CN1114292A - Process for producing high-pure ferrous sulfate using reclaimed acid from coking plant - Google Patents
Process for producing high-pure ferrous sulfate using reclaimed acid from coking plant Download PDFInfo
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- CN1114292A CN1114292A CN 94110362 CN94110362A CN1114292A CN 1114292 A CN1114292 A CN 1114292A CN 94110362 CN94110362 CN 94110362 CN 94110362 A CN94110362 A CN 94110362A CN 1114292 A CN1114292 A CN 1114292A
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- acid
- ferrous sulfate
- regenerating
- coking plant
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Abstract
The process for preparing high-purity (>99.0%) FeSO4.7H2O from regenerated acid, a waste acid produced during washing light benzene with sulfuric acid includes such steps as passing steam into the regenerated acid for heat-treatment, filtering, adding iron filings and water, passing steam again in it for reaction, filtering, concentration, crystallizing and drying, and features low cost and no environmental pollution.
Description
The present invention relates to the comprehensive utilization of sulfuric acid waste, be specially a kind of method of producing the high purity ferrous sulfate with reclaimed acid from coking plant.
Regenerating acid is the spent acid solution that light benzene produces in the sulfuric acid scrubbing process, its outward appearance is brownish black, owing to polymkeric substance such as a large amount of acid tars are arranged are present in the regenerating acid with suspension or emulsified state, solution is thickness comparatively, and general sulfur acid is 45～72%, sulfonated bodies is 1.5～5% (to be scaled carbon, sometimes can reach 15%), it is 0.1% that benzene belongs to hydrocarbon content, the residue after the calcination is 0.10～0.25%, iron level is 0.02～0.05%, and the density in the time of 20 ℃ is 1.35～1.61g/cm
3Owing to contain organism in the regenerating acid, have intensive acidity again, it purifies with the difficulty of utilizing bigger.The utilization of reclaimed acid from coking plant at present only limits to be used for as raw material the production of ammonium sulfate, but use undressed regenerating acid to be raw material, bring certain difficulty can for the production and the operation of ammonium sulfate, as cause mother liquor foaming, " congeeization " and the ammonium sulfate degree is diminished, color blackening etc., the while also influences the quality product of ammonium sulfate.Can widen the range of application of regenerating acid as regenerating acid being carried out purifying treatment (" fuel and chemical industry " the 23rd volume, the 6th phase, P312-316), but the processing costs height is difficult to carry out popularization, and easily environment is caused new pollution.Therefore, how the active and effective regenerating acid that utilizes is created high economic benefit and environmental benefit, is that present coking industry is badly in need of a difficult problem solving.
Ferrous sulfate (FeSO
47H
2O) be a kind of important chemical material,, also can be widely used in the processing of industrial pollution water as water purification agent except that as analytical reagent, photo-lithographed, the system ferrite raw material.With sulfuric acid (comprising sulfuric acid waste), iron filings are that to produce ferrous sulfate be a kind of mature methods to raw material in the prior art, but up to the present, do not see as yet and use the report that reclaimed acid from coking plant prepares the high purity ferrous sulfate, its major cause is: 1, owing to be dissolved with complicated polymkeric substance such as acid tar in the regenerating acid, if regenerating acid is directly used in the preparation ferrous sulfate without purifying treatment, impurity in the regenerating acid (as acid tar etc.) condenses seriously polluted in reaction vessel, easy-clear not, in the reacting by heating process, the extent of polymerization of organic impurities increases, the solution thickness, wayward response behaviour, both influence filtration, had a strong impact on the purity of ferrous sulfate again.If 2 at first take purifying treatment means such as extraction to regenerating acid, will inevitably increase the production cost of ferrous sulfate, and in decontamination process, easily introduce other reagent, also can cause new pollution to environment.
Purpose of the present invention just provides a kind of ideal and prepares the method for high purity ferrous sulfate with reclaimed acid from coking plant, and this method technology is simple, and low production cost can not pollute environment, is easy to promotion and implementation.
To achieve these goals, technical scheme of the present invention is: at first feed water vapor and carry out the pre-treatment of regenerating acid in the regenerating acid waste liquid, controlled temperature is 105～120 ℃, heats 0.5～2 hour, leaves standstill 12 hours, removes by filter polymeric impurities such as acid tar; Add iron filings and water according to sulfuric acid, iron filings and water respectively with the ratio of 1: 0.6～0.8: 1.4～2.0 (weight ratios) in regenerating acid solution, feed the water vapor heating, control reaction temperature is 84～105 ℃, when the solution pH value is 1.5～3.0, stops heating; Remove by filter impurity such as remaining iron filings, uncombined carbon,, improve the speed of condensing crystal, adopt reduction vaporization to concentrate, and the control vaporization temperature is 65～95 ℃, when filtrate density is 1.25～1.35g/cm for preventing the oxidation of ferrous sulfate
3The time, concentration process finishes, and filtrate is placed crystallization under the normal temperature; After crystallisation process is finished, go out crystallization (FeSO through centrifugation
47H
2O), crystallization is dry under≤40 ℃ ventilation condition, and the crystallization sulfur acid that obtains at last is ferrous 〉=and 99.0%.
In aforesaid method, the impurity such as small amount of acid tar that regenerating acid is separated after the water vapor heat treated can be used on coal-blending coking; Crystallization is with after mother liquor separates, but mother liquor reuse or concentrate and carry out reduction vaporization and concentrate so that further reclaim(ed) sulfuric acid is ferrous, not only improves the rate of recovery and also can reduce pollution to environment.
Advantage of the present invention:
1, technology is simple, and production cost is low, can not cause new pollution to environment, and is easy to implement to promote.
2, the ferrous sulfate purity height of preparing has been opened up a feasible way for the utilization of regenerating acid, has tangible economic benefit and environmental benefit.
Embodiment 1:
Regenerating acid is taken from refining benzene workshop, this steel coke-oven plant, sulfur acid 70.5% (weight) wherein, and density is 1.60g/cm
3Feed water vapor in regenerating acid solution, about 110 ℃ of controlled temperature heated 1 hour, left standstill 12 hours, filtered with filter cloth.Get 200 milliliters of regenerating acids after the filtration, add 350 milliliters in iron filings 140 grams, water respectively, the heating of feeding water vapor, control reaction temperature is 90 ℃, when the solution pH value is 3.0, stops heating, filter, then filtrate is transferred to and carried out reduction vaporization in the electrically heated there-necked flask and concentrate, the temperature of control solution is 85 ℃, when the density of solution is 1.25g/cm
3The time, solution is transferred in the crystallizer tank, and crystallization at normal temperatures, after crystallisation process is finished,, again crystallization is at room temperature dried up surperficial moisture content with fan with supercentrifuge fractional crystallization and mother liquor, the bottling sealing, its ferrous sulfate content of the crystallization that obtains at last is 99.8% (weight), and foreign matter content (%, wt): water-insoluble＜0.02; Muriate＜0.0002; Phosphoric acid salt＜0.0005; Manganese＜0.05; High ferro＜0.004; Copper＜0.0001; Zinc＜0.02; Arsenic＜0.00005; Ammoniacal liquor is throw out＜0.02 not.
Claims (2)
1, a kind ofly produce the method for high purity ferrous sulfate with reclaimed acid from coking plant, it is characterized in that: water vapor is fed in the regenerating acid waste liquid, and 105～120 ℃ of controlled temperature heated 0.5～2 hour, left standstill 12 hours, filtered; Add iron filings and water in regenerating acid, feed the water vapor heating, wherein, the weight ratio of sulfuric acid, iron filings and water is 1: 0.6～0.8: 1.4～2.0 in the regenerating acid, and control reaction temperature is 84～105 ℃, to the solution pH value be 1.5～3.0; Filter, filtrate is 1.25～1.35g/cm 65～95 ℃ of evaporation concentration until solution density
3, crystallization under the normal temperature; After Crystallization Separation goes out, dry under≤40 ℃ ventilation condition.
2, according to claim 1ly produce the method for high purity ferrous sulfate with reclaimed acid from coking plant, it is characterized in that: concentration process concentrates for the reduction vaporization under 65～95 ℃ of temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110362 CN1114292A (en) | 1994-06-30 | 1994-06-30 | Process for producing high-pure ferrous sulfate using reclaimed acid from coking plant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110362 CN1114292A (en) | 1994-06-30 | 1994-06-30 | Process for producing high-pure ferrous sulfate using reclaimed acid from coking plant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1114292A true CN1114292A (en) | 1996-01-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94110362 Pending CN1114292A (en) | 1994-06-30 | 1994-06-30 | Process for producing high-pure ferrous sulfate using reclaimed acid from coking plant |
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| CN (1) | CN1114292A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294087C (en) * | 2003-10-08 | 2007-01-10 | 山西焦化股份有限公司 | Method for treating waste acid from refining benzene for coking plant |
| CN101921000A (en) * | 2010-08-06 | 2010-12-22 | 安吉豪森药业有限公司 | Production method of pharmaceutical-grade ferrous sulfate |
| CN101759315B (en) * | 2010-01-07 | 2011-05-18 | 黄丹喜 | Method for recycling waste diluted sulfuric acid from acid washing solution of steel |
| CN105366736A (en) * | 2015-11-11 | 2016-03-02 | 何定 | Titanium white by-product copperas dehydration and drying method |
-
1994
- 1994-06-30 CN CN 94110362 patent/CN1114292A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294087C (en) * | 2003-10-08 | 2007-01-10 | 山西焦化股份有限公司 | Method for treating waste acid from refining benzene for coking plant |
| CN101759315B (en) * | 2010-01-07 | 2011-05-18 | 黄丹喜 | Method for recycling waste diluted sulfuric acid from acid washing solution of steel |
| CN101921000A (en) * | 2010-08-06 | 2010-12-22 | 安吉豪森药业有限公司 | Production method of pharmaceutical-grade ferrous sulfate |
| CN105366736A (en) * | 2015-11-11 | 2016-03-02 | 何定 | Titanium white by-product copperas dehydration and drying method |
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| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
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