CN102001636A - Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process - Google Patents
Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process Download PDFInfo
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Abstract
The invention discloses a method for producing broad-concentration phosphoric acid and clean plaster by a middle-low grade phosphorus ore wet process. The method comprises the following main procedures: (1) adding powder phosphorus ore and phosphoric acid to a semi-acid hydrolysis reaction tank for acid hydrolysis reaction at 95-105 DEG C, and carrying out solid-liquid separation on the slurry obtained by acid hydrolysis after full acid hydrolysis reaction; (2) transferring phosphoric acid clear liquid separated in procedure (1) into a crystallization tank, adding sulfuric acid and carrying out crystallization at 70-110 DEG C, and carrying out solid-liquid separation after full reaction, wherein, a liquid phase is the phosphoric acid to be prepared and a solid phase is the functional clean plaster to be prepared; and (3) transferring residue slurry separated in procedure (1) into a secondary acid hydrolysis reaction tank, adding water, carrying out secondary acid hydrolysis and recrystallization on the residue slurry at 65-80 DEG C, carrying out solid-liquid separation after full reaction, transferring the obtained separation liquid into procedure (2), and discharging the separated solid residues. The method of the invention has the characteristics of high production efficiency, high phosphorus resource recovery rate, strong production capacity, good economic benefit, strong operability and the like.
Description
Technical field
The present invention relates to the development and use of mid low grade phosphate rock, more specifically say, relating to a kind of is that raw material adopts the phosphoric acid of the wide concentration range of wet production and the method for functional clean gypsum with the mid low grade phosphate rock.
Background technology:
Along with the progressively exhaustion of world's phosphate rock resource, each state all pays special attention to the development and use of mid low grade phosphate rock.In state-owned many scholars the mid low grade phosphate rock wet production is furtherd investigate, Liu Daijun professor place seminar as chemical industry system of Sichuan University, be devoted for years to wet production research in mid low grade phosphate rock, and obtained many-sided achievement in research, as two-stage method two water conservancy projects skill (Liu Daijun etc. at high silicon phosphorus ore, utilize mid low grade phosphate rock to produce the method for secondary calcium phosphate, patent of invention, 99115057.0 ZL99115057.0 2004.6.2, authorize), de-magging and the technology that reclaims production magnesium chemical (Liu Daijun etc., the processing method of recovery magnesium from high-magnesium-phosphorus ore, ZL200610021647.8 at high-magnesium-phosphorus ore, authorize), passivator that the acidolysis of inhibition phosphorus ore iron aluminium impurity is leached and application method (Liu Daijun etc., 200910058574.3, authorize).Although the above two technology is by pilot scale, these technologies all are based on the improvement to traditional two water conservancy projects skill, and the phosphoric acid that obtains is 27%P
2O
5Following lower concentration phosphoric acid even the gypsum quality that obtains is higher, but also is dihydrate gypsum, if will also need through calcining as plaster of Paris, it is higher to consume energy; Device is bigger simultaneously, and production capacity is restricted.
China's phosphate rock resource is among the dilution day by day, considerable mid low grade phosphate rock crystal grain is tiny, ore dressing is difficulty very, adopt the wet processing of prior art to be difficult to utilize, owing to various foreign matter contents in the mid low grade phosphate rock are higher, reactive behavior is poor again, solid substance silts up in filtration seriously, the phosphogypsum of gained is the liquid content height not only, and the phosphorus loss is big, and is difficult to utilize.For these mid low grade phosphate rocks, half not only common wet technology is difficult to operation, and two stronger wet technologies of adaptability also are difficult to carry out.
Be in dilution day by day based on phosphate rock resource, existing wet processing is handled mid low grade phosphate rock and is difficult to obtain the ideal technique effect, and people are to the continuous present situation that increases of phosphorus chemical product demand, the urgent need exploitation is a kind of directly to obtain high-concentration phosphoric acid and high-quality building semi-hydrated gypsum, also can obtain the phosphoric acid and the high-quality functional dihydrate gypsum of low concentration, and can be adapted to the phosphoric acid of the wide concentration range of new wet production of the higher mid low grade phosphate rock of foreign matter content and the technical process of clean gypsum, require and the market requirement so that satisfy different industrial production.
Summary of the invention
The present invention is directed to the difficult problem of the mid low grade phosphate rock Wet-process phosphoric acid (WPPA) existence of prior art, be intended to propose a kind of new wet type method for producing---novel half water-two water conservancy project process, with mid low grade phosphate rock direct production high density or lower concentration phosphoric acid, the high-quality building semi-hydrated gypsum of by-product or functional dihydrate gypsum, make the lower mid low grade phosphate rock of quality be able to better development and use, and production efficiency and throughput height.
The method of utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum that the present invention proposes mainly comprises following operation:
(1) acidolysis separation circuit, powder phosphorus ore and phosphoric acid join the acidolysis reaction groove and carry out acidolysis reaction under 95～105 ℃, and the acidolysis concentration of phosphoric acid is to guarantee preparation phosphoric acid P
2O
5Concentration reaches 25～46%wt, fully behind the acidolysis reaction with acidolysis slip solid-liquid separation;
(2) Crystallization Separation operation, the separating obtained clear liquid of operation (1) is sent to the crystallization reaction groove, adds sulfuric acid and carry out crystallization reaction under 70～110 ℃, and the vitriolic add-on is by SO in the crystallization feed liquid
3Content 10～65g/L adds, and carries out solid-liquid separation after the sufficient crystallising reaction, the phosphoric acid of liquid phase for preparing, the functional clean gypsum of solid phase for preparing;
(3) dihydrate acid is separated and the recrystallization separation circuit, and the separating obtained slag of operation (1) slurry is sent to dihydrate acid and separates reactive tank, adds water and slag is starched is carried out acidolysis again under 65～80 ℃, and the add-on of water is for making the phosphoric acid P after the acidolysis again
2O
5Concentration remains on 13～22%wt scope, and the vitriolic add-on is by SO in the feed liquid
3Concentration 5～65g/L adds, and fully reacts the back solid-liquid separation, and parting liquid is sent to operation (2), separates solid slag discharging.
In technique scheme, can for the acidolysis process of operation (1) and the acidolysis process again of operation (3), can add a certain amount of sulfuric acid according to the situation of phosphorus ore impurities composition in one or in simultaneously, the impurity crystallization in the liquid phase is separated out.In most cases, in the acidolysis reaction process of operation (1), can not add sulfuric acid, and in the process of acidolysis reaction again of operation (3), will add sulfuric acid, make gypsum crystal carry out recrystallization, make the Rock Phosphate (72Min BPL) of failing to have reacted continue to decompose, thereby guarantee to separate out more phosphorus.The vitriolic add-on comprises and the crystallization reaction process of operation (2) depends on the foreign matter content in the phosphorus ore.For operation (1), the vitriolic add-on generally is controlled at the free acid SO in the acidolysis feed liquid
3Concentration is not more than 35g/L; For operation (3), the vitriolic add-on generally is controlled at the free acid SO in the acidolysis feed liquid again
3Concentration is not more than 65g/L, normally in 20～65g/L scope.
In the technique scheme, the acidolysis phosphoric acid concentration depends on the P in the phosphorus ore
2O
5The grade and the phosphoric acid concentration that will prepare.The phosphorus ore grade is low, the preparation phosphoric acid concentration is low, then acidolysis concentration of phosphoric acid can be hanged down, phosphorus ore is of high grade, preparation phosphoric acid concentration height, then acidolysis concentration of phosphoric acid can be higher, but in order to guarantee to produce the phosphoric acid of desired concn, the acidolysis concentration of phosphoric acid is normally than the lower slightly 1～6wt% of phosphoric acid concentration for preparing.
In technique scheme, be used for the powder phosphorus ore of acidolysis, it is thin that its granularity is wanted as far as possible, but also needn't be too thin, too carefully can increase energy consumption.It is the screen cloth of 0.125mm that its powder of general requirement has 70% mistake sieve diameter at least, to guarantee the effective constituent P in the phosphorus ore
2O
5In the acidolysis process, parsed.If the reactive behavior in ore deposit is good, also can make breeze 50% cross sieve diameter is the screen cloth of 0.5mm.
In technique scheme, the solid-liquid separation in the operation (3) generally adopts vacuum filtration, adds wash water in the filtration procedure filter residue is washed.In the sepn process of operation (3), separate solid-liquid separation section that the phosphoric acid obtain partly is sent to operation (2) as the solid-liquid separation washing water, the acidolysis section again that separating, washing clear liquid part is returned this operation usually is as the process water of acidolysis again.Solid-liquid separation in the operation (2) also adopts vacuum filtration, adds hot water in filtration procedure filter residue is washed, and the hot water temperature that filter residue is washed is generally 80～100 ℃ of scopes.Operation (2) is through the phosphoric acid of solid-liquid separation gained, and the acidolysis section that wherein a part is turned back to operation (1) is as recycled phosphoric acid, and normally that its solid-liquid separation washings is partially mixed in wherein, the acidolysis section that turns back to operation (1) is as acidolysis phosphoric acid.
The principle following (referring to Fig. 1) of the half water-two water conservancy project skill that the present invention proposes:
Phosphorus ore enters the acidolysis groove, at high temperature carries out acidolysis reaction with high concentrations of phosphoric acid.The principal reaction that takes place in the acidolysis groove is as follows:
Ca
5(PO
4)
3F+7H
3PO
4→5Ca(H
2PO
4)
2+HF
The remaining slag of acidolysis reaction comprises a large amount of acid non-soluble substances and semi-hydrated gypsum in starching.Slag that solid-liquid separation obtains slurry enters two water crystallization grooves and proceeds acidolysis reaction and recrystallization, reclaiming the phosphorus in the phosphorus ore, and obtains filtration efficiency preferably, carries out the dilute phosphoric acid that solid-liquid separation obtains subsequently and sends into the crystallization reaction operation, as the usefulness of filtering wash water.It is as follows that dihydrate acid is separated the main chemical reactions that takes place in the crystallization reactive tank:
5Ca(H
2PO
4)
2+5H
2SO
4+10H
2O→10H
3PO
4+5CaSO
4.2H
2O
Clear liquid after acidolysis reaction separates enters the crystallization reaction groove, generates clean calcium sulfate behind the adding sulfuric acid reaction.The crystallization reaction operation, adopt different processing condition can obtain different functional gypsum, if operational condition is controlled at half aqua region, after separating drying, can obtain having the high strength α type half water plaster of Paris of hydraulicity characteristics, parting liquid is the high concentrations of phosphoric acid that will prepare, and concentration is about more than 37%.Return a part as the acidolysis agent, product is sent the battery limit (BL); If operational condition is controlled at two aqua regions, then can obtain two clean crystallines, adjustment can obtain whisker through crystalline form, can be used for various fillers.The main chemical reactions that the crystallization reaction groove takes place is as follows:
5Ca(H
2PO
4)
2+5H
2SO
4+5/2H
2O→10H
3PO
4+5CaSO
4.1/2H
2O
5Ca(H
2PO
4)
2+5H
2SO
4+10H
2O→10H
3PO
4+5CaSO
4.2H
2O
The method of utilizing wide concentration range phosphoric acid of mid low grade phosphate rock wet production and clean gypsum that the present invention proposes, it is a kind of novel half water-two water conservancy project skill, owing to separate the separation that has realized in the process sludges such as acid non-soluble substances at hemihydrate acid, thereby in crystallisation process, can obtain the good clean semi-hydrated gypsum of strainability, can obtain P simultaneously
2O
5The high-concentration phosphoric acid of content more than 40%, and because the solid substance that part contains half crystalline dihydrate acid separate with recrystallization process in recrystallization, so the phosphorus yield is improved, and can obtain clean dihydrate gypsum.This novel process is the important improvement to common half water conservancy project skill or half water-two water conservancy project skill, has significant application value aspect the comprehensive utilization mid low grade phosphate rock.
The novel two water-half water phosphoric acid wet process technique that the present invention proposes can adopt P
2O
5Be not less than 15% low-grade phosphate ore direct production phosphoric acid and functional clean gypsum in the phosphoric acid concentration scope of broad, can save beneficiating process, the utilization ratio of resource reaches more than 95%.Technical process can obtain P
2O
5The high-concentration phosphoric acid of content more than 40% obtains white semi-hydrated gypsum simultaneously, because impurity and radioactive nuleus element in the gypsum are removed, can directly sell as material of construction.Technical process is through adjusting the dihydrate gypsum that also can obtain white, to meet the need of market.Also go for P on this technological principle
2O
5Be lower than 15% low-grade phosphate ore, but economic benefit is more weaker.
The novel two water-half water phosphoric acid wet process technique that adopts the present invention to propose utilizes mid low grade phosphate rock wet production high-concentration phosphoric acid and plaster of Paris that extraordinary economic benefit is arranged.To produce 1 ton of 47%P
2O
5Phosphoric acid calculates, and the norm quota of consumption and production cost are estimated can be referring to table 1.If by-product gypsum is by 450 yuan of tons, actual market price can reach about 700-800 unit for αBan Shuishigao.Phosphoric acid is if amounting to Cheng Chunpin calculates, and production cost only is 860 yuan/t P
2O
5
Table 1
| Sequence number | Main raw material(s) and specification | Unit | The norm quota of consumption | Unit price (unit) | Total price (unit) |
| 1 | Sulfuric acid (H 2SO 4＞98%, in 100%) | t | 0.586 | 350 | 205 |
| 2 | Phosphorus ore (P 2O 5～27％) | t | 0.864 | 450 | 389 |
| 5 | Electricity (380V) | kwh | 150 | 0.5 | 75 |
| 6 | Water (process water) | m 3 | 0.725 | 1.0 | 1 |
| 8 | Coal | t | 0.34 | 100 | 34 |
| 10 | Management, wage, depreciation, maintenance etc. | 150 | |||
| By-product gypsum | t | 1 | 450 | -450 |
| Workshop cost | 404 |
Novel two water-half water phosphoric acid wet method provided by the invention not only can utilize mid low grade phosphate rock to produce high-concentration phosphoric acid and plaster of Paris, and production efficiency and phosphor resource rate of recovery height, and throughput is big, and production cost is low, and is good in economic efficiency, strong operability.
Description of drawings
Accompanying drawing 1 is a basic technology block diagram of the present invention.
Accompanying drawing 2 is process frame charts of one embodiment of the present of invention.
Accompanying drawing 3 is process frame charts of an alternative embodiment of the invention.
Embodiment
To closing embodiment the present invention is specifically described below, so that personnel's the understanding of the present invention of affiliated technical field.Be necessary what this particularly pointed out to be; embodiment is used for just that the present invention will be further described; can not be interpreted as limiting the scope of the invention; affiliated art skilled person; to improvement and adjustment that the present invention makes non-intrinsically safe, should still belong to protection scope of the present invention according to the invention described above content.
In the following embodiments, except that specifying, described percentages of ingredients % is mass percent %wt.
Embodiment 1:
The technical process of present embodiment as shown in Figure 2.The P of certain phosphorus ore
2O
5Grade is 16～18%, phosphorus ore is processed into the powder of 80% mistake 0.125mm (120 order) screen cloth.1000 parts in ground phosphate rock is joined half tank R1 carry out acidolysis, the acidolysis reaction operational condition is: temperature is 95～105 ℃, and liquid-solid ratio is 4～6, and phosphoric acid concentration is 37～42%P
2O
5, 1～3 hour reaction times.The acidolysis slip that has reacted enters separator S1, carries out solid-liquid separation, and the clear liquid that obtains enters crystallizer tank R2, adds sulfuric acid and carries out crystallization reaction, and the crystallization operation condition is: control SO
3Concentration is 15～65g/L, and temperature is 100～110 ℃, crystallization reaction 3～6 hours.After the sufficient crystallising reaction, slip is isolated half water white gypsum through vacuum filter S2, and drying obtains 530～610 parts of α half water plaster of Paris, obtains P simultaneously
2O
5Concentration is 375～420 parts of the phosphoric acid of 38～43WT%, and remaining phosphoric acid returns half tank R1 as recycled phosphoric acid, and filtration procedure washs filter residue with 80～100 ℃ hot water.The slag slurry that comes out through separator S1 enters two tank R3, and adjusting phosphoric acid concentration with process water is 13～22WT%P
2O
5, add sulfuric acid and control SO
3Concentration is 20～55g/L, and operational condition is: temperature is 65～75 ℃, and liquid-solid ratio is 2～3,2～3 hours reaction times.The dihydrate gypsum that two water slips obtain after separating through filter S3 can be used as the usefulness of building block, and light washing lotion is returned this operation two tanks, and dense filtrate is 13～22WT%P
2O
5Phosphoric acid, as one of wash water of vacuum filter S2, enter half tank R1 after the washing.P in the phosphorus ore
2O
5Leaching yield is 95%～98%.
Embodiment 2:
The technical process of present embodiment as shown in Figure 3.Certain phosphorus ore grade is 22～28WT%P
2O
5The phosphorus ore powder granularity is 80% mistake 0.075mm (200 order) screen cloth.Add 1000 parts in ground phosphate rock, enter half tank R1 and carry out acidolysis, the acidolysis process adds sulfuric acid, and the acidolysis reaction operational condition is: temperature is 95～105 ℃, and liquid-solid ratio is 5～8, and phosphoric acid concentration is 40～45WT%P
2O
5, control SO
3Concentration is 10～20g/L, 1～2 hour reaction times.The acidolysis slip that has reacted enters separator S1, carries out solid-liquid separation with it.The clear liquid that obtains enters crystallizer tank R2, adds sulfuric acid and carries out crystallization reaction, and the crystallization reaction operational condition is: control SO
3Concentration is 10～45g/L, and temperature is 100～110 ℃, crystallization reaction 2～5 hours, and after the sufficient crystallising reaction, slip is isolated half water white gypsum through vacuum filter S2, and drying obtains 740～840 parts of α half water plaster of Paris, obtains P simultaneously
2O
5Concentration is 90～570 parts of the phosphatase 24s of 40～46WT%, and remaining phosphoric acid returns half tank R1, and filtration procedure washs filter residue with 80～100 ℃ hot water.The slag slurry that comes out through separator S1 enters two tank R3, and adjusting phosphoric acid concentration with process water is 13～22WT%P
2O
5, add sulfuric acid and control SO
3Concentration is 20～55g/L, and temperature is 65～75 ℃, and liquid-solid ratio is 2～3.Filtrate is delivered to vacuum filter S2 as wash water, enters half tank R1 after the washing.P in the phosphorus ore
2O
5Leaching yield is 96%～99%.
Embodiment 3:
The technical process of present embodiment as shown in Figure 2.The P of certain phosphorus ore
2O
5Grade is 16～18%, phosphorus ore is processed into the powder of 80% mistake 0.125mm (120 order) screen cloth.1000 parts in ground phosphate rock is joined half tank R1 carry out acidolysis, the acidolysis reaction operational condition is: temperature is 95～105 ℃, and liquid-solid ratio is 4～7, and phosphoric acid concentration is 37～42%P
2O
5, 1～3 hour reaction times.The acidolysis slip that has reacted enters separator S1, isolates solid formation with it, and the clear liquid that obtains enters crystallizer tank R2, adds sulfuric acid and carries out crystallization reaction, and the crystallization reaction operational condition is: control SO
3Concentration is 15～65g/L, and temperature is 70～85 ℃, crystallization reaction 2～6 hours.After the sufficient crystallising reaction, slip is isolated 628～723 parts in two water white gypsum through vacuum filter S2, obtains P simultaneously
2O
5Concentration is 88～725 parts of 22～33% phosphatase 24s, and remaining phosphoric acid returns half tank R1 as the acidolysis recycled phosphoric acid, and filtration procedure washs filter residue with 80～100 ℃ hot water.The slag slurry that comes out through separator S1 enters two tank R3, and adjusting phosphoric acid concentration with process water is 13～22%P
2O
5, add sulfuric acid and control SO
3Concentration is 20～55g/L, and temperature is 65～75 ℃, and liquid-solid ratio is 2～3,2～3 hours reaction times.The dihydrate gypsum that two water slips obtain after separating through filter S3 can be used as the usefulness of building block, and light washing lotion is returned this operation two tanks, and dense filtrate is 13～22%P
2O
5Phosphoric acid, can be used as one of wash water of vacuum filter S2, enter half tank R1 after the washing.P in the phosphorus ore
2O
5Leaching yield is 95%～98%.
Claims (10)
1. method of utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum is characterized in that mainly comprising following operation:
(1) acidolysis separation circuit, powder phosphorus ore and phosphoric acid join the acidolysis reaction groove, carry out acidolysis reaction under 95～105 ℃, and the acidolysis concentration of phosphoric acid is to guarantee preparation phosphoric acid P
2O
5Concentration reaches 25～46wt%, fully behind the acidolysis reaction with acidolysis slip solid-liquid separation;
(2) Crystallization Separation operation, the separating obtained phosphoric acid clear liquid of operation (1) is sent to the crystallization reaction groove, adds sulfuric acid and carry out crystallization reaction under 70～110 ℃, and the vitriolic add-on is by SO in the crystallization feed liquid
3Concentration 10～65g/L adds, and carries out solid-liquid separation after the sufficient crystallising reaction, the phosphoric acid of liquid phase for preparing, the clean gypsum of solid phase for preparing;
(3) dihydrate acid is separated and the recrystallization separation circuit, and the separating obtained slag of operation (1) slurry is sent to the acidolysis reaction groove, adds water and slag is starched is carried out acidolysis again and recrystallization under 65～80 ℃, and the add-on of water is for making the phosphoric acid P after the acidolysis again
2O
5Concentration remains on 13～22WT% scope, and the vitriolic add-on is by SO in the feed liquid
3Concentration 5～65g/L adds, and fully reacts the back solid-liquid separation, and parting liquid is sent to operation (2), separates solid slag discharging.
2. the method for utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum according to claim 1 is characterized in that adding sulfuric acid in operation (1) the acidolysis reaction process, and the vitriolic add-on is controlled at the free acid SO in the acidolysis feed liquid
3Concentration is not more than 35g/L.
3. the method for utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum according to claim 1 is characterized in that the acidolysis concentration of phosphoric acid is than the low 1～6%wt of preparation phosphoric acid concentration.
4. according to claim 1 or the 2 or 3 described methods of utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum, it is characterized in that the powder at least 50% mistake sieve diameter of powder phosphorus ore is the screen cloth of 0.5mm.
5. the method for utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum according to claim 4 is characterized in that the powder at least 70% mistake sieve diameter of powder phosphorus ore is the screen cloth of 0.125mm.
6. according to claim 1 or the 2 or 3 described methods of utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum, it is characterized in that the solid-liquid separation in the operation (3) adopts vacuum filtration, add wash water in the filtration procedure filter residue is washed.
7. according to claim 1 or the 2 or 3 described methods of utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum, it is characterized in that the solid-liquid separation in the operation (2) adopts vacuum filtration, in filtration procedure, add hot water filter residue is washed.
8. the method for utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum according to claim 7 is characterized in that the hot water temperature that filter residue is washed is 80～100 ℃.
9. according to claim 1 or the 2 or 3 described methods of utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum, it is characterized in that operation (2) turns back to operation (1) directly as the acidolysis recycled phosphoric acid through the phosphoric acid part of solid-liquid separation gained.
10. according to claim 1 or the 2 or 3 described methods of utilizing wide concentration phosphoric acid of mid low grade phosphate rock wet production and clean gypsum, it is characterized in that operation (3) separates segregation section that the separation dope obtain is sent to operation (2) as the solid-liquid separation washing water, the washing clear liquid returns this operation as the process water of acidolysis again.
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| CN111348632A (en) * | 2019-06-06 | 2020-06-30 | 贵州川恒化工股份有限公司 | Method for producing semi-hydrated phosphoric acid and co-producing α type high-strength gypsum from phosphorite |
| CN111422878A (en) * | 2020-04-20 | 2020-07-17 | 武汉工程大学 | Method for treating silico-calcium collophanite |
| CN111438002A (en) * | 2020-04-20 | 2020-07-24 | 武汉工程大学 | Method for treating silicon-calcium collophanite by 'floating-chemical' coupling |
| CN112194109A (en) * | 2020-09-30 | 2021-01-08 | 湖北宜化松滋肥业有限公司 | Method for producing phosphoric acid and coproducing gypsum by semi-water-dihydrate wet-process phosphoric acid process |
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| 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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| CN105253867A (en) * | 2015-09-18 | 2016-01-20 | 金正大生态工程集团股份有限公司 | Production method for by-product alpha-hemihydrate gypsum of wet-process phosphoric acid |
| US10745278B2 (en) | 2015-09-18 | 2020-08-18 | Kingenta Ecological Engineering Group Co., Ltd. | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process |
| US10696552B2 (en) | 2015-09-18 | 2020-06-30 | Kingenta Norsterra Chemical Co., Ltd. | Method for producing wet-process phosphoric acid and by-producing alpha-hemihydrate gypsum and high-purity and high-whiteness alpha-hemihydrate gypsum |
| CN106044730A (en) * | 2016-06-03 | 2016-10-26 | 四川宏达股份有限公司 | Method for producing wet-process phosphoric acid from high-grade phosphate ore |
| CN106044730B (en) * | 2016-06-03 | 2018-05-18 | 四川宏达股份有限公司 | Utilize the method for high-grade phosphorus ore production phosphoric acid by wet process |
| 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 |
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| CN109292744A (en) * | 2018-09-04 | 2019-02-01 | 安徽六国化工股份有限公司 | A kind of method that middle-low grade phosphate produces phosphoric acid by wet process and half water ardealite of α |
| 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 |
| CN109573972A (en) * | 2019-01-23 | 2019-04-05 | 山东鲁北企业集团总公司 | A kind of method of mid low grade phosphate rock production phosphoric acid and low silica cream |
| CN109573972B (en) * | 2019-01-23 | 2021-05-28 | 山东鲁北企业集团总公司 | Method for producing phosphoric acid and low-silicon gypsum from medium-low grade phosphorite |
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| CN111348632B (en) * | 2019-06-06 | 2021-12-03 | 贵州川恒化工股份有限公司 | Method for producing semi-hydrated phosphoric acid and co-producing alpha-type high-strength gypsum from phosphorite |
| CN110204237A (en) * | 2019-06-28 | 2019-09-06 | 贵州川恒化工股份有限公司 | The production method of cement retarder |
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| CN111438002A (en) * | 2020-04-20 | 2020-07-24 | 武汉工程大学 | Method for treating silicon-calcium collophanite by 'floating-chemical' coupling |
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| CN112194109A (en) * | 2020-09-30 | 2021-01-08 | 湖北宜化松滋肥业有限公司 | Method for producing phosphoric acid and coproducing gypsum by semi-water-dihydrate wet-process phosphoric acid process |
| CN112194109B (en) * | 2020-09-30 | 2022-06-21 | 湖北宜化松滋肥业有限公司 | Method for producing phosphoric acid and coproducing gypsum by semi-water-dihydrate wet-process phosphoric acid process |
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