press, obtains dilute phosphoric acid and phosphogypsum, and phosphogypsum clear water washs, and the phosphogypsum obtained is containing two water things 97%.As follows to the content analysis result of phosphogypsum (butt):
The phosphogypsum produced may be used for manufacturing the multiple plasterings such as Thistle board, gypsum block, plasterboard.
Claims (4)
1. improve the method for by-product phosphogypsum quality in production process of phosphoric acid, its feature comprises:
(1) in Wet-process Phosphoric Acid Production flow process, set up pretreatment process: namely first react with phosphoric acid and phosphorus concentrate, filter afterwards, the filtrate containing monocalcium phosphate, secondary calcium phosphate, phosphoric acid obtained is for the production of phosphoric acid; Control phosphoric acid in this operation and phosphorus concentrate liquid-solid ratio is 4: 1 ~ 8: 1, control 3 ~ 4 hours reaction times, control temperature 35 DEG C ~ 80 DEG C; Described phosphoric acid is the dilute phosphoric acid of 23% ~ 24% in the massfraction of Vanadium Pentoxide in FLAKES, described phosphorus concentrate in the grade of the massfraction of Vanadium Pentoxide in FLAKES for 32%;
(2) carry out extractive reaction with phosphorus ore, monocalcium phosphate, secondary calcium phosphate in sulfuric acid and filtrate, the extraction liquid obtained is the dilute phosphoric acid containing phosphogypsum; By analyzing filtrate calcium contents in this operation, calculate the theoretical amount of sulfuric acid according to the reaction formula of phosphoric acid extraction, then determine the sulfuric acid amount that adds; Extraction control temperature, at 35 DEG C ~ 80 DEG C, controls 3 ~ 4 hours reaction times; The described sulfuric acid amount added is 0.9 ~ 1.1 times of theoretical amount; The reaction formula of described extractive reaction is: Ca
2++ SO
4 2-=CaSO
4;
(3) extraction liquid filter filters, and obtains dilute phosphoric acid and phosphogypsum, and phosphogypsum clear water washs, and the phosphogypsum obtained is containing two water things 97%.
2. the method for claim 1, in it is characterized in that step (1), described phosphoric acid and phosphorus concentrate react and carry out in reactive tank or extraction tank
3. the method for claim 1, in it is characterized in that step (2), the massfraction of described sulfuric acid is 98%.
4. the method for claim 1, in it is characterized in that step (3), described filter is plate and frame(type)filter press or vacuum band-type filter machine.
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| CN201310395847.XA CN103496729B (en) | 2013-09-04 | 2013-09-04 | Improve the method for by-product phosphogypsum quality in production process of phosphoric acid |
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| CN103496729B true CN103496729B (en) | 2015-09-30 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN109896509B (en) * | 2019-04-22 | 2021-02-12 | 武汉工程大学 | Method for pre-treating and strengthening wet-process phosphoric acid extraction reaction |
| CN113072046B (en) * | 2021-04-09 | 2022-06-17 | 郑州大学 | Method for removing impurities and improving whiteness of phosphogypsum through flotation method |
Citations (3)
| 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 |
-
2013
- 2013-09-04 CN CN201310395847.XA patent/CN103496729B/en active Active
Patent Citations (3)
| 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 |
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