CN104495904B - A kind of production method of calcium chloride dihydrate - Google Patents
A kind of production method of calcium chloride dihydrate Download PDFInfo
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- CN104495904B CN104495904B CN201410833456.6A CN201410833456A CN104495904B CN 104495904 B CN104495904 B CN 104495904B CN 201410833456 A CN201410833456 A CN 201410833456A CN 104495904 B CN104495904 B CN 104495904B
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- calcium chloride
- magma
- water
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- exsiccator
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- 229940052299 calcium chloride dihydrate Drugs 0.000 title claims abstract description 51
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 90
- 239000001110 calcium chloride Substances 0.000 claims abstract description 86
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229960002713 calcium chloride Drugs 0.000 claims abstract description 51
- 238000001035 drying Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002352 surface water Substances 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000012141 concentrate Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 21
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 229960005069 calcium Drugs 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 9
- 239000007924 injection Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 239000007788 liquid Substances 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- 235000019738 Limestone Nutrition 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- 239000006028 limestone Substances 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 230000002411 adverse Effects 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003507 refrigerant Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 239000000498 cooling water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 25
- 238000005516 engineering process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004683 dihydrates Chemical class 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance 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
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005276 aerator Methods 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
- 230000008859 change Effects 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000004575 stone 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
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment 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 production method of a kind of calcium chloride dihydrate, comprises the following steps: a. concentrates: obtaining mass fraction after concentration is the CaCl of 68% ~ 70%2Concentrated solution；B. crystallization: magma after crystallization, described magma includes calcium chloride dihydrate crystal and surface water, and described surface water is CaCl2The calcium chloride water that mass fraction is 55% ~ 60%；The most pre-evanescence of heat water；D. it is dried: obtain CaCl after drying2The calcium chloride dihydrate product that mass content is 74% ~ 77%.The method have the advantages that the inventive method has technological process easy, it is easy to operate and control, apparatus structure advantage tight, energy-conservation, eco-friendly.
Description
Technical field
The invention belongs to field of fine chemical.More particularly it relates to an the production of granular calcium chloride dihydrate
Method.
Background technology
Industrial calcium chloride is divided into anhydrous calcium chloride, calcium chloride dihydrate and liquid calcium chloride.Industrial calcium chloride is typically by ammonia alkali
Slops in legal system soda manufacture prepares, and the most useful hydrochloric acid and limestone reaction prepare.Industrial calcium chloride is mainly used as cold
Freezing agent, anti-icing fluid, ice melting Snow Agent, fog dispersal dedusting agent etc., wherein, calcium chloride dihydrate is particularly well-suited to produce Snow Agent, additionally,
Slops during expoxy propane and epoxychloropropane produce also contains calcium chloride, has become as and produces the another of calcium chloride dihydrate
The method of kind.
Existing production method is by the slops in ammonia alkali legal system soda manufacture, after sedimentation removes solid impurity, steams
Sending out and concentrate and except sodium chloride, after being concentrated into 68 ~ 70% calcium chloride, enter flaker and carry out film-making, flake calcium chloride is done at fluid bed
Dry device is dried and produces calcium chloride (CaCl2) calcium chloride dihydrate of mass content >=74%.
As: Guangzhou medium ring all ages Environmental Projects Inc., Shandong Dong great Chemical Industry Company are producing expoxy propane process, mountain
Zibo, east Bao Ye building materials company, in producing epoxychloropropane, all uses the slops containing calcium chloride, concentrated to matter
The calcium chloride solution of amount mark 65 ~ 68%, then crystallizes through flaker, be dried in fluidized bed dryer produce solid content 73 ~
78%(mass content) calcium chloride 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 equipment company limited " liquid calcium chloride concentrated spray granulating and drying scheme book ",
Fluidized bed with spraying prilling produces calcium chloride dihydrate, stock solution solid content >=30%(mass content), it is evaporated to warp after finite concentration
Atomizer pump completes granulating and drying in delivering into fluidized bed with spraying drying-granulating machine.Inlet temperature is higher than 260 DEG C, the chlorination of spraying
Calcium drop, makes powder by cohesion coating pelletize.But existing production uses this technology, and the thermal efficiency is low, environment dust exceeding.
In fluid bed bed, different hydrate calcium chloride, experienced by the complicated course dissolved, vaporize, melt, solidify,
Mutually bond between granule, easily become block, easily go wrong in dry run.
For another example: Chinese patent CN200510033098 " production of propylene oxide method of wastewater treatment and quintuple effect evaporator device "
Disclose employing multi-effect evaporating device, the saponification slops in production of propylene oxide is concentrated, obtains the calcium chloride of 80 ~ 90%
Solution, crystallizes at crystallizer, generates calcium chloride product.As it is known by the man skilled in the art that the non-volatile matter in solution
Make the solution elevation of boiling point, 80 ~ 90% calcium chloride solutions boiling point at ambient pressure be 300 DEG C and more than, the saturation water that balances with it steams
Steam pressure reaches 10MPa.Therefore this technology is industrially difficult to.
For another example: Chinese patent CN201210549392 discloses the production method of a kind of pelletoidal calcium chloride dihydrate, by 65 ~
The calcium chloride water of 72%, in atomizer enters many pelletizing unit bed granulator, produces calcium chloride dihydrate.Aerator
The fluidized gas bloated 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 selects handbook " to be dried
Device " in point out, it is high that fluidized bed dryer has heat transfer coefficient, and the advantage that production capacity is big is pointed out, fluid bed drying material simultaneously
Granularity have certain placing restrictions on, easily in fluidized bed drying process, wall is produced viscosity and the thing of stifled bed phenomenon easily occurs
Material, should not use fluidized bed dryer.Pointing out again, the fluidized bed dryer thermal efficiency is about 30 ~ 60%.Fluidized bed dryer thermal effect
Rate is low.
Tangshan Sanyou Zhida Calcium Industry Co. Ltd. is in prosperous " exploitation of a water granular calcium chloride new product " (soda industry
2011 01) one the article pointed out, calcium chloride fluidized bed pelletizer easily causes calcium chloride and becomes pasty state, fills up whole fluidized bed
Body.
Introducing according to described " exsiccator ", fluid bed hot blast distribution economic velocity substantially boundary is 3 ~ 4m/s.Therefore, carefully
Granule is carried over, and needs big thin powder recovery processing means and dust arrester.The fine powder discharge of environment exceeds standard and annoyings two always
Water Calcium Chloride Production enterprise.
Summary of the invention
For deficiency of the prior art, the invention provides the production method of a kind of calcium chloride dihydrate, can solve existing
The defect that technology exists.
The present invention is achieved through the following technical solutions.
The production method of a kind of calcium chloride dihydrate, comprises the following steps: a. concentrates: obtain after concentration mass fraction be 68% ~
The CaCl of 70%2Concentrated solution；B. crystallization: magma after crystallization, described magma includes calcium chloride dihydrate crystal and surface water, described table
Face water is CaCl2The calcium chloride water that mass fraction is 55% ~ 60%；The most pre-evanescence of heat water；D. it is dried: obtain CaCl after drying2
The calcium chloride dihydrate product that mass content is 74% ~ 77%.
As preferably, in described step b, crystallizer refrigerant temperature is 45 DEG C ~ 100 DEG C.
As preferably, in described step c, preheating dehydrater feed end temperature is 110 DEG C ~ 120 DEG C, and discharge end temperature is
125℃~135℃。
As preferably, in described step c, preheating temperature for removing water is with described magma direction of propulsion linear rise.
As preferably, in described step d, baking 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 dehydrater feed end temperature is 112 DEG C ~ 117 DEG C, and discharge end temperature is
125℃~130℃。
As preferably, in described step d, baking temperature is 150 DEG C ~ 160 DEG C.
As preferably, further comprising the steps of in described production method: f. aerofluxus: to the water produced in step c and step d
Steam carries out suction condensation, produces negative pressure during suction, this negative pressure draw into the pressure in preheating dehydrater and exsiccator be 0.01 ~
0.09MPa, more preferably 0.04 ~ 0.05 MPa.
As preferably, the CaCl in described step a2Concentrated solution derive from the slops in ammonia alkali legal system soda manufacture or
Hydrochloric acid and limestone react the slops in the calcium chloride solution or expoxy propane obtained and epoxychloropropane production.
Compared with prior art, the method have the advantages that the inventive method has technological process easy, it is easy to
Operation and control, apparatus structure advantage tight, energy-conservation, eco-friendly.
Accompanying drawing explanation
Fig. 1 is CaCl2-H2O binary system phase diagram.
Fig. 2 is calcium chloride dihydrate production procedure sketch.
Fig. 3 is exsiccator equipment drawing.
Fig. 4 is hollow blade schematic diagram.
In figure: 1-pump；2-multi-effect evaporator；3-crystallizer；4-discharge gate；5-preheats dehydrater；6-discharge gate；7-aerofluxus
Mouthful；8-exsiccator；81-hollow blade；9-discharge gate；10-air vent；11-cooler；12-water stream injection pump unit.
Detailed description of the invention
Below in conjunction with the accompanying drawings with specific embodiment, the present invention is described in detail.
The present invention relates to the production method of a kind of calcium chloride dihydrate.The step of the production method of this calcium chloride dihydrate is such as
Under.
A, concentration.
Described slops, chloride containing calcium mass fraction is the solution of 10 ~ 12%, or reacts prepared with hydrochloric acid and limestone
Calcium chloride solution, after neutralized for described solution, supernatant, filtration, by pipeline in multi-effect evaporator 2 sent into by pump 1, through evaporation
Concentrate, its concentrated solution CaCl2Content improves to by weight 68 ~ 70%.
B, crystallization.
By pipeline by from the described concentrated solution obtained by step A, flow in crystallizer 3 by the pipeline of insulation, crystallization
Device 3 is a horizontal propelling continuous cooling crystallizer, indirectly cools down with 50 ~ 60 DEG C of warm water, obtains magma, and described magma includes containing
CaCl275.5%(mass fraction) calcium chloride dihydrate crystal and surface water.Surface water is containing CaCl2The calcium chloride of 55 ~ 60% is water-soluble
Liquid.
C, pre-evanescence of heat water.
Described magma, under the progradation of described crystallizer 3, is discharged from crystallizer discharge gate 4, enters preheating dehydrater
5.Preheating dehydrater 5 is a wedge hollow blade formula exsiccator.Described magma is added indirectly by conduction oil in preheating dehydrater 5
Heat, and except water.Described magma is heated by hollow blade, and advances to discharge gate 6.Conduction oil flow process becomes inverse with magma direction of propulsion
Stream, and to control conduction oil outlet temperature be 110 DEG C, with magma direction of propulsion, temperature linearity rises to 130 DEG C, part surface water
In moisture content be vaporized, discharge from air vent 7.The magma removing part moisture content is released from discharge gate 6.
D, be dried.
The magma of described removing part surface water, is discharged by discharge gate 6, enters exsiccator 8, and exsiccator 8 is a wedge shape
Hollow paddle type exsiccator.The magma of described removing part surface water in exsiccator 8 by the indirect heat drying of conduction oil.This institute
State magma to be heated by hollow blade 81, and advance to discharge gate 9.Conduction oil flow process becomes adverse current with magma direction of propulsion this described,
Import conduction oil temperature 150 ~ 160 DEG C, described magma is heated to be dried, and obtains the granular of chloride containing calcium 74 ~ 77% by weight
Calcium chloride dihydrate product.
E, cooling.
The product discharged from described discharge gate 9, enters cooler 11.Cooler 11 is a spiral with cooling jacket
Carrier, on helical runner, each helical blade has three otch, and cooler inwall has kneading tooth, makes the thing being fed forward
Material produces mixing, and cooling jacket is passed through cooling water.Calcium chloride dihydrate product after Bei Lengque is discharged to discharge gate, packs.
F, gas extraction system.
The water vapour that air vent 7 and air vent 10 are discharged, is aspirated condensation by water stream injection pump unit 12.Water stream injection pump unit 12
Swabbing action make preheating dehydrater 5 and exsiccator 8 in produce being dried of vacuum, beneficially evaporation of water and material.
The present invention is described in more detail below.
The present invention relates to the production method of a kind of calcium chloride dihydrate.
Calcium chloride dihydrate produces, and is to be 65 ~ 68%CaCl by the calcium chloride solution of high concentration, such as concentration2(mass fraction)
Or concentration is 65 ~ 70% CaCl2(mass fractions).This cooled crystallization of described solution, more heated be dried to obtain calcium chloride with
Weight is calculated as granular or lamellar or the spherical CaCl of 74 ~ 77%2·2H2The calcium chloride dihydrate product of O, wherein CaCl2·2H2O
Crystalline solid contains CaCl2For 75.5%(mass fraction).
The engineers and technicians of this area are well aware of, and calcium chloride has the formation of multiple combination water, consisting of: six
Hydrate CaCl2·6H2O contains CaCl250.68%；Tetrahydrate CaCl2·4H2O contains CaCl260.65%；Dihydrate
CaCl2·2H2O contains CaCl2 75.51%；Monohydrate CaCl2·H2O contains CaCl286.04%；Its formation combining water be by
Temperature is determined.
Fig. 1 is CaCl2——H2O binary system phase diagram, understands, in terms of calcium chloride weight 58 ~ 75% from phasor this described
CaCl2——H2O binary thing, the condition that calcium chloride dihydrate exists is 45 ~ 175 DEG C.
Prior art, such as Guangzhou medium ring all ages Environmental Projects Inc.'s technology, concentrated to 65 ~ 68% calcium chloride solution,
Crystallizing through flaker, crystallization becomes dihydrate CaCl2·2H2O flaky crystal body and concentration are 57%(mass fraction) chlorination
Calcium solution, these described solution those skilled in the art of the present technique are called " surface water ".Then it is dried in fluidized bed dryer.
Fluid bed inlet temperature 300 ~ 320 DEG C, at a temperature of this described 300 ~ 320, dihydrate CaCl2·2H2O flaky crystal body turns
Turn to monohydrate CaCl2·H2O and anhydrous CaCl2, therefore can not get calcium chloride dihydrate product.
Prior art, such as the fluidized bed with spraying dry technology of Jinan Zhong Chang drying equipment company limited, calcium chloride content
Be 45 ~ 50%(mass fraction) solution spraying enter fluid 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 that solid-liquid is biphase, at higher temperatures, such as
260 DEG C, integument is melted, and then produces the phenomenon forming agglomerate.
Embodiments of the present invention, are to control crystallization temperature, and the calcium chloride hydrate making generation is CaCl2·2H2O.Liquid simultaneously
Being in mutually under relatively low calcium chloride concentration, such as this described liquid phase chlorination calcium concentration by weight is 55 ~ 60%, is able to relatively low
At a temperature of H2O be vaporized.Checked in by " chemical process safety handbook ", the boiling temperature of CaCl2 aqueous solution such as table 1.
Table 1 CaCl2The boiling temperature (P=0.1MPa) of aqueous solution
An embodiment of the invention records, 68%(mass fraction) melt temperature of calcium chloride is 120 DEG C.
The more detailed step of the inventive method is as follows.
A, concentration.
Described slops, chloride containing calcium concentration is 10 ~ 12%(mass fraction) solution, or anti-with hydrochloric acid and limestone
The calcium chloride solution that should prepare, after neutralized for described solution, supernatant, filtration, is sent in multi-effect evaporator 2 through pipeline by pump 1,
Through evaporation and concentration, its concentrated solution CaCl2Content improves to by weight 68 ~ 70%.
The present inventor's step B2 in CN103342434B has been described with the method for concentration of multi-effect evaporator.
B, crystallization.
Being flowed in crystallizer 3 by the pipeline of insulation by described concentrated solution from step A by pipeline, crystallizer 3 is one
Individual horizontal propelling continuous cooling crystallizer, is cooled down as coolant indirectly by warm water.Refrigerant temperature preferably 45 ~ 100 DEG C, more preferably 50
~60℃.Obtain in terms of gross weight containing solid phase amount 45 ~ 50% and the magma containing amount of liquid phase 55 ~ 50%.The solid phase of described magma is
CaCl2·2H2The crystalline solid of O, liquid phase is containing CaCl255 ~ 60%(mass fraction) calcium chloride solution.
According to Fig. 1 CaCl2——H2O binary system phase diagram understands, and during mould temperature ＜ 45 DEG C, described concentrated solution is formed
CaCl2·4H2O+CaCl2·2H2The co-melting body of O, this described concentrated solution can form agglomerate；During mould temperature ＞ 120 DEG C, institute
The temperature stating concentrated solution is in more than the melt temperature of this concentrated solution, becomes fused solution, the moisture content vaporization temperature of this described fused solution
Degree is 180 DEG C, the vaporization difficulty of moisture content.
Described crystallizer is horizontal propelling continuous crystalizer, preferably horizontal spiral push-type continuous cooling crystallizer, this institute
Stating crystallizer is the equipment that this area engineers and technicians are understood.Such as go up what Hisoon prosperous chemical equipment technical research institute developed
In WLLJ type horizontal spiral push-type continuous cooling crystallizer, or preferred " handbook exsiccator is selected in petrochemical equipment design "
The QJ type hollow paddle type exsiccator introduced, this described exsiccator has heat transfer, the characteristic cooling down, stirring, can complete two water
The unit operation of crystallization of calcium chloride.
C, pre-evanescence of heat water.
Described magma, under the progradation of described crystallizer 3, is discharged from crystallizer discharge gate 4, enters preheating dehydrater
5.Preheating dehydrater 5 is a wedge hollow blade formula exsiccator.Described magma is added indirectly by conduction oil in preheating dehydrater 5
Heat, and except water.Described magma is heated by hollow blade, and advances to discharge gate 6.
One of the present invention preferred embodiment, and described magma, below melt temperature, is maintained stable crystal
With surface water, surface water is calcium chloride solution, so can make the CaCl of liquid phase in magma2Concentration is low, beneficially in liquid phase
H2The vaporization of O.
According to one embodiment of present invention, 68%(mass fraction) CaCl2Fusion point be 120 DEG C.By " chlorine industry
Physicochemical constant handbook " in check in the vapor pressure curve chart of calcium chloride solution, be shown in table 2 according to this chart list.
The vapour pressure of table 2 calcium chloride solution
57%(mass fraction is checked in by table 2) CaCl2The solution water vapor pressure when 117 DEG C is 0.05MPa, and this is described
Under water vapor pressure, water is vaporized.
According to the embodiment of the present invention, preheating dehydrater feed end temperature preferably 110 ~ 120 DEG C, more preferably 112 ~ 117
℃。
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%(mass fraction) CaCl2Fusion point be 135 DEG C.63%(mass is divided
Number) CaCl2The solution water vapor pressure when 130 DEG C is 0.05MPa, and under this described water vapor pressure, water is vaporized.
According to the embodiment of the present invention, preheating dehydrater discharge end temperature preferably 125 ~ 135 DEG C, more preferably 125 ~ 130
℃。
According to the embodiment of the present invention, the temperature of described preheating dehydrater, by feed end temperature preferred 112 ~ 117
DEG C, preferred 125 ~ 130 DEG C to discharge end temperature, the direction that described temperature advances with magma, temperature linearity rises.Its feature
It is that the temperature of this described magma is in the water in below the melt temperature of magma, magma surface water in preheating dehydrater this described
Vapourizing temperature more than.
According to the embodiment of the present invention, the pressure in preheating dehydrater 5 is 0 ~ 0.1MPa, preferably 0.04 ~ 0.06 MPa,
More preferably 0.04 ~ 0.05 MPa.
Described preheating dehydrater is wedge hollow blade drier.Wedge hollow blade drier is this area engineering
The equipment that personnel are known.Such as, Jiangsu Xianfeng Drying Engineering Co., Ltd. the JG type hollow paddle type exsiccator sold, often
The blade dryer that drying equipment Science and Technology Ltd. sells is tolerated it in state.
The heating agent that feature of this invention is that described wedge hollow blade drier is conduction oil.The import and export of heating agent set
Put 2 ~ 3, controlled the temperature of described magma, linear rise by regulation flow rate of heat medium.
D, be dried.
The magma of described removing part surface water, is discharged by discharge gate 6, enters exsiccator 8, and exsiccator 8 is a wedge shape
Hollow paddle type exsiccator.The magma of described removing part surface water in exsiccator 8 by the indirect heat drying of conduction oil.This institute
State magma to be heated by hollow blade 81, and advance to discharge gate 9.Conduction oil flow process becomes adverse current with magma direction of propulsion this described.
The described magma that described temperature is 125 ~ 130 DEG C entering exsiccator 8 discharged by step C discharge gate 6, mainly
Calcium chloride dihydrate crystalline solid, also surface water.It is the solution of chloride containing calcium 63 ~ 65% according to surface water described in the phasor of Fig. 1.Root
According to the vapor pressure characteristics of calcium chloride solution, this described surface water its steam pressure when 140 DEG C is 0.06 MPa.According to Fig. 1, brilliant
During slurry temperature ＞ 175 DEG C, crystalline solid starts to lose and combines water, is converted into water calcium chloride and an anhydrous calcium chloride.The present invention is the most dry
Dry temperature 140 ~ 175 DEG C, more preferably 150 ~ 160 DEG C.Described magma is heated to be dried, and obtains the granular of chloride containing calcium 74 ~ 77%
Calcium chloride dihydrate product.
Described exsiccator is hollow blade dryer.Hollow blade dryer is known to the art engineers and technicians
The equipment of dawn, the petrochemical equipment design that Sinopec Group Shanghai Engineering Co., Ltd.'s tissue is write selects handbook " to be dried
Device " in have detailed introduction.
E, cooling.
The product discharged from described discharge gate 9, enters cooler 11.Cooler 11 is a spiral with cooling jacket
Carrier, on helical runner, each helical blade has three otch, and cooler inwall has kneading tooth, makes the thing being fed forward
Material produces mixing, and cooling jacket is passed through cooling water.Calcium chloride dihydrate product after Bei Lengque is discharged to discharge gate, packs.
F, gas extraction system.
According to the embodiment of the present invention, do not produce, with being dried, the dust that environment is impacted except water.
The fluidized bed with spraying drying-granulating technology that prior art uses, the fine grained in fluid bed is often carried over, and needs Pang
Big thin powder recovery processing means and dust arrester.There is not fluidisation and big air-flow in embodiments of the present invention, therefore the thinnest
Grain dust.The water vapour that air vent 7 and air vent 10 are discharged in embodiments of the present invention, is aspirated by water stream injection pump unit 12
Condensation.The swabbing action of water stream injection pump unit 12 produces the steaming of vacuum, beneficially water in making preheating dehydrater 5 and exsiccator 8
Send out and material be dried.
Pressure preferably 0.01 ~ 0.09MPa in described preheating dehydrater 5 and exsiccator 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 highly dissoluble of calcium chloride dihydrate, by water
The injection water dissolution of ejector pump unit.
Water stream injection pump unit 12 is the equipment that this area engineers and technicians are familiar with, can be easily in " chemical process
Design manual " middle selection.
The process of calcium chloride dihydrate produced according to the invention is in crystallizer, preheating dehydrater, exsiccator and cooler
Carrying out, this said equipment described needs heat transfer at the part of appliance of contact calcium chloride material, and tolerates chloride ion and high temperature, as
Suitably metal material, preferably less than steel alloy, dual phase steel, titanium, Hastelloy.More preferably less than steel alloy, such as 10CrMoAl, double
Xiang Gang, such as 2507 dual phase steels.
According to the mode of the present invention, the industrial calcium chloride dihydrate powder granular products obtained, this described industry calcium chloride dihydrate
Product meets the index request of GB/T26520-2011 " calcium chloride dihydrate ".
In the present invention, the content of calcium chloride and various material thereof is all to use existing national technical standard or this technology neck
The known method in territory is analyzed.
Embodiment 1.
Take in multi-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker
In on electric furnace heated and boiled, evaporation and concentration become by weight 68.8% calcium chloride concentrated solution.Pour described concentrated solution into diameter
In the rustless steel crystallizing and drying tank with rake stirring paddle of 110mm height 150mm, crystallizing and drying tank is placed in 50 DEG C of warm water,
Stirring cooling 3min, obtains magma.Magma is placed in pre-evanescence of heat water in 110 DEG C of oil bath pans together with crystallizing and drying tank, preheating
Temperature, with stirring, 2.67 DEG C/min of heating rate in 15min, is directly risen to 150 DEG C by 110 DEG C, constantly stirs by removal process
Mixing, obtain granular " calcium chloride dihydrate " product 844g after being dried 17min, analyzing its calcium chloride content is that 74.57%(mass is divided
Number).Crystallizing and drying process lasts 35min.
The analysis method of calcium chloride is GB/T23941-2009 " industrial calcium chloride analysis method ".
Comparative example 1.
Take in multi-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker
In on electric furnace heated and boiled, evaporation and concentration becomes the calcium chloride concentrated solution of by weight 68.8%, is poured into by described concentrated solution with real
Execute in the rustless steel crystallizing and drying tank with rake stirring paddle that example 1 is identical, crystallizing and drying tank be placed in 155 DEG C of oil bath pans,
Oil bath temperature controls, at 153 ~ 155 DEG C, to be stirred continuously, and after lasting 30min, material clumps together bulk, and rake stirring paddle is stuck.
Continue after crushing material to stir with rake stirring paddle.After crystallizing and drying lasts 130min, obtain granular calcium chloride dihydrate product,
Analyzing its calcium chloride content is 71.16%(mass fraction).This described calcium chloride dihydrate product does not meets GB/T26520-2011
The technology requirement of " calcium chloride dihydrate ".Continue stirring, heat drying, continue to last 60min, obtained granular two water chlorination
Calcium product 851g, analyzing its calcium chloride content is 74.00%(mass fraction).According to mode described in this comparative example, obtain chlorine
Change calcium content 74.00%(mass fraction) " calcium chloride dihydrate " product, crystallizing and drying process lasts 190min.
Embodiment 2.
Take in multi-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker
In on electric furnace heat, evaporation and concentration become by weight 68% calcium chloride concentrated solution.Described concentrated solution is poured into and embodiment 1
In the identical rustless steel crystallizing and drying tank with rake stirring paddle, crystallizing and drying tank is placed in 40 DEG C of water-baths, stirring cooling
4min, obtains magma.Magma is placed in pre-evanescence of heat water in 110 DEG C of oil bath pans together with crystallizing and drying tank, preheats removal process
With stirring, after 5min, starting to be to slowly warm up to 130 DEG C, temperature-rise period continues 23min, and magma is not the most in molten condition.Dry
Dry step: be continuously heating to 150 DEG C, be stirred continuously, obtains granular " calcium chloride dihydrate " product 850g after being dried 14min, point
Analysing its calcium chloride content is 74.07%(mass fraction).Crystallizing and drying process lasts 46min.
Comparative example 2.
Take in multi-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker
In on electric furnace heat, evaporation and concentration become by weight 68.2% calcium chloride concentrated solution.Described concentrated solution is poured into and embodiment
In the 1 identical rustless steel crystallizing and drying tank with rake stirring paddle, crystallizing and drying tank is placed in room temperature water-bath about 30 DEG C, stirs
Mix cooling 4min, obtain magma.Magma is placed in pre-evanescence of heat water, pre-evanescence of heat in 110 DEG C of oil bath pans together with crystallizing and drying tank
Temperature, with stirring, is raised slowly to 120 DEG C after 10min by water process, and in tank, magma state is basically unchanged.Afterwards in 13min
2.3 DEG C/min of heating rate is warming up to 150 DEG C and is dried, and obtains granular " calcium chloride dihydrate " product after being dried 25min
828g, analyzing its calcium chloride content is 76%(mass fraction).Crystallizing and drying process lasts 52min.
Embodiment 3.
Take in multi-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker
In on electric furnace heat, evaporation and concentration become by weight 70% calcium chloride concentrated solution.Described concentrated solution is poured into and embodiment 1
In the identical rustless steel crystallizing and drying tank with rake stirring paddle, crystallizing and drying tank is placed in 45 DEG C of water-baths, stirring cooling
4min, obtains magma.Magma is placed in pre-evanescence of heat water in 110 DEG C of oil bath pans together with crystallizing and drying tank, preheats removal process
With stirring, after 5min, starting to be to slowly warm up to 135 DEG C, temperature-rise period continues 25min, and magma is not the most in molten condition.Dry
Dry step: be continuously heating to 175 DEG C, be stirred continuously, obtains granular " calcium chloride dihydrate " product 836g after being dried 10min, point
Analysing its calcium chloride content is 75.28%(mass fraction).Crystallizing and drying process lasts 44min.
Embodiment 4.
Take in multi-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker
In on electric furnace heat, evaporation and concentration become by weight 70% calcium chloride concentrated solution.Described concentrated solution is poured into and embodiment 1
In the identical rustless steel crystallizing and drying tank with rake stirring paddle, crystallizing and drying tank is placed in 50 DEG C of water-baths, stirring cooling
3min, obtains magma.Magma is placed in pre-evanescence of heat water in 112 DEG C of oil bath pans together with crystallizing and drying tank, preheats removal process
With stirring, after 5min, starting to be to slowly warm up to 125 DEG C, temperature-rise period continues 23min, and magma is not the most in molten condition.Dry
Dry step: be continuously heating to 160 DEG C, be stirred continuously, obtains granular " calcium chloride dihydrate " product 840g after being dried 14min, point
Analysing its calcium chloride content is 75%(mass fraction).Crystallizing and drying process lasts 45min.
Embodiment 5.
Take in multi-effect evaporator five effect following current vaporizer outputs by weight 35% calcium chloride solution 1800g in beaker
In on electric furnace heat, evaporation and concentration become by weight 68% calcium chloride concentrated solution.Described concentrated solution is poured into and embodiment 1
In the identical rustless steel crystallizing and drying tank with rake stirring paddle, crystallizing and drying tank is placed in 60 DEG C of water-baths, stirring cooling
3min, obtains magma.Magma is placed in pre-evanescence of heat water in 117 DEG C of oil bath pans together with crystallizing and drying tank, preheats removal process
With stirring, after 5min, starting to be to slowly warm up to 130 DEG C, temperature-rise period continues 20min, and magma is not the most in molten condition.Dry
Dry step: be continuously heating to 150 DEG C, be stirred continuously, obtains granular " calcium chloride dihydrate " product 818g after being dried 18min, point
Analysing its calcium chloride content is 77%(mass fraction).Crystallizing and drying process lasts 46min.
In above example, CaCl2Concentrated solution derives from the slops in ammonia alkali legal system soda manufacture or hydrochloric acid and Calx
Stone reacts the slops in the calcium chloride solution or expoxy propane obtained and epoxychloropropane production.
Claims (2)
1. the production method of a calcium chloride dihydrate, it is characterised in that comprise the following steps:
A. concentrate: after calcium chloride solution is neutralized, supernatant, filtration, by pipeline in multi-effect evaporator (2) sent into by pump (1), warp
Evaporation and concentration, obtains the CaCl that mass fraction is 68%～70% after concentration2Concentrated solution；
B. crystallization: being flowed in crystallizer (3) by the pipeline of insulation by the concentrated solution from step a, described crystallizer (3) is
Individual horizontal propelling continuous cooling crystallizer, crystallizer refrigerant temperature is 50 DEG C～60 DEG C, and the magma after crystallization includes two water chlorinations
Calcium crystal and surface water, described surface water is CaCl2The calcium chloride water that mass fraction is 55%～60%；
The most pre-evanescence of heat water: the magma in step b, under the progradation of described crystallizer (3), is arranged from crystallizer discharge gate (4)
Going out, enter in preheating dehydrater (5), preheating dehydrater (5) feed end temperature is 112 DEG C～117 DEG C, and discharge end temperature is 125
DEG C～130 DEG C, and preheating temperature for removing water with described magma direction of propulsion linear rise；Described preheating dehydrater (5) is a wedge
Shape hollow paddle type exsiccator, magma is heated indirectly by conduction oil in preheating dehydrater (5), and except water；Described magma is by sky
The heating of heart blade also advances to preheating dehydrater discharge gate, and conduction oil flow process becomes adverse current, part surface water with magma direction of propulsion
In moisture content be vaporized, from air vent (7) discharge, remove part surface water magma from preheating dehydrater discharge gate release；
D. it is dried: the magma removing part surface water is discharged into exsiccator (8), described exsiccator by preheating dehydrater discharge gate
(8) being a wedge hollow blade formula exsiccator, the magma removing part surface water is added indirectly by conduction oil in exsiccator (8)
Heated drying；The magma of this removing part surface water is by hollow blade (81) heating and advances to exsiccator discharge gate, conduction oil stream
Journey becomes adverse current, import conduction oil temperature 150～160 DEG C with the direction of propulsion of the magma of this removing part surface water, removes part
The magma of surface water is heated to be dried, and obtains chloride containing calcium 74～the granular calcium chloride dihydrate product of 77% by weight；
E. cooling: exsiccator discharge gate discharge product enter cooler (11), described cooler (11) be one with cooling
The auger conveyor of chuck, on helical runner, each helical blade has three otch, and cooler inwall has kneading tooth, make to
The material of front conveying produces mixing, and cooling jacket is passed through cooling water, and the calcium chloride dihydrate product after being cooled is to cooler discharge
Mouth is discharged；
F. aerofluxus: the water vapour that air vent is discharged, by water stream injection pump unit (12) suction condensation, described water stream injection pump unit (12)
Swabbing action make preheating dehydrater (5) and exsiccator (8) in produce negative pressure, this negative pressure makes the pressure in preheating dehydrater (5)
Be 0.01～0.09MPa, to make the pressure in exsiccator (8) be 0.01～0.09MPa.
The production method of a kind of calcium chloride dihydrate the most according to claim 1, it is characterised in that in described step a
CaCl2Concentrated solution derives from the slops in ammonia alkali legal system soda manufacture or hydrochloric acid and the limestone calcium chloride that obtains of reaction is molten
Liquid or expoxy propane and epoxychloropropane produce in slops.
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| 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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| 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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Address after: 315812 Zhejiang city of Ningbo province Donggang Daxie Development Zone No. 7 North Road Patentee after: Ningbo new materials Limited by Share Ltd Address before: 315812 Zhejiang city of Ningbo province Donggang Daxie Development Zone No. 7 North Road Patentee before: Ningbo Huanyang Chemical Co., Ltd. |