CN109264790A - A method of ferroso-ferric oxide and calcium chloride are prepared using pickle liquor - Google Patents
A method of ferroso-ferric oxide and calcium chloride are prepared using pickle liquor Download PDFInfo
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- CN109264790A CN109264790A CN201811246860.8A CN201811246860A CN109264790A CN 109264790 A CN109264790 A CN 109264790A CN 201811246860 A CN201811246860 A CN 201811246860A CN 109264790 A CN109264790 A CN 109264790A
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- calcium chloride
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- ferric oxide
- water
- iron
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 title claims abstract description 59
- 239000001110 calcium chloride Substances 0.000 title claims abstract description 58
- 229910001628 calcium chloride Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 35
- 235000021110 pickles Nutrition 0.000 title claims abstract description 30
- 229940056319 ferrosoferric oxide Drugs 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000002360 preparation method Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000002699 waste material Substances 0.000 claims abstract description 24
- 239000010802 sludge Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 68
- 229910052742 iron Inorganic materials 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000005554 pickling Methods 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 16
- 239000008235 industrial water Substances 0.000 claims description 16
- 230000001376 precipitating effect Effects 0.000 claims description 16
- 239000010959 steel Substances 0.000 claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 238000004880 explosion Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 13
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- -1 feature It is Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- WMFHUUKYIUOHRA-UHFFFAOYSA-N (3-phenoxyphenyl)methanamine;hydrochloride Chemical compound Cl.NCC1=CC=CC(OC=2C=CC=CC=2)=C1 WMFHUUKYIUOHRA-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 4
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000005276 aerator Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- 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
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Iron (AREA)
Abstract
The present invention discloses a kind of method for preparing ferroso-ferric oxide and calcium chloride using pickle liquor, belongs to industrial pollution waste reclamation technical field.It the described method comprises the following steps: S1: setting raw material collecting pit；S2: calcium hydroxide dissolution is used as regulator；S3: pickle liquor and regulator are evacuated to primary preparation pond and reconciled；S4: it is separated by solid-liquid separation by plate and frame sludge filter press；S5: ferroso-ferric oxide is recycled in finished product preparation pond；S6: calcium chloride water recycles calcium chloride solid；S7: evaporator steam reuse heating.S8: low concentration calcium chloride water can be used for selling, produce and use.The present invention is produced using implanted, using the existing Sewage Disposal of coating enterprise, installs designated equipment additional as required and regulator is produced, eliminate the transhipment process of pickle liquor, reduce waste acid treatment cost, contamination-free generates during this.
Description
Technical field
The invention belongs to acid pickle utilization technology fields, and in particular to a kind of to utilize four oxidation three of pickle liquor preparation
The method of iron and calcium chloride.
Background technique
Steel manufacture field needs to carry out outer surface pickling to coating steel.The process will usually use 16%-28%'s
Dilute hydrochloric acid is surface-treated pond medium carbon steel ironware, when concentration of hydrochloric acid normally cannot handle steel in chlorohydric acid pickling pond, needs
It wants outlet (including pickling solution and water lotion), this process generates pickle liquor, belongs to hazardous waste.It is well known that in recent years with
Attention of the country to ecological environment treatment, such pickling hazardous waste, if be discharged into natural environment, being can water supply
Serious pollution is caused in source, soil, is unfavorable for China's Ecological Civilization Construction.So pickling row is faced with increasing environmental protection
Pressure, part pickling enterprise are shut down due to environment protection emission problem trend.
According to data, the more mature technology of the processing of iron and steel pickling waste liquid includes as hot smelting technique, evaporation knot at present
Crystal technique, precipitating neutralize, and oxidation and coprecipitation method produces water purification agent technology etc..
(1) hot smelting technique is a kind of processing spent acid technique that hydrochloric acid and iron oxide red are recycled by high-temperature roasting, this kind of
Technological means invests relatively large, the high requirements on the equipment, and operating cost is higher.Compared to small-scale steel processing enterprise, than
The pickle liquor for being relatively suitable for large iron and steel enterprise is handled.
(2) then technique is relatively easy for evaporative crystallization technique, and treating capacity is big, and hydrochloric acid and iron resource are effectively recycled；But
It is disadvantage is that investment is larger, equipment material requires high, the easy occluding device of mother liquor crystallization, equipment seriously corroded, and operating cost compares
Height, and frerrous chloride product market capacity school is small.
(3) processing method of the most ancient iron and steel pickling waste liquid of precipitating/neutralisation.It is to utilize to have acid, alkali waste water to neutralize
Means handle acid-washing waste acid.The most commonly used is lime neutralisation, advantage is that lime is cheap and easy to get with respect to caustic soda etc.,
It can handle pickle liquor of different nature；Disadvantage then shows that sediment is more in N-process, and sediment utility value is low, causes
Secondary pollution, and the iron resource in waste liquid also do not recycled, do not meet sustainable development idea.
(4) oxidation and co-precipitation method is after neutralizing the free acid in acid pickle, by the way that oxidant is added or is passed through air oxygen
Change, the products such as iron oxide black, iron oxide yellow are obtained after high temperature dehydration.While advantage is to liquid waste processing, and iron is recycled
Resource；But it due to the limitation of production technology, handles post mother liquor and still contains a large amount of iron ion, not only waste iron resource, filter
Liquid need to carry out secondary treatment ability qualified discharge, add processing cost.
(5) producing water purification agent technology can use pickle liquor production ferric trichloride, poly-ferric chloride etc..This method advantage
It is that zero-emission may be implemented, but treating capacity is small, it can not fairly large processing pickle liquor.
Summary of the invention
The present invention is solved by providing a kind of method for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid
The technical issues of pickle liquor outlet in the prior art leads to environmental pollution.
To achieve the above object, the technical solution of the invention is as follows:
A method of ferroso-ferric oxide and calcium chloride are prepared using pickle liquor, comprising the following steps:
S1: setting raw material collecting pit, Pickling-shop waste liquid are collected by above-ground line and are concentrated；
S2: calcium hydroxide and water are added in mediator agent dissolving tank, is dissolved with blender for setting mediator agent dissolving tank
Calcium hydroxide aqueous solution is obtained, as regulator；
S3: raw material is evacuated to primary preparation pond by acid-proof pump, when material quantity reaches primary preparation by the primary preparation pond of setting
After the 40%-60% of pool volume, mediator agent is slowly evacuated to primary preparation pond with slush pump, then set using pressure-air production
It is standby to carry out gas explosion processing and stir, make material in primary preparation pond that oxidation reaction occur, when solution ph reaches in primary preparation pond
To 10-11 stabilization and then secondary addition pickle liquor, until tentatively being obtained after solution ph stabilizes to 8 in primary preparation pond
Iron containing compounds precipitating；
S4: being separated by solid-liquid separation by plate and frame sludge filter press, and iron containing compounds precipitating passes through plate and frame sludge press filtration
The separation of machine separating plate is delivered to two-stage system for pond, and the solution that pH value is 8 is delivered to by the separation of plate and frame sludge filter press pipeline
Industrial water supply reservoir；
S5: iron containing compounds precipitating by water pump transfers the solution in industrial water supply reservoir, using blender stir to
Muddy, then taken by pumping to finished product and prepare pond；
S6: finished product is prepared in pond, mediator agent is added in muddy iron containing compounds, and use pressure-air production equipment
Gas explosion processing is carried out, makes pH stable in finished product preparation pond that pickle liquor be added again, finished product is made to prepare pond between 10-11
Interior pH stable is after 8, then stop gas explosion, heated using steam after gas explosion becomes greenish-yellow secondary colour to mud color,
So that mud is become black, obtain ferroso-ferric oxide solid, then stop heating, solid-liquid is carried out by sheet frame pressure type sludge filter press
Separation, ferroso-ferric oxide solid are separated by sheet frame pressure type sludge filter press separating plate, and collection is delivered to warehouse storage, and liquid is logical
Plate and frame filter press pipeline is crossed to separate to high temperature calcium chloride water condensation sedimentation basin；
S7: calcium chloride water is cooling in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium, precipitating is precipitated, and supernatant is taken out
It takes to room temperature calcium chloride water and sells centralized pool, lower layer's calcium chloride hydrate precipitated liquid, which carries out gas explosion stirring, prevents sediment solid
Change；
S8: solidified the calcium chloride water in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium to obtain chlorine with evaporator
Change hydrate of calcium, collects unloading.
Preferably, calcium hydroxide purity is 95% or more in the step S2.
Preferably, it in the step S3 after waste liquid amount, which reaches primary, prepares the 50% of pool volume, will be adjusted with slush pump
Agent is slowly evacuated to primary preparation pond.
Preferably, industrial water supply reservoir and workshop in the step S4, regulator dissolving tank, primary preparation pond,
Two-stage system provides for pond for workshop, mediator agent dissolving tank, primary preparation pond, two-stage system for pond connection and uses water.
Preferably, solution ph is 8 in the industrial water supply reservoir.
Preferably, it is heated in finished product preparation pond using natural gas steam boiler in the step S6.
Preferably, blender is jacking stirrer in the step S2 and S5.
Preferably, in the step S7 room temperature calcium chloride water sale centralized pool in calcium chloride water can extract to
Industrial water supply reservoir.
Preferably, the raw material collecting pit, regulator dissolving tank, primary preparation pond, industrial water supply reservoir, finished product preparation
The pond body in pond, the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium and calcium chloride water storage pond uses the concrete of 200mm or more,
Liner is the glass reinforced plastic of 2 layers or more 3mm thickness.
The beneficial effects of the present invention are:
(1) present invention is produced using implanted, that is, utilizes the existing Sewage Disposal of coating enterprise, installs specified set additional as required
It is standby and produced using specified regulator, the transhipment process of pickle liquor is eliminated, coating enterprise waste acid treatment cost is reduced,
Contamination-free in production process simultaneously；It realizes the recycling cycling and reutilization of resource, solve the problems, such as that pickle liquor is handled, both for enterprise
Industry solves environmental requirement, " turns waste into wealth " again, recycles ferroso-ferric oxide, and economic interests are considerable；Equipment investment cost is relatively low,
Reduce fixed assets cost；On the basis of existing enterprise's land used, processing solid waste is reduced to greatest extent and increases land used newly.
(2) present invention is added water treatment agent in waste liquid (slag) and carries out using the iron ion contained in pickle liquor (slag)
Blending, while ironmaking reagent progress aerating oxidation is added and finally obtains four oxidations after the chloride complete oxidation in muddy water
Three-iron and calcium chloride, wherein ferroso-ferric oxide can be used as relevant enterprise raw materials for production, widely used, and calcium chloride is used for refrigeration equipment
Salt water, road ice melting agent and desiccant used etc., it is widely used.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Specific embodiment
For a better understanding of the technical solution of the present invention, in conjunction with appended figures and specific embodiments
Technical solution of the present invention is described in detail.
As shown in Figure 1, a kind of method for preparing ferroso-ferric oxide and calcium chloride using pickle liquor, comprising the following steps:
1. adding calcium hydroxide solution according to the iron-content and content of hydrochloric acid of pickle liquor and being stirred with aerator, make to give up
Hydrochloric acid and iron in liquid sufficiently react in primary preparation pond；
①Fe3O4+8HCl→FeCl2+2Fecl3+4H20
①Fe2O3+6HCL→2Fecl3+3H20
①FeO+2HCl→FeCl2+H2O
①Fe+2HCL→FeCl2+H2
②Ca(OH)2+FeCl2→Fe(OH)2↓+CaCl2
②Ca(OH)2+2HCl→2H2O+CaCl2
②3Ca(OH)2+2FeCl3→2Fe(OH)3↓+3CaCl2
③Fe2++Fe3++OH-→Fe(OH)2/Fe(OH)3(forming co-precipitation)
③Fe(OH)2+Fe(OH)3+ heating → FeOOH+Fe3O4(pH≤7.5)
③FeOOH+Fe2++ heating → Fe3O4+H+(pH≥9.2)
1. the main forms (pickle liquor generating process, main component) of raw material
2. finished product preparation pond in iron containing compounds precipitating in mediator agent is added again, by aerator be stirred to
Muddy, adding calcium hydroxide solution stablizes pH in pond within 10-11, and acid pickle is added again, stablizes pH in pond
After 8, aeration to mud color becomes greenish-yellow secondary colour (Fe2+For prase, Fe3+For brown color), then stop aeration,
It is heated at high temperature using steam, being heated to mud becomes black stopping heating, obtains Fe3O4Solid, solution are that calcium chloride is water-soluble
Liquid.
②Ca(OH)2+FeCl2→Fe(OH)2↓+CaCl2
②Ca(OH)2+2HCl→2H2O+CaCl2
②3Ca(OH)2+2FeCl3→2Fe(OH)3↓+3CaCl2
③Fe2++Fe3++OH-→Fe(OH)2/Fe(OH)3(forming co-precipitation)
③Fe(OH)2+Fe(OH)3+ heating → FeOOH+Fe3O4(pH≤7.5)
③FeOOH+Fe2++ heating → Fe3O4+H+(pH≥9.2)
2. 3. preparation process is mainly showed, it is above that only the main body reaction form of expression is illustrated.
3. under the conditions of 100 DEG C, solubility is 1590 grams per liters to calcium chloride in water, and under the conditions of 20 DEG C, calcium chloride is in water
Solubility is 740 grams per liters.There are about 50% after calcium chloride water natural cooling in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium
Precipitating is precipitated in calcium chloride, can extract supernatant liquor to room temperature calcium chloride water sale centralized pool and collect, and can transfer to life
Fisheries water supply reservoir uses.
Embodiment 1
A method of ferroso-ferric oxide and calcium chloride are prepared using pickle liquor, comprising the following steps:
S1: setting raw material collecting pit, Pickling-shop waste liquid are collected by above-ground line and are concentrated；
S2: calcium hydroxide and water that purity is 95% or more is added in setting mediator agent dissolving tank in mediator agent dissolving tank,
It is dissolved to obtain calcium hydroxide aqueous solution with jacking stirrer, as regulator；
S3: raw material is evacuated to primary preparation pond by acid-proof pump, when material quantity reaches primary preparation by the primary preparation pond of setting
After the 40%-60% of pool volume, mediator agent is slowly evacuated to primary preparation pond with slush pump, then set using pressure-air production
It is standby to carry out gas explosion processing and stir, make material in primary preparation pond that oxidation reaction occur, when solution ph reaches in primary preparation pond
To 10-11 stabilization and then secondary addition pickle liquor, until tentatively being obtained after solution ph stabilizes to 8 in primary preparation pond
Iron containing compounds precipitating；
S4: being separated by solid-liquid separation by plate and frame sludge filter press, and iron containing compounds precipitating passes through plate and frame sludge press filtration
The separation of machine separating plate is delivered to two-stage system for pond, and the solution that pH value is 8 is delivered to by the separation of plate and frame sludge filter press pipeline
Industrial water supply reservoir；Industrial water supply reservoir and workshop, regulator dissolving tank, primary preparation pond, two-stage system are for pond company
It connects, is provided for pond for workshop, mediator agent dissolving tank, primary preparation pond, two-stage system and use water；
S5: iron containing compounds precipitating transfers the solution in industrial water supply reservoir by water pump, using jacking stirrer
It stirs to muddy, then is taken by pumping to finished product and prepare pond；
S6: finished product is prepared in pond, mediator agent is added in muddy iron containing compounds, and use pressure-air production equipment
Gas explosion processing is carried out, makes pH stable in finished product preparation pond that pickle liquor be added again, finished product is made to prepare pond between 10-11
Interior pH stable is after 8, then stop gas explosion, heated using steam after gas explosion becomes greenish-yellow secondary colour to mud color,
So that mud is become black, obtain ferroso-ferric oxide solid, then stop heating, solid-liquid is carried out by sheet frame pressure type sludge filter press
Separation, ferroso-ferric oxide solid are separated by sheet frame pressure type sludge filter press separating plate, and collection is delivered to warehouse storage, and liquid is logical
Plate and frame filter press pipeline is crossed to separate to high temperature calcium chloride water condensation sedimentation basin；
S7: calcium chloride water is cooling in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium, precipitating is precipitated, and supernatant is taken out
It takes to room temperature calcium chloride water and sells centralized pool, lower layer's calcium chloride hydrate precipitated liquid, which carries out gas explosion stirring, prevents sediment solid
Change；
S8: solidified the calcium chloride water in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium to obtain chlorine with evaporator
Change hydrate of calcium, collects unloading；
S9: the calcium chloride water in room temperature calcium chloride water sale centralized pool can be extracted to industrial water supply reservoir；
Under the conditions of 100 DEG C, solubility is 1590 grams per liters to calcium chloride in water, and under the conditions of 20 DEG C, calcium chloride is molten in water
Xie Du is 740 grams per liters；There are about 50% chlorine after calcium chloride water natural cooling in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium
Change calcium and precipitating is precipitated, supernatant liquor can be extracted to room temperature calcium chloride water sale centralized pool and be collected, and can transferred to production
It is recycled with water supply reservoir.
The raw material collecting pit, regulator dissolving tank, primary preparation pond, industrial water supply reservoir, two-stage system are for pond, finished product
Prepare pond, the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium, room temperature calcium chloride water sale centralized pool pond body, using 200mm
Above concrete, liner are the glass reinforced plastic of 2 layers or more 3mm thickness, and evaporator reaches effect requirements.
Embodiment 2
Operating procedure is same as above, but in step s3, after material quantity, which reaches primary, prepares the 50% of pool volume, uses mud
Mediator agent is slowly evacuated to primary preparation pond by pump.
After the reaction was completed, calcium chloride solution is detected, iron ion is not detected, illustrate that the rate of recovery of iron reaches
100%, obtained ferroso-ferric oxide solid can be used as relevant enterprise raw materials for production, widely used.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills
Art field, is included within the scope of the present invention.
Claims (9)
1. a kind of method for preparing ferroso-ferric oxide and calcium chloride using pickle liquor, which comprises the following steps:
S1: setting raw material collecting pit, Pickling-shop waste liquid are collected by above-ground line and are concentrated；
S2: calcium hydroxide and water are added in mediator agent dissolving tank, is dissolved to obtain with blender for setting mediator agent dissolving tank
Calcium hydroxide aqueous solution, as regulator；
S3: raw material is evacuated to primary preparation pond by acid-proof pump by the primary preparation pond of setting, when material quantity reaches primary preparation pool capacity
After long-pending 40%-60%, mediator agent is slowly evacuated to primary preparation pond with slush pump, then using pressure-air production equipment into
The quick-fried processing of promoting the circulation of qi is simultaneously stirred, and makes material in primary preparation pond that oxidation reaction occur, when solution ph reaches 10- in primary preparation pond
11 stable and then secondary addition pickle liquors, until tentatively obtaining iron content after solution ph stabilizes to 8 in primary preparation pond
Compound precipitation；
S4: being separated by solid-liquid separation by plate and frame sludge filter press, and iron containing compounds precipitating passes through plate and frame sludge filter press point
Two-stage system is delivered to for pond from plate separation, and the solution that pH value is 8 is delivered to production by the separation of plate and frame sludge filter press pipeline
With water supply reservoir；
S5: iron containing compounds precipitating transfers the solution in industrial water supply reservoir by water pump, is stirred using blender to mud
Shape, then taken by pumping to finished product and prepare pond；
S6: finished product is prepared in pond, mediator agent is added in muddy iron containing compounds, and carry out using pressure-air production equipment
Gas explosion processing makes pH stable in finished product preparation pond that pickle liquor be added again between 10-11, makes pH in finished product preparation pond
Value is stablized after 8, then stop gas explosion, heated using steam, make mud after gas explosion becomes greenish-yellow secondary colour to mud color
Slurry becomes black, obtains ferroso-ferric oxide solid, then stops heating, carries out solid-liquid point by sheet frame pressure type sludge filter press
From ferroso-ferric oxide solid is separated by sheet frame pressure type sludge filter press separating plate, and collection is delivered to warehouse storage, and liquid passes through
Plate and frame filter press pipeline separates to high temperature calcium chloride water and condenses sedimentation basin；
S7: calcium chloride water is cooling in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium, precipitating is precipitated, by supernatant extract to
Room temperature calcium chloride water sells centralized pool, and lower layer's calcium chloride hydrate precipitated liquid, which carries out gas explosion stirring, prevents sediment from solidifying；
S8: solidified the calcium chloride water in the water-soluble liquid condensing sedimentation basin of high-temp chlorination calcium to obtain calcium chloride with evaporator
Hydrate collects unloading.
2. the method according to claim 1 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, feature
It is, calcium hydroxide purity is 95% or more in the step S2.
3. the method according to claim 1 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, feature
It is, in the step S3 after waste liquid amount, which reaches primary, prepares the 50% of pool volume, is slowly evacuated to regulator with slush pump
Primary preparation pond.
4. the method according to claim 1 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, feature
It is, industrial water supply reservoir and workshop, regulator dissolving tank, primary preparation pond, two-stage system are in the step S4 for pond
Connection provides for pond for workshop, mediator agent dissolving tank, primary preparation pond, two-stage system and uses water.
5. the method according to claim 1 or 4 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, special
Sign is that solution ph is 8 in the industrial water supply reservoir.
6. the method according to claim 1 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, feature
It is, is heated in finished product preparation pond using natural gas steam boiler in the step S6.
7. the method according to claim 1 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, feature
It is, blender is jacking stirrer in the step S2 and S5.
8. the method according to claim 1 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, feature
It is, the calcium chloride water in the step S7 in room temperature calcium chloride water sale centralized pool, which can be extracted to industrial water, to be supplied
Ying Chi.
9. the method according to claim 1 for preparing ferroso-ferric oxide and calcium chloride using iron and steel pickling waste liquid, feature
It is, the raw material collecting pit, regulator dissolving tank, primary preparation pond, industrial water supply reservoir, finished product prepare pond, high-temperature chlorine
Change the pond body in the water-soluble liquid condensing sedimentation basin of calcium and calcium chloride water storage pond using the concrete of 200mm or more, liner is 2 layers
The glass reinforced plastic of the above 3mm thickness.
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Cited By (1)
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| CN115872433A (en) * | 2022-09-26 | 2023-03-31 | 浙江天川环保科技有限公司 | Method for producing calcium chloride solution and iron oxide black raw material from iron-containing waste hydrochloric acid |
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