CN104846440A - Method for preparing high-purity calcium sulfate dihydrate crystal whisker by using metallurgic flue gas desulfurization gypsum recrystallization process - Google Patents
Method for preparing high-purity calcium sulfate dihydrate crystal whisker by using metallurgic flue gas desulfurization gypsum recrystallization process Download PDFInfo
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Abstract
The invention discloses a method for preparing a high-purity calcium sulfate dihydrate crystal whisker by using a metallurgic flue gas desulfurization gypsum recrystallization process. The method comprises the steps of pickling metallurgic flue gas desulfurization gypsum to remove a small deal of calcium carbonate or calcium oxide and soluble impurities; dissolving the gypsum by using a salt-containing acid solution to obtain a product used as a raw material for preparing the high-purity calcium sulfate dihydrate crystal whisker; adding a medium crystal agent to control the controllable growth of a calcium sulfate crystal whisker to form a calcium sulfate crystal whisker with controllable length-to-diameter ratio and complete crystal appearance, filtering and drying to obtain the calcium sulfate dehydrate crystal whisker. The recycling of the high-added-value calcium sulfate crystal whisker prepared from the metallurgic flue gas desulfurization gypsum is realized under normal-pressure and mild conditions according to the recrystallization principle. The raw material adopted in the method is available, the production process condition is simple, the added value of the high-purity crystal whisker is high, and the produced calcium sulfate dihydrate crystal whisker has the characteristics of small diameter, high length-to-diameter ratio, complete and uniform appearance and stable performance, can be used as a reinforcing material to be applied to an additive for industries such as plastics, rubber, papermaking, ceramics and the like and has a wide application prospect.
Description
Technical field
The invention belongs to the technical field of calcium sulfate crystal whiskers in chemical field, relate to the method for a kind of metallurgical gas desulfuration gypsum recrystallization legal system for high-purity Dihydrate gypsum whiskers, under being specifically related to a kind of condition of normal pressure, utilize recrystallization technology to prepare the method for high-purity Dihydrate gypsum whiskers, the method provides new Industrialization Way for the resource utilization of this industrial by-products of metallurgical gas desulfuration gypsum.
Background technology
China has the abundant plaster of paris and industry by-product gypsum resource, 2013, national manufacture by-product gypsum desulfurated plaster 7,800 ten thousand tons, and comprehensive utilization ratio is about 72%, and by-product phosphogypsum about 6,000 ten thousand tons, comprehensive utilization ratio is less than 15%.The industry by-product gypsum of large volume production row is low due to utilization ratio, stores up in a large number and causes serious environmental pollution, constrain the Sustainable development of relevant industries.Along with environmental protection pressure increases, more and more obtain the support energetically of national policy and relevant enterprise with the demand of industry by-product gypsum exploitation high value added product, for this reason, the development of calcium sulfate crystal whiskers project provides good condition.
Calcium sulfate crystal whiskers (Calcium Sulfate Whisker, CSW), another name crystal whisker of gypsum, also known as gypsum fiber, white fluffy solid is threadiness or whiskers body under microscope, refer to the similar staple fibre of shape of single crystal form growth under certain condition must shape single crystal, due to the atomic structural arrangement high-sequential when crystallization, so that crystallization shape is close to complete, the theoretical strength that its intensity is good for close to valency between material atom.Mean diameter 1 μm ~ 4 μm, mean length 30 μm ~ 500 μm, length-to-diameter ratio 10 ~ 200.Be divided into anhydrous, Ban Shui and two water CSW 3 kinds, anhydrous and half water CSW has higher intensity and use value.Its main character is as follows: (1) has excellent mechanical property: its section mostly is sexangle, rhombus, trilateral or strip shape, be different from the circular cross section of glass fibre etc., considerably increase length-to-diameter ratio, the requirement increasing plastics, fire-proof board length-to-diameter ratio (30 ~ 100) can be met; Tensile strength is 5 ~ 10 times of glass fibre; Do not decompose softening when temperature raises, intensity is free of losses almost, can be applicable to fire-retardant material; Without fatigue effect, after being ground into powder, cut-out, intensity is not also suffered a loss.(2) there is good consistency, excellent smoothness and regenerability.(3) toxicity is low: compared with other whiskers, toxicity is minimum.(4) cost is low: calcium sulfate crystal whiskers internal price is 8 yuan/and kg ~ 16 yuan/kg, be only 1/300 ~ 1/200 of silicon carbide whisker.There is important purposes at building, medicine, plastics, rubber and field of environment protection, be more used as matrix material reinforcing component at present.
Existing calcium sulphate crystal whisker preparation method mainly contains two large classes: a class is directly produced by grinding gypsum raw mineral materials, it is simply direct that this method produces calcium sulfate crystal whiskers, cost is not high, but the quality of calcium sulfate whiskers produced is unstable, waste material is too much, quality is difficult to the requirement reaching high-end packing material, only can use in low side material; Another kind of is produced by chemical synthesis process, the calcium sulfate whiskers stability that this method is produced is better, quality can meet the requirement of high-end packing material, but production cost is higher, in addition because be produce with chemical synthesis process, more waste material, waste liquid and waste gas can be produced in process of production, larger detrimentally affect is produced to environment.
A kind of method that secondary crystal prepares ester exchange at phosphorus is mentioned in publication number CN103628142A, (1) primary crystallization is mentioned: take the phosphogypsum after oven dry in the method, the sulphuric acid soln that massfraction is 8% ~ 15% is added in the ratio of solid-to-liquid ratio 1:100, being placed in bath temperature is that the water-bath of 80 ~ 100 DEG C stirs, rotating speed 200r/min ~ 300r/min, after reaction 30min ~ 60min, filtered while hot, discard insoluble substance, filtrate is crystallisation by cooling at room temperature, after suction filtration, filter cake is terra alba, drying for standby, filtrate is recycled and reused for the primary crystallization of phosphogypsum.(2) secondary crystal: take the terra alba obtained in step (1), the sulphuric acid soln that massfraction is 10% ~ 25% is added in the ratio of solid-to-liquid ratio 1:100, and add 5% ~ 20% crystallization in motion agent magnesium salts, be placed in the water-bath stirring reaction that bath temperature is 80 DEG C ~ 100 DEG C, rotating speed 200r/min ~ 300r/min, after solid dissolves completely, constant temperature 30min ~ 60min, stop stirring and heating, make solution natural cooling crystallization in a water bath, obtain Dihydrate gypsum whiskers after suction filtration, filtrate is then cycled to used in dissolving terra alba; By Dihydrate gypsum whiskers washing to neutrality, dry anhydrous calcium sulfate whisker at 200 DEG C.
In crystal whisker of gypsum growth control, Tsing-Hua University CN103014869A discloses a kind of controllable method for preparing of ultra-fine high length-diameter ratio anhydrous calcium sulfate whisker, mentions and adds size controlling agent: any one in sodium stearate, Sodium dodecylbenzene sulfonate, polyacrylamide and carboxymethyl cellulose.Shanghai University CN103288118A discloses the method for industry by-product gypsum dissociation and crystalline growth calcium sulfate crystal whiskers, and by adding in oleic acid, silane coupling agent or magnesium chloride, one or more control whisker morphology growth.
In a word, forefathers have carried out a few thing in the raw material of calcium sulfate crystal whiskers, production technique, diameter of whiskers and cut to lengthen, the problems such as (diameter are comparatively thick, length is shorter, pattern is uneven) that has that processing condition are harsh or product morphology is not good enough, limit the progress of correlation technique, and with the metallurgical gas desulfuration gypsum containing a small amount of calcium carbonate for raw material production crystal whisker of gypsum has no report.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art, there is provided a kind of metallurgical gas desulfuration gypsum recrystallization legal system for the method for high-purity Dihydrate gypsum whiskers, the method solves the environmental problem that metallurgical gas desulfuration gypsum brings, for metallurgical gas desulfuration gypsum provides new application approach.
The technical solution used in the present invention is as follows:
Metallurgical gas desulfuration gypsum recrystallization legal system, for a method for high-purity Dihydrate gypsum whiskers, comprises the steps:
Step (1), desulfurated plaster removal of impurities: the metallurgical gas desulfuration terra alba containing calcium carbonate and/or calcium oxide is broken to after granularity is less than 80 orders, adds and be mixed with slurry containing 0.5mol/L ~ 5mol/L sulphuric acid soln, control slurry concentration 10wt% ~ 40wt%; Stirring reaction 1h ~ 4h at 60 DEG C ~ 90 DEG C, after question response completes, stratification, lower floor's parget water washing and filtering is 5 ~ 7 to filtrate pH, dry for standby;
The content of described metallurgical gas desulfuration gypsum terra alba is greater than 70wt%;
Step (2), desulfurated plaster dissolves: being add 0.5wt% ~ 5wt% inorganic salt in the solution of 0.5mol/L ~ 5mol/L containing acid concentration, obtain hydrochloric solution after mixing;
Join processing through step (1) gypsum obtained in hydrochloric solution, be mixed with the slurry of concentration 10wt% ~ 40wt%, stirring reaction 1h ~ 4h at 60 DEG C ~ 90 DEG C, after question response completes, filtered while hot, gets filtrate;
Step (3), whisker preparation: add medium crystallization agent in the filtrate that step (2) obtains, add-on is 0.01wt% ~ 5wt%, Tc is 20 DEG C ~ 50 DEG C, to be crystallized complete after, filter, in 80 DEG C of baking ovens, dry 12h, is Dihydrate gypsum whiskers.
Further preferably, the speed of step (1) and the stirring described in step (2) is 100r/min ~ 400r/min.
Further preferably, the supernatant liquor that step (1) stratification obtains is mixed with the solution that acid concentration is 0.5mol/L ~ 5mol/L, continues to recycle.
Further preferably, the acid solution described in step (2) is hydrochloric acid, nitric acid or sulphur aqueous acid.
Further preferably, the inorganic salt described in step (2) are the combination of any one or more of sodium-chlor, Repone K, zinc chloride, magnesium chloride, aluminum chloride, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, Tai-Ace S 150, sodium phosphate, potassiumphosphate, zinc phosphate, trimagnesium phosphate and aluminum phosphate.When for composition, the ratio between each component is arbitrary.
Further preferably, the filter cake that step (2) heat filtering obtains returns and joins in hydrochloric solution together with gypsum, continues circular treatment.
Further preferably, the medium crystallization agent described in step (3) is inorganic salt and/or organic additive; When for composition, the ratio between each component is arbitrary;
Wherein, inorganic salt are one or more combination in sodium-chlor, Repone K, zinc chloride, magnesium chloride, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, Tai-Ace S 150, sodium phosphate, potassiumphosphate, zinc phosphate, trimagnesium phosphate and aluminum phosphate; When for composition, the ratio between each component is arbitrary;
Organic additive is one or more the combination in cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, oleic acid and sodium oleate.When for composition, the ratio between each component is arbitrary.
Further, preferably, step (3) is filtered the filtrate obtained and is back in step (2), prepares and is configured to containing acid the solution that acid concentration is 0.5mol/L ~ 5mol/L, continue to recycle with acid.
compared with prior art, its beneficial effect is in the present invention:
First, the present invention's gypsum raw material used is for containing a small amount of calcium carbonate or calcium oxide metallurgical gas desulfuration gypsum, and pre-treatment acid used is sulfuric acid, not only removes soluble impurity, and is conducive to calcium carbonate or calcium oxide to be converted into calcium sulfate, improves calcium utilization;
Secondly, the metallurgical desulfurated plaster that the present invention is used, containing micro-metals, be conducive to accelerating gypsum dissolution and whisker conversion, whole process reaction is very fast, and efficiency is high, and energy consumption is low;
Again, hydrochloric solution can improve gypsum dissolution degree, interpolation medium crystallization agent simultaneously recrystallization produces the (growth of interpolation medium crystallization agent control calcium sulfate crystal whiskers of high-purity Dihydrate gypsum whiskers, the calcium sulfate crystal whiskers that length-to-diameter ratio is controlled to be formed, crystal morphology is complete), solve the environmental problem that metallurgical gas desulfuration gypsum brings, for metallurgical gas desulfuration gypsum provides new application approach;
Finally, the present invention can with the industry by-product gypsum of whiteness about 40%, calcium sulphate content about 70% for raw material, prepare lily high-purity Dihydrate gypsum whiskers product (purity >=98%), be conducive to the recycling of industry by-product gypsum and the product development of calcium sulfate crystal whiskers;
Calcium sulfate crystal whiskers prepared by the inventive method, sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm;
The present invention, under normal pressure mild conditions, utilizes recrystallization principle, realizes the recycling that metallurgical gas desulfuration gypsum prepares high added value Dihydrate gypsum whiskers, for desulfurated plaster provides the Industrialization Way of a high added value;
The present invention is raw materials used to be easy to get, and manufacturing condition is simple, and high-purity whisker added value is high, it is little that the Dihydrate gypsum whiskers produced has diameter, and length-to-diameter ratio is high, the feature of the complete all even stable performance of pattern, can be used as plastics, rubber, papermaking and ceramic industry additive, have a extensive future.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of metallurgical gas desulfuration gypsum recrystallization legal system of the present invention for high-purity Dihydrate gypsum whiskers;
Fig. 2 is embodiment of the present invention metallurgical gas desulfuration gypsum original appearance figure;
Fig. 3 is the high-purity Dihydrate gypsum whiskers appearing diagram of embodiment 2;
Fig. 4 is the SEM figure of the high-purity Dihydrate gypsum whiskers of embodiment 2.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by buying the conventional products obtained.
In the present invention, slurry concentration refers in slurries, the content of slurry gross dry weight.
The present invention is unless otherwise stated, the equal representation quality percentage composition of percentage sign.
The metallurgical gas desulfuration gypsum original appearance figure that the embodiment of the present invention uses as shown in Figure 2.
Embodiment 1
As shown in Figure 1, metallurgical gas desulfuration gypsum is crushed to after granularity is less than 80 orders, take 100.00g, then with prepare 1.0mol/L sulphuric acid soln in advance and join in 1000mL beaker simultaneously, stir 30min, a small amount of calcium carbonate and calcium oxide etc. is made to be converted into calcium sulfate, question response completely after (in slurry bubble-free after producing again stirring reaction 10min), be warming up to 60 DEG C, mixing speed 150r/min, reaction 2h, question response completely rear (layering of desulfurated plaster recrystallization), stratification, pour out supernatant liquor (filtrate 1) (recycling), lower floor's gypsum (filter cake 1) is through washing, suction filtration, for subsequent use after drying.
Take above-mentioned pickling, dried desulfurated plaster 50.00g, together be added in 1000mL flask with the hydrochloric acid soln containing 1.0wt% ammonium chloride of 500mL, 2mol/L, be immersed in 90 DEG C of waters bath with thermostatic control by 2/3rds with upper volume, constant temperature also stirs 2h, after having reacted, suction filtration while hot, filter cake 2 reusable edible, filtrate is transferred in 1000mL beaker, adds the MgCl of medium crystallization agent 0.5wt%
2in filtrate, be positioned over crystallisation by cooling 12h in 20 DEG C of waters bath with thermostatic control.Suction filtration, filtrate 2 reusable edible after crystallization completes, then by filter cake dry 12h in 80 DEG C of baking ovens, obtain high-purity Dihydrate gypsum whiskers product 18.5g.Sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm.
Embodiment 2
Filtrate 2 in embodiment 1 is reclaimed 500ml, join in 1000mL beaker with desulfurated plaster 50.0g after pickling simultaneously, be immersed in 90 DEG C of waters bath with thermostatic control by 2/3rds with upper volume, constant temperature also stirs 4h, after having reacted, suction filtration while hot, filter cake reusable edible, filtrate is transferred in 1000mL beaker, adds the MgCl of medium crystallization agent 0.5wt%
2in filtrate, be positioned over crystallisation by cooling 12h in 50 DEG C of waters bath with thermostatic control.Suction filtration, washing after crystallization completes, filtrate reusable edible, then by filter cake dry 12h in 80 DEG C of baking ovens, obtains high-purity Dihydrate gypsum whiskers product 16.2g, and as indicated at 3, SEM figure as shown in Figure 4 for its appearing diagram.Sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm.
Embodiment 3
Take embodiment 1 pickling, dried desulfurated plaster 50.00g, with 500mL, 2mol/L containing mixing salt (Al
2(SO
4)
31.0wt% and CaCl
2hydrochloric acid soln 4.0wt%) is together added in 1000mL flask, be immersed in 90 DEG C of waters bath with thermostatic control by 2/3rds with upper volume, constant temperature also stirs 1h, after having reacted, suction filtration while hot, filter cake reusable edible, filtrate is transferred in 1000mL beaker, adds mixing medium crystallization agent (containing 0.5wt%MgCl
2, 0.5wt% sodium oleate) in filtrate, be positioned over crystallisation by cooling 12h in 20 DEG C of waters bath with thermostatic control.Suction filtration, filtrate 2 reusable edible after crystallization completes, then by filter cake dry 12h in 80 DEG C of baking ovens, obtain high-purity Dihydrate gypsum whiskers product 22.6g.Sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm.
Embodiment 4
Filtrate 2 in embodiment 3 is reclaimed 500mL, join in 1000mL beaker with desulfurated plaster 50.0g after pickling simultaneously, be immersed in 90 DEG C of waters bath with thermostatic control by 2/3rds with upper volume, constant temperature also stirs 1h, after having reacted, suction filtration while hot, filter cake reusable edible, filtrate is transferred in 1000mL beaker, adds mixing medium crystallization agent (0.5wt%MgCl
2with oleic acid 0.1wt%) in filtrate, be positioned over crystallisation by cooling 12h in 20 DEG C of waters bath with thermostatic control.Suction filtration, washing after crystallization completes, filtrate reusable edible, then by filter cake dry 12h in 80 DEG C of baking ovens, obtains high-purity Dihydrate gypsum whiskers product 18.2g.Sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm.
Embodiment 5
Metallurgical gas desulfuration gypsum recrystallization legal system, for a method for high-purity Dihydrate gypsum whiskers, comprises the steps:
Step (1), desulfurated plaster removal of impurities: the metallurgical gas desulfuration terra alba containing calcium carbonate and/or calcium oxide is broken to after granularity is less than 80 orders, add in the solution containing 0.5mol/L sulfuric acid and be mixed with slurry (in slurry, bubble-free produces), control slurry concentration 10wt%; With the speed stirring reaction 1h of 100r/min at 60 DEG C, after question response completes, stratification, lower floor's gypsum washes rear filtration with water, and being washed to the filtered liquid pH after filtration is 5 ~ 6, dry for standby; The supernatant liquor obtained by stratification is mixed with the solution containing 0.5mol/L sulfuric acid, continues to recycle;
The content of described metallurgical gas desulfuration gypsum terra alba is greater than 70wt%;
Step (2), desulfurated plaster dissolves: being add 0.5wt% inorganic salt in the solution of 0.5mol/L containing acid concentration, obtain the acid solution of saliferous after mixing; Described acid solution is salt aqueous acid; Described inorganic salt are sodium-chlor.
Joining in the acid solution of saliferous by processing through step (1) gypsum obtained, being mixed with the slurry of concentration 10wt%, then at temperature is 60 DEG C with the speed stirring reaction 1h of 100r/min, after question response completes, heat filtering, gets filtrate; Filter cake returns and joins in the acid solution of saliferous together with gypsum, continues circular treatment.
Step (3), whisker preparation: add medium crystallization agent in the filtrate that step (2) obtains, add-on is 0.01wt%, crystallization control temperature 20 DEG C, to be crystallized complete after, filter, filter cake dry, be Dihydrate gypsum whiskers.Filtrate is back in step (2), is mixed with the solution containing 0.5mol/L hydrochloric acid with hydrochloric acid, continues to recycle.Described medium crystallization agent is cetyl trimethylammonium bromide.
Sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm.
Embodiment 6
Metallurgical gas desulfuration gypsum recrystallization legal system, for a method for high-purity Dihydrate gypsum whiskers, comprises the steps:
Step (1), desulfurated plaster removal of impurities: the metallurgical gas desulfuration terra alba containing calcium oxide is broken to after granularity is less than 80 orders, is added in the solution containing 5mol/L sulfuric acid and is mixed with slurry, control slurry concentration 40wt%; With the speed stirring reaction 4h of 400r/min at 90 DEG C, after question response completes, stratification, lower floor's gypsum washes with water and is filtered to filtrate pH is 6 ~ 7, dry for standby; The supernatant liquid obtained by stratification is mixed with the solution containing 5mol/L sulfuric acid, continues to recycle;
The content of described metallurgical gas desulfuration gypsum terra alba is greater than 70wt%;
Step (2), desulfurated plaster dissolves: be add 5wt% inorganic salt in the solution of 5mol/L in acid concentration, obtain hydrochloric solution after mixing; Acid solution is aqueous nitric acid; Described inorganic salt are the combination of magnesium chloride and Tai-Ace S 150, and the ratio between magnesium chloride and Tai-Ace S 150 does not do requirement.
Joining processing through step (1) gypsum obtained in hydrochloric solution, being mixed with the slurry that concentration is 40wt%, with the speed stirring reaction 4h of 400r/min at 90 DEG C, after question response completes, filtered while hot, gets filtrate; Filter cake returns and joins in hydrochloric solution together with gypsum, continues circular treatment.
Step (3), whisker preparation: add medium crystallization agent in the filtrate that step (2) obtains, add-on is 5wt%, and Tc is 50 DEG C, to be crystallized complete after, filter, filter cake dry, be Dihydrate gypsum whiskers.Filtrate is back in step (2), prepares containing 5mol/L nitre aqueous acid, continue to recycle with nitric acid.
Medium crystallization agent is the mixture in Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, oleic acid and sodium oleate, and Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, ratio between oleic acid and sodium oleate do not do requirement.
Sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm.
Embodiment 7
Metallurgical gas desulfuration gypsum recrystallization legal system, for a method for high-purity Dihydrate gypsum whiskers, comprises the steps:
Step (1), desulfurated plaster removal of impurities: the metallurgical gas desulfuration gypsum (the ratio no requirement (NR) of calcium carbonate and calcium oxide) containing calcium carbonate and calcium oxide is crushed to after granularity is less than 80 orders, add in the solution containing 2mol/L sulfuric acid and be mixed with slurry, control slurry concentration 20wt%; With the speed stirring reaction 3h of 200r/min at 70 DEG C, after question response completes, stratification, lower floor's gypsum washes with water and is filtered to filtrate pH when being 6, dry for standby; The supernatant liquor obtained by stratification is mixed with the solution containing 0.5mol/L sulfuric acid, continues to recycle;
The content of described metallurgical gas desulfuration gypsum terra alba is greater than 70wt%;
Step (2), desulfurated plaster dissolves: be add 2wt% inorganic salt in the solution of 3mol/L in acid concentration, obtain hydrochloric solution after mixing; Acid solution is aqueous sulfuric acid; Described inorganic salt are the combination of aluminum chloride, sodium sulfate and potassiumphosphate, and aluminum chloride, ratio between sodium sulfate and potassiumphosphate do not do requirement.
Joining processing through step (1) gypsum obtained in hydrochloric solution, being mixed with the slurry that concentration is 20wt%, with the speed stirring reaction 3h of 200r/min at 80 DEG C, after question response completes, filtered while hot, gets filtrate; Filter cake returns and joins in hydrochloric solution together with gypsum, continues circular treatment.
Step (3), whisker preparation: add medium crystallization agent in the filtrate that step (2) obtains, add-on is 3wt%, and Tc is 30 DEG C, to be crystallized complete after, filter, in 80 DEG C of baking ovens, dry 12h, is Dihydrate gypsum whiskers.Filtrate is back in step (2), is mixed with the solution containing 3mol/L sulfuric acid with sulfuric acid, continues to recycle.
Medium crystallization agent is the combination of zinc chloride and magnesium chloride, and concrete ratio does not do requirement.
Sulfate dihydrate calcium contents >=99.00%(wt%), whiteness is greater than 98%, diameter 1 μm ~ 4 μm, length 20 μm ~ 500 μm, length-to-diameter ratio 10 μm ~ 100 μm.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (8)
1. metallurgical gas desulfuration gypsum recrystallization legal system is for a method for high-purity Dihydrate gypsum whiskers, it is characterized in that, comprises the steps:
Step (1), desulfurated plaster removal of impurities: the metallurgical gas desulfuration terra alba containing calcium carbonate and/or calcium oxide is broken to after granularity is less than 80 orders, adds and be mixed with slurry containing 0.5mol/L ~ 5mol/L sulphuric acid soln, control slurry concentration 10wt% ~ 40wt%; Stirring reaction 1h ~ 4h at 60 DEG C ~ 90 DEG C, after question response completes, stratification, lower floor's gypsum washes with water and is filtered to filtrate pH when being 5 ~ 7, dry for standby;
The content of described metallurgical gas desulfuration gypsum terra alba is greater than 70wt%;
Step (2), desulfurated plaster dissolves: be add 0.5wt% ~ 5wt% inorganic salt in the solution of 0.5mol/L ~ 5mol/L in acid concentration, obtain hydrochloric solution after mixing;
Join processing through step (1) gypsum obtained in hydrochloric solution, be mixed with the slurry of concentration 10wt% ~ 40wt%, stirring reaction 1h ~ 4h at 60 DEG C ~ 90 DEG C, after question response completes, filtered while hot, gets filtrate;
Step (3), whisker preparation: add medium crystallization agent in the filtrate that step (2) obtains, add-on is 0.01wt% ~ 5wt%, Tc is 20 DEG C ~ 50 DEG C, to be crystallized complete after, filter, filter cake is dry 12h in 80 DEG C of baking ovens, is Dihydrate gypsum whiskers.
2. metallurgical gas desulfuration gypsum recrystallization legal system according to claim 1 is for the method for high-purity Dihydrate gypsum whiskers, it is characterized in that, step (1) and the stirring velocity described in step (2) are 100r/min ~ 400r/min.
3. metallurgical gas desulfuration gypsum recrystallization legal system according to claim 1 is for the method for high-purity Dihydrate gypsum whiskers, it is characterized in that, the supernatant liquor that step (1) stratification obtains is mixed with the solution that acid concentration is 0.5mol/L ~ 5mol/L, continues to recycle.
4. metallurgical gas desulfuration gypsum recrystallization legal system according to claim 1 is for the method for high-purity Dihydrate gypsum whiskers, it is characterized in that, the acid solution described in step (2) is hydrochloric acid, nitric acid or sulphur aqueous acid.
5. metallurgical gas desulfuration gypsum recrystallization legal system according to claim 1 is for the method for high-purity Dihydrate gypsum whiskers, it is characterized in that, the inorganic salt described in step (2) are the combination of any one or more of sodium-chlor, Repone K, zinc chloride, magnesium chloride, aluminum chloride, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, Tai-Ace S 150, sodium phosphate, potassiumphosphate, zinc phosphate, trimagnesium phosphate and aluminum phosphate.
6. metallurgical gas desulfuration gypsum recrystallization legal system according to claim 1 is for the method for high-purity Dihydrate gypsum whiskers, it is characterized in that, the filter cake that step (2) filtered while hot obtains returns and joins in hydrochloric solution together with gypsum, continues circular treatment.
7. metallurgical gas desulfuration gypsum recrystallization legal system according to claim 1 is for the method for high-purity Dihydrate gypsum whiskers, it is characterized in that, the medium crystallization agent described in step (3) is inorganic salt and/or organic additive;
Wherein, inorganic salt are one or more combination in sodium-chlor, Repone K, zinc chloride, magnesium chloride, sodium sulfate, potassium sulfate, zinc sulfate, magnesium sulfate, Tai-Ace S 150, sodium phosphate, potassiumphosphate, zinc phosphate, trimagnesium phosphate and aluminum phosphate;
Organic additive is one or more the combination in cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate, oleic acid and sodium oleate.
8. metallurgical gas desulfuration gypsum recrystallization legal system according to claim 1 is for the method for high-purity Dihydrate gypsum whiskers, it is characterized in that, step (3) is filtered the filtrate obtained and is back in step (2), is mixed with the solution that acid concentration is 0.5mol/L ~ 5mol/L, continues to recycle.
Priority Applications (1)
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| CN105671627A (en) * | 2016-03-31 | 2016-06-15 | 武汉理工大学 | Method for preparing high-purity dihydrate gypsum whiskers by using industrial byproduct calcium chloride |
| CN105664692A (en) * | 2016-01-11 | 2016-06-15 | 青岛科技大学 | Method for deep removal of SO2 from flue gas by calcium-magnesium fusion technique and co-production of gypsum whisker |
| CN105819485A (en) * | 2016-03-29 | 2016-08-03 | 云南华联锌铟股份有限公司 | Method and device for producing gypsum from zinc smelting acid-containing solution |
| CN106044827A (en) * | 2016-07-12 | 2016-10-26 | 山东胜伟园林科技有限公司 | Impurity removing method for desulfurization gypsum of coal-fired power plant |
| CN106187379A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of preparation method of the porous desulfurated plaster for alkaline land improving |
| CN106186029A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of inorganic modified method of the desulfurated plaster for alkaline land improving |
| CN106186030A (en) * | 2016-07-11 | 2016-12-07 | 山东胜伟园林科技有限公司 | The preparation method of a kind of desulfurated plaster and in the application of saline-alkali land vegetation plantation |
| CN106190148A (en) * | 2016-07-12 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of manufacture method of the desulfurated plaster in efficient improvement salt-soda soil |
| CN106801259A (en) * | 2017-01-17 | 2017-06-06 | 辽宁工程技术大学 | A kind of method that mechanical force activating desulfurated plaster prepares calcium sulfate crystal whiskers |
| CN107254710A (en) * | 2017-07-13 | 2017-10-17 | 湘潭大学 | A kind of preparation method of the calcium sulfate crystal whiskers of low unit weight |
| 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 |
| CN109706526A (en) * | 2019-03-14 | 2019-05-03 | 江苏一夫科技股份有限公司 | It is a kind of to prepare Dihydrate gypsum whiskers, the method for hemihydrate calcium sulfate crystal whisker and product as made from it |
| WO2020199350A1 (en) * | 2019-03-30 | 2020-10-08 | 厦门大学 | High-performance calcium sulfate whisker material and preparation process therefor |
| CN111778560A (en) * | 2019-04-04 | 2020-10-16 | 西南科技大学 | Controllable preparation method of nano anhydrous calcium sulfate fiber |
| CN112342624A (en) * | 2020-10-26 | 2021-02-09 | 西华大学 | Preparation method of alpha calcium sulfate hemihydrate crystal whisker |
| CN112760716A (en) * | 2021-01-15 | 2021-05-07 | 海南蓝岛环保产业股份有限公司 | Phosphorus-containing desulfurized gypsum recycling treatment method |
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| CN105664692B (en) * | 2016-01-11 | 2018-12-04 | 青岛科技大学 | SO in flue gas is removed in depth in a kind of calcium and magnesium fusion method2The method of coproduction crystal whisker of gypsum |
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| CN105671627A (en) * | 2016-03-31 | 2016-06-15 | 武汉理工大学 | Method for preparing high-purity dihydrate gypsum whiskers by using industrial byproduct calcium chloride |
| CN106186029B (en) * | 2016-07-11 | 2018-03-13 | 山东胜伟园林科技有限公司 | A kind of inorganic modified method of desulfurated plaster for alkaline land improving |
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| CN106044827A (en) * | 2016-07-12 | 2016-10-26 | 山东胜伟园林科技有限公司 | Impurity removing method for desulfurization gypsum of coal-fired power plant |
| CN106190148A (en) * | 2016-07-12 | 2016-12-07 | 山东胜伟园林科技有限公司 | A kind of manufacture method of the desulfurated plaster in efficient improvement salt-soda soil |
| CN106801259A (en) * | 2017-01-17 | 2017-06-06 | 辽宁工程技术大学 | A kind of method that mechanical force activating desulfurated plaster prepares calcium sulfate crystal whiskers |
| CN107254710B (en) * | 2017-07-13 | 2019-09-17 | 湘潭大学 | A kind of preparation method of the calcium sulfate crystal whiskers of low bulk density |
| CN107254710A (en) * | 2017-07-13 | 2017-10-17 | 湘潭大学 | A kind of preparation method of the calcium sulfate crystal whiskers of low unit weight |
| 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 |
| CN109706526A (en) * | 2019-03-14 | 2019-05-03 | 江苏一夫科技股份有限公司 | It is a kind of to prepare Dihydrate gypsum whiskers, the method for hemihydrate calcium sulfate crystal whisker and product as made from it |
| WO2020199350A1 (en) * | 2019-03-30 | 2020-10-08 | 厦门大学 | High-performance calcium sulfate whisker material and preparation process therefor |
| CN111778560A (en) * | 2019-04-04 | 2020-10-16 | 西南科技大学 | Controllable preparation method of nano anhydrous calcium sulfate fiber |
| CN112342624A (en) * | 2020-10-26 | 2021-02-09 | 西华大学 | Preparation method of alpha calcium sulfate hemihydrate crystal whisker |
| CN112342624B (en) * | 2020-10-26 | 2021-08-10 | 西华大学 | Preparation method of alpha calcium sulfate hemihydrate crystal whisker |
| CN112760716A (en) * | 2021-01-15 | 2021-05-07 | 海南蓝岛环保产业股份有限公司 | Phosphorus-containing desulfurized gypsum recycling treatment method |
| CN112760716B (en) * | 2021-01-15 | 2024-05-24 | 海南蓝岛环保产业股份有限公司 | Recycling treatment method of phosphogypsum |
| CN113235134A (en) * | 2021-04-20 | 2021-08-10 | 昆明冶金研究院有限公司 | Method for separating fluorine and chlorine from zinc sulfate solution and recycling zinc sulfate solution and application of method |
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Address after: 650031 No. 86 Yuantong North Road, Yunnan, Kunming Patentee after: Kunming Metallurgical Research Institute Co., Ltd Address before: 650031, 86 North Tong Road, Wuhua District, Yunnan, Kunming Patentee before: Kunming Metallurgical Research Institute |