CN103395816A - Process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle - Google Patents
Process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle Download PDFInfo
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- CN103395816A CN103395816A CN2013103077231A CN201310307723A CN103395816A CN 103395816 A CN103395816 A CN 103395816A CN 2013103077231 A CN2013103077231 A CN 2013103077231A CN 201310307723 A CN201310307723 A CN 201310307723A CN 103395816 A CN103395816 A CN 103395816A
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Abstract
The invention relates to a process for producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle, and belongs to the technical field of waste liquor treatment in aramid fiber II production. The process comprises the following steps of: acid pickle pretreating, feeding, reacting and crystallizing, thickening, filtering, precipitating and the like. According to the invention, a problem that a process for treating acid pickle to recycle byproduct calcium sulphate dihydrate in the prior art cannot be directly used for treating the acid pickle generated in an aramid fiber II spinning process to recycle the byproduct calcium sulphate dihydrate due to different fields and different treated acid pickle is solved. The process for continuously producing calcium sulphate dihydrate by utilizing aramid fiber II spinning acid pickle, provided by the invention, can be used for treating the acid pickle generated in the aramid fiber II spinning to efficiently produce calcium sulphate with high quality.
Description
Technical field
The present invention relates to the technique of liquid waste disposal and recycling in a kind of aramid II, more particularly, the present invention relates to a kind of technique of utilizing the aramid II spent acid solution to produce terra alba, belong to aramid II produce in the liquid waste disposal technique field.
Background technology
PPTA (PPTA) fiber is the very wide special fibre material of application prospect that 20 century 70s grow up, because it has high strength, high-modulus, resistant to elevated temperatures excellent properties, at space flight, aviation, communication field, be applied widely, in national defense construction and the development of the national economy, occupy an important position, have far-reaching influence and meaning.
In the production of aramid II, in last spinning process, need to use acid bath, can produce discarded dilute sulfuric acid solution, wherein for bearing of Waste acid treating device, process the task of 50000 tons of the useless dilution heat of sulfuric acid of annual 8% left and right.Because dilute sulphuric acid directly discharges the severe contamination local environment, must after governance for reaching standard, just can discharge, general treatment process, such as neutralization or concentrated, cost is higher, and less than the high byproduct of economic worth, produce, for rationally administering and utilize this part spent acid resource, anxious to be studied go out a kind of can the low-cost processes spent acid and can produce the spent acid treatment process of high value byproduct.
Terra alba, i.e. gypsum, medium-to-high grade calcium sulfate is mainly used in the fields such as food, medicine, chemical industry, paint, beer fermentation, cement, edible mushrooms, granulation of fertilizer, foodstuff additive, chemical industry stopping composition.And the spent acid solution in the production technique of aramid II just can be used for the remanufacture terra alba, improves salvage value, produces extra economic worth.
It is CN102275970A that State Intellectual Property Office discloses a publication number in 2011.12.14, and name is called the patent of invention of " titanium white waste acid wastewater utilization method ", and this patent discloses a kind of titanium white waste acid wastewater utilization method, belongs to field of metallurgy.The inventive method is to solve the technical problem that can not low-cost take full advantage of titanium white waste acid waste water in prior art.Titanium white waste acid wastewater utilization method comprises the following steps: a, in hydrochloric acid soln, add Wingdale, fully reaction obtains calcium chloride solution; B, in calcium chloride solution, add titanium white waste acid or waste water, fully after reaction, filter to obtain terra alba and filtrate, described terra alba drying is processed and is obtained the product gypsum; C, using step b gained filtrate as the raw material of producing calcium chloride solution and Wingdale reaction, after repeating step a and b are once above, in step b gained filtrate, add sodium hydroxide solution, fully after reaction, filter the throw out that obtains sodium chloride solution and be rich in iron, titanium, vanadium, scandium and gallium.The inventive method is with low cost, can solve the problem of titanium white waste acid and waste water environmental pollution, has good promotion prospect.
In above-mentioned patent, put down in writing in the titanium white production field, mainly adopted Titanium White Production By Sulfuric Acid Process, the spent acid that Titanium White Production By Sulfuric Acid Process produces is referred to as titanium white waste acid, and the essential substance of titanium white waste acid consists of: sulfuric acid, iron, titanium, vanadium, scandium and gallium.And in the spinning process of aramid II, the spent acid solution that its acid bath produces mainly contains: content is 6～10% sulfuric acid; A small amount of oligopolymer and fracture of wire; The silicone oil of trace and iron, sodium, nickel ion; All the other are water.Although in prior art, there is the sulfuric acid that utilizes in spent acid solution to prepare the technique of terra alba, but its technical field, composition in waste liquid and treatment process are not identical, can not be directly used in the spent acid solution that produces in the aramid II spinning process and process, and can't high quality, efficient, continuous by-product terra alba.
Summary of the invention
The present invention is intended to solve spent acid solution of the prior art and processes the technique that reclaims the by-product terra alba, due to the field difference, the spent acid solution difference of processing, can not be directly used in the spent acid solution that produces in the aramid II spinning process and process the problem that reclaims the by-product terra alba, a kind of technique of utilizing the aramid II spent acid solution to produce continuously terra alba is provided, can be for the spent acid solution of aramid II spinning generation, process, high quality, produce terra alba efficiently, refuse reclamation not only, and can produce the product that economic worth is higher.
In order to realize the foregoing invention purpose, its concrete technical scheme is as follows:
A kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba is characterized in that: comprise following processing step:
A, spent acid solution pre-treatment
Aramid II spinning spent acid solution is filtered by strainer, then pass through surge tank, control the sulfuric acid concentration fluctuation range in described aramid II spinning spent acid solution;
B, charging
To in steps A, through pretreated aramid II spinning spent acid solution, add in the reactive crystallization device, simultaneously in the reactive crystallization device, add calcium carbonate slurry, sulfuric acid and the mol ratio between the calcium carbonate in coarse whiting in the pretreated aramid II spinning of described process spent acid solution are 1.02～1.12:1;
C, reactive crystallization
The mixing speed of controlling the reactive crystallization device is 150～200r/min, and the adjusting process water flow velocity is 2～6m3/h, makes, through pretreated aramid II spinning spent acid solution and calcium carbonate slurry reactive crystallization, to obtain the reactive crystallization slurry;
D, dense
The reactive crystallization slurry that step C is obtained passes in dense device, carries out solid-liquid separation, improves the mass concentration of terra alba in the reactive crystallization slurry;
E, filtration
Reactive crystallization slurry through dense device in step D is passed into to vacuum band-type filter machine, filter;
F, precipitation
To input to through the slurry that filters the settling tank precipitation, solid and liquid separation, the parting liquid that obtains and precipitation, precipitation is product terra alba of the present invention.
Preferably, the present invention is in steps A, and the precision of described strainer is 150～250 orders.
Preferably, the present invention is in steps A, and the volume of described surge tank is 8～12 times that described aramid II spinning spent acid solution per hour produces volume.
Preferably, the present invention is in step B, and the coarse whiting mass percent in described calcium carbonate slurry is 8～10%, and wherein the coarse whiting granularity is 150～200 orders, CaCO
3Content>=95%, whiteness>=93%.
Preferably, the present invention is in step D, and in described raising reactive crystallization slurry, the mass concentration of terra alba refers to the mass concentration of terra alba in the reactive crystallization slurry is brought up to 35～45%.
Preferably, the present invention in step e, the vacuum degree control of described vacuum band-type filter machine is-0.06～-0.08MPa, the water content of the reactive crystallization slurry that filters through vacuum band-type filter machine is controlled to be≤22%, whiteness >=85%.
Preferably, the technique of aramid II spinning spent acid solution production terra alba of utilizing of the present invention is in first cycle, after step F obtained terra alba by precipitation, the parting liquid part reuse that obtains was to reactive crystallization, dense and filtration step, and another part is for preparing calcium carbonate slurry.
Further, described settling tank is communicated with by two paths with described reactive crystallization device, forms inner cycle channel.
Further, the process water overflow in described dense device is to vacuum band-type filter machine and settling tank.
The useful technique effect that the present invention brings:
1, the invention solves spent acid solution of the prior art and process the technique that reclaims the by-product terra alba, due to the field difference, the spent acid solution difference of processing, can not be directly used in the spent acid solution that produces in the aramid II spinning process and process the problem that reclaims the by-product terra alba, a kind of technique of utilizing the aramid II spent acid solution to produce continuously terra alba is provided, can be for the spent acid solution of aramid II spinning generation, process, high quality, produce terra alba efficiently, refuse reclamation not only, and can produce the product that economic worth is higher.The useless diluted acid that the improvement aramid fiber of economical rationality is a large amount of.The method flow process is shorter, and equipment investment is less, and is simple to operate, is convenient to control, and turns waste into wealth, and reduces the environmental protection treatment cost, and energy consumption is lower.The present invention, in the step of charging and reaction, can make reaction carry out continuously and evenly by controlling suitable stirring velocity and process water flow velocity, and be conducive to growing up of crystal grain, is beneficial to reaction and carries out continuously, and the calcium carbonate residual volume increases.So, by controlling inlet amount, stirring velocity and process water flow velocity, being controlled the reaction times is 2～3 hours, and the crystallization control granularity is at 0.1～0.4mm, thereby greatly improved the quality quantity of production efficiency and the finished product, pH value when the control of above-mentioned inlet amount can also be controlled reaction is 6～8, improves the utilization ratio of the acid in spent acid, has improved the rate of recovery and the quality of product.
2, the present invention is preferred, and the precision of the strainer in steps A is 150～250 orders, can effectively remove oligopolymer and fracture of wire; The present invention is preferred, and in steps A, the volume of described surge tank is 8～12 times that described aramid II spinning spent acid solution per hour produces volume.The selection of the proportionlity between the volume that above-mentioned surge tank solvent and spent acid solution per hour produce can be controlled the often concentration difference between adjacent two hours<5% of described aramid II spinning spent acid solution, can effectively prevent the big ups and downs of spent acid solution concentration; And select surge tank little to the stable input of concentration maintenance, without adding power and other raw material.
4, the present invention is preferred, and in step B, the coarse whiting mass percent in described calcium carbonate slurry is 8～10%, and wherein the coarse whiting granularity is 150～200 orders, CaCO
3Content>=95%, whiteness>=93%, and in the reactive crystallization device, pH is 6～8.Above-mentioned selection for pH in coarse whiting raw material standard and reactive crystallization device is conducive to carrying out smoothly of subsequent reactions crystallization.Wherein the selection of granularity can prevent coarse whiting raw material surface attachment reaction thing, stops to react and carries out; The selection of calcium carbonate slurry concentration both had been beneficial to preparation and had carried, and was not easy precipitation and stopped up, and can not waste power again, had reduced cost.
5, the present invention is preferred, after technique completes one-period, parting liquid in settling tank carries out recycle, and a part is back to reactive crystallization, dense and filtration step as process water and washing water, and another part is for preparing calcium carbonate slurry, can not re-use migrant worker's industry water like this, turn waste into wealth, reduce the environmental protection treatment cost, energy consumption is lower, realize continuous online recycling spent acid, produced terra alba; And the outer displacement mass after precipitation is stable, and the pH value is neutral, and other index all reaches the sewage discharge national grade ii standard.
Embodiment
Embodiment 1
A kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba comprises following processing step:
A, spent acid solution pre-treatment
Aramid II spinning spent acid solution is filtered by strainer, then pass through surge tank, control the sulfuric acid concentration fluctuation range in described aramid II spinning spent acid solution;
B, charging
To in steps A, through pretreated aramid II spinning spent acid solution, add in the reactive crystallization device, simultaneously in the reactive crystallization device, add calcium carbonate slurry, sulfuric acid and the mol ratio between the calcium carbonate in coarse whiting in the pretreated aramid II spinning of described process spent acid solution are 1.02:1;
C, reactive crystallization
The mixing speed of controlling the reactive crystallization device is 150r/min, and the adjusting process water flow velocity is 2m3/h, makes, through pretreated aramid II spinning spent acid solution and calcium carbonate slurry reactive crystallization, to obtain the reactive crystallization slurry;
D, dense
The reactive crystallization slurry that step C is obtained passes in dense device, carries out solid-liquid separation, improves the mass concentration of terra alba in the reactive crystallization slurry;
E, filtration
Reactive crystallization slurry through dense device in step D is passed into to vacuum band-type filter machine, filter;
F, precipitation
To input to through the slurry that filters the settling tank precipitation, solid and liquid separation, the parting liquid that obtains and precipitation, precipitation is product terra alba of the present invention.
Embodiment 2
A kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba comprises following processing step:
A, spent acid solution pre-treatment
Aramid II spinning spent acid solution is filtered by strainer, then pass through surge tank, control the sulfuric acid concentration fluctuation range in described aramid II spinning spent acid solution;
B, charging
To in steps A, through pretreated aramid II spinning spent acid solution, add in the reactive crystallization device, simultaneously in the reactive crystallization device, add calcium carbonate slurry, sulfuric acid and the mol ratio between the calcium carbonate in coarse whiting in the pretreated aramid II spinning of described process spent acid solution are 1.12:1;
C, reactive crystallization
The mixing speed of controlling the reactive crystallization device is 200r/min, and the adjusting process water flow velocity is 6m3/h, makes, through pretreated aramid II spinning spent acid solution and calcium carbonate slurry reactive crystallization, to obtain the reactive crystallization slurry;
D, dense
The reactive crystallization slurry that step C is obtained passes in dense device, carries out solid-liquid separation, improves the mass concentration of terra alba in the reactive crystallization slurry;
E, filtration
Reactive crystallization slurry through dense device in step D is passed into to vacuum band-type filter machine, filter;
F, precipitation
To input to through the slurry that filters the settling tank precipitation, solid and liquid separation, the parting liquid that obtains and precipitation, precipitation is product terra alba of the present invention.
Embodiment 3
A kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba comprises following processing step:
A, spent acid solution pre-treatment
Aramid II spinning spent acid solution is filtered by strainer, then pass through surge tank, control the sulfuric acid concentration fluctuation range in described aramid II spinning spent acid solution;
B, charging
To in steps A, through pretreated aramid II spinning spent acid solution, add in the reactive crystallization device, simultaneously in the reactive crystallization device, add calcium carbonate slurry, sulfuric acid and the mol ratio between the calcium carbonate in coarse whiting in the pretreated aramid II spinning of described process spent acid solution are 1.07:1;
C, reactive crystallization
The mixing speed of controlling the reactive crystallization device is 175r/min, and the adjusting process water flow velocity is 4m3/h, makes, through pretreated aramid II spinning spent acid solution and calcium carbonate slurry reactive crystallization, to obtain the reactive crystallization slurry;
D, dense
The reactive crystallization slurry that step C is obtained passes in dense device, carries out solid-liquid separation, improves the mass concentration of terra alba in the reactive crystallization slurry;
E, filtration
Reactive crystallization slurry through dense device in step D is passed into to vacuum band-type filter machine, filter;
F, precipitation
To input to through the slurry that filters the settling tank precipitation, solid and liquid separation, the parting liquid that obtains and precipitation, precipitation is product terra alba of the present invention.
Embodiment 4
A kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba comprises following processing step:
A, spent acid solution pre-treatment
Aramid II spinning spent acid solution is filtered by strainer, then pass through surge tank, control the sulfuric acid concentration fluctuation range in described aramid II spinning spent acid solution;
B, charging
To in steps A, through pretreated aramid II spinning spent acid solution, add in the reactive crystallization device, simultaneously in the reactive crystallization device, add calcium carbonate slurry, sulfuric acid and the mol ratio between the calcium carbonate in coarse whiting in the pretreated aramid II spinning of described process spent acid solution are 1.1:1;
C, reactive crystallization
The mixing speed of controlling the reactive crystallization device is 186r/min, and the adjusting process water flow velocity is 5m3/h, makes, through pretreated aramid II spinning spent acid solution and calcium carbonate slurry reactive crystallization, to obtain the reactive crystallization slurry;
D, dense
The reactive crystallization slurry that step C is obtained passes in dense device, carries out solid-liquid separation, improves the mass concentration of terra alba in the reactive crystallization slurry;
E, filtration
Reactive crystallization slurry through dense device in step D is passed into to vacuum band-type filter machine, filter;
F, precipitation
To input to through the slurry that filters the settling tank precipitation, solid and liquid separation, the parting liquid that obtains and precipitation, precipitation is product terra alba of the present invention.
Embodiment 5
On the basis of embodiment 1-4, preferred:
In steps A, the precision of described strainer is 150 orders.
In steps A, the volume of described surge tank is 8 times that described aramid II spinning spent acid solution per hour produces volume.
In step B, the coarse whiting mass percent in described calcium carbonate slurry is 8%, and wherein the coarse whiting granularity is 150 orders, CaCO
3Content is 95%, and whiteness is 93%.
In step D, in described raising reactive crystallization slurry, the mass concentration of terra alba refers to the mass concentration of terra alba in the reactive crystallization slurry is brought up to 35%.
In step e, the vacuum degree control of described vacuum band-type filter machine is-0.06MPa, and the water content of the reactive crystallization slurry that filters through vacuum band-type filter machine is controlled to be 5%, and whiteness is 85%.
Embodiment 6
On the basis of embodiment 1-4, preferred:
In steps A, the precision of described strainer is 250 orders.
In steps A, the volume of described surge tank is 12 times that described aramid II spinning spent acid solution per hour produces volume.
In step B, the coarse whiting mass percent in described calcium carbonate slurry is 10%, and wherein the coarse whiting granularity is 200 orders, CaCO
3Content is 99%, and whiteness is 98%.
In step D, in described raising reactive crystallization slurry, the mass concentration of terra alba refers to the mass concentration of terra alba in the reactive crystallization slurry is brought up to 45%.
In step e, the vacuum degree control of described vacuum band-type filter machine is-0.08MPa, and the water content of the reactive crystallization slurry that filters through vacuum band-type filter machine is controlled to be 22%, and whiteness is 95%.
Embodiment 7
On the basis of embodiment 1-4, preferred:
In steps A, the precision of described strainer is 200 orders.
In steps A, the volume of described surge tank is 10 times that described aramid II spinning spent acid solution per hour produces volume.
In step B, the coarse whiting mass percent in described calcium carbonate slurry is 9%, and wherein the coarse whiting granularity is 175 orders, CaCO
3Content is 97%, and whiteness is 95.5%.
In step D, in described raising reactive crystallization slurry, the mass concentration of terra alba refers to the mass concentration of terra alba in the reactive crystallization slurry is brought up to 40%.
In step e, the vacuum degree control of described vacuum band-type filter machine is-0.07MPa, and the water content of the reactive crystallization slurry that filters through vacuum band-type filter machine is controlled to be 13.5%, and whiteness is 90%.
Embodiment 8
On the basis of embodiment 1-4, preferred:
In steps A, the precision of described strainer is 210 orders.
In steps A, the volume of described surge tank is 9.5 times that described aramid II spinning spent acid solution per hour produces volume.
In step B, the coarse whiting mass percent in described calcium carbonate slurry is 8.5%, and wherein the coarse whiting granularity is 165 orders, CaCO
3Content is 98%, and whiteness is 96%.
In step D, in described raising reactive crystallization slurry, the mass concentration of terra alba refers to the mass concentration of terra alba in the reactive crystallization slurry is brought up to 42%.
In step e, the vacuum degree control of described vacuum band-type filter machine is-0.075MPa, and the water content of the reactive crystallization slurry that filters through vacuum band-type filter machine is controlled to be 17%, and whiteness is 88%.
Embodiment 9
On the basis of embodiment 1-8, preferred:
The described technique of aramid II spinning spent acid solution production terra alba of utilizing is in first cycle, after step F obtains terra alba by precipitation, the parting liquid part reuse that obtains is to reactive crystallization, dense and filtration step, and another part is for preparing calcium carbonate slurry.
Described settling tank is communicated with by two paths with described reactive crystallization device, forms inner cycle channel.
Process water overflow in described dense device is to vacuum band-type filter machine and settling tank.
In the method for above-mentioned utilization process water:
The process water flow velocity is under the condition of 2～6m3/h in meeting the reactive crystallization step, and the reactive crystallization device is 9～13m3/h by pipeline to the flow velocity of settling tank overflow; Simultaneously, dense device is all 2～3m3/h to the spillway discharge of vacuum band-type filter machine and settling tank.
Claims (9)
1. technique of utilizing aramid II spinning spent acid solution to produce terra alba is characterized in that: comprise following processing step:
A, spent acid solution pre-treatment
Aramid II spinning spent acid solution is filtered by strainer, then pass through surge tank, control the sulfuric acid concentration fluctuation range in described aramid II spinning spent acid solution;
B, charging
To in steps A, through pretreated aramid II spinning spent acid solution, add in the reactive crystallization device, simultaneously in the reactive crystallization device, add calcium carbonate slurry, sulfuric acid and the mol ratio between the calcium carbonate in coarse whiting in the pretreated aramid II spinning of described process spent acid solution are 1.02～1.12:1;
C, reactive crystallization
The mixing speed of controlling the reactive crystallization device is 150～200r/min, and the adjusting process water flow velocity is 2～6m3/h, makes, through pretreated aramid II spinning spent acid solution and calcium carbonate slurry reactive crystallization, to obtain the reactive crystallization slurry;
D, dense
The reactive crystallization slurry that step C is obtained passes in dense device, carries out solid-liquid separation, improves the mass concentration of terra alba in the reactive crystallization slurry;
E, filtration
Reactive crystallization slurry through dense device in step D is passed into to vacuum band-type filter machine, filter;
F, precipitation
To input to through the slurry that filters the settling tank precipitation, solid and liquid separation, the parting liquid that obtains and precipitation, precipitation is product terra alba of the present invention.
2. a kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba according to claim 1, it is characterized in that: in steps A, the precision of described strainer is 150～250 orders.
3. a kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba according to claim 1 and 2, it is characterized in that: in steps A, the volume of described surge tank is 8～12 times that described aramid II spinning spent acid solution per hour produces volume.
4. a kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba according to claim 1, it is characterized in that: in step B, the coarse whiting mass percent in described calcium carbonate slurry is 8～10%, and wherein the coarse whiting granularity is 150～200 orders, CaCO
3Content>=95%, whiteness>=93%.
5. a kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba according to claim 1, it is characterized in that: in step D, in described raising reactive crystallization slurry, the mass concentration of terra alba refers to the mass concentration of terra alba in the reactive crystallization slurry is brought up to 35～45%.
6. a kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba according to claim 1, it is characterized in that: in step e, the vacuum degree control of described vacuum band-type filter machine is-0.06～-0.08MPa, the water content of the reactive crystallization slurry that filters through vacuum band-type filter machine is controlled to be≤and 22%, whiteness >=85%.
7. a kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba according to claim 1, it is characterized in that: the described technique of aramid II spinning spent acid solution production terra alba of utilizing is in first cycle, after step F obtains terra alba by precipitation, the parting liquid part reuse that obtains is to reactive crystallization, dense and filtration step, and another part is for preparing calcium carbonate slurry.
8. a kind of technique of utilizing aramid II spinning spent acid solution to produce terra alba according to claim 7, it is characterized in that: described settling tank is communicated with by two paths with described reactive crystallization device, the formation inner cycle channel.
9. according to claim 7 or 8 described a kind of techniques of utilizing aramid II spinning spent acid solution to produce terra alba, it is characterized in that: the process water overflow in described dense device is to vacuum band-type filter machine and settling tank.
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Cited By (5)
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| CN103693670A (en) * | 2013-12-16 | 2014-04-02 | 乳源瑶族自治县东阳光化成箔有限公司 | Production method of calcium sulphate dehydrate and production device thereof |
| CN104016398A (en) * | 2014-06-23 | 2014-09-03 | 武善东 | Method of producing sulfate by using dilute sulphuric acid in industrial wastewater |
| CN109502625A (en) * | 2018-12-26 | 2019-03-22 | 蓝星（成都）新材料有限公司 | The technique that gypsum is prepared using acid pickle |
| CN111018382A (en) * | 2019-12-30 | 2020-04-17 | 中芳特纤股份有限公司 | Method for preparing high-strength gypsum by using para-aramid spinning waste acid and waste silk |
| CN111484062A (en) * | 2020-04-15 | 2020-08-04 | 江苏一夫科技股份有限公司 | Calcium sulfate dihydrate, preparation method and application thereof |
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