CN104495904A - Production method for calcium chloride dihydrate - Google Patents
Production method for calcium chloride dihydrate Download PDFInfo
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- CN104495904A CN104495904A CN201410833456.6A CN201410833456A CN104495904A CN 104495904 A CN104495904 A CN 104495904A CN 201410833456 A CN201410833456 A CN 201410833456A CN 104495904 A CN104495904 A CN 104495904A
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- CN
- China
- Prior art keywords
- production method
- dichloride dihydrate
- calcium chloride
- calcium
- water
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 title claims description 59
- 229940052299 calcium chloride dihydrate Drugs 0.000 title description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000001110 calcium chloride Substances 0.000 claims abstract description 59
- 235000011148 calcium chloride Nutrition 0.000 claims abstract description 59
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 59
- 238000001035 drying Methods 0.000 claims abstract description 59
- 239000002352 surface water Substances 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003507 refrigerant Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 42
- 238000000034 method Methods 0.000 abstract description 21
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract 1
- 229960002713 calcium chloride Drugs 0.000 description 49
- 238000003756 stirring Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 23
- 238000001816 cooling Methods 0.000 description 18
- 238000001704 evaporation Methods 0.000 description 13
- 230000008020 evaporation Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 229960005069 calcium Drugs 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 7
- 238000013022 venting Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- WMFHUUKYIUOHRA-UHFFFAOYSA-N (3-phenoxyphenyl)methanamine;hydrochloride Chemical compound Cl.NCC1=CC=CC(OC=2C=CC=CC=2)=C1 WMFHUUKYIUOHRA-UHFFFAOYSA-N 0.000 description 1
- -1 10CrMoAl Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YMIFCOGYMQTQBP-UHFFFAOYSA-L calcium;dichloride;hydrate Chemical compound O.[Cl-].[Cl-].[Ca+2] YMIFCOGYMQTQBP-UHFFFAOYSA-L 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/30—Concentrating; Dehydrating; Preventing the adsorption of moisture or caking
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a production method for calcium chloride dehydrate. The production method comprises the following steps: a, concentrating, namely concentrating to obtain a CaCl2 concentrated solution with mass fraction of 68%-70%; b, crystallizing, namely crystallizing to obtain crystal slurry which comprises a calcium chloride dehydrate crystal and surface water, wherein the surface water is a calcium chloride aqueous solution with the CaCl2 mass fraction of 55%-60%; c, preheating and removing water; and d, drying, namely drying to obtain a calcium chloride dehydrate product with the CaCl2 mass content of 74%-77%. The production method has the advantages of being simple and convenient in process flow, easy to operate and control, energy-saving and environment-friendly in device structure.
Description
Technical field
The invention belongs to field of fine chemical.More specifically, the present invention relates to a kind of production method of granular Calcium dichloride dihydrate.
Background technology
Industrial calcium chloride is divided into Calcium Chloride Powder Anhydrous, Calcium dichloride dihydrate and liquid calcium chloride.Industrial calcium chloride is generally obtained by the slops in ammonia alkali legal system soda manufacture, and also useful hydrochloric acid and Wingdale reaction obtain.Industrial calcium chloride is mainly used as refrigerant, deicing fluid, ice melting Snow Agent, fog dispersal dedusting agent etc., wherein, Calcium dichloride dihydrate is specially adapted to production Snow Agent, in addition, propylene oxide and epoxy chloropropane produce in slops also containing calcium chloride, become another method of producing Calcium dichloride dihydrate.
Existing production method is by the slops in ammonia alkali legal system soda manufacture, after sedimentation removing solid impurity, evaporation concentration also removes sodium-chlor, after being concentrated into 68 ~ 70% calcium chloride, enter flaker and carry out film-making, flake calcium chloride is dry in fluidized bed dryer produces calcium chloride (CaCl
2) Calcium dichloride dihydrate of mass content>=74%.
As: in Guangzhou, all ages Environmental Projects Inc., Shandong Dong great Chemical Industry Company are producing in epoxy chloropropane in production propylene oxide process, Shandong Zibo Bao Ye building materials company ring, all adopt the slops containing calcium chloride, through being concentrated into the calcium chloride solution of massfraction 65 ~ 68%, then through flaker crystallization, dryly in fluidized bed dryer produce solid content 73 ~ 78%(mass content) Calcium dichloride dihydrate.Fluidized bed dryer inlet temperature 300 ~ 320 DEG C, temperature of outgoing air 110 ~ 120 DEG C.
For another example: explanation in Jinan Zhong Chang drying plant company limited " liquid calcium chloride concentrated spray granulating and drying scheme book "; fluidized bed with spraying granulation process produces Calcium dichloride dihydrate; stoste solid content >=30%(mass content), deliver in fluidized bed with spraying drying-granulating machine through atomizer pump after being evaporated to finite concentration and complete granulating and drying.Inlet temperature is higher than 260 DEG C, and the calcium chloride drop of spraying, makes powder by the granulation of cohesion coating.But existing production adopts this technology, and thermo-efficiency is low, environment dust exceeding.
In fluidized-bed bed, different hydrate calcium chloride, experienced by dissolve, vaporize, melting, the complicated course of solidifying, mutually bond between particle, easily become block, easily go wrong in drying process.
For another example: Chinese patent CN200510033098 " production of propylene oxide method of wastewater treatment and quintuple effect evaporator device " discloses employing multi-effect evaporating device, saponification slops in production of propylene oxide is concentrated, obtain the calcium chloride solution of 80 ~ 90%, carry out crystallization at crystallizer, generate calcium chloride product.Those skilled in the art know, the nonvolatile substances in solution makes the solution elevation of boiling point, 80 ~ 90% calcium chloride solutions boiling point be at ambient pressure 300 DEG C and more than, reach 10MPa with the saturated vapor pressure of its balance.Therefore this technology is industrially difficult to realize.
For another example: Chinese patent CN201210549392 discloses a kind of production method of pelletoidal calcium chloride dihydrate, the calcium chloride water of 65 ~ 72% is entered in many pelletizing unit bed granulator through atomizing nozzle, produce Calcium dichloride dihydrate.The fluidized gas that gas blower bloats is 170 ~ 210 DEG C and 110 ~ 150 DEG C.
The petrochemical equipment design that Sinopec Group Shanghai Engineering Co., Ltd.'s tissue is write is selected in handbook " moisture eliminator " and is pointed out, it is high that fluidized bed dryer has heat transfer coefficient, the advantage that throughput is large, point out simultaneously, the granularity of fluidised bed drying material has certain placing restrictions on, easily in fluidized bed drying process, viscosity produced to wall and the material of stifled bed phenomenon easily occurs, should not fluidized bed dryer be adopted.Point out again, fluidized bed dryer thermo-efficiency is about 30 ~ 60%.Fluidized bed dryer thermo-efficiency is low.
Tangshan Sanyou Zhida Calcium Industry Co. Ltd. the article pointed out in prosperous " exploitation of a water granular calcium chloride product innovation " (soda industry 2011-01), and calcium chloride fluidized bed pelletizer is easy to cause calcium chloride to become pasty state, fills up whole fluidized bed body.
Introduce according to described " moisture eliminator ", fluidized-bed hot blast distribution economic velocity roughly boundary is 3 ~ 4m/s.Therefore, fine particle is taken out of, needs large thin powder recovery treatment unit and cleaning apparatus.The fine powder discharge of environment exceeds standard and annoyings Calcium dichloride dihydrate manufacturing enterprise always.
Prior art, such as, in Guangzhou ring all ages Environmental Projects Inc.'s technology, through being concentrated into the calcium chloride solution of 65 ~ 68%, through flaker crystallization, crystallization becomes dihydrate CaCl
22H
2o plate crystal body and concentration are 57%(massfraction) calcium chloride solution, described in this, solution those skilled in the art of the present technique are called " surface water ".Then dry in fluidized bed dryer.Fluidized-bed inlet temperature 300 ~ 320 DEG C, at 300 ~ 320 temperature described in this, dihydrate CaCl
22H
2o plate crystal body is converted into monohydrate CaCl
2h
2o and anhydrous CaCl
2, therefore can not get Calcium dichloride dihydrate product.
Prior art, the such as fluidized bed with spraying dry technology of Jinan Zhong Chang drying plant company limited, calcium chloride content is 45 ~ 50%(massfraction) solution spray enter fluidized-bed bed, be wrapped in particle surface, at a higher temperature, such as 140 DEG C of moisture are vaporized, and integument calcium chloride concentration improves, and form the mixture of solid-liquid two-phase, at higher temperatures, such as 260 DEG C, integument is melted, so produce the phenomenon forming agglomerate.
Embodiments of the present invention are crystallization control temperature, make the calcium chloride hydrate of generation be CaCl
22H
2o.Under simultaneously liquid phase is in lower calcium chloride concentration, such as liquid phase chlorination calcium described in this by weight concentration be 55 ~ 60%, be able to H-2O at a lower temperature and be vaporized.Checked in by " chemical process safety handbook ", the boiling temperature of the CaCl2 aqueous solution is as table 1.
Table 1 CaCl
2the boiling temperature (P=0.1MPa) of the aqueous solution
An embodiment of the invention record, 68%(massfraction) melt temperature of calcium chloride is 120 DEG C.
The more detailed step of the inventive method is as follows.
A, concentrated.
Described slops, chloride containing calcium concn is 10 ~ 12%(massfraction) solution, or with hydrochloric acid and the obtained calcium chloride solution of Wingdale reaction, by described solution after neutralization, supernatant, filtration, send in multiple-effect evaporator 2 through pipeline by pump 1, through evaporation concentration, its concentrated solution CaCl
2content is increased to by weight 68 ~ 70%.
The present inventor step B2 in CN103342434B has described the concentration method of multiple-effect evaporator.
B, crystallization.
Flowed in crystallizer 3 by the pipeline of insulation by described concentrated solution from steps A by pipeline, crystallizer 3 is horizontal propelling continuous cooling crystallizers, is indirectly cooled as refrigerant by warm water.Refrigerant temperature preferably 45 ~ 100 DEG C, more preferably 50 ~ 60 DEG C.Obtain with total weight containing solid phase amount 45 ~ 50% and the magma containing amount of liquid phase 55 ~ 50%.The solid phase of described magma is CaCl
22H
2the xln of O, liquid phase is containing CaCl
255 ~ 60%(massfraction) calcium chloride solution.
According to Fig. 1 CaCl
2---H
2o binary system phase diagram is known, and during mould temperature < 45 DEG C, CaCl formed by described concentrated solution
24H
2o+CaCl
22H
2the common melt body of O, concentrated solution described in this can form agglomerate; During mould temperature > 120 DEG C, the temperature of described concentrated solution is in more than the melt temperature of this concentrated solution, becomes fused solution, and the moisture content vaporization temperature of fused solution described in this is 180 DEG C, the vaporization difficulty of moisture content.
Described crystallizer is horizontal propelling continuous crystallizer, preferred horizontal spiral push-type continuous cooling crystallizer, and crystallizer described in this is the equipment that this area engineering technical personnel understand.Such as go up the WLLJ type horizontal spiral push-type continuous cooling crystallizer of Hisoon prosperous chemical equipment technical institute development, or the QJ type hollow paddle type moisture eliminator preferably introduced in " handbook moisture eliminator is selected in petrochemical equipment design ", moisture eliminator described in this has the characteristic of heat transfer, cooling, stirring, can complete the unit operation of Calcium dichloride dihydrate crystallization.
C, preheating dewater.
Described magma, under the prograding of described crystallizer 3, is discharged from crystallizer discharge gate 4, is entered preheating water eliminator 5.Preheating water eliminator 5 is wedge hollow blade formula moisture eliminators.Described magma by thermal oil indirect heating, and to dewater in preheating water eliminator 5.Described magma is heated by hollow blade, and advances to discharge gate 6.
Of the present invention one preferred embodiment, described magma, below melt temperature, is kept stable crystal and surface water, and surface water is calcium chloride solution, can make the CaCl of the liquid phase in magma like this
2concentration is low, is conducive to H in liquid phase
2the vaporization of O.
According to one embodiment of present invention, 68%(massfraction) CaCl
2fluxing point be 120 DEG C.By the vapor-pressure curve chart checking in calcium chloride solution in " chlorine industry physicochemical constant handbook ", according to this chart list for shown in table 2.
The vapour pressure of table 2 calcium chloride solution
57%(massfraction is checked in by table 2) CaCl
2the water vapor pressure of solution 117 DEG C time is 0.05MPa, and under water vapor pressure described in this, water is vaporized.
According to the embodiment of the present invention, preheating water eliminator feed end temperature preferably 110 ~ 120 DEG C, more preferably 112 ~ 117 DEG C.
According to the embodiment of the present invention, in the liquid phase in described magma, water is vaporized, and the calcium chloride content of magma raises.
According to one embodiment of present invention, 72%(massfraction) CaCl
2fluxing point be 135 DEG C.63%(massfraction) CaCl
2the water vapor pressure of solution 130 DEG C time is 0.05MPa, and under water vapor pressure described in this, water is vaporized.
According to the embodiment of the present invention, preheating water eliminator discharge end temperature preferably 125 ~ 135 DEG C, more preferably 125 ~ 130 DEG C.
According to the embodiment of the present invention, the temperature of described preheating water eliminator, preferred 112 ~ 117 DEG C by feed end temperature, preferred 125 ~ 130 DEG C to discharge end temperature, the direction that described temperature advances with magma, temperature linearity rises.More than the vaporization temperature of the water below the melt temperature that it is characterized in that being in the temperature of magma described in this preheating water eliminator described in this magma, in magma surface water.
According to the embodiment of the present invention, the pressure in preheating water eliminator 5 is 0 ~ 0.1MPa, preferably 0.04 ~ 0.06 MPa, more preferably 0.04 ~ 0.05 MPa.
Described preheating water eliminator is wedge hollow blade drier.Wedge hollow blade drier is the equipment that this area engineering technical personnel know.Such as, the JG type hollow paddle type moisture eliminator sold by Jiangsu Xianfeng Drying Engineering Co., Ltd., the blade dryer that drying plant Science and Technology Ltd. sells is tolerated it in Changzhou.
A feature of the present invention is the heating agent of described wedge hollow blade drier is thermal oil.The import and export of heating agent arrange 2 ~ 3, by the temperature regulating flow rate of heat medium to control described magma, linearly rise.
D, drying.
The magma of described remove portion surface water, is discharged by discharge gate 6, enters moisture eliminator 8, and moisture eliminator 8 is wedge hollow blade formula moisture eliminators.The magma of described remove portion surface water is dry by thermal oil indirect heating in moisture eliminator 8.Magma described in this is heated by hollow blade 81, and advances to discharge gate 9.Thermal oil flow process becomes adverse current with magma direction of propulsion described in this.
The described temperature entering moisture eliminator 8 of being discharged by step C discharge gate 6 is the described magma of 125 ~ 130 DEG C, mainly Calcium dichloride dihydrate xln, also has surface water.According to the phasor of Fig. 1, surface water is the solution of chloride containing calcium 63 ~ 65%.According to the vapor pressure characteristics of calcium chloride solution, its vapor pressure 140 DEG C time of surface water described in this is 0.06 MPa.According to Fig. 1, during magma temperature > 175 DEG C, xln starts to lose Bound moisture, is converted into water calcium chloride and a Calcium Chloride Powder Anhydrous.The preferred drying temperature of the present invention 140 ~ 175 DEG C, more preferably 150 ~ 160 DEG C.Described magma, by heat drying, obtains the granular Calcium dichloride dihydrate product of chloride containing calcium 74 ~ 77%.
Described moisture eliminator is hollow blade dryer.Hollow blade dryer is the equipment that the art engineering technical personnel know, and the petrochemical equipment design that Sinopec Group Shanghai Engineering Co., Ltd.'s tissue is write is selected in handbook " moisture eliminator " detailed introduction.
E, cooling.
From the product that described discharge gate 9 is discharged, enter water cooler 11.Water cooler 11 is the spiral conveyers with cooling jacket, and on helical runner, each screw-blade has three otch, and water cooler inwall has kneading tooth, and make the material be fed forward produce mixing, cooling jacket passes into water coolant.Calcium dichloride dihydrate product after cooled is discharged to discharge gate, packs.
F, exhaust system.
According to the embodiment of the present invention, dewater and dry do not produce the dust that environment is impacted.
The fluidized bed with spraying drying-granulating technology that prior art adopts, the fine particle in fluidized-bed is often taken out of, needs huge thin powder recovery treatment unit and cleaning apparatus.There is not fluidisation and air flow in embodiments of the present invention, so there is no grain dust.The water vapor of venting port 7 and venting port 10 discharge, aspirates condensation by water jet pump unit 12 in embodiments of the present invention.The suction function of water jet pump unit 12 makes to produce vacuum tightness in preheating water eliminator 5 and moisture eliminator 8, is conducive to the drying of evaporation of water and material.
Pressure preferably 0.01 ~ 0.09MPa in described preheating water eliminator 5 and moisture eliminator 8, more preferably 0.04 ~ 0.05 MPa.
According to the embodiment of the present invention, a small amount of dust produced once in a while, because the high resolution of Calcium dichloride dihydrate, is dissolved by the injection water of water jet pump unit.
Water jet pump unit 12 be this area engineering technical personnel the equipment be familiar with, can select in " chemical process safety handbook " easily.
The process of Calcium dichloride dihydrate produced according to the invention is carried out in crystallizer, preheating water eliminator, moisture eliminator and water cooler, this aforesaid device described needs heat transfer at the equipment unit of contact calcium chloride material, and tolerate chlorion and high temperature, as suitable metallic substance, preferred low alloy steel, dual phase steel, titanium, Hastelloy.More preferably low alloy steel, such as 10CrMoAl, dual phase steel, such as 2507 dual phase steels.
According to mode of the present invention, the industrial Calcium dichloride dihydrate powder granular products obtained, described in this, industrial Calcium dichloride dihydrate product meets the index request of GB/T26520-2011 " Calcium dichloride dihydrate ".
In the present invention, the content of calcium chloride and various material thereof is all adopt the known method of existing national technical standard or the art to carry out analyzing.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of production method of Calcium dichloride dihydrate, the defect that prior art exists can be solved.
The present invention is achieved through the following technical solutions.
A production method for Calcium dichloride dihydrate, comprises the following steps: a. concentrates: obtaining massfraction after concentrated is the CaCl of 68% ~ 70%
2concentrated solution; B. crystallization: magma after crystallization, described magma comprises Calcium dichloride dihydrate crystal and surface water, and described surface water is CaCl
2massfraction be the calcium chloride water of 55% ~ 60%; C. preheating dewaters; D. dry: after drying, to obtain CaCl
2mass content be 74% ~ 77% Calcium dichloride dihydrate product.
As preferably, in described step b, crystallizer refrigerant temperature is 45 DEG C ~ 100 DEG C.
As preferably, in described step c, preheating water eliminator feed end temperature is 110 DEG C ~ 120 DEG C, and discharge end temperature is 125 DEG C ~ 135 DEG C.
As preferably, in described step c, preheating temperature for removing water linearly rises with described magma direction of propulsion.
As preferably, in described steps d, drying temperature is 140 DEG C ~ 175 DEG C.
As preferably, in described step b, crystallizer refrigerant temperature is 50 DEG C ~ 60 DEG C.
As preferably, in described step c, preheating water eliminator feed end temperature is 112 DEG C ~ 117 DEG C, and discharge end temperature is 125 DEG C ~ 130 DEG C.
As preferably, in described steps d, drying temperature is 150 DEG C ~ 160 DEG C.
As preferably, further comprising the steps of in described production method: f. is vented: carry out suction condensation to the water vapour produced in step c and steps d, produce negative pressure during suction, this negative pressure pressure drawn in preheating water eliminator and moisture eliminator is 0.01 ~ 0.09MPa, more preferably 0.04 ~ 0.05 MPa.
As preferably, the CaCl in described step a
2concentrated solution derive from calcium chloride solution or propylene oxide that slops in ammonia alkali legal system soda manufacture or hydrochloric acid and Wingdale be obtained by reacting and epoxy chloropropane produce in slops.
Compared with prior art, the present invention has following beneficial effect: it is easy that the inventive method has technical process, is easy to operate and control, tight, energy-conservation, the eco-friendly advantage of apparatus structure.
Accompanying drawing explanation
Fig. 1 is CaCl
2-H
2o binary system phase diagram.
Fig. 2 is Calcium dichloride dihydrate Production Flow Chart sketch.
Fig. 3 is moisture eliminator equipment drawing.
Fig. 4 is hollow blade schematic diagram.
In figure: 1-pump; 2-multiple-effect evaporator; 3-crystallizer; 4-discharge gate; 5-preheating water eliminator; 6-discharge gate; 7-venting port; 8-moisture eliminator; 81-hollow blade; 9-discharge gate; 10-venting port; 11-water cooler; 12-water jet pump unit.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is described in detail.
The present invention relates to a kind of production method of Calcium dichloride dihydrate.The step of the production method of this Calcium dichloride dihydrate is as follows.
A, concentrated.
Described slops, chloride containing calcium massfraction is the solution of 10 ~ 12%, or with the calcium chloride solution that hydrochloric acid and Wingdale reaction obtain, by described solution after neutralization, supernatant, filtration, send in multiple-effect evaporator 2 by pipeline through pump 1, through evaporation concentration, its concentrated solution CaCl
2content is increased to by weight 68 ~ 70%.
B, crystallization.
The described concentrated solution will obtained from steps A by pipeline, flowed in crystallizer 3 by the pipeline of insulation, crystallizer 3 is horizontal propelling continuous cooling crystallizers, and indirectly cool with 50 ~ 60 DEG C of warm water, obtain magma, described magma comprises containing CaCl
275.5%(massfraction) Calcium dichloride dihydrate crystal and surface water.Surface water is containing CaCl
2the calcium chloride water of 55 ~ 60%.
C, preheating dewater.
Described magma, under the prograding of described crystallizer 3, is discharged from crystallizer discharge gate 4, is entered preheating water eliminator 5.Preheating water eliminator 5 is wedge hollow blade formula moisture eliminators.Described magma by thermal oil indirect heating, and to dewater in preheating water eliminator 5.Described magma is heated by hollow blade, and advances to discharge gate 6.Thermal oil flow process becomes adverse current with magma direction of propulsion, and to control thermal oil temperature out be 110 DEG C, and with magma direction of propulsion, temperature linearity rises to 130 DEG C, and the moisture content in part surface water is vaporized, and discharges from venting port 7.The magma of remove portion moisture content is released from discharge gate 6.
D, drying.
The magma of described remove portion surface water, is discharged by discharge gate 6, enters moisture eliminator 8, and moisture eliminator 8 is wedge hollow blade formula moisture eliminators.The magma of described remove portion surface water is dry by thermal oil indirect heating in moisture eliminator 8.Magma described in this is heated by hollow blade 81, and advances to discharge gate 9.Thermal oil flow process becomes adverse current with magma direction of propulsion described in this, inlet guide hot oil temperature 150 ~ 160 DEG C, and described magma, by heat drying, obtains the granular Calcium dichloride dihydrate product of chloride containing calcium 74 ~ 77% by weight.
E, cooling.
From the product that described discharge gate 9 is discharged, enter water cooler 11.Water cooler 11 is the spiral conveyers with cooling jacket, and on helical runner, each screw-blade has three otch, and water cooler inwall has kneading tooth, and make the material be fed forward produce mixing, cooling jacket passes into water coolant.Calcium dichloride dihydrate product after cooled is discharged to discharge gate, packs.
F, exhaust system.
The water vapor that venting port 7 and venting port 10 are discharged, aspirates condensation by water jet pump unit 12.The suction function of water jet pump unit 12 makes to produce vacuum tightness in preheating water eliminator 5 and moisture eliminator 8, is conducive to the drying of evaporation of water and material.
In more detail the present invention will be described below.
The present invention relates to a kind of production method of Calcium dichloride dihydrate.
Calcium dichloride dihydrate is produced, and be by the calcium chloride solution of high density, such as concentration is 65 ~ 68%CaCl
2(massfraction) or concentration are 65 ~ 70% CaCl2(massfractions).Described in this, solution is through crystallisation by cooling, then obtains through heat drying granular or sheet or the spherical CaCl that calcium chloride is 74 ~ 77% by weight
22H
2the Calcium dichloride dihydrate product of O, wherein CaCl
22H2O xln is containing CaCl
2for 75.5%(massfraction).
The engineering technical personnel of this area know clearly, calcium chloride has the formation of multiple Bound moisture, and it consists of: hexahydrate CaCl
26H
2o is containing CaCl
250.68%; Tetrahydrate CaCl
24H
2o is containing CaCl
260.65%; Dihydrate CaCl
22H
2o is containing CaCl
275.51%; Monohydrate CaCl
2h
2o is containing CaCl
286.04%; The formation of its Bound moisture determined by temperature.
Fig. 1 is CaCl
2---H
2o binary system phase diagram, known from phasor described in this, with the CaCl of calcium chloride weighing scale 58 ~ 75%
2---H
2o binary thing, Calcium dichloride dihydrate existent condition is 45 ~ 175 DEG C.
embodiment 1.
To get in multiple-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker on electric furnace heated and boiled, evaporation concentration becomes the calcium chloride concentrated solution of by weight 68.8%.Described concentrated solution is poured into diameter 110mm height 150mm with in the stainless steel crystallizing and drying tank of rake stirring rake, crystallizing and drying tank is placed in 50 DEG C of warm water, stir cooling 3min, obtain magma.Magma is placed in 110 DEG C of oil bath pan preheatings together with crystallizing and drying tank dewater, preheating removal process is with stirring, temperature rise rate 2.67 DEG C/min in 15min, temperature is directly risen to 150 DEG C by 110 DEG C, continuous stirring, obtain granular " Calcium dichloride dihydrate " product 844g after dry 17min, analyzing its calcium chloride content is 74.57%(massfraction).Crystallizing and drying process lasts 35min.
The analytical procedure of calcium chloride is GB/T23941-2009 " industrial calcium chloride analytical procedure ".
comparative example 1.
To get in multiple-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker on electric furnace heated and boiled, evaporation concentration becomes the calcium chloride concentrated solution of by weight 68.8%, described concentrated solution is poured into identical with embodiment 1 with in the stainless steel crystallizing and drying tank of rake stirring rake, crystallizing and drying tank is placed in 155 DEG C of oil bath pans, oil bath temperature controls, at 153 ~ 155 DEG C, constantly to stir, after lasting 30min, material clumps together bulk, and rake stirring rake is stuck.Continue after crushing material to stir with rake stirring rake.After crystallizing and drying lasts 130min, obtain granular Calcium dichloride dihydrate product, analyzing its calcium chloride content is 71.16%(massfraction).Described in this, Calcium dichloride dihydrate product does not meet the technical requirements of GB/T26520-2011 " Calcium dichloride dihydrate ".Continue to stir, heat drying, continues to last 60min, the granular Calcium dichloride dihydrate product 851g obtained, and analyzing its calcium chloride content is 74.00%(massfraction).According to mode described in this comparative example, obtain calcium chloride content 74.00%(massfraction) " Calcium dichloride dihydrate " product, crystallizing and drying process lasts 190min.
embodiment 2.
To get in multiple-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g heat on electric furnace in beaker, evaporation concentration becomes the calcium chloride concentrated solution of by weight 68%.Described concentrated solution is poured into identical with embodiment 1 with in the stainless steel crystallizing and drying tank of rake stirring rake, crystallizing and drying tank is placed in 40 DEG C of water-baths, stir cooling 4min, obtain magma.Magma is placed in 110 DEG C of oil bath pan preheatings together with crystallizing and drying tank dewater, preheating removal process is with stirring, and after 5min, start slowly to be warming up to 130 DEG C, temperature-rise period continues 23min, and magma is not substantially in molten state.Drying step: continue to be warming up to 150 DEG C, constantly stir, obtains granular " Calcium dichloride dihydrate " product 850g after dry 14min, analyzing its calcium chloride content is 74.07%(massfraction).Crystallizing and drying process lasts 46min.
comparative example 2.
To get in multiple-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g heat on electric furnace in beaker, evaporation concentration becomes the calcium chloride concentrated solution of by weight 68.2%.Described concentrated solution is poured into identical with embodiment 1 with in the stainless steel crystallizing and drying tank of rake stirring rake, crystallizing and drying tank is placed in normal temperature water-bath about 30 DEG C, stir cooling 4min, obtain magma.Magma is placed in 110 DEG C of oil bath pan preheatings together with crystallizing and drying tank dewater, preheating removal process is with stirring, and after 10min, temperature is slowly risen to 120 DEG C, in tank, magma state is substantially constant.In 13min, temperature rise rate 2.3 DEG C/min is warming up to 150 DEG C and carries out drying afterwards, and obtain granular " Calcium dichloride dihydrate " product 828g after dry 25min, analyzing its calcium chloride content is 76%(massfraction).Crystallizing and drying process lasts 52min.
embodiment 3.
To get in multiple-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g heat on electric furnace in beaker, evaporation concentration becomes the calcium chloride concentrated solution of by weight 70%.Described concentrated solution is poured into identical with embodiment 1 with in the stainless steel crystallizing and drying tank of rake stirring rake, crystallizing and drying tank is placed in 45 DEG C of water-baths, stir cooling 4min, obtain magma.Magma is placed in 110 DEG C of oil bath pan preheatings together with crystallizing and drying tank dewater, preheating removal process is with stirring, and after 5min, start slowly to be warming up to 135 DEG C, temperature-rise period continues 25min, and magma is not substantially in molten state.Drying step: continue to be warming up to 175 DEG C, constantly stir, obtains granular " Calcium dichloride dihydrate " product 836g after dry 10min, analyzing its calcium chloride content is 75.28%(massfraction).Crystallizing and drying process lasts 44min.
embodiment 4.
To get in multiple-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g heat on electric furnace in beaker, evaporation concentration becomes the calcium chloride concentrated solution of by weight 70%.Described concentrated solution is poured into identical with embodiment 1 with in the stainless steel crystallizing and drying tank of rake stirring rake, crystallizing and drying tank is placed in 50 DEG C of water-baths, stir cooling 3min, obtain magma.Magma is placed in 112 DEG C of oil bath pan preheatings together with crystallizing and drying tank dewater, preheating removal process is with stirring, and after 5min, start slowly to be warming up to 125 DEG C, temperature-rise period continues 23min, and magma is not substantially in molten state.Drying step: continue to be warming up to 160 DEG C, constantly stir, obtains granular " Calcium dichloride dihydrate " product 840g after dry 14min, analyzing its calcium chloride content is 75%(massfraction).Crystallizing and drying process lasts 45min.
embodiment 5.
To get in multiple-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g heat on electric furnace in beaker, evaporation concentration becomes the calcium chloride concentrated solution of by weight 68%.Described concentrated solution is poured into identical with embodiment 1 with in the stainless steel crystallizing and drying tank of rake stirring rake, crystallizing and drying tank is placed in 60 DEG C of water-baths, stir cooling 3min, obtain magma.Magma is placed in 117 DEG C of oil bath pan preheatings together with crystallizing and drying tank dewater, preheating removal process is with stirring, and after 5min, start slowly to be warming up to 130 DEG C, temperature-rise period continues 20min, and magma is not substantially in molten state.Drying step: continue to be warming up to 150 DEG C, constantly stir, obtains granular " Calcium dichloride dihydrate " product 818g after dry 18min, analyzing its calcium chloride content is 77%(massfraction).Crystallizing and drying process lasts 46min.
In above embodiment, CaCl
2concentrated solution derive from calcium chloride solution or propylene oxide that slops in ammonia alkali legal system soda manufacture or hydrochloric acid and Wingdale be obtained by reacting and epoxy chloropropane produce in slops.
Claims (10)
1. a production method for Calcium dichloride dihydrate, is characterized in that, comprises the following steps: a. concentrates: obtaining massfraction after concentrated is the CaCl of 68% ~ 70%
2concentrated solution; B. crystallization: magma after crystallization, described magma comprises Calcium dichloride dihydrate crystal and surface water, and described surface water is CaCl
2massfraction be the calcium chloride water of 55% ~ 60%; C. preheating dewaters; D. dry: after drying, to obtain CaCl
2mass content be 74% ~ 77% Calcium dichloride dihydrate product.
2. the production method of a kind of Calcium dichloride dihydrate according to claim 1, is characterized in that, in described step b, crystallizer refrigerant temperature is 45 DEG C ~ 100 DEG C.
3. the production method of a kind of Calcium dichloride dihydrate according to claim 2, is characterized in that, in described step c, preheating water eliminator feed end temperature is 110 DEG C ~ 120 DEG C, and discharge end temperature is 125 DEG C ~ 135 DEG C.
4. the production method of a kind of Calcium dichloride dihydrate according to claim 3, is characterized in that, in described step c, preheating temperature for removing water linearly rises with described magma direction of propulsion.
5. the production method of a kind of Calcium dichloride dihydrate according to claim 4, is characterized in that, in described steps d, drying temperature is 140 DEG C ~ 175 DEG C.
6. the production method of a kind of Calcium dichloride dihydrate according to claim 5, is characterized in that, in described step b, crystallizer refrigerant temperature is 50 DEG C ~ 60 DEG C.
7. the production method of a kind of Calcium dichloride dihydrate according to claim 6, is characterized in that, in described step c, preheating water eliminator feed end temperature is 112 DEG C ~ 117 DEG C, and discharge end temperature is 125 DEG C ~ 130 DEG C.
8. the production method of a kind of Calcium dichloride dihydrate according to claim 7, is characterized in that, in described steps d, drying temperature is 150 DEG C ~ 160 DEG C.
9. the production method of a kind of Calcium dichloride dihydrate according to any one of claim 1 to 8, it is characterized in that, further comprising the steps of: f. is vented: carry out suction condensation to the water vapour produced in step c and steps d, produce negative pressure during suction, this negative pressure pressure drawn in preheating water eliminator and moisture eliminator is 0.01 ~ 0.09MPa.
10. the production method of a kind of Calcium dichloride dihydrate according to claim 9, is characterized in that, the CaCl in described step a
2concentrated solution derive from calcium chloride solution or propylene oxide that slops in ammonia alkali legal system soda manufacture or hydrochloric acid and Wingdale be obtained by reacting and epoxy chloropropane produce in slops.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858702A (en) * | 2016-05-24 | 2016-08-17 | 江苏新泰材料科技股份有限公司 | Technology for calcium chloride with fluoride-containing hydrochloric acid |
| CN115417442A (en) * | 2022-09-23 | 2022-12-02 | 浙江佳境环保科技有限公司 | Calcium chloride regeneration system |
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| JPS5734023A (en) * | 1980-07-29 | 1982-02-24 | Tokuyama Soda Co Ltd | Concentration of calcium chloride aqueous solution |
| RU2258037C2 (en) * | 2003-10-08 | 2005-08-10 | Открытое акционерное общество "АВИСМА титано-магниевый комбинат" | Granulated calcium chloride manufacture process and installation |
| CN1673104A (en) * | 2005-02-03 | 2005-09-28 | 刘德沛 | Waste water treating method and multi-effect evaporator for propylene oxide production |
| CN101712661A (en) * | 2009-12-01 | 2010-05-26 | 宁波东港电化有限责任公司 | Method for producing epoxy chloropropane |
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| JPS5734023A (en) * | 1980-07-29 | 1982-02-24 | Tokuyama Soda Co Ltd | Concentration of calcium chloride aqueous solution |
| RU2258037C2 (en) * | 2003-10-08 | 2005-08-10 | Открытое акционерное общество "АВИСМА титано-магниевый комбинат" | Granulated calcium chloride manufacture process and installation |
| CN1673104A (en) * | 2005-02-03 | 2005-09-28 | 刘德沛 | Waste water treating method and multi-effect evaporator for propylene oxide production |
| CN101712661A (en) * | 2009-12-01 | 2010-05-26 | 宁波东港电化有限责任公司 | Method for producing epoxy chloropropane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105858702A (en) * | 2016-05-24 | 2016-08-17 | 江苏新泰材料科技股份有限公司 | Technology for calcium chloride with fluoride-containing hydrochloric acid |
| CN115417442A (en) * | 2022-09-23 | 2022-12-02 | 浙江佳境环保科技有限公司 | Calcium chloride regeneration system |
| CN115417442B (en) * | 2022-09-23 | 2023-09-22 | 浙江佳境环保科技有限公司 | Calcium chloride regeneration system |
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