CN105217694A - A kind of method preparing red iron oxide and ammonium chloride - Google Patents
A kind of method preparing red iron oxide and ammonium chloride Download PDFInfo
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- CN105217694A CN105217694A CN201510529222.7A CN201510529222A CN105217694A CN 105217694 A CN105217694 A CN 105217694A CN 201510529222 A CN201510529222 A CN 201510529222A CN 105217694 A CN105217694 A CN 105217694A
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- iron oxide
- red iron
- temperature oxidation
- ammonium chloride
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 50
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000002253 acid Substances 0.000 claims abstract description 49
- 230000003647 oxidation Effects 0.000 claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 49
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 19
- 239000010959 steel Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 230000003750 conditioning effect Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005246 galvanizing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 17
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 13
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 7
- 238000003837 high-temperature calcination Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940095991 ferrous disulfide Drugs 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of method preparing red iron oxide and ammonium chloride, belong to technical field of waste resourceful treatment.First spent acid and steel scrap are considered to be worth doing or steel scrap scrap stock mixing and stirring to obtain iron be all Fe
2+solution (by the Fe in spent acid
3+restore All is Fe
2+); By the solution ammoniacal liquor adjust ph obtained, pass into air or oxygen low-temperature oxidation simultaneously; By the solution warms to 70 after low-temperature oxidation ~ 95 DEG C, by the pH value of hydrochloric acid conditioning solution, pass into temperature oxidation in air or oxygen; Filtered by suspension liquid and obtain filter cake and filtrate, after washing filter cake, under temperature is 80 ~ 130 DEG C of conditions, dry 30 ~ 180min obtains the red iron oxide that color even is bright-coloured, purity is greater than 99.5wt%; The filtrate obtained and washing water are carried out vacuum distilling and obtains crystallisate, crystallisate dry 30 ~ 180min under temperature is 80 ~ 130 DEG C of conditions is obtained the NH that purity is greater than 99.5wt%
4cl.The method production high purity ammonium chloride and high-strength red iron oxide.
Description
Technical field
The present invention relates to a kind of method preparing red iron oxide and ammonium chloride, belong to technical field of waste resourceful treatment.
Background technology
Along with the fast development of nearly China's pot galvanize decades industry, output and the kind of pot galvanize product increase year by year.The production technique of pot galvanize as shown in Figure 1, can create a large amount of waste residues, waste liquid and waste gas in pickling, hot dip process process.If do not carry out recycling treatment to these waste residues, waste liquid and waste gas, not only can bring huge environmental pollution, and cause the wasting of resources.The waste liquid that zinc-plated industry produces is spent acid substantially entirely, and its chemical composition is: Fe
2+/ Fe
3+content ~ 200g/L, HCl content ~ 1wt%, the Zn of trace
2+deng.
In waste acid resource process, domestic have a lot of researchist to carry out correlative study, can be divided into high-temperature calcination, wet oxidation-calcining and acid-base neutralisation-calcining etc. from the processing method adopted.
High-temperature calcination aspect: Chinese patent ZL201310554055.2 discloses a kind of method that ferric oxide is prepared in high-temperature calcination, the vitriol of iron and ferrous disulfide is adopted to mix at 1.8 ~ 11: 1 in molar ratio, obtain mixture, then by mixture roasting 0.5 ~ 3h at 550 ~ 800 DEG C, sulfurous gas and red iron oxide is obtained.But such technique needs high-temperature calcination, there is facility investment and the high shortcoming of energy consumption, and the purity of product is lower, just as described in that patent, its product purity is only more than 80%.Wet oxidation-calcining aspect: Chinese patent ZL201410007225.X discloses the technique that ferric oxide is prepared in a kind of solution oxide, solid-liquor separation and high-temperature calcination, adopts acid FeCl
2solution prepares FeCl through solution oxide
3solution, regulates PH to make Fe
3+from solution, Fe (OH) is isolated with the form of precipitation
3, then prepare Fe through filtration, oven dry and high-temperature calcination
2o
3, this technique needs high-temperature calcination (calcining temperature 600 ~ 800 DEG C) equally,
There is facility investment and all higher shortcoming of energy consumption equally, the ferric oxide purity that the method is produced in addition also only has more than 98.3%, does not also describe the tinting strength of ferric oxide and the uniformity coefficient of color.
As can be seen here, there are problems in existing production ferric oxide flow process, the spent acid of pot galvanize industry in addition output is huge, is badly in need of new waste acid resource metallization processes, improves the economic benefit of enterprise, promote energy-saving and emission-reduction and the industrial upgrading of zinc-plated industry.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of method preparing red iron oxide and ammonium chloride.The method is by techniques such as reduction, low-temperature oxidation, the oxidation of middle temperature, filtration, washing, vacuum distilling and oven dry, and production high purity ammonium chloride and high-strength red iron oxide, the present invention is achieved through the following technical solutions.
Prepare a method for red iron oxide and ammonium chloride, its concrete steps comprise as follows:
(1) purifying is reduced: first spent acid and steel scrap to be considered to be worth doing or steel scrap scrap stock are that to obtain iron be all Fe to 20 ~ 1000: 1ml/g mixing and stirring according to liquid-solid ratio
2+solution (by the Fe in spent acid
3+restore All is Fe
2+);
(2) low-temperature oxidation: solution step (1) obtained is 9.0 ~ 12.5 by ammoniacal liquor adjust ph under temperature is 3 ~ 15 DEG C of conditions, passes into air or oxygen low-temperature oxidation 150 ~ 800min, by the Fe in spent acid simultaneously
2+be converted into γ-FeOOH;
(3) temperature oxidation in: by solution warms to 70 ~ 95 DEG C after step (2) low-temperature oxidation, be 2.3 ~ 4.9 by the pH value of hydrochloric acid conditioning solution, pass into temperature oxidation 12 ~ 100h in air or oxygen, in the process by add ammoniacal liquor maintain pH value be 2.3 ~ 4.9, the iron simultaneously added in step (1) is all Fe
2+solution make solution Fe in step (3)
2+content be 1 ~ 15g/L, make the γ-FeOOH in spent acid constantly carry out transformation of crystal, and be grown to red iron oxide;
(4) red iron oxide is prepared: after the middle temperature oxidation of step (3), filtered by suspension liquid and obtain filter cake and filtrate, after washing filter cake, under temperature is 80 ~ 130 DEG C of conditions, dry 30 ~ 180min obtains the red iron oxide that color even is bright-coloured, purity is greater than 99.5wt%;
(5) prepare ammonium chloride: the filtrate obtain step (4) and washing water carry out vacuum distilling and obtain crystallisate, crystallisate dry 30 ~ 180min under temperature is 80 ~ 130 DEG C of conditions is obtained the NH that purity is greater than 99.5wt%
4cl.
Spent acid in described step (1) is the spent acid produced in hot galvanizing process, comprises following mass percent component: FeCl
28% ~ 40%, FeCl
30.1% ~ 5%, HCl0.2% ~ 4%, impurity (salt etc. of calcium, magnesium, manganese) content 0.05% ~ 0.3%, surplus is water.
The amount passing into air or oxygen in described step (2) is 0.2 ~ 5m
3cube solution
-1h
-1.
The amount passing into air or oxygen in described step (3) is 2 ~ 20m
3cube solution
-1h
-1.
The invention has the beneficial effects as follows:
(1) the present invention adopt steel scrap consider to be worth doing and steel scrap scrap stock (waste material produced in pot galvanize enterprise production process) will containing Fe
3+spent acid be reduced to highly purified FeCl
2solution, and consume the residual HCl in spent acid, high-purity iron oxide redly provide qualified raw material for preparing, this is that preparing in the technique of iron oxide red of other Invention Announces is not available.
(2) under the condition of low-temperature oxidation, FeCl
2the speed being converted into γ-FeOOH is slow, makes the FeCl in spent acid
2γ-the FeOOH being converted into crystal formation consistent provides good dynamic conditions.
(3) technique of the present invention is the production technique under gentle electrochemical conditions, and during middle temperature oxidation, temperature only has 70 ~ 95 DEG C, and during oven dry ferric oxide, top temperature only has 130 DEG C, and facility investment is little, and production cost is low, environmental friendliness.
(4) adopt the color even of institute of the present invention production red iron oxide bright-coloured, tinting strength is high, and purity can reach more than 99.6%, may be used for making paints and the high-end product such as paint.
(5) ammoniacal liquor added in production process is converted into ammonium chloride, does not in addition need to add other medicament, as short compound modifying agent, flocculation agent and oxygenant etc., can not introduce other elements and reduce the purity of iron oxide yellow and ammonium chloride.
(6) technique of the present invention can the highly purified ammonium chloride of output, and ammonium chloride is one of raw material of zinc-plated industry, can reduce enterprise's production cost.
(7) as can be seen from Figure 2, production technique of the present invention is closed circuit, does not again produce waste liquid and waste residue, meets the industry policy of China's energy-saving and emission-reduction.
Accompanying drawing explanation
Fig. 1 is steel tube hot galvanizing process flow sheet in prior art;
Fig. 2 is present invention process schema.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
As shown in Figure 2, this prepares the method for red iron oxide and ammonium chloride, and its concrete steps comprise as follows:
(1) reduce: first spent acid and steel scrap to be considered to be worth doing or steel scrap scrap stock are that to obtain iron be all Fe to 20: 1ml/g mixing and stirring according to liquid-solid ratio
2+solution (by the Fe in spent acid
3+restore All is Fe
2+); Wherein spent acid is the spent acid produced in hot galvanizing process, comprises following mass percent component: FeCl
240%, FeCl
35%, HCl4%, foreign matter content 0.3%, surplus is water;
(2) low-temperature oxidation: solution step (1) obtained is 9.2 by ammoniacal liquor adjust ph under temperature is 3 DEG C of conditions, passes into air low temperature oxidation 150min, makes the FeCl in spent acid
2be converted into γ-FeOOH; The amount wherein passing into air is 0.3m
3cube solution
-1h
-1;
(3) temperature oxidation in: by the solution warms to 70 DEG C after step (2) low-temperature oxidation, be 2.3 by the pH value of hydrochloric acid conditioning solution, to pass in air temperature oxidation 24h, by adding ammoniacal liquor, to maintain pH value be 2.3 in the process, and the iron simultaneously added in step (1) is all Fe
2+solution make solution Fe in step (3)
2+content be 1g/L, make the γ-FeOOH in spent acid constantly carry out transformation of crystal, and be grown to ferric oxide; The amount wherein passing into air is 3m
3cube solution
-1h
-1;
(4) prepare red iron oxide: after the middle temperature oxidation of step (3), solution is carried out filtration and obtains filter cake and filtrate, after washing filter cake, under temperature is 110 DEG C of conditions, dry 150min obtains that color even is bright-coloured, purity is the red iron oxide of 99.50wt%;
(5) prepare ammonium chloride: the filtrate obtain step (4) and washing water carry out vacuum distilling and obtain crystallisate, crystallisate dry 150min under temperature is 110 DEG C of conditions is obtained the NH that purity is 99.50wt%
4cl.
Embodiment 2
As shown in Figure 2, this prepares the method for red iron oxide and ammonium chloride, and its concrete steps comprise as follows:
(1) reduce: first spent acid and steel scrap to be considered to be worth doing or steel scrap scrap stock are that to obtain iron be all Fe to 50: 1ml/g mixing and stirring according to liquid-solid ratio
2+solution (by the Fe in spent acid
3+restore All is Fe
2+); Wherein spent acid is the spent acid produced in hot galvanizing process, comprises following mass percent component: FeCl
28%, FeCl
30.1%, HCl0.2%, foreign matter content 0.05%, surplus is water;
(2) low-temperature oxidation: solution step (1) obtained is 11.9 by ammoniacal liquor adjust ph under temperature is 5 DEG C of conditions, passes into air low temperature oxidation 360min, makes the FeCl in spent acid
2be converted into γ-FeOOH; The amount wherein passing into air is 3.5m
3cube solution
-1h
-1;
(3) temperature oxidation in: by the solution warms to 75 DEG C after step (2) low-temperature oxidation, be 3.4 by the pH value of hydrochloric acid conditioning solution, to pass in air temperature oxidation 56h, by adding ammoniacal liquor, to maintain pH value be 3.4 in the process, and the iron simultaneously added in step (1) is all Fe
2+solution make solution Fe in step (3)
2+content be 7.5g/L, make the γ-FeOOH in spent acid constantly carry out transformation of crystal, and be grown to ferric oxide; The amount wherein passing into air is 13.2m
3cube solution
-1h
-1;
(4) prepare red iron oxide: after the middle temperature oxidation of step (3), solution is carried out filtration and obtains filter cake and filtrate, after washing filter cake, under temperature is 115 DEG C of conditions, dry 120min obtains that color even is bright-coloured, purity is the red iron oxide of 99.51wt%;
(5) prepare ammonium chloride: the filtrate obtain step (4) and washing water carry out vacuum distilling and obtain crystallisate, crystallisate dry 120min under temperature is 115 DEG C of conditions is obtained the NH that purity is 99.51wt%
4cl.
Embodiment 3
As shown in Figure 2, this prepares the method for red iron oxide and ammonium chloride, and its concrete steps comprise as follows:
(1) reduce: first spent acid and steel scrap to be considered to be worth doing or steel scrap scrap stock are that to obtain iron be all Fe to 500: 1ml/g mixing and stirring according to liquid-solid ratio
2+solution (by the Fe in spent acid
3+restore All is Fe
2+); Wherein spent acid is the spent acid produced in hot galvanizing process, comprises following mass percent component: FeCl
225%, FeCl
34%, HCl3%, foreign matter content 0.25%, surplus is water;
(2) low-temperature oxidation: solution step (1) obtained is 11.5 by ammoniacal liquor adjust ph under temperature is 7 DEG C of conditions, passes into air low temperature oxidation 400min, makes the FeCl in spent acid
2be converted into γ-FeOOH; The amount wherein passing into air is 3.2m
3cube solution
-1h
-1;
(3) temperature oxidation in: by the solution warms to 80 DEG C after step (2) low-temperature oxidation, be 4.5 by the pH value of hydrochloric acid conditioning solution, to pass in air temperature oxidation 16h, by adding ammoniacal liquor, to maintain pH value be 4.5 in the process, and the iron simultaneously added in step (1) is all Fe
2+solution make solution Fe in step (3)
2+content be 13.5g/L, make the γ-FeOOH in spent acid constantly carry out transformation of crystal, and be grown to ferric oxide; The amount wherein passing into air is 15.5m
3cube solution
-1h
-1;
(4) prepare red iron oxide: after the middle temperature oxidation of step (3), solution is carried out filtration and obtains filter cake and filtrate, after washing filter cake, under temperature is 120 DEG C of conditions, dry 100min obtains that color even is bright-coloured, purity is the red iron oxide of 99.52wt%;
(5) prepare ammonium chloride: the filtrate obtain step (4) and washing water carry out vacuum distilling and obtain crystallisate, crystallisate dry 100min under temperature is 120 DEG C of conditions is obtained the NH that purity is 99.52wt%
4cl.
Embodiment 4
As shown in Figure 2, this prepares the method for red iron oxide and ammonium chloride, and its concrete steps comprise as follows:
(1) reduce: first spent acid and steel scrap to be considered to be worth doing or steel scrap scrap stock are that to obtain iron be all Fe to 1000: 1ml/g mixing and stirring according to liquid-solid ratio
2+solution (by the Fe in spent acid
3+restore All is Fe
2+); Wherein spent acid is the spent acid produced in hot galvanizing process, comprises following mass percent component: FeCl
230%, FeCl
33%, HCl2%, foreign matter content 0.2%, surplus is water;
(2) low-temperature oxidation: solution step (1) obtained is 12.5 by ammoniacal liquor adjust ph under temperature is 7 DEG C of conditions, passes into air low temperature oxidation 800min, makes the FeCl in spent acid
2be converted into γ-FeOOH; The amount wherein passing into air is 0.2m
3cube solution
-1h
-1;
(3) temperature oxidation in: by the solution warms to 93 DEG C after step (2) low-temperature oxidation, be 4.9 by the pH value of hydrochloric acid conditioning solution, to pass in air temperature oxidation 12h, by adding ammoniacal liquor, to maintain pH value be 4.9 in the process, and the iron simultaneously added in step (1) is all Fe
2+solution make solution Fe in step (3)
2+content be 13.5g/L, make the γ-FeOOH in spent acid constantly carry out transformation of crystal, and be grown to ferric oxide; The amount wherein passing into air is 2m
3cube solution
-1h
-1;
(4) prepare red iron oxide: after the middle temperature oxidation of step (3), solution is carried out filtration and obtains filter cake and filtrate, after washing filter cake, under temperature is 130 DEG C of conditions, dry 30min obtains that color even is bright-coloured, purity is the red iron oxide of 99.53wt%;
(5) prepare ammonium chloride: the filtrate obtain step (4) and washing water carry out vacuum distilling and obtain crystallisate, crystallisate dry 30min under temperature is 130 DEG C of conditions is obtained the NH that purity is 99.53wt%
4cl.
Embodiment 5
As shown in Figure 2, this prepares the method for red iron oxide and ammonium chloride, and its concrete steps comprise as follows:
(1) reduce: first spent acid and steel scrap to be considered to be worth doing or steel scrap scrap stock are that to obtain iron be all Fe to 700: 1ml/g mixing and stirring according to liquid-solid ratio
2+solution (by the Fe in spent acid
3+restore All is Fe
2+); Wherein spent acid is the spent acid produced in hot galvanizing process, comprises following mass percent component: FeCl
220%, FeCl
32%, HCl3%, foreign matter content 0.05%, surplus is water;
(2) low-temperature oxidation: solution step (1) obtained is 9.0 by ammoniacal liquor adjust ph under temperature is 15 DEG C of conditions, passes into air low temperature oxidation 700min, makes the FeCl in spent acid
2be converted into γ-FeOOH; The amount wherein passing into air is 5m
3cube solution
-1h
-1;
(3) temperature oxidation in: by the solution warms to 95 DEG C after step (2) low-temperature oxidation, be 4.6 by the pH value of hydrochloric acid conditioning solution, to pass in air temperature oxidation 90h, by adding ammoniacal liquor, to maintain pH value be 4.6 in the process, and the iron simultaneously added in step (1) is all Fe
2+solution make solution Fe in step (3)
2+content be 15g/L, make the γ-FeOOH in spent acid constantly carry out transformation of crystal, and be grown to ferric oxide; The amount wherein passing into air is 20m
3cube solution
-1h
-1;
(4) prepare red iron oxide: after the middle temperature oxidation of step (3), solution is carried out filtration and obtains filter cake and filtrate, after washing filter cake, under temperature is 80 DEG C of conditions, dry 180min obtains that color even is bright-coloured, purity is the red iron oxide of 99.54wt%;
(5) prepare ammonium chloride: the filtrate obtain step (4) and washing water carry out vacuum distilling and obtain crystallisate, crystallisate dry 180min under temperature is 80 DEG C of conditions is obtained the NH that purity is 99.54wt%
4cl.
Below by reference to the accompanying drawings the specific embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (4)
1. prepare a method for red iron oxide and ammonium chloride, it is characterized in that concrete steps comprise as follows:
(1) purifying is reduced: first spent acid and steel scrap to be considered to be worth doing or steel scrap scrap stock are that to obtain iron be all Fe to 20 ~ 1000: 1ml/g mixing and stirring according to liquid-solid ratio
2+solution;
(2) low-temperature oxidation: solution step (1) obtained is 9.0 ~ 12.5 by ammoniacal liquor adjust ph under temperature is 3 ~ 15 DEG C of conditions, passes into air or oxygen low-temperature oxidation 150 ~ 800min;
(3) temperature oxidation in: by solution warms to 70 ~ 95 DEG C after step (2) low-temperature oxidation, be 2.3 ~ 4.9 by the pH value of hydrochloric acid conditioning solution, pass into temperature oxidation 12 ~ 100h in air or oxygen, in the process by add ammoniacal liquor maintain pH value be 2.3 ~ 4.9, the iron simultaneously added in step (1) is all Fe
2+solution make solution Fe in step (3)
2+content be 1 ~ 15g/L;
(4) red iron oxide is prepared: after the middle temperature oxidation of step (3), suspension liquid is carried out filtration and obtains filter cake and filtrate, after washing filter cake, under temperature is 80 ~ 130 DEG C of conditions, dry 30 ~ 180min obtains the red iron oxide that color even is bright-coloured, purity is greater than 99.5wt%;
(5) prepare ammonium chloride: the filtrate obtain step (4) and washing water carry out vacuum distilling and obtain crystallisate, crystallisate dry 30 ~ 180min under temperature is 80 ~ 130 DEG C of conditions is obtained the NH that purity is greater than 99.5wt%
4cl.
2. the method preparing red iron oxide and ammonium chloride according to claim 1, is characterized in that: the spent acid in described step (1) is the spent acid produced in hot galvanizing process, comprises following mass percent component: FeCl
28% ~ 40%, FeCl
30.1% ~ 5%, HCl0.2% ~ 4%, foreign matter content 0.05% ~ 0.3%, surplus is water.
3. the method preparing red iron oxide and ammonium chloride according to claim 1, is characterized in that: the amount passing into air or oxygen in described step (2) is 0.2 ~ 5m
3cube solution
-1h
-1.
4. the method preparing red iron oxide and ammonium chloride according to claim 1, is characterized in that: the amount passing into air or oxygen in described step (3) is 2 ~ 20m
3cube solution
-1h
-1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564960A (en) * | 2016-10-28 | 2017-04-19 | 昆明理工大学 | Synthesis tank for iron oxide red |
| CN106564959A (en) * | 2016-10-28 | 2017-04-19 | 昆明理工大学 | Iron oxide red seed crystal preparation tank and preparation method of iron oxide red seed crystals |
| CN107686133A (en) * | 2017-09-22 | 2018-02-13 | 王浩 | A kind of method using calcium carbide waste residue treatment steel spent acid |
| CN109987637A (en) * | 2017-12-30 | 2019-07-09 | 天津友发钢管集团股份有限公司 | A method of iron oxide yellow is prepared using red soil |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103373A (en) * | 1987-05-06 | 1988-11-23 | 黄卓林 | Reclaim the method for iron oxide red and sulphur ammonium in the spent pickle liquor |
| CN1039571A (en) * | 1988-07-17 | 1990-02-14 | 李桂石 | The processing method of utilizing the waste liquid behind the steel derusting to produce product |
| US6530987B1 (en) * | 1998-03-20 | 2003-03-11 | Bayer Aktiengesellschaft | Method for producing iron oxide pigments from waste acid resulting from TiO2 production |
| CN1415665A (en) * | 2002-12-04 | 2003-05-07 | 中国化工建设总公司常州涂料化工研究院 | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white |
| CN1766005A (en) * | 2005-08-23 | 2006-05-03 | 奚长生 | Method for preparing high purity iron oxide yellow and iron oxide red using titanium dioxide byproduct ferrous sulfate |
| CN101607741A (en) * | 2008-06-19 | 2009-12-23 | 张晓东 | Utilize byproduct ferrous sulfate of titanium dioxide to prepare the method for red iron oxide |
| CN101638704A (en) * | 2009-08-17 | 2010-02-03 | 昆明理工大学 | Method for extracting iron from copper smelting waste residue |
| CN102390870A (en) * | 2011-08-16 | 2012-03-28 | 南通宝聚颜料有限公司 | Preparation method of superfine iron oxide red pigment with high glossiness and pure red tone |
| CN102703689A (en) * | 2012-06-14 | 2012-10-03 | 沈阳化工大学 | Process method for extracting and separating iron from industrial waste iron mud and preparing iron oxide red |
| CN103193277A (en) * | 2013-04-07 | 2013-07-10 | 昆明理工大学 | Method for preparing iron oxide red pigment through copperas |
-
2015
- 2015-08-26 CN CN201510529222.7A patent/CN105217694A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103373A (en) * | 1987-05-06 | 1988-11-23 | 黄卓林 | Reclaim the method for iron oxide red and sulphur ammonium in the spent pickle liquor |
| CN1039571A (en) * | 1988-07-17 | 1990-02-14 | 李桂石 | The processing method of utilizing the waste liquid behind the steel derusting to produce product |
| US6530987B1 (en) * | 1998-03-20 | 2003-03-11 | Bayer Aktiengesellschaft | Method for producing iron oxide pigments from waste acid resulting from TiO2 production |
| CN1415665A (en) * | 2002-12-04 | 2003-05-07 | 中国化工建设总公司常州涂料化工研究院 | Method for producing the red pigment of ferric oxide from ferrous sulphate of byproduct abolished by titanium white |
| CN1766005A (en) * | 2005-08-23 | 2006-05-03 | 奚长生 | Method for preparing high purity iron oxide yellow and iron oxide red using titanium dioxide byproduct ferrous sulfate |
| CN101607741A (en) * | 2008-06-19 | 2009-12-23 | 张晓东 | Utilize byproduct ferrous sulfate of titanium dioxide to prepare the method for red iron oxide |
| CN101638704A (en) * | 2009-08-17 | 2010-02-03 | 昆明理工大学 | Method for extracting iron from copper smelting waste residue |
| CN102390870A (en) * | 2011-08-16 | 2012-03-28 | 南通宝聚颜料有限公司 | Preparation method of superfine iron oxide red pigment with high glossiness and pure red tone |
| CN102703689A (en) * | 2012-06-14 | 2012-10-03 | 沈阳化工大学 | Process method for extracting and separating iron from industrial waste iron mud and preparing iron oxide red |
| CN103193277A (en) * | 2013-04-07 | 2013-07-10 | 昆明理工大学 | Method for preparing iron oxide red pigment through copperas |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564960A (en) * | 2016-10-28 | 2017-04-19 | 昆明理工大学 | Synthesis tank for iron oxide red |
| CN106564959A (en) * | 2016-10-28 | 2017-04-19 | 昆明理工大学 | Iron oxide red seed crystal preparation tank and preparation method of iron oxide red seed crystals |
| CN106564960B (en) * | 2016-10-28 | 2017-11-10 | 昆明理工大学 | A kind of iron oxide red synth sink |
| CN106564959B (en) * | 2016-10-28 | 2017-11-10 | 昆明理工大学 | A kind of iron oxide red seed crystal preparation vessel and preparation method thereof |
| CN107686133A (en) * | 2017-09-22 | 2018-02-13 | 王浩 | A kind of method using calcium carbide waste residue treatment steel spent acid |
| CN109987637A (en) * | 2017-12-30 | 2019-07-09 | 天津友发钢管集团股份有限公司 | A method of iron oxide yellow is prepared using red soil |
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