CN104562180A - Method for preparing calcium sulfate whisker from phosphogypsum - Google Patents
Method for preparing calcium sulfate whisker from phosphogypsum Download PDFInfo
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Abstract
The invention discloses a method for preparing calcium sulfate whisker from phosphogypsum. The method comprises the following steps: (1) crushing and grinding phosphogypsum serving as a raw material to obtain phosphogypsum powder; (2) mixing the obtained phosphogypsum powder and diluted acid to obtain a mixture, placing the mixture in a reactor with a stirring device, reacting by controlling a certain temperature to obtain an acidic mixed solution containing calcium, sulfate ions and insoluble matters; (3) filtering the obtained mixed solution while the solution is hot to obtain an acidic filtrate; and (4) cooling the obtained acidic filtrate and crystallizing, filtering, washing and drying to obtain the calcium sulfate whisker product. The calcium sulfate dihydrate whisker with large length-diameter ratio is directly prepared from the raw material by virtue of one-step acid leaching impurity removal method instead of pretreatment impurity removal and thus the advantages that the process flow is simple, the production cost is low, the energy consumption is small and the acidic wastewater and washing water can be recyclable are achieved; the obtained calcium sulfate whisker has the characteristics of high purity, large length-diameter ratio and the like and is conductive to popularization and application.
Description
Technical field
The present invention relates to a kind of method of preparing calcium sulphate whiskers from ardealite, belong to the technical field of industrial solid castoff recycling, ceramic and environment protection.
Background technology
Phosphogypsum be produce in process phosphoric acid discharge with CaSO
42H
2o is the solid waste of main component, and containing phosphoric acid salt, fluorochemical, other vitriol and organic matters etc.Often produce 1 ton of phosphoric acid and approximately produce 5 tons of phosphogypsums, the storage capacity of Chinese phosphogypsum is up to more than 10 hundred million tons.Storing up in a large number of phosphogypsum, not only land occupation, and pollution is in various degree caused to environment.Therefore, the recycling of phosphogypsum has very important resources and environment meaning.
Calcium sulfate crystal whiskers grows with single crystal form, has uniform cross-sectional area, complete profile, perfect internal structure, in needle-like, fibrous single crystal.Because of its have reinforcement, acid and alkali-resistance, anticorrosive, be easy to processing, the excellent physicochemical property such as nontoxic, therefore be widely used in as strengthening and toughening agent or functional filler in resin, plastics, rubber, coating, papermaking, pitch, friction and sealing material, also can directly as filtering material, heat preserving and insulating material etc.The mean diameter of calcium sulfate crystal whiskers is 1 ~ 8 μm, and mean length is 30 ~ 200 μm.
Publication number is the Chinese invention patent of CN101311355A, discloses a kind of preparation method of calcium sulfate crystal whiskers.The method utilizes highly basic to regulate the pH value of phosphogypsum slurry to be alkalescence, stir process 20 ~ 30min at temperature is 90 ~ 200 DEG C, and filtering the filter residue obtained is the first intermediate product; First intermediate product is mixed with certain density slurries, deposit in case at magnesium nitrate, stir process 20 ~ 30min at the temperature of 100 ~ 200 DEG C, filtering the filtrate obtained under keeping the temperature of 80 ~ 150 DEG C is the second intermediate product, and the second intermediate product cooling crystallization obtains product calcium sulfate crystal whiskers.The method complex process, production efficiency is lower, and needs to add chemical additives.Publication number is CN102115142A Chinese invention patent, discloses a kind of preparation method of industrial sulphuric acid calcium.The method take phosphogypsum as raw material, soluble impurity is removed in first washing, recycling hydrochloric acid removes insoluble phosphate and other insoluble impuritiess, and last filtering separation obtains the filter residue containing calcium sulfate and other vitriol, is dried, pulverizes acquisition industrial sulphuric acid calcium.The calcium sulfate purity that the method obtains is low, is difficult to widespread use.
Summary of the invention
In order to solve the defects such as the difficult removal of impurities of the preparing calcium sulphate whiskers from ardealite that exists in above-mentioned prior art, operational path be complicated, the object of this invention is to provide that a kind of technique is simple, a step removal of impurities, by the method for preparing calcium sulphate whiskers from ardealite.
To achieve these goals, the present invention adopts following technical scheme: a kind of method of preparing calcium sulphate whiskers from ardealite, comprises step as follows:
1) get phosphogypsum raw material crushing and grinding, obtaining granularity is 20 ~ 600 object phosphogypsum powders;
2) by step 1) phosphogypsum powder and diluted acid be 10Kg/m by solid-to-liquid ratio
3~ 200Kg/m
3be placed in reactor to stir, reheat after dissolving and filter, obtain acid filtrate and filter residue respectively;
3) by step 2) acid filtrate that obtains carries out ripening, obtains the acid suspension liquid containing calcium sulfate crystal whiskers; Then this acid suspension liquid is filtered, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Calcium sulfate crystal whiskers filter residue process water wherein rinses, and rinses pH value to its wash filtrate for neutral, drier under-15 DEG C ~ 90 DEG C environment, obtains described calcium sulfate crystal whiskers.
Above-mentioned steps 2) in the mass percent concentration of diluted acid used be 1.0% ~ 25.0%, the temperature of heating for dissolving is 60 DEG C ~ 120 DEG C, and dissolution time is 0.5h ~ 8h.
Above-mentioned diluted acid can be selected dilute hydrochloric acid, dust technology or reclaim in diluted acid at least a kind.
The preparation steps of above-mentioned recovery diluted acid is: the acid waste liquid after A) being filtered by acid suspension liquid and the rear pH value of flushing are that neutral wash filtrate stirs into mixed solution with the volume ratio of 1:1 ~ 4:1; B) this mixed solution is added hydrochloric acid or/and nitric acid is mixed with above-mentioned recovery diluted acid for 10:1 ~ 40:1 by volume; The mass percent concentration of this recovery diluted acid is identical with the mass percent concentration of above-mentioned dilute hydrochloric acid or dust technology.
Above-mentioned steps 3) in ripening comprise cooling and Crystallizing treatment; Wherein, cooling is by step 2) the temperature of acid filtrate be down to 10 DEG C ~ 40 DEG C; Crystallizing treatment separates out calcium sulfate crystal whiskers with the reduction Step crystallization of described acid filtrate temperature, and its crystallization time is 2h ~ 24h.
With calcium sulfate crystal whiskers prepared by aforesaid method, its thing is terra alba mutually, its diameter at 5 ~ 30 μm, length at 100 ~ 2000 μm, length-to-diameter ratio 10 ~ 400.
Owing to have employed technique scheme, beneficial effect of the present invention is as follows: 1) prepare calcium sulfate crystal whiskers with phosphogypsum one step acidleach removal of impurities, whole building-up process adopts a step pickling process to complete, and simplifies the technical process of prior art, reduces energy consumption; 2) phosphogypsum is without the need to pre-treatment removal of impurities, direct acidleach, and while obtaining calcium sulfate crystal whiskers and magazins' layout, phosphogypsum dissolution rate is large, is conducive to extensive recycling phosphogypsum; 3) after primary first-order equation terminates, acid waste liquid and wash filtrate can reclaim, the recovery diluted acid be mixed with, and alternative dilute hydrochloric acid or dust technology re-use, and save cost, improve the utilization ratio of chemical assistant; 4) the calcium sulfate crystal whiskers purity of synthesizing and whiteness high, whisker length-to-diameter ratio is large, is macroscopic fibrous crystal whisker materials.
Accompanying drawing explanation
Fig. 1 is the XRD figure of calcium sulfate crystal whiskers prepared by example 1.
Fig. 2 is the outward appearance photo of calcium sulfate crystal whiskers prepared by example 1.
Fig. 3 is the photo of the opticmicroscope of calcium sulfate crystal whiskers prepared by example 1.
Fig. 4 is the XRD figure of calcium sulfate crystal whiskers prepared by example 2.
Fig. 5 is the outward appearance photo of calcium sulfate crystal whiskers prepared by example 2.
Fig. 6 is the photo of the opticmicroscope of calcium sulfate crystal whiskers prepared by example 2.
Fig. 7 is the XRD figure of calcium sulfate crystal whiskers prepared by example 3.
Fig. 8 is the outward appearance photo of calcium sulfate crystal whiskers prepared by example 3.
Fig. 9 is the photo of the opticmicroscope of calcium sulfate crystal whiskers prepared by example 3.
Figure 10 is the XRD figure of calcium sulfate crystal whiskers prepared by example 4.
Figure 11 is the outward appearance photo of calcium sulfate crystal whiskers prepared by example 4.
Figure 12 is the photo of the opticmicroscope of calcium sulfate crystal whiskers prepared by example 4.
Figure 13 is the XRD figure of calcium sulfate crystal whiskers prepared by example 5.
Figure 14 is the outward appearance photo of calcium sulfate crystal whiskers prepared by example 5.
Figure 15 is the photo of the opticmicroscope of calcium sulfate crystal whiskers prepared by example 5.
Figure 16 is the XRD figure of calcium sulfate crystal whiskers prepared by example 6.
Figure 17 is the outward appearance photo of calcium sulfate crystal whiskers prepared by example 6.
Figure 18 is the photo of the opticmicroscope of calcium sulfate crystal whiskers prepared by example 6.
Figure 19 is the XRD figure of calcium sulfate crystal whiskers prepared by example 7.
Figure 20 is the outward appearance photo of calcium sulfate crystal whiskers prepared by example 7.
Figure 21 is the photo of the opticmicroscope of calcium sulfate crystal whiskers prepared by example 7.
Embodiment
The method of the present invention's preparing calcium sulphate whiskers from ardealite, comprises step as follows:
1) phosphogypsum raw material crushing is got and grinding becomes granularity to be 20 ~ 600 object phosphogypsum powders;
2) by step 1) phosphogypsum powder and diluted acid be 10Kg/m by solid-to-liquid ratio
3~ 200Kg/m
3be placed in reactor to stir, reheat after dissolving and filter, obtain acid filtrate and filter residue respectively;
3) by step 2) acid filtrate carry out ripening, obtain the acid suspension liquid containing calcium sulfate crystal whiskers, then this acid suspension liquid filtered, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Calcium sulfate crystal whiskers filter residue process water wherein rinses, and rinses pH value to its wash filtrate in neutral, drier under-15 DEG C ~ 90 DEG C environment, obtains described calcium sulfate crystal whiskers.
Above-mentioned steps 2) diluted acid used, its mass percent concentration is 1.0% ~ 25.0%, and the temperature of heating for dissolving is 60 DEG C ~ 100 DEG C, and dissolution time is 0.5h ~ 10h.
Diluted acid used can be selected dilute hydrochloric acid, dust technology or reclaim in diluted acid at least a kind.
Above-mentioned steps 3) in ripening comprise cooling and Crystallizing treatment; Wherein, cooling is that the temperature of described acid filtrate is down to 10 DEG C ~ 40 DEG C; Crystallizing treatment separates out calcium sulfate crystal whiskers with the reduction Step crystallization of described acid filtrate temperature, and its crystallization time is 2h ~ 24h;
Wherein, can also reclaim acid waste liquid and wash filtrate, then be mixed with recovery diluted acid, return step 2) middle use.The preparation steps of this recovery diluted acid is: the acid waste liquid after A) being filtered by acid suspension liquid and the rear pH value of flushing are that neutral wash filtrate stirs into mixed solution with the volume ratio of 1:1 ~ 4:1; B) in mixed solution, add hydrochloric acid or/and nitric acid for 10:1 ~ 40:1 by volume, after mixing, make above-mentioned recovery diluted acid; Its mass percent concentration reclaiming diluted acid is identical with the mass percent concentration of aforementioned dilute hydrochloric acid used or dust technology.
The thing of the calcium sulfate crystal whiskers utilizing the present invention to prepare is terra alba mutually, its diameter at 5 ~ 30 μm, length at 100 ~ 2000 μm, length-to-diameter ratio 10 ~ 400.
Also by reference to the accompanying drawings technical scheme of the present invention is described in further detail below by specific examples.
Example 1:
By the method for preparing calcium sulphate whiskers from ardealite, comprise step as follows:
1) phosphogypsum raw material being obtained granularity through ball mill grinding is 100 object phosphogypsum powders.
2) by step 1) the phosphogypsum powder that obtains and mass percent concentration be that the dilute hydrochloric acid of 25.0% is according to solid-to-liquid ratio 200Kg/m
3mix, and the reactor being placed in band whipping appts stirs; Then, be energized to the heating material to 100 in reactor DEG C, stir 2h, obtain the acid mixed solution of calcic and sulfate ion and acid non-soluble substance; The acid mixed solution filtered while hot obtained is separated, obtains acid filtrate and filter residue respectively.Filter residue is discarded or is separately used as him.
3) ripening is carried out to above-mentioned acid filtrate, Temperature fall to 20 DEG C, Crystallizing treatment 24h, obtain the acid suspension liquid containing calcium sulfate crystal whiskers; Then adopt pressure filter to filter to this acid suspension liquid, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Again acquisition calcium sulfate crystal whiskers filter residue process water is repeatedly rinsed, to the pH value of its wash filtrate reaches neutrality; Filter residue is dried ventilation at normal temperatures, obtains described calcium sulfate crystal whiskers.
Acid waste liquid in this example and wash filtrate can also be recycled.Concrete way is: above-mentioned acid waste liquid and wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1, then is mixed with the volume ratio of 10:1 the recovery diluted acid that mass percent concentration is 25.0% with hydrochloric acid, returns step 2) middle use.
The photo of the XRD figure of the calcium sulfate crystal whiskers obtained in this example, outward appearance photo, opticmicroscope as shown in Figure 1, Figure 2, Figure 3 shows.The principal crystalline phase of the calcium sulfate crystal whiskers of preparation is dihydrate gypsum, and characteristic diffraction peak intensity is high, and peak type is sharp-pointed, good crystallinity; Calcium sulfate crystal whiskers exterior appearance is white whiskers matter, and length-to-diameter ratio is large, diameter at 5 ~ 10 μm, length at 1000 ~ 2000 μm, length-to-diameter ratio 100 ~ 400.
Example 2:
The step of this case method is substantially identical with example 1, does not repeat them here.
Its difference is, in following step:
1) phosphogypsum raw material being obtained granularity through ball mill grinding is 20 object phosphogypsum powders.
2) by step 1) the phosphogypsum powder that obtains and mass percent concentration be that the dilute hydrochloric acid of 1.0% is according to solid-to-liquid ratio 10Kg/m
3mix, and the reactor being placed in band whipping appts stirs; Then the material in reactor is adopted and be steam heated to 60 DEG C, stir 8h, obtain the acid mixed solution of calcic and sulfate ion and acid non-soluble substance; The acid mixed solution filtered while hot obtained is separated, obtains acid filtrate and filter residue respectively.
3) ripening is carried out to above-mentioned acid filtrate, adopt air-cooled by greenhouse cooling to 20 DEG C, Crystallizing treatment 24h, obtain the acid suspension liquid containing calcium sulfate crystal whiskers; Then adopt pressure filter to filter to this acid suspension liquid, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Acquisition calcium sulfate crystal whiskers filter residue process water is repeatedly rinsed, to the pH value of its wash filtrate reaches neutrality; By filter residue lyophilize at-15 DEG C, obtain calcium sulfate crystal whiskers.
Above-mentioned acid waste liquid and wash filtrate can also be recycled.Concrete way is: above-mentioned acid waste liquid and wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1, then is mixed with the volume ratio of 40:1 the recovery diluted acid that mass percent concentration is 1.0% with hydrochloric acid, returns step 2) middle use.
The photo of the XRD figure of the calcium sulfate crystal whiskers obtained in this example, outward appearance photo, opticmicroscope is as shown in Fig. 4, Fig. 5, Fig. 6.The principal crystalline phase of prepared calcium sulfate crystal whiskers is dihydrate gypsum, and characteristic diffraction peak intensity is high, and peak type is sharp-pointed, good crystallinity; Calcium sulfate crystal whiskers exterior appearance is white whiskers matter, and length-to-diameter ratio is large, 5 ~ 15 μm, length at 1000 ~ 2000 μm, length-to-diameter ratio 100 ~ 400.
Example 3:
The step of this case method is substantially identical with example 1, does not repeat them here.
Its difference is, in following step:
1) phosphogypsum raw material being obtained granularity through ball mill grinding is 600 object phosphogypsum powders.
2) by step 1) the phosphogypsum powder that obtains and mass percent concentration be that the dilute hydrochloric acid of 7.2% is according to solid-to-liquid ratio 70Kg/m
3mix, and the reactor being placed in band whipping appts stirs; Then the material in reactor is adopted and be steam heated to 95 DEG C, stir 0.5h, obtain the acid mixed solution of calcic and sulfate ion and acid non-soluble substance; The acid mixed solution filtered while hot obtained is separated, obtains acid filtrate and filter residue respectively.
3) carry out ripening to above-mentioned acid filtrate, adopt water-cooled by greenhouse cooling to 10 DEG C, Crystallizing treatment 10h, obtains the acid suspension liquid containing calcium sulfate crystal whiskers; Then adopt pressure filter to filter to this acid suspension liquid, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Acquisition calcium sulfate crystal whiskers filter residue process water is repeatedly rinsed, to the pH value of its wash filtrate reaches neutrality; By filter residue lyophilize at-10 DEG C, obtain described calcium sulfate crystal whiskers.
Above-mentioned acid waste liquid and wash filtrate can also be recycled.Concrete way is: above-mentioned acid waste liquid and wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1, then is mixed with the volume ratio of 30:1 the recovery diluted acid that mass percent concentration is 7.2% with hydrochloric acid, returns step 2) middle use.
The photo of the XRD figure of the calcium sulfate crystal whiskers obtained in this example, outward appearance photo, opticmicroscope is as shown in Fig. 7, Fig. 8, Fig. 9.The principal crystalline phase of prepared calcium sulfate crystal whiskers is dihydrate gypsum, and characteristic diffraction peak intensity is high, and peak type is sharp-pointed, good crystallinity; Calcium sulfate crystal whiskers exterior appearance is white whiskers matter, and length-to-diameter ratio is little, diameter at 15 ~ 30 μm, length at 200 ~ 800 μm, length-to-diameter ratio 20 ~ 60.
Example 4:
The step of this case method is substantially identical with example 1, does not repeat them here.
Its difference is, in following step:
1) phosphogypsum raw material being obtained granularity through ball mill grinding is 300 object phosphogypsum powders.
2) by step 1) the phosphogypsum powder that obtains and mass percent concentration be that the dilute hydrochloric acid of 25.0% is according to solid-to-liquid ratio 100Kg/m
3mix, and the reactor being placed in band whipping appts stirs; Then adopt coal furnace to be heated to 80 DEG C to the material in reactor, stir 4h, obtain the acid mixed solution of calcic and sulfate ion and acid non-soluble substance; The acid mixed solution filtered while hot obtained is separated, obtains acid filtrate and filter residue respectively.
3) carry out ripening to above-mentioned acid filtrate, adopt water-cooled by greenhouse cooling to 40 DEG C, Crystallizing treatment 2h, obtains the acid suspension liquid containing calcium sulfate crystal whiskers; Then adopt pressure filter to filter to this acid suspension liquid, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Acquisition calcium sulfate crystal whiskers filter residue process water is repeatedly rinsed, to the pH value of its wash filtrate reaches neutrality; By filter residue 80 DEG C of oven dry, obtain described calcium sulfate crystal whiskers.
Above-mentioned acid waste liquid and wash filtrate can also be recycled.Concrete way is: above-mentioned acid waste liquid and wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1, then to be mixed with mass percent concentration with hydrochloric acid with the volume ratio of 20:1 be 15.0% recovery diluted acid, returns step 2) in use.
The photo of the XRD figure of the calcium sulfate crystal whiskers obtained in this example, outward appearance photo, opticmicroscope is as shown in Figure 10, Figure 11, Figure 12.The principal crystalline phase of prepared calcium sulfate crystal whiskers is dihydrate gypsum, and characteristic diffraction peak intensity is high, and peak type is sharp-pointed, good crystallinity; Calcium sulfate crystal whiskers exterior appearance is white whiskers matter, and major diameter is little, the diameter of calcium sulfate crystal whiskers at 10 ~ 25 μm, length at 100 ~ 600 μm, length-to-diameter ratio 10 ~ 60.
Example 5:
The step of this case method is substantially identical with example 1, does not repeat them here.
Its difference is, in following step:
1) phosphogypsum raw material being obtained granularity through ball mill grinding is 200 object phosphogypsum powders.
2) by step 1) the phosphogypsum powder that obtains and mass percent concentration be that the dust technology of 1.0% is according to solid-to-liquid ratio 50Kg/m
3mix, and the reactor being placed in band whipping appts stirs; Then adopt oil oven to be heated to 75 DEG C to the material in reactor, stir 6h, obtain the acid mixed solution of calcic and sulfate ion and acid non-soluble substance; The acid mixed solution filtered while hot obtained is separated, obtains acid filtrate and filter residue respectively.
3) ripening is carried out to above-mentioned acid filtrate, adopt air-cooled by greenhouse cooling to 15 DEG C, Crystallizing treatment 8h, obtain the acid suspension liquid containing calcium sulfate crystal whiskers; Then adopt pressure filter to filter to this acid suspension liquid, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Acquisition calcium sulfate crystal whiskers filter residue process water is repeatedly rinsed, to the pH value of its wash filtrate reaches neutrality; By filter residue 100 DEG C of oven dry, obtain described calcium sulfate crystal whiskers.
Above-mentioned acid waste liquid and wash filtrate can also be recycled.Concrete way is: above-mentioned acid waste liquid and wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1, then to be mixed with mass percent concentration with nitric acid with the volume ratio of 40:1 be 1.0% recovery diluted acid, returns step 2) in use.
The photo of the XRD figure of the calcium sulfate crystal whiskers obtained in this example, outward appearance photo, opticmicroscope is as shown in Figure 13, Figure 14, Figure 15.The principal crystalline phase of prepared calcium sulfate crystal whiskers is dihydrate gypsum, and characteristic diffraction peak intensity is high, and peak type is sharp-pointed, good crystallinity; Calcium sulfate crystal whiskers exterior appearance is white whiskers matter, and major diameter is smaller, diameter at 10 ~ 25 μm, length at 500 ~ 1000 μm, length-to-diameter ratio 50 ~ 100.
Example 6:
The step of this case method is substantially identical with example 1, does not repeat them here.
Its difference is, in following step:
1) phosphogypsum raw material being obtained granularity through ball mill grinding is 200 object phosphogypsum powders.
2) by step 1) the phosphogypsum powder that obtains and mass percent concentration be that the dust technology of 10.5% is according to solid-to-liquid ratio 100Kg/m
3mix, and the reactor being placed in band whipping appts stirs; Then electrically heated to 120 DEG C is adopted to the material in reactor, stir 0.5h, obtain the acid mixed solution of calcic and sulfate ion and acid non-soluble substance; The acid mixed solution filtered while hot obtained is separated, obtains acid filtrate and filter residue respectively.
3) carry out ripening to above-mentioned acid filtrate, adopt water-cooled by greenhouse cooling to 25 DEG C, Crystallizing treatment 15h, obtains the acid suspension liquid containing calcium sulfate crystal whiskers; Then adopt pressure filter to filter to this acid suspension liquid, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Acquisition calcium sulfate crystal whiskers filter residue process water is repeatedly rinsed, to the pH value of its wash filtrate reaches neutrality; By filter residue 60 DEG C of oven dry, obtain described calcium sulfate crystal whiskers.
Above-mentioned acid waste liquid and wash filtrate can also be recycled.Concrete way is: above-mentioned acid waste liquid and wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1, then to be mixed with mass percent concentration with nitric acid with the volume ratio of 25:1 be 10.5% recovery diluted acid, returns step 2) in use.
The photo of the XRD figure of the calcium sulfate crystal whiskers obtained in this example, outward appearance photo, opticmicroscope is as shown in Figure 16, Figure 17, Figure 18.The principal crystalline phase of prepared calcium sulfate crystal whiskers is dihydrate gypsum, and characteristic diffraction peak intensity is high, and peak type is sharp-pointed, good crystallinity; Calcium sulfate crystal whiskers exterior appearance is white whiskers matter, and major diameter is large, diameter at 6 ~ 17 μm, length at 1050 ~ 2200 μm, length-to-diameter ratio 108 ~ 400.
Example 7:
The step of this case method is substantially identical with example 1, does not repeat them here.
Its difference is, in following step:
1) phosphogypsum raw material being obtained granularity through ball mill grinding is 80 object phosphogypsum powders.
2) by step 1) the phosphogypsum powder and the mass percent concentration that obtain be 7.2% mix diluted acid (dilute hydrochloric acid and dust technology are by volume for 1:1 configures) according to solid-to-liquid ratio 70Kg/m
3mix, and the reactor being placed in band whipping appts stirs; Then flue gas heating to 110 DEG C is adopted to the material in reactor, stir 7h, obtain the acid mixed solution of calcic and sulfate ion and acid non-soluble substance; The acid mixed solution filtered while hot obtained is separated, obtains acid filtrate and filter residue respectively.
3) carry out ripening to above-mentioned acid filtrate, adopt water-cooled by greenhouse cooling to 30 DEG C, Crystallizing treatment 8h, obtains the acid suspension liquid containing calcium sulfate crystal whiskers; Then adopt pressure filter to filter to this acid suspension liquid, obtain calcium sulfate crystal whiskers filter residue and acid waste liquid; Acquisition calcium sulfate crystal whiskers filter residue process water is repeatedly rinsed, to the pH value of its wash filtrate reaches neutrality; By filter residue 70 DEG C of oven dry, obtain described calcium sulfate crystal whiskers.
Above-mentioned acid waste liquid and wash filtrate can also be recycled.Concrete way is: above-mentioned acid waste liquid and wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1, be that to be mixed with mass percent concentration with the volume ratio of 30:1 be 7.2% recovery diluted acid for the hydrochloric acid of 1:1 and nitric acid mixing acid again with volume ratio, return step 2) in use.
The photo of the XRD figure of the calcium sulfate crystal whiskers obtained in this example, outward appearance photo, opticmicroscope is as shown in Figure 19, Figure 20, Figure 21.The principal crystalline phase of prepared calcium sulfate crystal whiskers is dihydrate gypsum, and characteristic diffraction peak intensity is high, and peak type is sharp-pointed, good crystallinity; Calcium sulfate crystal whiskers exterior appearance is white whiskers matter, and length-to-diameter ratio is taken second place in example 6, diameter at 4 ~ 15 μm, length at 1008 ~ 2060 μm, length-to-diameter ratio 104 ~ 398.
Claims (6)
1., by a method for preparing calcium sulphate whiskers from ardealite, comprise step as follows:
1) phosphogypsum raw material crushing is got and grinding becomes granularity to be 20 ~ 600 object phosphogypsum powders;
2) by step 1) phosphogypsum powder and diluted acid be 10Kg/m by solid-to-liquid ratio
3~ 200Kg/m
3be placed in reactor to stir, reheat after dissolving and filter, obtain acid filtrate and filter residue respectively;
3) by step 2) acid filtrate carry out ripening, obtain the acid suspension liquid containing calcium sulfate crystal whiskers; This acid suspension liquid is filtered, obtains calcium sulfate crystal whiskers filter residue and acid waste liquid; Calcium sulfate crystal whiskers filter residue process water wherein rinses, and rinses pH value to wash filtrate for neutral, drier under-15 DEG C ~ 100 DEG C environment, obtains described calcium sulfate crystal whiskers.
2. method according to claim 1, is characterized in that: above-mentioned steps 2) diluted acid used, its mass percent concentration is 1.0% ~ 25.0%; The temperature of described heating for dissolving is 60 DEG C ~ 120 DEG C, and dissolution time is 0.5h ~ 8h.
3. method according to claim 2, is characterized in that: described diluted acid is dilute hydrochloric acid, dust technology or to reclaim in diluted acid at least a kind.
4. method according to claim 3, is characterized in that: the preparation steps of described recovery diluted acid is: A) described acid waste liquid and described wash filtrate are stirred into mixed solution with the volume ratio of 1:1 ~ 4:1; B) mixed solution is added hydrochloric acid or/and nitric acid is mixed with described recovery diluted acid for 10:1 ~ 40:1 by volume; The mass percent concentration of described recovery diluted acid is identical with the mass percent concentration of described dilute hydrochloric acid or described dust technology.
5. the method according to any one of claim 1-4, is characterized in that: step 3) described in ripening comprise cooling and Crystallizing treatment; Wherein, cooling is that the temperature of described acid filtrate is down to 10 DEG C ~ 40 DEG C; Crystallizing treatment separates out described calcium sulfate crystal whiskers with the reduction Step crystallization of described acid filtrate temperature, and its crystallization time is 2h ~ 24h.
6. method according to claim 5, is characterized in that: the thing of described calcium sulfate crystal whiskers is terra alba mutually, its diameter at 5 ~ 30 μm, length at 100 ~ 2000 μm, length-to-diameter ratio 10 ~ 400.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105332058A (en) * | 2015-11-06 | 2016-02-17 | 云南力达一矿物技术有限公司 | Method for preparing gypsum whiskers for papermaking from phosphogypsum under normal pressure in circulating dissolving method |
| CN105401219A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Normal pressure acidification method for preparing anhydrous calcium sulfate whiskers |
| CN106222748A (en) * | 2016-07-29 | 2016-12-14 | 西南科技大学 | A kind of continuous producing method of ultrafine gypsum |
| CN106480507A (en) * | 2016-11-15 | 2017-03-08 | 曲靖师范学院 | A kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker |
| CN106698497A (en) * | 2017-01-22 | 2017-05-24 | 武汉工程大学 | Method for preparing calcium sulfate from ardealite |
| CN107419335A (en) * | 2017-07-13 | 2017-12-01 | 湖北三宁化工股份有限公司 | The method that hydrochloric acid method Cycle-decomposition ardealite and phosphorus mine tailing prepare calcium sulfate crystal whiskers |
| CN107557870A (en) * | 2017-09-08 | 2018-01-09 | 云南磷化集团有限公司 | A kind of method with preparing calcium sulphate whiskers from ardealite |
| CN109666796A (en) * | 2018-09-05 | 2019-04-23 | 大连博融新材料有限公司 | It is a kind of containing in vanadium and the recovery method of slag |
| CN109909059A (en) * | 2019-03-18 | 2019-06-21 | 宁夏金瑞源工贸有限公司 | The beneficiation method of mud stone in a kind of separation gypsum |
| CN112499588A (en) * | 2020-12-15 | 2021-03-16 | 淮阴工学院 | Method for removing sulfuric acid in reactor for preparing chloroethane from sulfur dioxide-containing hydrochloric acid |
| CN113563644A (en) * | 2021-08-03 | 2021-10-29 | 刘炳利 | Core filling system for manufacturing phosphogypsum whiskers |
| CN115043619A (en) * | 2022-06-21 | 2022-09-13 | 宜都兴发化工有限公司 | Preparation method of self-gelling fiber composite material |
| CN115924952A (en) * | 2022-12-14 | 2023-04-07 | 西南科技大学 | Anhydrite powder, gypsum whisker and preparation method thereof |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105332058A (en) * | 2015-11-06 | 2016-02-17 | 云南力达一矿物技术有限公司 | Method for preparing gypsum whiskers for papermaking from phosphogypsum under normal pressure in circulating dissolving method |
| CN105332058B (en) * | 2015-11-06 | 2019-02-19 | 云南力达一矿物技术有限公司 | The method that dissolution method produces gypsum for paper whisker is recycled under ardealite normal pressure |
| CN105401219B (en) * | 2015-12-31 | 2018-03-20 | 中国科学院青海盐湖研究所 | A kind of method that normal pressure acidization prepares anhydrous calcium sulfate whisker |
| CN105401219A (en) * | 2015-12-31 | 2016-03-16 | 中国科学院青海盐湖研究所 | Normal pressure acidification method for preparing anhydrous calcium sulfate whiskers |
| CN106222748A (en) * | 2016-07-29 | 2016-12-14 | 西南科技大学 | A kind of continuous producing method of ultrafine gypsum |
| CN106480507A (en) * | 2016-11-15 | 2017-03-08 | 曲靖师范学院 | A kind of new technology of ardealite preparation low cost hemihydrate calcium sulfate crystal whisker |
| CN106698497A (en) * | 2017-01-22 | 2017-05-24 | 武汉工程大学 | Method for preparing calcium sulfate from ardealite |
| CN107419335A (en) * | 2017-07-13 | 2017-12-01 | 湖北三宁化工股份有限公司 | The method that hydrochloric acid method Cycle-decomposition ardealite and phosphorus mine tailing prepare calcium sulfate crystal whiskers |
| CN107557870A (en) * | 2017-09-08 | 2018-01-09 | 云南磷化集团有限公司 | A kind of method with preparing calcium sulphate whiskers from ardealite |
| CN109666796A (en) * | 2018-09-05 | 2019-04-23 | 大连博融新材料有限公司 | It is a kind of containing in vanadium and the recovery method of slag |
| CN109909059A (en) * | 2019-03-18 | 2019-06-21 | 宁夏金瑞源工贸有限公司 | The beneficiation method of mud stone in a kind of separation gypsum |
| CN109909059B (en) * | 2019-03-18 | 2020-11-10 | 宁夏金瑞源工贸有限公司 | Mineral processing method for separating mudstone from gypsum |
| CN112499588A (en) * | 2020-12-15 | 2021-03-16 | 淮阴工学院 | Method for removing sulfuric acid in reactor for preparing chloroethane from sulfur dioxide-containing hydrochloric acid |
| CN112499588B (en) * | 2020-12-15 | 2022-03-18 | 淮阴工学院 | Method for removing sulfuric acid in reactor for preparing chloroethane from sulfur dioxide-containing hydrochloric acid |
| CN113563644A (en) * | 2021-08-03 | 2021-10-29 | 刘炳利 | Core filling system for manufacturing phosphogypsum whiskers |
| CN115043619A (en) * | 2022-06-21 | 2022-09-13 | 宜都兴发化工有限公司 | Preparation method of self-gelling fiber composite material |
| CN115043619B (en) * | 2022-06-21 | 2023-09-12 | 宜都兴发化工有限公司 | Preparation method of self-gelling fiber composite material |
| CN115924952A (en) * | 2022-12-14 | 2023-04-07 | 西南科技大学 | Anhydrite powder, gypsum whisker and preparation method thereof |
| CN115924952B (en) * | 2022-12-14 | 2024-05-03 | 西南科技大学 | Anhydrite powder, gypsum whisker and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111188087A (en) | 2020-05-22 |
| CN111188087B (en) | 2021-10-26 |
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