CN100545324C - The preparation method of a kind of calcium sulfate crystal whiskers and phosphoric acid - Google Patents

The preparation method of a kind of calcium sulfate crystal whiskers and phosphoric acid Download PDF

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CN100545324C
CN100545324C CNB2007100658069A CN200710065806A CN100545324C CN 100545324 C CN100545324 C CN 100545324C CN B2007100658069 A CNB2007100658069 A CN B2007100658069A CN 200710065806 A CN200710065806 A CN 200710065806A CN 100545324 C CN100545324 C CN 100545324C
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phosphoric acid
calcium sulfate
composite additive
sulfate crystal
crystal whiskers
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CN101092734A (en
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陈爱中
赵金秀
何培
李勤
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YUNNAN CHANGQINGSHU CHEMICALS CO Ltd
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YUNNAN CHANGQINGSHU CHEMICALS CO Ltd
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Abstract

The present invention is the preparation method of a kind of calcium sulfate crystal whiskers and phosphoric acid.Present method comprises phosphorus ore decomposition, slurry filtration separation, calcium sulfate crystal whiskers and separation, washing, drying course, it is characterized in that in the phosphorus ore decomposition course, adding the composite additive first, in the calcium sulfate crystal whiskers crystallisation process, add composite additive second, directly produce phosphoric acid and calcium sulfate crystal whiskers through twice filtering separation; The composite additive first is made up of humic acid and diatomite, humic acid: diatomite=1: 2-10; Composite additive second is made up of two kinds of materials, and first kind of X is the compound sodium laurylsulfonate that contains the sodium group, and second kind of Y is vitriol or the phosphoric acid salt that contains magnesium, aluminium, X: Y=2-5: 1; The addition of composite additive first is the 0.5%-5.0% of phosphorus ore amount, and the addition of composite additive second is the 0.1%-2.0% of the theoretical growing amount of crystal whisker of gypsum.The present invention is fully used various raw materials, and especially the calcium in the Rock Phosphate (72Min BPL) also becomes a part of product, not only greatly reduces the quantity of the solid waste of discharging in the Wet-process Phosphoric Acid Production, and has reduced production cost.

Description

The preparation method of a kind of calcium sulfate crystal whiskers and phosphoric acid
Technical field
The present invention relates to the preparation method of a kind of calcium sulfate crystal whiskers and phosphoric acid.
Background technology
Whisker be meant have the fixed shape of cross section, complete profile, perfect internal structure, the fibrous single crystal that length-to-diameter ratio is 5-1000.The excellent property of crystal whisker of gypsum, be widely used, can be used for fields such as matrix material enhancing, friction materials, environmental engineering, asphalt modification, coating and paint.At present, the production method of crystal whisker of gypsum mainly contains two kinds of the hot method of hydraulic pressure, sulfuric acid and soluble calcium salt reaction methods.
In the Wet-process Phosphoric Acid Production field, general knownly think that the nitration mixture decomposing phosphate rock of sulfuric acid and phosphoric acid carries out in two steps: phosphorus ore is produced monocalcium phosphate, monocalcium phosphate and sulfuric acid reaction generation crystal of calcium sulfate and phosphoric acid by phosphorolytic cleavage, and its chemical reaction is as follows:
Ca 5F(PO 4) 3+7H 3PO 4+5H 2O＝5Ca(H 2PO 4) 2+H 2O+HF (1)
5Ca(H 2PO 4) 2+5H 2SO 4+10H 2O＝10H 3PO 4+5CaSO 4·1/2H 2O (2)
Monocalcium phosphate Ca (the H that the first step reaction generates 2PO 4) 2Certain solubleness (being 58mg/g under the production status) is arranged in phosphoric acid, and it is to H 3PO 4Disassociation certain shock absorption is arranged, the first step reaction is proceeded to a certain degree just weakens, reaction not exclusively.The reaction of second step is the reaction that can carry out rapidly, and temperature is certain, SO in the liquid phase 3During excessive concentration, can generate a large amount of tiny, be difficult to filtering crystal of calcium sulfate, and this crystallization easily is deposited on the phosphorus ore particle surface and forms integument.If SO 3Concentration appropriateness, the reaction of second step can carry out spurring the carrying out of the first step reaction simultaneously fully.Under appropriate reaction conditions, phosphorus ore is carried out substep acid decompose that to produce phosphoric acid by wet process (two water laws) more reasonable, superior.
In traditional Wet-process Phosphoric Acid Production, the chemical energy and the Dilution of sulphuric acid thermolysis phosphorus ore that utilize sulfuric acid to provide have generated phosphoric acid simultaneously and have contained P 2O 5, F -, SiO 2Deng the synthetic gypsum of impurity, this gypsum is looked the difference of raw material and production technique and is utilized or is forced to and bank up, and the Rock Phosphate (72Min BPL) grade is low more, and foreign matter content is high more, and phosphogypsum is difficult to utilize more, and the phosphorus ore that industry standard is given for wet processes should satisfy P 2O 5〉=28%.By the national environmental protection Policy Conditions, phosphogypsum is a kind of harm solid waste.Along with going deep into of industrial application exploitation, the rich phosphorus ore of the low impurity of higher-grade reduces gradually, and methods such as general employing scouring, flotation make the P in the Rock Phosphate (72Min BPL) 2O 5Be able to enrichment, but P in the ore dressing process 2O 5Yield be generally less than 85%, beneficiation cost is higher, and to solve efflux wastewater problem of environment pollution caused in the ore dressing process, therefore improve the adaptability of phosphoric acid plant to phosphorus ore, be raw material production phosphoric acid directly with raw ore (homogenizing or non-homogenizing), improve the Rock Phosphate (72Min BPL) phosphorus utilization, reduce production costs, receive much attention.
In addition, the depleted phosphogypsum has been wasted calcium constituent in the Rock Phosphate (72Min BPL) and sulfate radical in the sulfuric acid simultaneously.Improve the comprehensive utilization of resources rate, reduce effluxing the social responsibility that dangerous solid waste is a manufacturing enterprise, enterprise also can therefrom obtain favorable economic benefit.
Application number is that 200510022547.2 patent documentation also discloses and can utilize mid low grade phosphate rock stone to be raw material production phosphoric acid by wet process and white gypsum, but used Rock Phosphate (72Min BPL) grade is P 2O 5〉=18%, major impurity content MgO≤2.0wt% adopts " two-stage reaction, multi-stage counter current extraction ", and products obtained therefrom is phosphoric acid and white gypsum.
Application number is that 200410024348.0 patent documentation also discloses the method for making crystal whisker of gypsum in phosphoric acid, its method is a stepwise reaction in production process of phosphoric acid, the phosphoric acid leaching liquid is added in the sulphuric acid soln that concentration is 30%-35% gradually under 90-95 ℃ condition stirring reaction 120-150 minute.
Summary of the invention
The purpose of this invention is to provide a kind of Preparation methods of gypsum whiskers method, it has very high adaptability to mineral, low-grade, high impure mineral is produced calcium sulfate crystal whiskers in can directly using, and mineral rate of decomposition and rate of recovery height, less demanding to the anticorrosion rank of production process, and resources such as the phosphorus in the mineral, calcium, fluorine, boron, chlorine can obtain high value-added product.
Technical scheme of the present invention is: on the basis of adopting phosphorolytic cleavage phosphorus ore known technology, for solving low P 2O 5, high impurity phosphorus ore inferior utilize problem, the present invention has added composite additive, under its effect, by a phosphorus ore decomposition, a calcium sulfate crystal whiskers crystallization, twice filtering separation direct production phosphoric acid and calcium sulfate crystal whiskers, makes P in the Rock Phosphate (72Min BPL) 2O 5, CaO and the H that is used for the sulfuric acid of production process +And SO 4 2-All obtain utilizing, reached higher comprehensive utilization of resources rate.
The present invention meets following chemical principle:
1. main chemical reactions
Ca 5F(PO 4) 3+7H 3PO 4+5H 2O＝5Ca(H 2PO 4) 2+H 2O+HF (1)
CaCO 3+2H 3PO 4＝Ca(H 2PO 4) 2+H 2O+CO 2?↑ (2)
MgCO 3+2H 3PO 4＝Mg(H 2PO 4) 2+H 2O+CO 2?↑ (3)
Fe 2O 3(Al 2O 3)+2H 3PO 4＝2FePO 4(AlPO 4)+3H 2O (4)
4HF+2SiO 2＝SiF 4↑+2H 2O (5)
5Ca(H 2PO 4) 2+5H 2SO 4+10H 2O＝10H 3PO 4+5CaSO 4·nH 2O (6)
(n＝0，1/2，2)
Adding composite additive first makes reaction (1)-(5) as far as possible fully, simultaneously owing to the use of composite additive (first), and the Ca (H after being convenient to the Rock Phosphate (72Min BPL) decomposition and making decomposition 2PO 4) 2Separate phosphorus ore resolution ratio 〉=95% as much as possible with other impurity.
Present method comprises phosphorus ore decomposition, slurry filtration separation, calcium sulfate crystal whiskers and separation, washing, drying course, it is characterized in that in the phosphorus ore decomposition course, adding the composite additive first, in the calcium sulfate crystal whiskers crystallisation process, add composite additive second, directly produce phosphoric acid and calcium sulfate crystal whiskers through twice filtering separation; The composite additive first is made up of humic acid and diatomite, humic acid: diatomite=1: 2-10; Composite additive second is made up of two kinds of materials, and first kind of X is the compound that contains the sodium group, and as sodium laurylsulfonate, second kind of Y is vitriol or the phosphoric acid salt that contains magnesium, aluminium, X: Y=2-5: 1; The addition of composite additive first is the 0.5%-5.0% of phosphorus ore amount, and the addition of composite additive second is the 0.1%-2.0% of the theoretical growing amount of crystal whisker of gypsum.
Used Rock Phosphate (72Min BPL) grade is: P 2O 5Content 〉=15%wt, MgO≤8%wt, Fe 2O 3+ Al 2O 3≤ 8%wt, the P of phosphoric acid 2O 5Content is 18%-35%.
Add P at the phosphorus ore decomposition course 2O 5Concentration is the phosphoric acid of 18%-35%, and add-on is a phosphorus ore: phosphoric acid=1: 8-15, and keeping slurry temperature is 60-85 ℃, the reaction times is not more than 3 hours;
In the calcium sulfate crystal whiskers crystallisation process, the vitriolic usage quantity is 102% of a Theoretical Calculation amount; The control differing temps obtains containing the calcium sulfate crystal whiskers of different crystal water, and temperature range is a normal temperature to 95 ℃, and the reaction times is 0.5-2 hour, and production pressure is normal pressure.
The present invention adopts the method for filtering under pressure or vacuum filtration, with the liquid-solid separation of reacted slip, banking up after solid washes with water, (elementary washing water are used for from the washing water of sulfuric acid calcium pyroborate washing, the final step washing water are technology hot water, keep water balance and water-saving purpose to reach), washing rate 〉=99%.Reaction slurry in the reactive tank can get product-calcium sulfate crystal whiskers and phosphoric acid through vacuum filtration, and a part of phosphoric acid is got back to extractive reaction groove and phosphorus ore reaction, and another part becomes finished product phosphoric acid.Bring most of impurity of device, separated in process of production discharger into mineral.
The middle low grade ore that the present invention can utilize the conventional wet phosphoric acid production directly not use, direct production half water, sulfate dihydrate calcium pyroborate and phosphoric acid by wet process.
The present invention is equally applicable to utilize other calcium minerals to be the raw material production calcium sulfate crystal whiskers, obtains the acid of the contained acid group correspondence of mineral substance simultaneously.As being raw material with lime borate, calcium chloride, product also can obtain byproducts such as boric acid, hydrochloric acid simultaneously except that obtaining two water, Ban Shui, anhydrous calcium sulfate whisker.
The present invention has following positively effect compared with the prior art:
Utilized calcium and the two kinds of resources of phosphorus in the Rock Phosphate (72Min BPL), made full use of chemical energy and the sulfate ion in the sulfuric acid, because the adding of composite additive first makes low-grade phosphate ore obtain higher rate of decomposition; The calcium sulfate crystal whiskers that obtains some kinds of different crystal water content under the effect of composite additive second (is CaSO 4, CaSO 4.1/2H 2O, CaSO 4.2H 2And obtain and the corresponding high-quality acid of the contained acid group of raw mineral materials (byproduct) O).The present invention is fully used various raw materials, and especially the calcium in the Rock Phosphate (72Min BPL) also becomes a part of product, not only greatly reduces the quantity of the solid waste of discharging in the Wet-process Phosphoric Acid Production, and has reduced production cost.
The present invention has very high adaptability to phosphorus ore, and low-grade, high impure mineral is produced calcium sulfate crystal whiskers in can directly using; Phosphorus ore resolution ratio and rate of recovery height; Requirement for anticorrosion to production unit is not high; Resources such as the calcium in the mineral, fluorine, boron, chlorine can be fully used, and produce high value-added product.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Wherein, 1 for decomposing, and 2 for filtering, and 3 is storage tank, and 4 are neutralization.
Embodiment
Embodiment 1:
1) gets P 2O 5Content is 18% ground phosphate rock 120Kg, adds composite additive first 6Kg, adds P 2O 5Concentration is 22% phosphatase 11 440Kg, and keeping slurry temperature is 60 ℃, and the reaction times is 3 hours; Wherein: the composite additive first is made up of with silicon-containing material such as diatomite humic acid (the available humic acid that contains sodium humate, potassium humate and humic acid magnesium), and ratio is a humic acid: diatomite=1: 2;
2) way that adopts filtering under pressure or vacuum filtration is with the liquid-solid separation of reacted slip, and solid is banked up after being washed with water to neutrality; Filter the gained clear liquid and send into next response procedures use;
3) above-mentioned filtration gained clear liquid is under the effect that adds composite additive second, with concentration be 55% sulfuric acid reaction, the addition of composite additive second is 1.5% of the theoretical growing amount of crystal whisker of gypsum output; The vitriolic usage quantity is 102% of a Theoretical Calculation amount; Generate phosphoric acid and calcium sulfate crystal whiskers in reactive tank, temperature is controlled at 50 ℃, and the reaction times is 1 hour; Composite additive second is made up of two kinds of compounds Xs and Y, and X is a sodium laurylsulfonate, and Y is the vitriol that contains magnesium, aluminium, X: Y=3: 1;
4) slip in the reactive tank can get product-calcium sulfate crystal whiskers and phosphoric acid through vacuum filtration, and a part of phosphoric acid is got back to extractive reaction groove and phosphorus ore reaction, and another part becomes finished product phosphoric acid.Bring most of impurity of device, separated in process of production discharger into mineral.
Embodiment 2:
1) gets P 2O 5Content is 25% ground phosphate rock 120Kg, adds composite additive first 1Kg, adds P 2O 5Concentration is 20% phosphatase 11 320Kg, and keeping slurry temperature is 70 ℃, and the reaction times is 2.5 hours.Wherein: the composite additive first is made up of humic acid and silicon-containing material diatomite, and ratio is a humic acid: diatomite=1: 5.
2) way that adopts filtering under pressure or vacuum filtration is with the liquid-solid separation of reacted slip, and solid is banked up after being washed with water to neutrality; Filter the gained clear liquid and send into next response procedures use;
3) filter the gained clear liquid under the effect that adds composite additive second, with concentration be 35% sulfuric acid reaction, the addition of composite additive is 1.0% of the theoretical growing amount of crystal whisker of gypsum output; The vitriolic usage quantity is 102% of a Theoretical Calculation amount; Generate phosphoric acid and calcium sulfate crystal whiskers in reactive tank, temperature is controlled at 80 ℃, and the reaction times is 1 hour; Composite additive second is made up of two kinds of compounds Xs and Y, and X is a sodium laurylsulfonate, and Y is the phosphoric acid salt that contains magnesium, aluminium, X: Y=2: 1.
4) slip in the reactive tank can get product-calcium sulfate crystal whiskers and phosphoric acid through vacuum filtration, and a part of phosphoric acid is got back to extractive reaction groove and phosphorus ore reaction, and another part becomes finished product phosphoric acid.Bring most of impurity of device, separated in process of production discharger into mineral.
Embodiment 3:
1) gets P 2O 5Content is 28% ground phosphate rock 120Kg, adds composite additive first 0.6Kg, adds P 2O 5Concentration is 20% phosphatase 11 500Kg, and keeping slurry temperature is 80 ℃, and the reaction times is 2.5 hours.Wherein: the composite additive first is made up of humic acid and diatomite, and ratio is a humic acid: diatomite=1: 10.
2) way that adopts filtering under pressure or vacuum filtration is with the liquid-solid separation of reacted slip, and solid is banked up with washing to neutrality; Filter the gained clear liquid and send into next response procedures use;
3) filter the gained clear liquid under the effect that adds composite additive second, with concentration be 25% sulfuric acid reaction, the addition of composite additive is 0.5% of the theoretical growing amount of crystal whisker of gypsum output; The vitriolic usage quantity is 102% of a Theoretical Calculation amount; Generate phosphoric acid and calcium sulfate crystal whiskers in reactive tank, temperature is controlled at 90 ℃, and the reaction times is 1 hour; Composite additive second is made up of two kinds of compounds Xs and Y, and X is a sodium laurylsulfonate, and Y is the vitriol that contains magnesium, aluminium, X: Y=5: 1.
4) slip in the reactive tank can get product-calcium sulfate crystal whiskers and phosphoric acid through vacuum filtration, and a part of phosphoric acid is got back to extractive reaction groove and phosphorus ore reaction, and another part becomes finished product phosphoric acid.Bring most of impurity of device, separated in process of production discharger into mineral.

Claims (4)

1. Preparation methods of gypsum whiskers method, present method comprises phosphorus ore decomposition, slurry filtration separation, calcium sulfate crystal whiskers crystallization and separation, washing, drying course, it is characterized in that in the phosphorus ore decomposition course, adding the composite additive first, after filtration, separate filtrate, adding sulfuric acid and composite additive second are carried out the calcium sulfate crystal whiskers crystallisation process in this filtrate, separate after filtration more directly to produce phosphoric acid and calcium sulfate crystal whiskers; The composite additive first is that humic acid and diatomite are formed; Humic acid: diatomite=1: 2-10; Composite additive second is made up of two kinds of materials, and first kind of X is the compound sodium laurylsulfonate that contains the sodium group, and second kind of Y is vitriol or the phosphoric acid salt that contains magnesium, aluminium, X: Y=2-5: 1; The addition of composite additive first is the 0.5%-5.0% of phosphorus ore amount, and the addition of composite additive second is the 0.1%-2.0% of the theoretical growing amount of calcium sulfate crystal whiskers.
2. Preparation methods of gypsum whiskers method according to claim 1 is characterized in that used Rock Phosphate (72Min BPL) grade is: P 2O 5Content 〉=15wt%, MgO≤8wt%, Fe 2O 3+ Al 2O 3≤ 8wt%.
3. Preparation methods of gypsum whiskers method according to claim 1 is characterized in that the phosphorus ore decomposition course adds P 2O 5Concentration is the phosphoric acid of 18%-35%, and add-on is a phosphorus ore: phosphoric acid=1: 8-15, and keeping slurry temperature is temperature 60-85 ℃, the reaction times is not more than 3 hours.
4. Preparation methods of gypsum whiskers method according to claim 1 is characterized in that in the calcium sulfate crystal whiskers crystallisation process that the vitriolic usage quantity is 102% of a Theoretical Calculation amount; The control differing temps obtains containing the calcium sulfate crystal whiskers of different crystal water, and temperature range is a normal temperature to 95 ℃, and the reaction times is 0.5-2 hour, and production pressure is normal pressure.
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101311355B (en) * 2008-04-24 2012-05-02 云南民族大学 Process for preparing calcium sulphate whiskers from ardealite
CN101586255B (en) * 2009-06-08 2011-05-04 安徽工业大学 Preparation method of calcium sulphate dihydrate crystal whisker
CN101736404B (en) * 2010-01-22 2012-04-25 四川大学 Co-production method of calcium sulfate whisker and phosphoric acid
CN102286783B (en) * 2011-09-30 2013-05-22 瓮福（集团）有限责任公司 New method for preparing calcium sulfate whiskers
CN102534801A (en) * 2012-02-23 2012-07-04 云南民族大学 Method for improving quality of calcium sulfate whiskers
CN104328481A (en) * 2014-10-14 2015-02-04 瓮福（集团）有限责任公司 Method for preparing gypsum whisker by using phosphate tailings and raffinate phosphoric acid
CN105133003B (en) * 2015-09-18 2018-02-06 金正大诺泰尔化学有限公司 A kind of production method of phosphoric acid by wet process by-product αsemiwatergypsum whisker
CN113882021A (en) * 2021-10-12 2022-01-04 贵州大学 Method for preparing calcium sulfate whisker by phosphogypsum high-temperature high-pressure method

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Publication number Priority date Publication date Assignee Title
CN1584130A (en) * 2004-06-14 2005-02-23 青岛科技大学 Method for producing land plaster whiskers from phosphoric acid
CN1648291A (en) * 2004-11-30 2005-08-03 上海耀华纳米科技有限公司 Process for preparing whisker calcium sulfate
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1584130A (en) * 2004-06-14 2005-02-23 青岛科技大学 Method for producing land plaster whiskers from phosphoric acid
CN1648291A (en) * 2004-11-30 2005-08-03 上海耀华纳米科技有限公司 Process for preparing whisker calcium sulfate
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

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