CN105236496A - Production method for preparing black iron oxide with ammonia circulation method - Google Patents
Production method for preparing black iron oxide with ammonia circulation method Download PDFInfo
- Publication number
- CN105236496A CN105236496A CN201510822311.0A CN201510822311A CN105236496A CN 105236496 A CN105236496 A CN 105236496A CN 201510822311 A CN201510822311 A CN 201510822311A CN 105236496 A CN105236496 A CN 105236496A
- Authority
- CN
- China
- Prior art keywords
- ammonia
- iron oxide
- oxide black
- ammonium sulfate
- black iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 106
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 title abstract 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 40
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 10
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims description 28
- 238000001704 evaporation Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 9
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 235000003891 ferrous sulphate Nutrition 0.000 abstract description 3
- 239000011790 ferrous sulphate Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 4
- 239000002002 slurry Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- -1 Z 250 Chemical compound 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001417490 Sillaginidae Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011405 expansive cement Substances 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000010936 titanium 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
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/08—Chromium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention relates to a method for preparing black iron oxide with an ammonia circulation method. The method includes the specific steps that a ferrous sulfate solution is loaded into a reaction container, ammonium hydroxide is added while heating stirring, and colloidal fluid containing Fe(OH)2 and (NH4)SO4 is prepared; oxygen is introduced into the reaction container to prepare black iron oxide slurry; the black iron oxide slurry is subjected to filtering, washing, rotary flashing and blending, and the finished black iron oxide is obtained with ammonium sulfate mother liquor as a byproduct; the ammonium sulfate mother liquor is concentrated to be introduced into an ammonia recycling reaction tank and reacted with ammonia recycling agents in the ammonia recycling reaction tank, sulfate and ammonia gas are generated, the generated ammonia gas is delivered to an ammonia purifier to be purified and then compressed through an ammonia compressor to be injected into the reaction container for producing the black iron oxide, and the ammonia circularly participates in production of the black iron oxide in the reaction process accordingly. By means of the method, the problems that when the black iron oxide is prepared with an ammonia-method technology, ammonium sulfate in mother liquor is excessively high in recycling cost and excessively large in energy consumption, and obtained ammonium sulfate serving as the byproduct lacks the market, so that the ammonia-method preparing technology can not be practically adopted are solved.
Description
Technical field
The present invention relates to a kind of production method of iron oxide black, specifically a kind of ammonia circulation ammonia process prepares the production method of iron oxide black.
Background technology
Iron oxide black, i.e. Z 250, molecular formula is Fe
3o
4, be black powder, water insoluble, have magnetic, tinting strength and opacifying power are very high.As a kind of important iron pigment, iron oxide black consumption in watercolor, ink is very large, and the main raw material of the magnetic carbon powder that duplicating machine is special is exactly aciculiform iron oxide black.In addition, iron oxide black, because of its feature such as nontoxic, pollution-free, also can be used for the production of superior cosmetics.
At present, the conventional production technique of China's iron oxide black mainly contains three kinds, is additive process, settlement-oxidation method and ammonia process respectively.
Additive process is mixed with liquid caustic soda by copperas solution, and reaction generates Fe (OH)
2, then add appropriate iron oxide yellow tankage in proportion and carry out addition reaction, generate iron oxide black.In China, iron oxide black is all prepared by additive process by the manufacturing enterprise of scale.
Settlement-oxidation method is mixed with liquid caustic soda by copperas solution, and reaction generates Fe (OH)
2, then pass into atmospheric oxidation, obtained iron oxide black.But the liquid caustic soda consumption of this preparation method is large, and production cost is higher, therefore uses less.
Ammonia process is added by ammoniacal liquor in the copperas solution after purification, controls solution ph about 9 ~ 10, obtained containing Fe (OH)
2(NH
4) SO
4colloidal fluid; Then be warming up to 90 ~ 95 DEG C, pass into atmospheric oxidation simultaneously, obtained iron oxide black slip, more after filtration, washing, drying, fine grinding, blending, obtain iron oxide black finished product; Filtrate can obtain ammonium sulfate after evaporation.The quality of the iron oxide black obtained by this preparation method can reach country-level product standard, and production cost also decreases.
Although the advantage of ammonia process technique has a lot, for many years, the application of ammonia process technique really in production practice is considerably less.Trace it to its cause, except the technical problem solved in application documents that the application number of the applicant's earlier application is 201510315658.6, also comprise following some:
First, owing to can produce a large amount of liquid containing ammonium sulfate mother liquors in production process, and ammonium sulfate concentrations is wherein lower, needs to evaporate a large amount of moisture, make the burden of evaporation unit heavier during mother liquid evaporation dehydration, and energy-output ratio in evaporative process is huge.
Secondly, the maximum whereabouts of by product ammonium sulfate produces compound manure, but because the sulfate radical in this kind of fertilizer accounts for the ratio of nearly 80%, and sulfate radical because of the overwhelming majority can not be absorbed by crops and remain in soil, after life-time service, can cause soil compaction even salinization, its nitrogen content is lower in addition, therefore its market demand is little, and there is downward trend year by year.This just makes the byproduct of ammonia process technique oxygenerating iron oxide black---and the market of ammonium sulfate very causes anxiety.
Thus, manufacturing enterprise wants the energy of at substantial to remove process disposing mother liquor ammonium sulfate on the one hand, another aspect gained ammonium sulfate is bulk deposition because of sales resistance, causes the difficult situation of losing more than gain, and this becomes the bottle-neck factor that restriction ammonia process technique is applied undoubtedly.
Summary of the invention
Object of the present invention is just to provide the production method that a kind of ammonia circulation ammonia process prepares iron oxide black, prepares iron oxide black to cause because the too high and gained by product ammonium sulfate of the cost recovery of ammonium sulfate in mother liquor is at a discount ammonia process preparation technology cannot the actual problem adopted to solve ammonia process technique.
The object of the present invention is achieved like this: a kind of ammonia circulation ammonia process prepares the production method of iron oxide black, loads copperas solution, be warmed up to 90 ~ 95 in reaction vessel
oc, adds ammoniacal liquor under stirring, controls the pH value of reaction soln 9 ~ 10, obtained containing Fe (OH)
2(NH
4) SO
4colloidal fluid; In reaction vessel, pass into oxygen be oxidized, obtained iron oxide black slip; Iron oxide black slip after filtration, washing, rotary flash distillation and blending, namely obtain iron oxide black finished product, the by product of production process is ammonium sulfate liquor; Ammonium sulfate liquor is passed in recovery ammonia retort after concentrated, react with recovery ammonia agent wherein, generate vitriol and ammonia, after the ammonia of generation being transported to ammonia purifier purification, be injected in the reaction vessel producing iron oxide black through ammonia compressor pressurization again, ammonia is circulated in above-mentioned reaction process and participates in the production of iron oxide black, form the production method that a kind of ammonia circulation ammonia process being different from traditional technology prepares iron oxide black thus.
Ferrous sulfate can dilute with tap water or production mother liquor, to remove impurity wherein, then conveniently technique makes the ferrous sulfate after purification and ammoniacal liquor and oxygen reaction, generate iron oxide black and ammonium sulfate, leach iron oxide black wherein after reaction terminates, remaining solution is by product---ammonium sulfate liquor.
Described recovery ammonia agent can be the oxide compound of the metallic element of second and third main group, oxyhydroxide or carbonate.
Described recovery ammonia agent can also be first and second, four, six, seven, the oxide compound of the transition metal of eight subgroups, oxyhydroxide, carbonate or calcining.
Described recovery ammonia agent can also be the oxide compound of each element of Mg, Al, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ti, Zr, oxyhydroxide, carbonate or calcining.
Preferred recovery ammonia agent is CuO, Cu
2(CO
3) (OH)
2, Ca (OH)
2, CaCO
3, ZnO, TiFeO
3or Cr
2feO
4.
In above-mentioned reaction process, described ammonium sulfate liquor be first evaporated to saturated after pass into again in recovery ammonia retort.
In above-mentioned reaction process, described ammonium sulfate liquor is first through evaporation, crystallization, and the ammonium sulfate fine powder obtained passes in recovery ammonia retort again.
Ammonia process is prepared the mother liquor of a large amount of liquid containing ammonium sulfates produced in production process of ferric oxide black by the present invention and recovery ammonia agent is reacted, dexterously it is utilized, to iron oxide black important raw materials for production---ammonia reclaims, simultaneously also for sulfate radical have found better home to return to.This not only can greatly reduce the huge energy consumed when traditional processing technology reclaims the ammonium sulfate in ammonium sulfate liquor, has saved the energy, has reduced production cost; And the ammonia reclaimed is back to use in the production process of iron oxide black as raw material, saves the buying of ammoniacal liquor, storage and trucking costs, greatly reduced raw materials cost.
Due to the present invention by reclaim ammonia through purification after direct reuse in the production process of iron oxide black, thus substantially reduce the water content (water content of industrial ammonia used in existing ammonia process technique reaches 80% more than) of to be brought into by industrial ammonia in reaction system, improve the ammonium sulfate concentrations in mother liquor, thus also correspondingly reduce the load of ammonium sulfate evaporation unit, decrease corresponding energy consumption.
Simultaneously, reclaim the purposes of the metal sulfate obtained in ammonia process widely, it is the important source material of the industries such as building, chemical industry, considerable economic return can be brought to manufacturing enterprise, thus avoid traditional ammonia process and produce the byproduct bulk deposition that iron oxide black causes, the difficult situation finding no market, do not have economic interests.The byproduct calcium sulfate being such as raw material with the compound of calcium is the indispensable raw material of slag sulphate cement, also be the important source material that all kinds of building whitewashes agent, agglutinate, plasterboard, expansive cement swelling agent etc., thus, its market outlook are good, product marketing is good, has appreciable economic worth.Other metal sulfates, as zinc sulfate, copper sulfate, chromium sulphate etc., are also very worthy indispensable industrial chemicals.
The invention provides the production method that a kind of brand-new ammonia circulation ammonia process prepares iron oxide black, solve and suppress ammonia process to prepare a great problem of iron oxide black technique in suitability for industrialized production application for many years, not only there is huge economic benefit, and there is far-reaching social effect.
Embodiment
The present invention is set forth further below in conjunction with specific embodiment.
In the preparation method of iron oxide black of the present invention, the production technique that the reaction technique of producing iron oxide black and ammonia process prepare iron oxide black is substantially identical, the key distinction be utilize recovery ammonia agent to iron oxide black produce in gained by product---the ammonia in ammonium sulfate liquor reclaims, and the ammonia of recovery is back to use ammonia process as raw material prepares in the production process of iron oxide black, form the production method that ammonia circulation ammonia process prepares iron oxide black thus.
Embodiment 1:
The concrete production process that ammonia circulation ammonia process of the present invention prepares the production method of iron oxide black is as follows:
1, the copperas solution after removal of impurities is added in reaction vessel, be warming up to 90 ~ 95
oc, then adds the industrial ammonia that volumetric concentration is 20%, stirs while adding, and adjust ph, about 9 ~ 10, is obtained by reacting Fe (OH)
2(NH
4) SO
4colloidal fluid.
2, in reaction vessel, pass into oxygen (or air), carry out oxidizing reaction, generate iron oxide black slip.
3, adopt filter-pressing process to leach iron oxide black, form filter cake, namely obtain iron oxide black finished product by after filter cake washing, drying, filtrate is the mother liquor containing ammonium sulfate.
4, the mother liquid evaporation of liquid containing ammonium sulfate is become ammonium sulfate saturated solution, be passed into again (zinc oxide is as recovery ammonia agent) in the recovery ammonia retort being contained with zinc oxide concentrate powder (particle diameter is less than 75 μm), and control ammonium sulfate and the mol of zinc oxide and measure than being 1.1 ~ 1.8,320 ~ 350 DEG C are warming up to gradually after stirring, react 2 ~ 4 hours, release until no longer include ammonia.
5, the method reaction residues in step 4 specified by the hydrometallurgy of zinc with hot water dissolving, after purification and impurity removal, press filtration, evaporation, cooling, crystallization, centrifuge dripping, obtains zinc sulfate crystal; And gained ammonia is after ammonia purifier purification, is pressed into by ammonia compressor and fills in the reaction vessel of the copperas solution purified.
6, making the solution ph in retort reach after 9 ~ 10 when returning the ammonia in the retort of producing iron oxide black, performing step 2 and subsequent step, circulating successively.Principal reaction is:
ZnO+(NH
4)
2SO
4=ZnSO
4+H
2O+2NH
3
ZnSO
4+7H
2O=ZnSO
4 ·7H
2O
Utilize iron oxide black preparation method of the present invention, except the first tank initial in production process all adopts industrial ammonia, only a small amount of ammoniacal liquor need be regularly filled in follow-up production process, raw materials cost is not only made to reduce 50% more than thus, and the moisture content greatly reduced in liquid containing ammonium sulfate mother liquor, when evaporating liquid containing ammonium sulfate mother liquor, being reduced about 50% by the water yield of evaporating is corresponding, thus greatly reducing energy consumption.
Embodiment 2:
The preparation method of the present embodiment is substantially with embodiment 1, difference is, cupric oxide fine ore (particle diameter is less than 75 μm) is selected in the recovery ammonia agent used in step 4, ammonium sulfate and the mol of cupric oxide measure than being that 1.05 ~ 2.0(reduces with grade and increases, reduce with granularity refinement), temperature of reaction is 320 ~ 350 DEG C, reaction times is 2 ~ 4 hours, reaction residues, through the hot water dissolving of pH≤6, smelts the method purification and impurity removal of regulation, press filtration according to wet copper, evaporation, crystallisation by cooling, centrifuge dripping, obtains copper sulfate crystal.Principal reaction is:
CuO+(NH
4)
2SO
4=CuSO
4+2NH
3+H
2O
CuSO
4+5H
2O=CuSO
4 ·5H
2O
Embodiment 3:
The preparation method of the present embodiment is substantially with embodiment 1, and difference is, chromite powder (particle diameter is less than 75 μm) is selected in recovery ammonia agent used in step 4, ammonium sulfate and Cr
2feO
4metering than for by metering excessive 1 ~ 3 times (relevant with granularity), temperature of reaction is 350 DEG C, reaction times be 2 ~ 4 hours (relevant with the size of reaction vessel, be as the criterion until no longer include ammonia releasing), the water dissolution of reaction residues pH≤5, below by the disposal methods of known acid-soluble chromite.Principal reaction is:
Cr
2FeO
4+4(NH
4)
2SO
4=Cr
2(SO
4)
3+4H
2O+FeSO
4+8NH
3
Embodiment 4:
The preparation method of the present embodiment is substantially with embodiment 1, and difference is, white lime is selected in recovery ammonia agent used in step 4, ammonium sulfate and Ca (OH)
2mol metering than being 1.05, temperature of reaction is 320 ~ 350 DEG C, and the reaction times is 1 ~ 2 hour, to without ammonia releasing, reactant and anhydrous calciumsulphate:
Ca(OH)
2+(NH
4)
2SO
4=CaSO
4+2NH
3+H
2O
Or temperature of reaction is 180 ~ 200 DEG C, obtain semi-hydrated gypsum and the plaster of Paris:
Ca(OH)
2+(NH
4)
2SO
4=CaSO
4 ·0.5H
2O+0.5H
2O+2NH
3
Embodiment 5:
The preparation method of the present embodiment is substantially with embodiment 1, and difference is, Wingdale is selected in recovery ammonia agent used in step 4, ammonium sulfate and CaCO
3mol metering than being 1.1, temperature of reaction is 350 DEG C, and the reaction times is 1 ~ 2 hour, to without ammonia releasing, gained solid product and anhydrous slufuric acid calcium powder namely what is called " anhydrite ":
CaCO
3+(NH
4)
2SO
4=CaSO
4+2NH
3+H
2O+CO
2
The reaction process of other recovery ammonia agent recovery ammonia is similar to the situation in above embodiment, does not repeat them here.
Claims (7)
1. ammonia circulation ammonia process prepares a production method for iron oxide black, in reaction vessel, load copperas solution, is warmed up to 90 ~ 95
oc, adds ammoniacal liquor under stirring, controls the pH value of reaction soln 9 ~ 10, obtained containing Fe (OH)
2(NH
4) SO
4colloidal fluid; In reaction vessel, pass into oxygen be oxidized, obtained iron oxide black slip; Iron oxide black slip after filtration, washing, rotary flash distillation and blending, namely iron oxide black finished product is obtained, the by product of production process is ammonium sulfate liquor, it is characterized in that, ammonium sulfate liquor is passed in recovery ammonia retort after concentrated, react with recovery ammonia agent wherein, generate vitriol and ammonia, after the ammonia of generation being transported to ammonia purifier purification, be injected in the reaction vessel producing iron oxide black through ammonia compressor pressurization again, ammonia circulated in above-mentioned reaction process and participates in the production of iron oxide black.
2. ammonia circulation ammonia process according to claim 1 prepares the production method of iron oxide black, it is characterized in that, described recovery ammonia agent is the oxide compound of the metallic element of second and third main group, oxyhydroxide or carbonate.
3. ammonia circulation ammonia process according to claim 1 prepares the production method of iron oxide black, it is characterized in that, described recovery ammonia agent is first and second, four, six, seven, the oxide compound of the transition metal of eight subgroups, oxyhydroxide, carbonate or calcining.
4. ammonia circulation ammonia process according to claim 1 prepares the production method of iron oxide black, it is characterized in that, described recovery ammonia agent is the oxide compound of each element of Mg, Al, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ti, Zr, oxyhydroxide, carbonate or calcining.
5. ammonia circulation ammonia process according to claim 1 prepares the production method of iron oxide black, it is characterized in that, described recovery ammonia agent is CuO, Cu
2(CO
3) (OH)
2, Ca (OH)
2, CaCO
3, ZnO, TiFeO
3or Cr
2feO
4.
6. the ammonia circulation ammonia process according to any one of claim 1 ~ 5 prepares the production method of iron oxide black, it is characterized in that, described ammonium sulfate liquor be first evaporated to saturated after pass into again in recovery ammonia retort.
7. the ammonia circulation ammonia process according to any one of claim 1 ~ 5 prepares the production method of iron oxide black, it is characterized in that, described ammonium sulfate liquor is first through evaporation, crystallization, and the ammonium sulfate fine powder obtained passes in recovery ammonia retort again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510822311.0A CN105236496A (en) | 2015-11-24 | 2015-11-24 | Production method for preparing black iron oxide with ammonia circulation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510822311.0A CN105236496A (en) | 2015-11-24 | 2015-11-24 | Production method for preparing black iron oxide with ammonia circulation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105236496A true CN105236496A (en) | 2016-01-13 |
Family
ID=55034385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510822311.0A Pending CN105236496A (en) | 2015-11-24 | 2015-11-24 | Production method for preparing black iron oxide with ammonia circulation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105236496A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265512A (en) * | 2017-06-26 | 2017-10-20 | 杭州金丰环保科技有限公司 | A kind of method that hermetically sealed dioxygen oxidation method produces iron oxide yellow |
| CN107265511A (en) * | 2017-06-26 | 2017-10-20 | 杭州金丰环保科技有限公司 | A kind of method for producing iron oxide yellow |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684322A (en) * | 1979-12-11 | 1981-07-09 | Seitetsu Kagaku Co Ltd | Manufacture of black iron oxide pigment |
| US6416723B1 (en) * | 1998-03-20 | 2002-07-09 | Bayer Aktiengesellschaft | Method for reprocessing waste acid to form gypsum and iron oxide |
| CN102086039A (en) * | 2010-12-28 | 2011-06-08 | 漯河市兴茂钛业有限公司 | Method for preparing ammonium sulfate and Fe3O4 from titanium dioxide production waste acid solution |
| CN104071849A (en) * | 2013-03-25 | 2014-10-01 | 北京三聚环保新材料股份有限公司 | Method both for preparation of iron oxide black and combined production of ammonium sulfate |
| CN104828876A (en) * | 2015-05-25 | 2015-08-12 | 北京矿冶研究总院 | Method for producing ferroferric oxide by using iron scale |
-
2015
- 2015-11-24 CN CN201510822311.0A patent/CN105236496A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684322A (en) * | 1979-12-11 | 1981-07-09 | Seitetsu Kagaku Co Ltd | Manufacture of black iron oxide pigment |
| US6416723B1 (en) * | 1998-03-20 | 2002-07-09 | Bayer Aktiengesellschaft | Method for reprocessing waste acid to form gypsum and iron oxide |
| CN102086039A (en) * | 2010-12-28 | 2011-06-08 | 漯河市兴茂钛业有限公司 | Method for preparing ammonium sulfate and Fe3O4 from titanium dioxide production waste acid solution |
| CN104071849A (en) * | 2013-03-25 | 2014-10-01 | 北京三聚环保新材料股份有限公司 | Method both for preparation of iron oxide black and combined production of ammonium sulfate |
| CN104828876A (en) * | 2015-05-25 | 2015-08-12 | 北京矿冶研究总院 | Method for producing ferroferric oxide by using iron scale |
Non-Patent Citations (2)
| Title |
|---|
| 朱井安: "氧化铁黑生产工艺的优化", 《广东化工》 * |
| 郭秋宁等: "利用钛白副产品FeSO4制备氧化铁黑", 《广西化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265512A (en) * | 2017-06-26 | 2017-10-20 | 杭州金丰环保科技有限公司 | A kind of method that hermetically sealed dioxygen oxidation method produces iron oxide yellow |
| CN107265511A (en) * | 2017-06-26 | 2017-10-20 | 杭州金丰环保科技有限公司 | A kind of method for producing iron oxide yellow |
| CN107265511B (en) * | 2017-06-26 | 2018-11-20 | 杭州金丰环保科技有限公司 | A method of producing iron oxide yellow |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103922416B (en) | A kind of method of Separation and Recovery iron from red mud | |
| CN102534238A (en) | Harmless and comprehensive utilization method for vanadium-extraction liquid leached residue | |
| CN101607741B (en) | Method for preparing iron oxide red by byproduct ferrous sulfate of titanium dioxide | |
| CN101792185B (en) | Method for preparing lamellar ferric oxide by ferreous solution ammonia precipitation method | |
| CN104152687B (en) | Aluminium, vanadium, molybdenum, the production technology of nickel element three-waste free discharge are extracted from black shale | |
| CN101531355A (en) | Method for preparing high purity ferric phosphate using ferrous sulfate as by-product of white titanium pigment | |
| CN102383179B (en) | A kind of method that industrial waste acid and phosphogypsum fully utilize | |
| CN101168852A (en) | Mass production method for calcium sulfate whisker | |
| CN104628206A (en) | Recycling technique of lithium iron phosphate production wastewater | |
| CN107098372A (en) | A kind of method that hydrochloric acid decomposes phosphorus mine tailing extracting sulfuric acid calcium pyroborate and magnesium hydroxide | |
| CN101920998A (en) | Method for preparing manganese sulfate from waste byproducts obtained in the production of titanium white and low-grade pyrolusite | |
| CN102424426B (en) | Method for preparing iron oxide red and sodium phosphate by using yellow phosphorus by-product phosphor-iron slag | |
| CN107082653A (en) | A kind of utilization calcium and magnesium mud is the method that raw material prepares moderate-element Liquid Fertilizer | |
| CN101575106A (en) | Coproduction technology of calcium sulphate crystal whiskers and magnesium hydrate crystal whiskers by plaster-ammonium rotation method | |
| CN101486481A (en) | Method for coproduction of ammonia sulfate and superfine light calcium carbonate from fluorgypsum | |
| CN105236496A (en) | Production method for preparing black iron oxide with ammonia circulation method | |
| CN1749173A (en) | Comprehensively utilizing new process for ferrous sulfate | |
| CN106629806A (en) | Method for producing dihydrate gypsum from waste liquid in laterite nickel ore wet process | |
| CN109399594A (en) | A kind of cleaning method of mid low grade phosphate rock powder | |
| CN101920994A (en) | Method for preparing vanadyl sulfate | |
| CN107792840A (en) | A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate | |
| CN101760630A (en) | Method for recovering copper from copper sulfate solution | |
| CN104692787A (en) | Solidifying comprehensive recovery method of electroplating sludge ferrite | |
| CN103613135A (en) | Integrated utilization environmental-pollution-controlling new technology for ammonium molybdate production waste water | |
| CN101830749B (en) | Method for preparing compound fertilizer by using waste produced in process of preparing oxalate by using potato starchy residues |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160113 |
|
| RJ01 | Rejection of invention patent application after publication |