CN109896551A - The solidification manufacturing method and its solidification manufacture system of ferric chloride (FeCl36H2O) - Google Patents
The solidification manufacturing method and its solidification manufacture system of ferric chloride (FeCl36H2O) Download PDFInfo
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- CN109896551A CN109896551A CN201810982162.8A CN201810982162A CN109896551A CN 109896551 A CN109896551 A CN 109896551A CN 201810982162 A CN201810982162 A CN 201810982162A CN 109896551 A CN109896551 A CN 109896551A
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- Prior art keywords
- fecl36h2o
- aforementioned
- ferric chloride
- solidification
- iron
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 title claims abstract description 79
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 70
- 238000007711 solidification Methods 0.000 title claims abstract description 59
- 230000008023 solidification Effects 0.000 title claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 185
- 229910052742 iron Inorganic materials 0.000 claims abstract description 95
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 45
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 41
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000004821 distillation Methods 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 235000021110 pickles Nutrition 0.000 claims abstract description 12
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims description 37
- 238000007254 oxidation reaction Methods 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000006386 neutralization reaction Methods 0.000 claims description 26
- 238000007710 freezing Methods 0.000 claims description 25
- 230000008014 freezing Effects 0.000 claims description 25
- -1 iron ion Chemical class 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010129 solution processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of solidification manufacturing method of ferric chloride (FeCl36H2O), pass through solidification manufacture system manufacture, it is main first with the acid pickle containing hydrochloric acid, iron, or iron, hydrochloric acid, water is raw material, obtain ferrous chloride solution, then, oxidant is added in ferrous chloride solution, obtain chlorination iron liquid, and in negative-pressure vacuum environment, between 30 DEG C~100 DEG C of operating temperature, heat chlorination iron liquid, obtain distillation waste water, and the chlorination iron liquid after concentration, finally, in low temperature drying environment, with -20 DEG C~+20 DEG C of operating temperature, it freezes and dries the chlorination iron liquid after aforementioned concentration, chlorination iron liquid after making concentration is long brilliant in exothermic process, purity is obtained between 60%~99% ferric chloride (FeCl36H2O) solid.Whereby, the present invention not containing sulfate radicals or organic solvent, and be able to use acid pickle and form environmental friendly regenerated product, acquired iron chloride concentration expressed in percentage by weight is stablized, and not only processing procedure can meet ecological requirements, and can simplify processing procedure and Improving The Quality of Products.
Description
Technical field
The present invention relates to a kind of ferric chloride (FeCl36H2O)s, a kind of solidification manufacturing method more particularly to ferric chloride (FeCl36H2O) and
It solidifies manufacture system.
Background technique
Ferric chloride (FeCl36H2O) (FeCl3.6H2O), there is powerful metathesis for various metal materials, therefore, using model
It encloses quite extensively, is usually used in the etching of the circuit etching or metal parts of electronic product, or be used as water treatment agent, metallurgical industry
Chlorinating agent, dye industry oxidant and mordant etc..
Such as China Patent Publication No. CN104003451 Patent Case, China Patent No. CN106745321 patent
The preparation method of existing ferric chloride (FeCl36H2O) disclosed in case, China Patent No. CN102701290 Patent Case, mainly all
It is by ferric chloride solution FeCl3After evaporation and concentration, using cooling and solid-state ferric chloride (FeCl36H2O) FeCl is collected3·6H2O.And it is preceding
The difference for stating Patent Case is:
CN104003451 Patent Case is with anhydrous ferric chloride FeCl3(solid granular) is raw material, and uses organic solvent
The solution FeCl of concentration is obtained by extraction3, centrifuge is recycled to collect solid FeCl3·6H2O.Since raw material itself is into
Product, and including organic solvent, therefore, not only higher cost, and long-term sucking can cause undesirable influence to operator's human body.
CN106745321 Patent Case is with solid-state frerrous chloride FeCl2Hydrochloric acid is added, FeCl is made2Solution, and utilize nitrous
Sour sodium is as oxidant by aforementioned FeCl2Solution oxide is at FeCl3Solution after being concentrated by evaporation and puts into solid-state crystal seed FeCl3It is cold
But it crystallizes, obtains suspension, and aforementioned suspension is separated by solid-liquid separation to get solid finished product FeCl3·6H2O(s).Due to needing to throw
Enter solid-state crystal seed, and using nitrogenous oxidant as raw material, it is therefore, not only at high cost, and nitrogenouz wastes can be generated, it will be to ring
Border impacts.
CN102701290 Patent Case adds iron that FeCl is made with acid pickle2Solution, recycle chlorine as oxidant will before
State FeCl2Solution oxide is at FeCl3Solution, and the temperature is maintained to be not greater than 80 DEG C, it is stirred for after being cooled to 20 DEG C~30 DEG C
And put into solid-state crystal seed FeCl3Form FeCl3Supersaturated solution, then be statically placed in 5 DEG C~10 DEG C insulating boxs and stand 5~8 hours, i.e.,
Obtain solid finished product FeCl3·6H2O(s).Due to need to equally put into crystal seed, and the control of its temperature is more complicated, causes processing procedure multiple
It is miscellaneous.
Summary of the invention
The purpose of the present invention is to provide a kind of processing procedures can meet ecological requirements, and can simplify processing procedure, and is promoted and produced
The solidification manufacturing method and its solidification manufacture system of the ferric chloride (FeCl36H2O) of quality.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention comprising the steps of:
Using the acid pickle containing hydrochloric acid, iron or iron, hydrochloric acid, water as raw material, ferrous chloride solution is obtained.
Oxidant is added in ferrous chloride solution, obtains the chlorination iron liquid that iron ion concentration expressed in percentage by weight is m.
In negative-pressure vacuum environment, to heat chlorination iron liquid between 30 DEG C~100 DEG C of operating temperature, it is useless to obtain distillation
After water, and concentration and iron ion concentration expressed in percentage by weight is the chlorination iron liquid of n, wherein n > m.
Chlorination in low temperature drying environment, with -20 DEG C~+20 DEG C of operating temperature, after freezing and dry aforementioned concentration
Iron liquid, the chlorination iron liquid after making concentration is long brilliant in exothermic process, obtains purity between 60%~99% ferric chloride (FeCl36H2O)
Solid.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention when using acid pickle, iron as raw material, further adds through aeration
After heat, heavy metal precipitation, filtering, aforementioned ferrous chloride solution is obtained.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention, m=30%~48%, n=48%~63%.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention, aforementioned oxidizer can be liquid chlorine, sodium chlorate, hydroxide
Potassium is one of.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention, obtains ferrous chloride solution simultaneously, the HCl gas of generation,
Hydrogen, further and after air neutralisation treatment, discharge is extraneous.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention, the environment of aforementioned negative pressure vacuum are to utilize to be connected to receiving
There is the water pump of the container of ferrous chloride solution, generates the water flow washed away from top to bottom, and then pumping is generated to the gas in aforesaid receptacle
Suction effect makes to form negative-pressure vacuum environment in container.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention can be first in aforementioned negative pressure after obtaining ferrous chloride solution
Under vacuum environment, after being concentrated and ferrous ion concentration expressed in percentage by weight circle is in 37%~48% ferrous chloride solution, adds
Oxidant is aoxidized.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention, aforementioned low temperature drying environment can using water proof cooling,
Air-cooled cooling, stirring cooling are one of.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention is made by the cold service of aforementioned low temperature drying environment
Aforementioned chlorination iron liquid generated condensation of moisture in exothermic process, and the external world is discharged in the aqueous vapor of aforementioned condensation.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention, before the iron chloride liquid freeze-drying after aforementioned concentration,
Chlorination iron liquid after aforementioned concentration further after granulation is handled, obtains suspension chlorination iron coarse crystallization body and liquid clout, aforementioned
Suspension chlorination iron coarse crystallization body in aforementioned low temperature drying environment, obtains purity circle in 60%~99% six water after forming
Ferric trichloride solid.
The solidification manufacturing method of ferric chloride (FeCl36H2O) of the invention, after the recycling of aforementioned liquids clout, after aforementioned concentration is added
Ferric chloride solution obtain purity circle in 60%~99% ferric chloride (FeCl36H2O) solid and in aforementioned low temperature drying environment.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention includes frerrous chloride manufacturing device, oxidation unit, negative pressure
Vacuum plant and low temperature drying device.
The frerrous chloride manufacturing device includes reaction vessel, for the acid pickle containing hydrochloric acid, iron or iron, hydrochloric acid, water etc.
Raw material reacts in the reaction vessel, obtains ferrous chloride solution.
The oxidation unit includes oxidation container, is reacted in the oxidation container for aforementioned ferrous chloride solution, oxidant,
Obtain the chlorination iron liquid that iron ion concentration expressed in percentage by weight is m.
The negative-pressure vacuum device includes closed container, the closed container be configured to operating temperature between 30 DEG C~
100 DEG C of negative-pressure vacuum environment heats in the closed container for aforementioned chlorination iron liquid, obtains distillation waste water, and after concentration
And iron ion concentration expressed in percentage by weight is the chlorination iron liquid of n, wherein n > m.
The low temperature drying device includes freezing room, and the drying unit for excluding aqueous vapor in the freezing room, described
Freezing room is configured to operating temperature between -20 DEG C~+20 DEG C of low temperature drying environment, exists for the chlorination iron liquid after aforementioned concentration
Heat release in the freezing room, and it is long brilliant in exothermic process, purity is obtained between 60%~99% ferric chloride (FeCl36H2O) solid.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, the frerrous chloride manufacturing device further include being connected to institute
The hydrochloric acid container of reaction vessel is stated, the hydrochloric acid container is for hydrochloric acid needed for supplying reaction process.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, the frerrous chloride manufacturing device further include being connected to institute
The air neutralisation unit of reaction vessel Yu the hydrochloric acid container is stated, the air neutralisation unit is used to import extraneous air, make
The reaction vessel, hydrochloric acid container during the reaction caused by HCl gas, hydrogen further with air neutralisation treatment
Afterwards, it is expelled directly out the external world.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, the oxidation unit further include being connected to the oxidation to hold
The recovery unit of device, the recovery unit are used to store ferrous chloride solution, and the recycling oxidation container is produced in reacting
Raw extra chlorine, oxidizing gas.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, the oxidation unit further include being connected to the oxidation to hold
The air neutralisation unit of device and the recovery unit, the air neutralisation unit are used to import extraneous air, make the oxidation
Container during the reaction caused by HCl gas, hydrogen, extra chlorine, oxidizing gas further with air neutralisation treatment
Afterwards, it is expelled directly out the external world.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, the negative-pressure vacuum device further include be connected to it is described close
The condenser pipe of container is closed, and is connected to the vacuum barrel of the condenser pipe, the condenser pipe is for condensing aforementioned chlorination iron liquid in institute
The aqueous vapor generated when being heated in closed container is stated, aqueous vapor is made to form distillation waste water, the vacuum barrel is useless for collecting aforementioned distillation
Water.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, the negative-pressure vacuum device further include be connected to it is described cold
The water pump of solidifying pipe, the closed container, the water pump generate the water flow washed away from top to bottom, and then to the condenser pipe, described
Gas in closed container generates swabbing action, makes to form negative-pressure vacuum environment in the closed container.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, low temperature drying device further includes heat exchange unit, described
Heat exchange unit is for making the freezing room cool down.
The solidification manufacture system of ferric chloride (FeCl36H2O) of the invention, the drying unit, which has, is mounted on the freezing room
Multiple fans.
Beneficial effects of the present invention: the present invention not containing sulfate radicals or organic solvent, and be able to use acid pickle and form environmental protection
Reconstituted product, acquired iron chloride concentration expressed in percentage by weight are stablized, and not only processing procedure can meet ecological requirements, and can simplify system
Journey and Improving The Quality of Products.
Detailed description of the invention
Other features of the invention and effect will be clearly presented in the embodiment referring to schema, in which:
Fig. 1 is a schematic diagram, illustrates one embodiment of the solidification manufacture system of ferric chloride (FeCl36H2O) of the present invention；
Fig. 2 is a flow chart, illustrates a kind of solidification manufacturing method of the embodiment；And
Fig. 3 is a flow chart, illustrates another solidification manufacturing method of the embodiment.
Specific embodiment
Refering to fig. 1, one embodiment of the solidification manufacture system of ferric chloride (FeCl36H2O) of the present invention includes a frerrous chloride
The negative-pressure vacuum device 3 of oxidation unit 2, one of manufacturing device 1, one and a low temperature drying device 4.
The frerrous chloride manufacturing device 1 includes a reaction vessel 11, a salt for being connected to the reaction vessel 11
Sour container 12, and it is connected to an air neutralisation unit 13 of the reaction vessel 11 and the hydrochloric acid container 12.The reaction
The acid pickle containing hydrochloric acid, iron ore material or natural iron material (such as iron powder, iron ore), hydrochloric acid, water original are accommodated in container 11
Material.The hydrochloric acid container 12 is for hydrochloric acid needed for supplying reaction process.The air neutralisation unit 13 is used to import extraneous
Air, the gas mixing that air and the reaction vessel 11, the hydrochloric acid container 12 is discharged, reaches neutralization.
The oxidation unit 2 includes an oxidation container 21 for being connected to the reaction vessel 11, is connected to the oxidation
One recovery unit 22 of container 21, and be connected in an air of the oxidation container 21 and the recovery unit 22 and single
Member 23.The oxidation container 21 is used to accommodate reactant, the oxidant of the reaction vessel 11, and ferrous chloride solution is made to be converted to chlorine
Change iron liquid.The recovery unit 22 is for storing ferrous chloride solution, and the extra chlorine of recycling.The air neutralisation unit is for leading
Enter extraneous air, the gas mixing that air and the oxidation container 21, the recovery unit 22 is discharged reaches neutralization effect
Fruit.
The negative-pressure vacuum device 3 include a closed container 31 for being connected to the oxidation container 21, be connected to it is described
One condenser pipe 32 of closed container 31, a vacuum barrel 33 for being connected to the condenser pipe 32, and it is connected to the condenser pipe
32, a water pump 34 of the closed container 31.The closed container 31 is configured to operating temperature between 30 DEG C~100 DEG C
One negative-pressure vacuum environment, and the reactant for accommodating the oxidation container 21.The condenser pipe 32 is used for condensed reactants
The aqueous vapor generated when being heated in the closed container 31 makes aqueous vapor form distillation waste water.Before the vacuum barrel 33 is for collecting
State distillation waste water.The water pump 34 generates the water flow washed away from top to bottom, and then to the condenser pipe 32, the closed container 31
Interior gas generates swabbing action, and the closed container 31 is made to be constructed negative-pressure vacuum environment.
The low temperature drying device 4 includes 41, heat exchange units 42 of a freezing room and a drying unit 43.
It is suitable for that multiple molds 5 are arranged in the freezing room 41, the mold 5 accommodates aforementioned reactants.The heat exchange unit 42
For making the freezing room 41 cool down.The drying unit 43 has the multiple fans 431 for being mounted on the freezing room 41, is used for
Exclude aqueous vapor in the freezing room 41.Whereby, the freezing room 41 is made to be configured to operating temperature between -20 DEG C~+20 DEG C
One low temperature drying environment.
Refering to fig. 1, Fig. 2 illustrates a kind of solidification manufacturing method of the invention below in conjunction with the embodiment:
(ferrous chloride solution processing procedure 6)
There are two types of embodiments altogether for ferrous chloride solution processing procedure 1 of the invention.
1st kind of embodiment: the reaction vessel 11, warp is added using the acid pickle containing hydrochloric acid, iron ore, iron material as raw material
After being aerated heating, heavy metal precipitation, filtering, the ferrous chloride solution of industrial level is obtained.
2nd kind of embodiment: using natural iron material (such as iron powder, iron ore), hydrochloric acid, water as raw material, the reaction is added
Container 11 obtains the ferrous chloride solution for meeting tap water medication specification grade.It in the present embodiment, is with iron concentration expressed in percentage by weight
Between 85%~98% iron material, hydrogen chloride concentration expressed in percentage by weight 32% hydrochloric acid, Ji Shuiwei raw material.
On processing procedure, aforementioned two kinds of embodiments can control iron, chlorination by the frerrous chloride manufacturing device 1
The ratio of hydrogen, water, and it is small between 8~36 between 30 DEG C Celsius~90 DEG C and processing time between 0~5, process temperatures in pH value
When process conditions in, obtain ferrous ion (Fe2+) concentration expressed in percentage by weight between 30%~36% ferrous chloride solution.
Chemical equation: Fe+2HCl → FeCl2+H2
It is worth noting that other than it can obtain ferrous chloride solution, can also generate hydrochloric acid in ferrous chloride solution processing procedure 6
Gas, hydrogen etc., no extra waste water generate.And aforementioned HCl gas, hydrogen etc. further with the air neutralisation unit 13
In air neutralisation treatment after, so that it may meet environmental regulation, be expelled directly out the external world.
(oxidation process 7)
Aforementioned ferrous chloride solution is imported into the oxidation container 21, and oxidant is added, and passes through the oxidation unit 2,
In the redox time in 4~10 hours process conditions, iron ion (Fe is obtained3+) concentration expressed in percentage by weight be m chlorination
Iron liquid.In the present embodiment, m=30%~48%.
The ferrous chloride solution of aforementioned oxidizer cooperation industrial level or the frerrous chloride for meeting tap water medication specification grade
It is one of to can be liquid chlorine, sodium chlorate, potassium hydroxide for liquid, thus is distinguished into 2 kinds of embodiments.
1st kind of embodiment: sodium chlorate (NaClO is added in aforementioned industrial grade ferrous chloride solution3) or potassium hydroxide
(KOH), iron ion (Fe is obtained3+) concentration expressed in percentage by weight be m between 30%~48% chlorination iron liquid.
Chemical equation 1:
7FeCl2+NaClO3+6HCl→7FeCl3+3H2O+Na+
Chemical equation 2:
2FeCl2+2HCl+6KOH→2Fe(OH)3 -+6KCl+H2
2nd kind of embodiment: liquid chlorine is added in the aforementioned ferrous chloride solution for meeting tap water medication specification grade, obtains
Iron ion (Fe3+) concentration expressed in percentage by weight be m between 30~48% chlorination iron liquid.
Chemical equation: 2FeCl2+Cl2→2FeCl3
Aforementioned two kinds of embodiments can control obtained chlorination iron liquid composition by the oxidation unit 2,
In, redox value (ORP) is between 600~1200, and between 0.1%~3%, insoluble matter (s/s) contains ion ionization rate (acid)
Measure 0.02wt%.
It is worth noting that other than it can obtain chlorination iron liquid, can also generate HCl gas, hydrogen in oxidation process 7
Gas, extra chlorine and oxidizing gas, no extra waste water generate.Aforementioned extra chlorine, oxidizing gas can be by the recovery units 22
Recycling.And aforementioned HCl gas, hydrogen, and remaining chlorine, oxidizing gas are then further and in the air neutralisation unit 23
Air neutralisation treatment after, so that it may meet environmental regulation, be expelled directly out the external world.
(processing procedure 8 is concentrated in negative pressure of vacuum)
Aforementioned ferrous chloride solution is imported into the closed container 31 and passes through the negative-pressure vacuum in negative-pressure vacuum environment
Device 3 with operation temperature between 30 DEG C Celsius~100 DEG C and concentration time under conditions of 4~8 hours, by aforementioned chlorination
Water evaporation in iron liquid is aqueous vapor, makes aforementioned aqueous vapor after the condenser pipe 32 condensation, forms pH value between 1~3 distillation
Waste water, and concentrate in the vacuum barrel 33.Aforementioned chlorination iron liquid is concentrated to get iron ion (Fe because of water evaporation3+) weight percent
Concentration is the chlorination iron liquid of n, and rufous, and n > m is presented in liquid color.In the present embodiment, n is 48%~63%, if dense
When the yield of contracting afterchlorinate iron liquid is 11KL, generated distillation waste water is 1~4KL.
In the present embodiment, aforementioned negative pressure vacuum environment is to utilize to be connected to the closed container 31, the condenser pipe 32
With the water pump 34 of the vacuum barrel 33, the water flow washed away from top to bottom is generated, and then to the condenser pipe 32, the closed container
Gas in 31 generates swabbing action, and the closed container 31 is made to be constructed negative-pressure vacuum environment.Whereby, make under negative pressure state
The boiling point of chlorination iron liquid reduces, and can just evaporate under conditions of operation temperature is between 30 DEG C Celsius~100 DEG C.
It is worth noting that in negative pressure of vacuum concentration processing procedure 8, in addition to the chlorination iron liquid after be concentrated, distillation are given up
Outside water, no extra waste is generated.And aforementioned distillation waste water is after the sedimentation of raw water (i.e. natural water) acid-base neutralization, so that it may accord with
Environmental regulation is closed, the external world is expelled directly out.
In addition, aforementioned ferrous chloride solution can first carry out aforementioned vacuum negative pressure and processing procedure is concentrated before carrying out aforementioned oxidation processing procedure 7
8, obtain ferrous ion (Fe2+) concentration expressed in percentage by weight between 48%~63% ferrous chloride solution, then, the protochloride that will be obtained
Iron liquid carries out aforementioned oxidation processing procedure 7 and negative pressure of vacuum concentration processing procedure 8 again makes the iron ion (Fe of aforementioned ferric chloride solution whereby3+)
Concentration expressed in percentage by weight improves, and the related iron ion (Fe for making aforementioned concentration afterchlorinate ferrous solution3+) the dense raising of weight percent.
(freeze-drying curing process 9)
Chlorination iron liquid after aforementioned concentration is rested in the mold 5 in the freezing room 41, chlorination iron liquid is made to exist
It is long brilliant during the standing of the freezing room 41.Aforementioned low temperature drying environment can also use water proof cooling, air-cooled cooling or stir
Cooling is mixed, when being not limited.
It therefore, in the present embodiment, is to make to be cooled to Celsius -20 in the freezing room 41 by the heat exchange unit 42
DEG C~+20 DEG C, and with the fan 431 of the drying unit 43, exclude aqueous vapor in the freezing room 41.Whereby, make described
Freezing room 41 is configured to operating temperature between -20 DEG C~+20 DEG C of low temperature drying environment.
Whereby, so that it may under the cold service and desiccation of aforementioned low temperature drying environment, aforementioned chlorination iron liquid be made to exist
Generated condensation of moisture in exothermic process, and after the discharge of the aqueous vapor of aforementioned condensation is extraneous, drying effect is promoted, iron chloride is made
Liquid maintains persistently long brilliant solidification between -20 DEG C Celsius~+20 DEG C of operating temperature, and is controlled by the low temperature drying device 4
Behind chlorination iron liquid about 6~8 hours after iron chloride curing time, freezing and dry aforementioned concentration, 4~16 hours are stood, so that it may
Purity is obtained between 60%~99% ferric chloride (FeCl36H2O) solid (FeCl with demoulding3.6H2O)。
It is worth noting that aforementioned iron chloride concentration expressed in percentage by weight depend on (oxidation process 7) in chlorination iron liquid iron from
Son (Fe3+) iron ion (Fe of chlorination iron liquid in concentration expressed in percentage by weight, and (negative pressure of vacuum be concentrated processing procedure 8)3+) weight percent is dense
Degree.
And aforementioned ferric chloride (FeCl36H2O) solid can mating mold design, complete appearance and the golden yellow without sharp comer is presented
Block or yellowish red color block, in composition, redox value (ORP) between 800~1000, ion ionization rate (acid) between
0.1~3%, insoluble matter (s/s) content 0.02wt%, the concentration expressed in percentage by weight of chlorine is between 41%~36%.
Refering to fig. 1, Fig. 3 illustrates another solidification manufacturing method of the invention below in conjunction with the embodiment:
It is roughly the same with the first described solidification manufacturing process refering to Fig. 3, it equally include (ferrous chloride solution processing procedure
6), (oxidation process 7), (processing procedure 8 is concentrated in negative pressure of vacuum), and (freeze-drying curing process 9), are different in:
(negative pressure of vacuum be concentrated processing procedure 8) afterwards, before (freeze-drying curing process 9), also comprising (being granulated processing procedure 10).
The chlorination iron liquid after aforementioned concentration is mainly placed in a pelletizer (not shown), it is thick that suspension chlorination iron can be obtained
Crystalline solid and liquid clout.Then, aforementioned suspension chlorination iron coarse crystallization body is passing through an extruding granulator (not shown) or sky
After the molding of gas granulator (not shown), so that it may foregoing freeze dry solidification processing procedure 9 is carried out, and in aforementioned low temperature drying environment
In, freeze-drying 2~4 hours are stood, obtain purity between 60%~99% graininess ferric chloride (FeCl36H2O) solid.And it is aforementioned
After the recycling of liquid clout, the ferric chloride solution after aforementioned concentration can be added, and repeat and carry out freeze-drying curing process 9,
Purity is obtained between 60%~99% ferric chloride (FeCl36H2O) solid.
Expansion details can be deduced from the description above due to having usually intellectual in this field, do not added
It is bright.
Via above explanation, the advantages of previous embodiment, can be summarized as follows:
1, the present invention not containing sulfate radicals or organic solvent, by-product such as HCl gas, hydrogen etc., and distillation waste water are into one
Step and air neutralisation treatment, or after the sedimentation of raw water acid-base neutralization, so that it may meet environmental regulation, is expelled directly out the external world, not only
No pollution to the environment, and ecological requirements can be met.
2, the present invention is able to use acid pickle and forms environmental friendly regenerated product, and is freeze-dried in curing process 4, does not need to add
Enter crystal seed, it is at low cost.
3 and the present invention be in negative-pressure vacuum environment concentration chlorination iron liquid, be not only able to reduce chlorination iron liquid boiling point,
Operation temperature is reduced, and simplifies processing procedure and processing time, and acquired iron chloride concentration expressed in percentage by weight is stablized.
Furthermore 4, the present invention is that freeze-drying curing process 9 is carried out in low temperature drying environment, can pass through aforementioned low temperature
The cold service and desiccation of dry environment promote drying effect and Improving The Quality of Products, finished product are made to be not easy to deliquesce, and store up
It is more long to deposit easy, convenient transportation, pot-life.
5, using aforementioned low temperature drying environment, to manage the curing time of the ferrous chloride solution after aforementioned concentration, the amount of reaching
The benefit of production.
As described above, only the embodiment of the present invention is when cannot be limited the scope of implementation of the present invention with this, i.e., all
According to simple equivalent changes and modifications made by claims of the present invention and description, all still belong to the scope of the present invention.
Claims (20)
1. a kind of solidification manufacturing method of ferric chloride (FeCl36H2O) comprising the steps of:
Using the acid pickle containing hydrochloric acid, iron or iron, hydrochloric acid, water as raw material, ferrous chloride solution is obtained；
Oxidant is added in ferrous chloride solution, obtains the chlorination iron liquid that iron ion concentration expressed in percentage by weight is m；
In negative-pressure vacuum environment, to heat chlorination iron liquid between 30 DEG C~100 DEG C of operating temperature, distillation waste water is obtained, and
After concentration and iron ion concentration expressed in percentage by weight is the chlorination iron liquid of n, wherein n > m；And
In low temperature drying environment, with -20 DEG C~+20 DEG C of operating temperature, the chlorination iron liquid after aforementioned concentration is freezed and dries,
Chlorination iron liquid after making concentration is long brilliant in exothermic process, obtains purity between 60%~99% ferric chloride (FeCl36H2O) solid.
2. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: be with acid pickle, iron
When raw material, further after aeration heating, heavy metal precipitation, filtering, aforementioned ferrous chloride solution is obtained.
3. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: m=30%~48%,
N=48%~63%.
4. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: aforementioned oxidizer can be with
It is liquid chlorine, sodium chlorate, potassium hydroxide one of which.
5. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: obtain ferrous chloride solution
Meanwhile HCl gas, the hydrogen of generation, further and after air neutralisation treatment, discharge is extraneous.
6. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: aforementioned negative pressure vacuum
Environment is to generate the water flow washed away from top to bottom, and then to preceding using the water pump for being connected to the container for accommodating ferrous chloride solution
The gas stated in container generates swabbing action, makes to form negative-pressure vacuum environment in container.
7. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: obtain ferrous chloride solution
Afterwards, can be first under aforementioned negative pressure vacuum environment, after being concentrated and ferrous ion concentration expressed in percentage by weight is between 37%~48%
Ferrous chloride solution, add oxidant and aoxidized.
8. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: aforementioned low temperature drying ring
It border can be one of using water proof cooling, air-cooled cooling, stirring cooling.
9. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: dry by aforementioned low temperature
The cold service of dry environment, makes aforementioned chlorination iron liquid generated condensation of moisture in exothermic process, and by the water of aforementioned condensation
Gas discharge is extraneous.
10. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 1, it is characterised in that: after aforementioned concentration
Iron chloride liquid freeze-drying before, after granulation is handled, it is thick further to obtain suspension chlorination iron for the chlorination iron liquid after aforementioned concentration
Crystalline solid and liquid clout, aforementioned suspension chlorination iron coarse crystallization body in aforementioned low temperature drying environment, obtain pure after forming
Spend the ferric chloride (FeCl36H2O) solid between 60%~99%.
11. the solidification manufacturing method of ferric chloride (FeCl36H2O) according to claim 10, it is characterised in that: aforementioned liquids clout
After recycling, ferric chloride solution after aforementioned concentration is added, and in aforementioned low temperature drying environment, obtain purity between 60%~
99% ferric chloride (FeCl36H2O) solid.
12. a kind of solidification manufacture system of ferric chloride (FeCl36H2O), it is characterised in that: the solidification manufacture system includes:
Frerrous chloride manufacturing device, including reaction vessel, for the raw materials such as the acid pickle containing hydrochloric acid, iron or iron, hydrochloric acid, water,
Reaction, obtains ferrous chloride solution in the reaction vessel；
Oxidation unit, including oxidation container react in the oxidation container for aforementioned ferrous chloride solution, oxidant, obtain iron
Ion weight percentage concentration is the chlorination iron liquid of m；
Negative-pressure vacuum device, including closed container, it is negative between 30 DEG C~100 DEG C that the closed container is configured to operating temperature
Press vacuum environment, heated in the closed container for aforementioned chlorination iron liquid, obtain distillation waste water, and concentration after and iron ion weight
Measure the chlorination iron liquid that percentage concentration is n, wherein n > m；And
Low temperature drying device, including freezing room, and the drying unit for excluding aqueous vapor in the freezing room, the freezing room quilt
Operating temperature is configured between -20 DEG C~+20 DEG C of low temperature drying environment, for the chlorination iron liquid after aforementioned concentration in the freezing
Heat release in cabin, and it is long brilliant in exothermic process, purity is obtained between 60%~99% ferric chloride (FeCl36H2O) solid.
13. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 12, it is characterised in that: the frerrous chloride
Manufacturing device further includes the hydrochloric acid container for being connected to the reaction vessel, and the hydrochloric acid container is for supplying needed for reaction process
Hydrochloric acid.
14. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 13, it is characterised in that: the frerrous chloride
Manufacturing device further includes being connected to the air neutralisation unit of the reaction vessel Yu the hydrochloric acid container, the air neutralisation unit
For importing extraneous air, making the reaction vessel, hydrochloric acid container, generated HCl gas, hydrogen exist during the reaction
Further and after air neutralisation treatment, it is expelled directly out the external world.
15. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 12, it is characterised in that: the oxidation unit
It further include the recovery unit for being connected to the oxidation container, the recovery unit is used to store ferrous chloride solution, and described in recycling
Oxidation container generated extra chlorine, oxidizing gas in reacting.
16. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 15, it is characterised in that: the oxidation unit
It further include the air neutralisation unit for being connected to the oxidation container Yu the recovery unit, the air neutralisation unit is for importing
Extraneous air makes the oxidation container generated HCl gas, hydrogen, extra chlorine, oxidizing gas during the reaction
Further and after air neutralisation treatment, it is expelled directly out the external world.
17. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 12, it is characterised in that: the negative-pressure vacuum
Device further includes the condenser pipe for being connected to the closed container, and is connected to the vacuum barrel of the condenser pipe, and the condensation is effective
The aqueous vapor generated when condensing aforementioned chlorination iron liquid and being heated in the closed container makes aqueous vapor form distillation waste water, described true
Empty barrel is for collecting aforementioned distillation waste water.
18. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 17, it is characterised in that: the negative-pressure vacuum
Device further includes the water pump for being connected to the condenser pipe, the closed container, and the water pump generates the water flow washed away from top to bottom,
And then swabbing action is generated to the gas in the condenser pipe, the closed container, keep formation negative pressure in the closed container true
Altitude.
19. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 12, it is characterised in that: low temperature drying device
It further include heat exchange unit, the heat exchange unit is for making the freezing room cool down.
20. the solidification manufacture system of ferric chloride (FeCl36H2O) according to claim 19, it is characterised in that: the drying unit
With the multiple fans for being mounted on the freezing room.
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| TW106143214A TWI637913B (en) | 2017-12-08 | 2017-12-08 | Curing manufacturing method of hexahydrate ferric chloride and curing manufacturing system thereof |
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| CN111422914A (en) * | 2020-03-26 | 2020-07-17 | 斯瑞尔环境科技股份有限公司 | Production method of granular crystalline ferric chloride |
| WO2022045988A1 (en) * | 2020-08-24 | 2022-03-03 | Pitaya Yangpichit | Method of production of ferric chloride solution by induction heating of solid iron |
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| US4614643A (en) * | 1982-12-08 | 1986-09-30 | Stauffer Chemical Company | Process for treating liquid chlorinated hydrocarbon wastes containing iron |
| TWM558797U (en) * | 2017-12-08 | 2018-04-21 | Ye jun liang | Solidifying and manufacturing system of ferric tri-chloride hexahydrate |
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| CN103159263A (en) * | 2013-04-02 | 2013-06-19 | 宜宾天原集团股份有限公司 | Treatment method of artificial rutile mother solution |
| CN103570080A (en) * | 2013-11-08 | 2014-02-12 | 中南大学 | Method for comprehensively recovering ferric trichloride from titanium tetrachloride settling sludge |
| CN104150667A (en) * | 2014-07-18 | 2014-11-19 | 安徽千和新材料科技发展有限公司 | Resourceful treatment method of waste acid liquid generated by washing surfaces of hot rolled plates |
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| CN111422914A (en) * | 2020-03-26 | 2020-07-17 | 斯瑞尔环境科技股份有限公司 | Production method of granular crystalline ferric chloride |
| WO2022045988A1 (en) * | 2020-08-24 | 2022-03-03 | Pitaya Yangpichit | Method of production of ferric chloride solution by induction heating of solid iron |
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| TWI637913B (en) | 2018-10-11 |
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