CN101367538A - Method for preparing calcium sulphate with sulfate containing bittern and calcium containing bittern - Google Patents
Method for preparing calcium sulphate with sulfate containing bittern and calcium containing bittern Download PDFInfo
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- CN101367538A CN101367538A CNA2008101521655A CN200810152165A CN101367538A CN 101367538 A CN101367538 A CN 101367538A CN A2008101521655 A CNA2008101521655 A CN A2008101521655A CN 200810152165 A CN200810152165 A CN 200810152165A CN 101367538 A CN101367538 A CN 101367538A
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- bittern water
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Abstract
The invention relates to a method for preparing the calcium sulfate with the sulfate-contained brine and the calcium-salt-contained brine; the two refined brines in a crystallization control reactor are uniformly and consecutively mixed with the cycling liquid inside a cycling lifting device to form dihydrate calcium sulfate crystal with large grain diameter; the dehydrate calcium sulfate crystal is centrifugally washed and dried to prepare the product of the high-purity dehydrate calcium sulfate. The flow rate of the refined sulfate-contained brine that is continuously added in a reaction crystallization barrel is determined according to the ratio between the flow rate of the refined sulfate-contained brine and the flow rate of the cycling liquid in the cycling lifting device in the reactor of 1:10 to 1:30. The flow rate of the refined calcium-salt-contained brine that is consecutively added is determined according to the mol ratio of 1:1 between the sulfate radical ion and the calcium ion in the refined sulfate-contained brine and the calcium-salt-contained brine.
Description
Technical field
The present invention relates to the preparation technique of calcium sulfate in the field of inorganic chemical engineering, particularly utilize sulfur acid bittern water and calcic bittern water to produce the method for calcium sulfate.
Background technology
Calcium sulfate (CaSO
42H
2O) have purposes widely, can be used as foodstuff additive, industrial stopping composition etc.Calcium sulfate (CaSO
42H
2O) be commonly called as terra alba (plaster stone), its production method mainly contains comminuting method, the precipitator method and phosphoric acid by wet process by-product method.Comminuting method is to adopt the plaster of paris to make through pulverizing, removal impurity, drying, and it contains purity and depends primarily on plaster of paris grade.It is raw material with calcium chloride, ammonium sulfate mainly that the precipitator method are produced, and generates the sulfate dihydrate calcium deposit by replacement(metathesis)reaction, produces through separating, washing.Phosphoric acid by wet process by-product method is to utilize that the sulfuric acid decomposing phosphate rock is made of stones to be got in the process phosphoric acid, by-product calcium sulfate, and the temperature of decomposing phosphate rock stone is in the time of 65～80 ℃, and by product is a terra alba.
At calcium sulfate (CaSO
42H
2O) in the production method, phosphoric acid by wet process by-product method can not the higher calcium sulfate product of production purity, its removal of impurities calcining can only be produced plaster of Paris.The higher terra alba (plaster stone) of production purity mainly adopts the comminuting method and the precipitator method, and comminuting method only could be produced when plaster of paris grade is higher.Traditional precipitator method are to be the higher terra alba of raw material production purity (plaster stone) with calcium chloride, ammonium sulfate, because raw material calcium chloride, ammonium sulfate price are higher, cause production cost higher.How to produce high-quality sulfate dihydrate calcium product cheaply, still be in the continuous exploratory development.
In salt manufacturing and other marine chemical industry production processes, the a large amount of sulfur acid bittern waters of by-product, for making full use of other chemical resources in the sulfur acid bittern water, the general bittern of calcium chloride or calcic bittern water and sulfur-bearing hydrochlorate that adopts mixes different substances together, and makes wherein sulfate radical and calcium ion generate calcium sulfate to remove sulfate radical wherein.Traditional bittern mixes different substances together technology, two kinds of feed liquids are intermittently mixed or simple mixed continuously, in mixing process, the calcium sulfate degree of supersaturation is very big, have at short notice on a large amount of tiny terra albas generations and the paddle and wall attached to reactor, the calcium sulfate dihydrate particles in the solution is also very tiny.Because calcium sulfate dihydrate particles is tiny, its surface and intergranular are carried a large amount of other soluble impurities secretly, and tiny terra alba is difficult to and liquid phase separation.It promptly is through repeatedly washing and centrifugation that tradition is mixed different substances together the terra alba that technology generates, and dried product does not still reach calcium sulfate in " foodstuff additive calcium sulfate (GB1892-2007) " (doing level) content greater than 98% requirement.Traditional bittern mixes different substances together the terra alba of technology institute by-product and also carries a large amount of potassium, sodium, magnesium ion secretly, if with above-mentioned terra alba calcined dehydration, the sodium oxide in the product, potassium oxide, content of magnesia do not reach the requirement of " plaster of Paris " new standard.
Therefore, traditional bittern mixes different substances together the terra alba of technology by-product, no matter as foodstuff additive or with its calcined dehydration as plaster of Paris, all do not reach the specification of quality of present related products.The terra alba of institute's by-product can only be stored up as waste residue, has not only wasted the calcium sulfate resource, goes back pollution on the environment.
Summary of the invention
The present invention is directed to present sulfur acid bittern water and calcic bittern water and mix different substances together the requirement that the terra alba of by-product does not reach the related products quality, release utilizes sulfur acid bittern water and calcic bittern water to produce the method for higher degree terra alba, by in the crystallization control reactor, carrying out the crystallization control reaction, prepare big particle diameter, high purity terra alba.
Described sulfur acid bittern water is meant the aqueous solution that contains two or more ions and sulfate ion in chlorion, sodium ion, potassium ion, the magnesium ion.Described calcic bittern water is meant the aqueous solution of calcium chloride or contains the mixed aqueous solution of Repone K, sodium-chlor, magnesium chloride and calcium chloride.
The operation of utilizing sulfur acid bittern water and calcic bittern water to produce the method for calcium sulfate involved in the present invention comprises: brine refining, crystallization control reaction, sedimentation, centrifuge washing, drying etc.
1, brine refining
With sulfur acid bittern water and the sedimentation in settling vessel respectively of calcic bittern water, remove the wherein insoluble impurities of larger particles, supernatant liquid must be made with extra care sulfur acid bittern water and refining calcic bittern water after filtration.In the treating process, sedimentation and filter and to carry out at normal temperatures, temperature range-10～40 ℃, filter type can adopt husky filter or filter press.
2, crystallization control reaction
Crystallization control is reflected in the crystallization control reactor and carries out, purified sulfur acid bittern water and calcic bittern water are joined in the reactive crystallization bucket of reactor continuously, the continuous uniform mixing of circulation fluid of two kinds of bittern and circularly enhancing device in the reactive crystallization bucket forms the terra alba crystallization of greater particle size.
Described crystallization control reactor outward appearance is funnel-form, and its housing is made of top cylinder and bottom cone.Lower housing portion cone awl bottom is provided with slag discharging device, near on the bottom cone conical surface of slag discharging device discharge gate is arranged.The upper outside of housing top cylinder has ring-type overflow circle, and the bottom of overflow circle is provided with overflow port.
Have in the crystallization control reactor and the co-axial reactive crystallization bucket of housing top cylinder.The reactive crystallization bucket is the open cylinder in bottom, and opening for feed is arranged at the top, and inside is provided with the circularly enhancing device.The circularly enhancing device is the mixing tank that has the turbine type paddle, and the turbine type paddle is arranged in the open elongated cylinder in bottom, can make the feed liquid that enters from reactive crystallization bucket bottom cyclic motion from bottom to top in bucket.
The process of crystallization control reaction is as follows:
Purified sulfur acid bittern water and calcic bittern water are added continuously from two opening for feeds in reactive crystallization bucket top respectively, two kinds of bittern drop to behind the reactive crystallization bucket bottom in the reactive crystallization bucket and the continuous uniform mixing of circulation fluid under the effect of circularly enhancing device, sulfate ion in the bittern and calcium ion form the terra alba crystallization of greater particle size in conjunction with growing on the terra alba crystal seed that forms calcium sulfate and carry in circulation fluid.
After the terra alba crystallization dropped to reactive crystallization bucket bottom, the short grained terra alba of part was thus lifted in the reactive crystallization bucket with circulation fluid, as the crystal seed of crystal of calcium sulfate.Some short grained terra alba rises with mother liquor between reactive crystallization bucket and housing in addition, and the formation overflow is finished liquid and flow to the overflow circle, enters down the sedimentation operation that goes on foot after overflow port is discharged.The tiny terra alba slurry of sedimentation operation can be answered back by the terra alba slurry at reactive crystallization bucket top and be joined continuously in the reactive crystallization bucket, also can be with its individual curing.The macrobead terra alba crystallization that drops to reactive crystallization bucket bottom falls to the reactor awl end, forms macrobead terra alba slurry.The mean particle size of the macrobead terra alba of bottom is at 0.1～0.3mm, and when solid-to-liquid ratio reached 20～35% in the macrobead terra alba slurry, macrobead terra alba slurry was discharged by the bottom discharging mouth.
The controlled variable of crystallization control reaction is: the flow of the refining sulfur acid bittern water that in the reactive crystallization bucket, adds continuously, determine in the ratio of circulating fluid flow rate than 1: 10～1: 30 of circularly enhancing device in refining sulfur acid bittern water flow and the reactor; The continuous flow of the refining calcic bittern water that adds is that 1: 1 ratio is determined in the mol ratio of sulfate ion and calcium ion in purified sulfate brine that adds and the refining calcic bittern water.Crystallization control reaction is carried out at normal temperatures, temperature range-10～40 ℃.
3, sedimentation
Finish liquid by the overflow that the crystallization control reactor overflow goes out, drain into settling vessel by the overflow port of crystallization control reactor, tiny terra alba wherein is settled down to the bottom of settling vessel, forms tiny terra alba slurry.Tiny terra alba slurry can be used as crystal seed and is answered back by the terra alba slurry at reactive crystallization bucket top and join continuously in the reactive crystallization bucket, also can the discharge system after individual curing.The clear liquid overflow on settling vessel upper strata is used as other Chemical Manufacture raw materials to clean solution tank.
4, centrifuge washing
Discharge macrobead terra alba slurry by the bottom discharging mouth and join in the whizzer, remove the mother liquor of wherein carrying secretly, obtain the macrobead terra alba.The macrobead terra alba adds the water agitator treating, must make with extra care the terra alba slurry.Refining terra alba stock pump is gone into centrifuge dewatering, and terra alba must wet.
5, drying
By the wet terra alba of centrifuge washing, dry in moisture eliminator, get the sulfate dihydrate calcium product.Can select rotating drum dryer, vibrated fluidized bed for use according to the industrial scale moisture eliminator, 100～105 ℃ of drying temperatures.
The present invention utilizes the physicochemical property of crystal of calcium sulfate, adopts the crystallization control technology to produce the sulfate dihydrate calcium product that granularity is big, purity is high.The characteristic of utilizing that calcium sulfate solubleness in the aqueous solution is lower, separating out with terra alba under the normal temperature, the mol ratio by sulfate radical and calcium ion in the control is fully separated out calcium sulfate, and produces the sulfate dihydrate calcium product; In the reactive crystallization bucket of crystallization control reactor, utilize the supersaturation of terra alba in two kinds of bittern mixing processes to be crystallization power, throughput ratio by controlling circulate soln three in refining sulfur acid bittern water, calcic bittern water and the crystallization control reactor and three's complete mixing flow stir, effectively reduce the degree of supersaturation of calcium sulfate in the reactive crystallization bucket, suppress the generation of too much terra alba nucleus, the terra alba crystallization is effectively increased.Along with the growth of terra alba crystalline, the amount of carrying secretly of its surface impurity ionic adsorptive capacity and mother liquor is effectively reduced, the purity of terra alba effectively improves.
Advantages such as it is simple that the present invention has technological process, and the product particle homogeneous quality is good.Be not subjected to polluting under the condition of (lead, arsenic, selenium, fluorine content are no more than the upper limit of tap water requirement in the bittern) at sulfur acid bittern water and calcic bittern water, adopt technology of the present invention, the median size of product terra alba is at 0.1～0.3mm, dry back calcium sulphate content (butt) can reach more than 98.0%, and other indexs also reach the requirement of GB1852-2007 foodstuff additive calcium sulfate.
Description of drawings
Fig. 1 produces the terra alba process flow sheet for sulfur acid bittern water and the calcic bittern water of utilizing of the present invention.
Fig. 2 is crystallization control structure of reactor figure involved in the present invention.
Description of symbols among the figure:
1, reactor shell 2, top cylinder
3, bottom cone 4, slag discharging device
5, discharge gate 6, circularly enhancing device
7, reactive crystallization bucket 8, overflow port
9, overflow circle 10, terra alba slurry are answered back
11, calcic bittern water import 12, the import of sulfur acid bittern water
Embodiment
Fig. 1 shows the structure of producing the crystallization control reactor that method adopted of calcium sulfate of the present invention.As shown in Figure 1, the housing 1 of crystallization control reactor is made of top cylinder 2 and bottom cone 3.The awl bottom of bottom cone 3 is provided with slag discharging device 4, near on the cone conical surface of slag discharging device 4 discharge gate 5 is arranged.The upper outside of top cylinder 2 has ring-type overflow circle 9, and the bottom of overflow circle 9 is provided with overflow port 8.Have in the crystallization control reactor and housing top cylinder 2 co-axial reactive crystallization buckets 7.Three opening for feeds are arranged at the top of reactive crystallization bucket 7, comprise that sulfur acid bittern water import 12, the import 11 of calcic bittern water and terra alba slurry answers back 10.The inside of reactive crystallization bucket 7 is provided with circularly enhancing device 6.Circularly enhancing device 6 is the mixing tanks that have the turbine type paddle, and the turbine type paddle is arranged in the open elongated cylinder in bottom, can make the feed liquid that enters from reactive crystallization bucket 7 bottoms cyclic motion from bottom to top in bucket.The cubic capacity of crystallization control reactor shown in Figure 1 is 25m
3, the volume of reactive crystallization bucket 7 is 8m
3, the circulation fluid of circularly enhancing device 6 promotes flow can be at 50～150m
3/ h regulates.
Fig. 2 produces the process flow sheet of the method for calcium sulfate for the present invention utilizes sulfur acid bittern water and calcic bittern water, illustrates that in conjunction with Fig. 2 and Fig. 1 the present invention produces the embodiment of calcium sulfate method.
Embodiment 1:
Get sulfur acid bittern water and calcic bittern water, at first adopt settling vessel that the part insolubles is removed in its sedimentation, and discharge by the settling vessel bottom.The upper phase of settling vessel overflow is pumped into plate-and-frame filter press, and liquid phase is refining sulfur acid bittern water and refining calcic bittern water.The chemical constitution that detects refining sulfur acid bittern water is: K
+13g/l, Na
+60.7g/l, Mg
2+51.74g/l, SO
4 2-64g/l, Cl
-175g/l; The chemical constitution of refining calcic bittern water is: K
+13g/l, Na
+60.7g/l, Ca
2+85.17g/l, Cl
-198.6g/l.
To carry out reactive crystallization in sedimentation purified sulfur acid bittern water and the calcic bittern water adding crystallization control reactor.
Earlier by SO in refining sulfur acid bittern water and the refining calcic bittern water
4 2-: Ca
2+1: 1 ratio of mol ratio, in the crystallization control reactor, add two kinds of bittern simultaneously continuously by the sulfur acid bittern water import 12 of reactive crystallization bucket 7 and calcic bittern water import 11.When the liquid level of the bittern in the crystallization control device surpasses circularly enhancing device 6 when suitable for reading, ON cycle lifting gear 6.It is 50m that the circulation fluid of Control Circulation lifting gear 6 promotes flow
3/ h.
Then, press 5m
3The flow of/h adds refining sulfur acid bittern water by sulfur acid bittern water import 12 continuously to the crystallization control reactor.Simultaneously, press 1.57m
3The flow of/h adds refining calcic bittern water (SO in refining sulfur acid bittern water and the refining calcic bittern water by calcic bittern water import 11 continuously to the crystallization control reactor
4 2-: Ca
2+Mol ratio be 1: 1).Crystallization control reactor feed temperature is-5 ℃.
Along with the continuous adding of refining sulfur acid bittern water and refining calcic bittern water, the overflow that contains parts of fine small-particle terra alba is finished liquid and is flow to overflow port 8 by the overflow circle 9 of crystallization control reactor, and flows out the crystallization control reactor, flow to settling vessel again.The tiny terra alba slurry that discharge settling vessel bottom is answered back by the terra alba slurry of crystallization control reactor as crystal seed and 10 is entered reactive crystallization bucket 7 continuously.
Along with the continuous adding of refining sulfur acid bittern water and refining calcic bittern water, the macrobead terra alba deposits to crystallization control reactor awl bottom.When solid-to-liquid ratio reaches 20% in the macrobead terra alba slurry, open the discharge valve of bottom discharging mouth 5, and start slag discharging device 4 discharge terra alba slurries.
The macrobead terra alba slurry of discharging joins and removes the mother liquor of carrying secretly in the whizzer, adds the water agitator treating again, pumps into centrifuge dewatering then, again through the dry sulfate dihydrate calcium product that gets of rotating drum dryer.100 ℃ of drying temperatures.
Analyzing and testing crystal of calcium sulfate product, median size 0.15mm, calcium sulphate content (butt) is 98.3%.
Embodiment 2:
Get sulfur acid bittern water and calcic bittern water, at first adopt settling vessel that the part insolubles is removed in its sedimentation, and discharge by the settling vessel bottom.The upper phase of settling vessel overflow is pumped into plate-and-frame filter press, and liquid phase is refining sulfur acid bittern water and refining calcic bittern water.The chemical constitution that detects refining sulfur acid bittern water is: K
+13g/l, Na
+60.7g/l, Mg
2+48.20g/l, SO
4 2-50g/l, Cl
-175g/l; The chemical constitution of refining calcic bittern water is: K
+13g/l, Na
+60.7g/l, Ca
2+60g/l, Cl
-180.46g/l.
To carry out reactive crystallization in sedimentation purified sulfur acid bittern water and the calcic bittern water adding crystallization control reactor.
Earlier by SO in refining sulfur acid bittern water and the refining calcic bittern water
4 2-: Ca
2+1: 1 ratio of mol ratio, in the crystallization control reactor, add two kinds of bittern simultaneously continuously by the sulfur acid bittern water import 12 of reactive crystallization bucket 7 and calcic bittern water import 11.When the liquid level of the bittern in the crystallization control device surpasses circularly enhancing device 6 when suitable for reading, ON cycle lifting gear 6.It is 90m that the circulation fluid of Control Circulation lifting gear 6 promotes flow
3/ h.
Then, press 6m
3The flow of/h adds refining sulfur acid bittern water by sulfur acid bittern water import 12 continuously to the crystallization control reactor.Simultaneously, press 2.08m
3The flow of/h adds refining calcic bittern water (SO in refining sulfur acid bittern water and the refining calcic bittern water by calcic bittern water import 11 continuously to the crystallization control reactor
4 2-: Ca
2+Mol ratio be 1: 1).Crystallization control reactor feed temperature is-5 ℃.
Along with the continuous adding of refining sulfur acid bittern water and refining calcic bittern water, the overflow that contains parts of fine small-particle terra alba is finished liquid and is flow to overflow port 8 by the overflow circle 9 of crystallization control reactor, and flows out the crystallization control reactor, flow to settling vessel again.The tiny terra alba slurry that discharge settling vessel bottom is answered back by the terra alba slurry of crystallization control reactor as crystal seed and 10 is entered reactive crystallization bucket 7 continuously.
Along with the continuous adding of refining sulfur acid bittern water and refining calcic bittern water, the macrobead terra alba deposits to crystallization control reactor awl bottom.When solid-to-liquid ratio reaches 25% in the macrobead terra alba slurry, open the discharge valve of bottom discharging mouth 5, and start slag discharging device 4 discharge terra alba slurries.
The macrobead terra alba slurry of discharging joins and removes the mother liquor of carrying secretly in the whizzer, adds the water agitator treating again, pumps into centrifuge dewatering then, again through the dry sulfate dihydrate calcium product that gets of rotating drum dryer.100 ℃ of drying temperatures.
Analyzing and testing crystal of calcium sulfate product, median size 0.18mm, calcium sulphate content (butt) is 98.5%.
Embodiment 3:
Get sulfur acid bittern water and calcic bittern water, at first adopt settling vessel that the part insolubles is removed in its sedimentation, and discharge by the settling vessel bottom.The upper phase of settling vessel overflow is pumped into plate-and-frame filter press, and liquid phase is refining sulfur acid bittern water and refining calcic bittern water.The chemical constitution that detects refining sulfur acid bittern water is: Na
+116.7g/l, SO
4 2-80g/l, Cl
-121.30g/l; The chemical constitution of refining calcic bittern water is: Na
+51.83g/l, Ca
2+85g/l, Cl
-230.66g/l.
To carry out reactive crystallization in sedimentation purified sulfur acid bittern water and the calcic bittern water adding crystallization control reactor.
Earlier by SO in refining sulfur acid bittern water and the refining calcic bittern water
4 2-: Ca
2+1: 1 ratio of mol ratio, in the crystallization control reactor, add two kinds of bittern simultaneously continuously by the sulfur acid bittern water import 12 of reactive crystallization bucket 7 and calcic bittern water import 11.When the liquid level of the bittern in the crystallization control device surpasses circularly enhancing device 6 when suitable for reading, ON cycle lifting gear 6.It is 120m that the circulation fluid of Control Circulation lifting gear 6 promotes flow
3/ h.
Then, by 7.5m
3The flow of/h adds refining sulfur acid bittern water by sulfur acid bittern water import 12 continuously to the crystallization control reactor.Simultaneously, press 2.94m
3The flow of/h adds refining calcic bittern water (SO in refining sulfur acid bittern water and the refining calcic bittern water by calcic bittern water import 11 continuously to the crystallization control reactor
4 2-: Ca
2+Mol ratio be 1: 1).Crystallization control reactor feed temperature is 25 ℃.
Along with the continuous adding of refining sulfur acid bittern water and refining calcic bittern water, the overflow that contains parts of fine small-particle terra alba is finished liquid and is flow to overflow port 8 by the overflow circle 9 of crystallization control reactor, and flows out the crystallization control reactor, flow to settling vessel again.The tiny terra alba slurry that discharge settling vessel bottom is answered back by the terra alba slurry of crystallization control reactor as crystal seed and 10 is entered reactive crystallization bucket 7 continuously.
Along with the continuous adding of refining sulfur acid bittern water and refining calcic bittern water, the macrobead terra alba deposits to crystallization control reactor awl bottom.When solid-to-liquid ratio reaches 30% in the macrobead terra alba slurry, open the discharge valve of bottom discharging mouth 5, and start slag discharging device 4 discharge terra alba slurries.
The macrobead terra alba slurry of discharging joins and removes the mother liquor of carrying secretly in the whizzer, adds the water agitator treating again, pumps into centrifuge dewatering then, again through the dry sulfate dihydrate calcium product that gets of rotating drum dryer.100 ℃ of drying temperatures.
Analyzing and testing crystal of calcium sulfate product, median size 0.25mm, calcium sulphate content (butt) is 98.6%.
Claims (6)
1. a method of utilizing sulfur acid bittern water and calcic bittern water to produce calcium sulfate is characterized in that, comprises brine refining, crystallization control reaction, sedimentation, centrifuge washing and drying process; The brine refining operation is with sulfur acid bittern water and the sedimentation in settling vessel respectively of calcic bittern water, filters supernatant liquid and must make with extra care sulfur acid bittern water and refining calcic bittern water; The crystallization control reaction process carries out in the crystallization control reactor, purified sulfur acid bittern water and calcic bittern water are joined in the reactive crystallization bucket of reactor continuously, the continuous uniform mixing of circulation fluid of two kinds of bittern and circularly enhancing device in the reactive crystallization bucket forms the terra alba crystallization of greater particle size; The sedimentation operation is that tiny terra alba sedimentation in the liquid is finished in the overflow that the crystallization control reactor overflow goes out, and forms tiny terra alba slurry; The centrifuge washing operation is crystallization control reactor bottom discharge gate to be discharged macrobead terra alba slurry join in the whizzer, removes mother liquor, adds the water agitator treating, reenters centrifuge dewatering, and terra alba must wet; Drying process is that wet terra alba is dry in moisture eliminator, gets the sulfate dihydrate calcium product.
2. according to claim 1 utilize sulfur acid bittern water and calcic bittern water produce calcium sulfate method, it is characterized in that, the flow of the refining sulfur acid bittern water that adds continuously in the reactive crystallization bucket is determined in the ratio of circulating fluid flow rate than 1: 10～1: 30 of circularly enhancing device in refining sulfur acid bittern water flow and the reactor.
3. according to claim 1 utilize sulfur acid bittern water and calcic bittern water produce calcium sulfate method, it is characterized in that, the continuous flow of the refining calcic bittern water that adds is that 1: 1 ratio is determined in the mol ratio of sulfate ion and calcium ion in POV bittern water that adds and the refining calcic bittern water.
4. according to claim 1 utilize sulfur acid bittern water and calcic bittern water produce calcium sulfate method, it is characterized in that crystallization control reaction is carried out at normal temperatures, temperature range-10～40 ℃.
5. according to claim 1 utilize sulfur acid bittern water and calcic bittern water produce calcium sulfate method, it is characterized in that 100～105 ℃ of the wet drying temperature of terra alba in moisture eliminator.
6. the applied crystallization control reactor of method of producing calcium sulfate according to claim 1, it is characterized in that, the housing of crystallization control reactor is made of top cylinder and bottom cone, lower housing portion cone awl bottom is provided with slag discharging device, near on the bottom cone conical surface of slag discharging device discharge gate is arranged, the upper outside of housing top cylinder has ring-type overflow circle, and the bottom of overflow circle is provided with overflow port; Have in the crystallization control reactor and the co-axial reactive crystallization bucket of housing top cylinder, the reactive crystallization bucket is the open cylinder in bottom, and opening for feed is arranged at the top, and inside is provided with the circularly enhancing device; The circularly enhancing device is the mixing tank that has the turbine type paddle, and the turbine type paddle is arranged in the open elongated cylinder in bottom, can make the feed liquid that enters from reactive crystallization bucket bottom cyclic motion from bottom to top in bucket.
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| CN103011230A (en) * | 2012-12-31 | 2013-04-03 | 东莞市粤源包装有限公司 | Low-cost method for preparing nano calcium sulfate |
| CN103011230B (en) * | 2012-12-31 | 2014-10-22 | 广东源盛生态环保科技有限公司 | Low-cost method for preparing nano calcium sulfate |
| US20160318784A1 (en) * | 2013-12-20 | 2016-11-03 | Oriel Seasalt Company Limited | Sea Water Harvesting Process |
| US10843951B2 (en) * | 2013-12-20 | 2020-11-24 | Oriel Seasalt Company Limited | Sea water harvesting process |
| CN107973330A (en) * | 2017-12-30 | 2018-05-01 | 唐山三友化工股份有限公司 | Alkaline residue supernatant and anhydrous sodium sulphate prepare calcium sulphate dihydrate, the device of strong brine and its production method |
| CN109133111A (en) * | 2018-10-19 | 2019-01-04 | 中国石油化工集团有限公司 | A kind of recoverying and utilizing method of caldo high during saltcake well turns to adopt |
| CN109402721A (en) * | 2018-12-14 | 2019-03-01 | 中国科学院青海盐湖研究所 | A method of preparing calcium sulfate crystal whiskers from brine |
| CN115259199A (en) * | 2021-04-29 | 2022-11-01 | 中国科学院过程工程研究所 | Preparation method of defluorinating agent and resource utilization method of fluorine-containing solution |
| CN115259199B (en) * | 2021-04-29 | 2023-12-12 | 中国科学院过程工程研究所 | Preparation method of defluorinating agent and resource utilization method of fluorine-containing solution |
| CN113582215A (en) * | 2021-08-13 | 2021-11-02 | 苏州聚智同创环保科技有限公司 | Treatment process for preparing alpha high-strength gypsum from brine produced in well and mineral salt production |
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