CN1208019A - Liquid phase process producing ferric oxide, potassium sulfate and ammonium chloride - Google Patents
Liquid phase process producing ferric oxide, potassium sulfate and ammonium chloride Download PDFInfo
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- CN1208019A CN1208019A CN 98102567 CN98102567A CN1208019A CN 1208019 A CN1208019 A CN 1208019A CN 98102567 CN98102567 CN 98102567 CN 98102567 A CN98102567 A CN 98102567A CN 1208019 A CN1208019 A CN 1208019A
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- potassium sulfate
- ammonium chloride
- sulfate
- ferric oxide
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Abstract
The present invention relates to the production of ferric oxide, potassium sulfate and ammonium chloride, especially liquid phase process producing the said three products. All the three products have obvious industrial value and quality reaching relevant national standards.
Description
The present invention belongs to the field of chemical production, and relates to a method for producing industrial iron oxide, potassium sulfate and ammonium chloride (technological process). 1. Industrial iron oxide is the most basic raw material for producing ferrite magnetic materials, which are widely used in various communications, broadcast television, computer and other electronic industries; the potassium sulfate is mainly used for chlorine-free commercial crops, such as tobacco, tea, fruit trees, grapes, potatoes, medicinal materials, high-grade vegetables and the like. Therefore, the industrial iron oxide and the potassium sulfate have wide market prospects. 2. Technical route for producing industrial iron oxide and potassium sulfate at home and abroad 2.1 technical route for producing industrial iron oxide 2.1.1 ferrous sulfate is introduced into dilute alkali (NaOH) solution2Oxidation to form α -iron hydroxide [ α - (FeO) OH]Then the α -Fe is generated by high-temperature roasting2O3. 2.1.2 ferrous sulfate in concentrated alkali (NaOH) solution with O2Formation of Fe (OH)3And Fe (OH)2And high-temperature roasting to generate α -Fe2O3. 2.1.3 ferrous chloride (FeCl)2) Introducing O into concentrated alkali (NaOH) solution2Oxidizing to form iron hydroxide, and reducing at high temperature to form Fe3O4Then oxidized at 200-300 ℃ to form α -Fe2O3. (the above reference:
1、Penniman RS，Zoph NM.1921，US.Patent，1368784；
2、Camras M.1954，US.Patent，2694695；
3、Van Oosterhout GW.1965，Proc.Int.Conf.on Magnetism，Nottingham，
P.529；
4、Yamamoto N.1968，Buil.Inst.Chem.Res.Kyoto Uaiv.，46，28；
5、Leutner B，et al.1973，US.Patent，3769087；
6、Umano S.1975，Japan Patent，7580499；
7、Koster EG，et al.1976，Ger Patent，2447386；
8、Лукащина，Е.Н.Технология химии，
1980(1)：8-10
9. soviet Union patent, CCCP, 1975, 478042
10. Wohlfarth, Liu Zengtun, et al, magnetic materials-handbook of characteristics of magnetically ordered substances, volume II.
Beijing, electronics Press 1993, 266) 336)2.1.4 common features of the above-mentioned process schemes ① intermediates are all iron-forming hydroxide colloids which are difficult to filter and cannot be washed sufficiently with water to remove impurities, ② reaction in NaOH solution, coating water film containing sodium sulfate or sodium chloride on the surface of iron hydroxide colloid to affect the quality of iron oxide, ③ waste sodium sulfate or sodium chloride, 2.2 potassium sulfate production process scheme 2.2.1 Mannheim (Mannheim, also called sulfuric acid process)
At present, half of the total yield of potassium sulfate in the world is produced by the method, and the reaction of the method is carried out in two steps:
the byproduct of 27% hydrochloric acid is 1.5 tons for each 1 ton of potassium sulfate. 2.2.2 double decomposition method
The raw material for production contains Na2SO4、(NH4)2SO4、CaSO4、MgSO4And the like. The conversion rate of potassium is low, only 28.9% -84%, and by-products of NaCl and CaCl are produced2、MgCl2And the like, are difficult to handle. 2.2.3 association method
The raw materials and chemical reactions are the same as those of the Mannheim process, except that an organic alcohol and an organic amine associative agent are added to replace the second step reaction which can be carried out by the Mannheim process at high temperature. 2.2.4 solvent extraction
The most popular method of IMI company in Israel utilizes an extractant to complete the reaction of the second step of the Mannheim method which can be completed only by high temperature. The corrosivity is reduced, the equipment investment is reduced by about half, but the cost of the extracting agent is high, so the production cost is high.
The main problem with the above process is that waste (waste or liquid) is produced or the production cost is too high.
(see above:
1. panlonghua main weaving, practical small chemical production and large and complete, first volume: inorganic chemical products, compound fertilizers, pesticides, veterinary drugs, chemical industry publishers 1996, 415-
2. Wanjiaming, the production status and market prospects of potassium sulfate at home and abroad, scientific and technical information of chemical commodities, 1995 (2): 26-30
3. Boy-meaning peace foreign K2SO4Production review marine lake salt and chemical, 1995, 24 (2): 42-44
4. Kouzhua, potassium sulfate production and consumption at home and abroad, Hubei chemical industry, 1995, (3): 11-14
5. Dongwang, general outline of potassium sulfate production in China, dynamic chemical engineering and technology, 1995, (7): 4-5
6. Yangjin study, research on new process for producing potassium sulfate, lake salt and chemical engineering, 1995, 24 (2): 1-3
7. Zhang Fu dao, a new breakthrough in potassium sulfate production technology in China, soil fertilizer, 1997 (1): 46
8. The patent: a method for preparing potassium sulfate, CN1093679
9. The patent: manual of potassium sulfate and ammonium sulfate from potassium chloride and water ion (II) sulfate, CA 104: 170872u
10. The patent: use water iron (II) sulfate for preparation of ammonium nitrate and iron oxides, CA 114: 26639n)3. the inventor cooperated with Nanjing Chang technology chemistry GmbH in 1994 and 1996, and prepared the solid phase chemistryThe potassium sulfate and the by-products of ferric oxide and ammonium chloride are produced by the method. The solid phase method is characterized in that under the condition of solid phase, Fe3+With SO4 2-Conversion of complex into stable Fe2O(SO4)2The ligand is dissolved by proper amount of sulfuric acid, and ammonia is added to produce ammonium sulfate and ferric hydroxide.
In view of the problems existing in the industrial iron oxide production at home and abroad at present, the invention aims to find a process method for completing the main chemical reaction steps for producing the iron oxide in a solution state at normal temperature and normal pressure, and byproducts in the production process have obvious industrial value.
The invention organically combines the production of industrial ferric oxide, potassium sulfate and ammonium chloride together, and three products are produced by one set of process flow. The invention has the following characteristics: the invention utilizes waste ferrous sulfate of titanium dioxide factory, steel factory, grease chemical plant and other factories as raw materials, is comprehensive utilization of industrial waste, makes the best use of the whole production process, does not discharge waste, and meets the requirement of clean production; the intermediate product for producing the industrial iron oxide is FeCO3Precipitation, sufficient washing and impurity removal, stable product, high iron conversion rate up to more than 95 percent; the technology adopts special medium to separate potassium sulfate from ammonium chloride completely, the conversion rate of potassium is high and can reach more than 98%, and the recovery rate of ammonia can reach 99%. The quality of the three products all meets the relevant national standards, wherein the industrial iron oxide meets the indexes specified by SJ/T10383-93 first-class products of China department of electronic industry, the agricultural potassium sulfate meets the indexes specified by national standard ZB/TG21006-89 first-class products, and the agricultural ammonium chloride meets the indexes specified by national standard GB2946-92 first-class products. In order to distinguish from the technology of the inventor, namely 1994 and 1996, which cooperates with Nanjing Chang technology chemistry Limited and uses a solid phase chemical coordination method to produce potassium sulfate and byproducts of ferric oxide and ammonium chloride, the method for producing the ferric oxide, the potassium sulfate and the ammonium chloride is called as a liquid phase method. The main process route of the invention 1, ferrous sulfate dissolution and impurity removal
The technology utilizes waste ferrous sulfate of other industries, and impurities are required to be removed because the waste ferrous sulfate contains more impurities. Except using Fe powder NH3pH of 2-8 (optimized range)Enclosing: pH4-6), and recrystallizing ferrous sulfate at low temperature (10-20 deg.C). The recrystallized ferrous sulfate is re-dissolved into ferrous sulfate solution. 2. Production of ferrous carbonate
At normal temperature (more than 1 ℃ and less than 100 ℃ and optimized temperature range of 50-80 ℃), adding carbonate (potassium carbonate, ammonium carbonate and other carbonates) into the ferrous sulfate solution redissolved, introducing liquid ammonia, and generating ferrous carbonate precipitate with the aid of oxidant (air, KOH, potassium permanganate and other oxidants). 3. Roasting to prepare iron oxide
Roasting ferrous carbonate at 900-950 deg.c to produce α -ferric oxide, 4. production of potassium sulfate and ammonium chloride
Adding potassium chloride into supernatant (ammonium sulfate solution) after ferrous carbonate precipitation for double decomposition reaction to generate potassium sulfate and ammonium chloride, adding NH3Precipitating the potassium sulfate, separating the potassium sulfate by a centrifugal hydro-extracting machine, and drying to obtain a finished product. The solution after separating the potassium sulfate is ammonium chloride mother liquor, cooling after evaporation, precipitating ammonium chloride, and centrifuging to obtain the finished product.
The technological process adopted by the invention is shown in figure 1. FIG. 1 is a process flow diagram of the present invention.
The production method combines the production processes of the ferric oxide and the potassium sulfate in the same process, and obtains the ammonium chloride which has industrial value and the quality of which reaches the national relevant standard. In the process of the invention, after the ferrous sulfate is recrystallized and redissolved, carbonate is added into the solution to generate ferrous carbonate precipitate, thus overcoming the problems of difficult filtration and difficult washing to remove impurities caused by the formation of hydroxide of colloidal iron in the prior production process (including a solid phase method), simplifying the production process, saving a large amount of water resources and labor force, and certainly reducing the production cost.
The invention has high yield of final products, and the conversion rate of iron is up to more than 95 percent; the conversion rate of potassium is up to more than 98%, and the recovery rate of ammonia can reach 99%.
The invention uses the waste ferrous sulfate of titanium dioxide factory, steel factory, grease chemical plant and other factories as raw material, which is the comprehensive utilization of industrial waste, the whole production process makes the best use of things, no waste is discharged, and the requirement of clean production is achieved.
Claims (3)
1, a method (process flow) for producing industrial iron oxide, which is characterized in that: the whole production process not only produces the main product of ferric oxide, but also produces byproducts of potassium sulfate and ammonium chloride with industrial value, and the products all reach the relevant national quality standards.
The method for producing iron oxide according to claim 1, wherein the reaction comprises the following steps: adding carbonate into the ferrous sulfate solution to directly generate ferrous carbonate precipitate.
The method of claim 1, wherein the main chemical reaction steps including potassium sulfate and ammonium chloride as by-products are carried out in solution at normal temperature and pressure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98102567 CN1208019A (en) | 1998-07-01 | 1998-07-01 | Liquid phase process producing ferric oxide, potassium sulfate and ammonium chloride |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 98102567 CN1208019A (en) | 1998-07-01 | 1998-07-01 | Liquid phase process producing ferric oxide, potassium sulfate and ammonium chloride |
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| CN1208019A true CN1208019A (en) | 1999-02-17 |
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| CN 98102567 Pending CN1208019A (en) | 1998-07-01 | 1998-07-01 | Liquid phase process producing ferric oxide, potassium sulfate and ammonium chloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010010581A (en) * | 1999-07-21 | 2001-02-15 | 김수태 | Process for preparing potassium sulfate and ferrous chloride from ferrous sulfate |
| CN104445426A (en) * | 2014-11-28 | 2015-03-25 | 衡阳市金化科技有限公司 | Method for producing iron oxide yellow and iron oxide red by brine and ferrous sulphate solution obtained by production of titanium dioxide |
-
1998
- 1998-07-01 CN CN 98102567 patent/CN1208019A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010010581A (en) * | 1999-07-21 | 2001-02-15 | 김수태 | Process for preparing potassium sulfate and ferrous chloride from ferrous sulfate |
| CN104445426A (en) * | 2014-11-28 | 2015-03-25 | 衡阳市金化科技有限公司 | Method for producing iron oxide yellow and iron oxide red by brine and ferrous sulphate solution obtained by production of titanium dioxide |
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