CN101037246A - Non-pollution polymeric iron sulfate sulfur production technique by dioxide reverse absorption tower process - Google Patents
Non-pollution polymeric iron sulfate sulfur production technique by dioxide reverse absorption tower process Download PDFInfo
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- CN101037246A CN101037246A CN 200610057522 CN200610057522A CN101037246A CN 101037246 A CN101037246 A CN 101037246A CN 200610057522 CN200610057522 CN 200610057522 CN 200610057522 A CN200610057522 A CN 200610057522A CN 101037246 A CN101037246 A CN 101037246A
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Abstract
The present invention relates to a preparation method of poly-ferric sulfate, wherein the mixed powder of ferric sulfate hydrate and siderite serves as the main material. 10~95 wt.% of ferric sulfate hydrate and 90~5 wt.% of siderite are crushed up to 5~325 mesh, together with one or the mixture of several of the modifier phosphate radical, aluminum ion and organic macromolecule aqueous solution of 0~10 wt.% are mixed to form a mixed powder to be filled into the absorbing column; a mixed gas of sulfur dioxide and air is fed into the absorbing column from the upper part, the sulfur dioxide reacts with oxygen to create sulfuric acid with a reaction temperature of 20~90 DEG C and the ferrous ion of the ferric sulfate hydrate and siderite is oxidized to iron ion; under the condition of plus pressure in the adsorbing column, the created poly-ferric sulfate dissolved into the water of crystallization generated by the oxidation of ferric sulfate hydrate to form a high concentrated solution which is partially mixed with the nonabsorbing gas and then is subjected to filter pressing by means of the filter sand layer at the bottom of the absorbing column so as to form high concentrated poly-ferric sulfate. The present invention is a continuous reaction technology with a rapid reaction rate, a lower cost and nonpollution.
Description
Technical field
The present invention relates to a kind of production technique of flocculation agent, particularly a kind of CR production polyaluminum sulfate iron process.
Technical background
Bodied ferric sulfate is a kind of common flocculation agent, at present production method mainly be have following several:
1) ferrous sulfate direct oxidation method: the employed oxygenant of present method is mainly hydrogen peroxide, sodium chlorate, chlorine etc., preparation technology as Chinese patent application number 03125205.2 described a kind of polymerization phosphorus ferric sulfate, it is characterized in that: earlier ferrous sulfate is added in the 70-80 ℃ of water, make it to reach capacity, be cooled to 50-60 ℃ then, filter, choose following oxygenant or in the catalyzer one or more: hydrogen peroxide, sodium chlorate, Potcrate, trisodium phosphate, make ferrous iron be converted into ferric iron, get filtrate and place reactor as the reaction feed liquid, add sodium chlorate and trisodium phosphate, wherein, nFe2+: nNaClO3=1mol: 0.10-0.20mol, nFe2+: nNa4P3O7=1mol: 0.015-0.030mol, reacted 20-30 minute, and promptly made liquid product, liquid product is dried between 50-60 ℃ promptly make the reddish-brown solid phase prod.There is following problem in the method that this ferrous sulfate direct oxidation method prepares polymerization phosphorus ferric sulfate: oxygenant price height, and in the production process owing in fact also need to add sulfuric acid, so production cost is higher; Hydrogen peroxide oxidation process is owing to exist the decomposing hydrogen dioxide solution problem, and material loss is serious; Chlorine, sodium chlorate etc. cause chlorine to pollute easily and raw material need be through strict examining and could obtain, and there is the stability of the poly-iron of meeting influence in sodium ion; Ferrous sulfate solubleness is low, and therefore the product that is synthesized is the bodied ferric sulfate dilute solution, and the oven drying at low temperature energy consumption is very big.Owing to there are the problems referred to above, the producer of mass production bodied ferric sulfate does not all adopt this class direct oxidation method in the world at present.
2) ferrous sulfate catalytic oxidation: the employed oxygenant of present method is an air or oxygen, the main nitric acid that uses, nitrate and nitrite are catalyzer, oxidation is synthetic under pressurized state, as the production method of electric power as described in the Chinese patent application patent No. 200310105964.4 of Mu Shunyong with coagulant polymeric ferric sulfate, with titanium powder plant system product ferrous sulfate is main raw material, ferrous sulfate and vitriolic weight proportion are 0.128, earlier give the oxidation copperas solution with air, add Sodium Nitrite and pure oxygen from catalytic oxidizer again, oxidation ferrous sulfate and sulfuric acid mixed solution, do not need heating and pressurizing, make the reaction times shorten 50%, catalyst levels reduces 40%, again through compound, process such as stable is produced respond well electric power coagulant polymeric ferric sulfate.These class methods are present bodied ferric sulfate main production, and polymerization time is generally between 1-24 hour.There is following problem in these class methods at present: reaction process needs to add earlier some sulfuric acid equally, so production cost is unavoidably than higher; Produce strong carcinogens in the catalyzer use, exhaust pollution is serious, existing part article takes transition metal ion such as Manganse Dioxide or Br-, I-ion as catalyzer, method with the atmospheric oxidation synthesizing polymeric ferric sulfate, though these methods can be avoided strong pollution, the catalyst separating difficulty, speed of response is slow, often need pressurization, cause production cost to improve and be not employed as yet.
3) use conventional absorption tower: the direct drip washing of ferrous sulfate aqueous solution absorbs sulfurous gas and oxygen mixed gas, produce sulfuric acid/ferrous sulfate mixture, making bodied ferric sulfate again neutralizes, this method is not owing to need to add sulfuric acid, therefore cost is quite cheap, is used for bargh's production in a large number and soaks the ore deposit raw material.This class production concentration is very low, and absorption rate of sulfur dioxide descends when hanging down pH value, and reaction product is not suitable as the water treatment flocculation agent to the absorption tower seriously corroded very much.
4) use sulfuric acid and spathic iron ore, iron ore, pyrite cinder direct reaction or slaking to prepare the bodied ferric sulfate method: but the poly-iron product of present method direct production high density, need to use expensive sulfuric acid, and add the small amounts agent, reaction times will reach 2-48 hour usually, exothermic heat of reaction is comparatively severe simultaneously, often cause bodied ferric sulfate to decompose because of surpassing 90 degrees centigrade, so product stability is relatively poor, cost is also slightly high, does not enter the big production phase at present.
Summary of the invention
The purpose of this invention is to provide the CR production polyaluminum sulfate iron process that a kind of production unit is simple, production cost is low, speed of response is fast.
Sulfurous gas reverse absorption tower method CR production polyaluminum sulfate iron process of the present invention is with the industrial by-products ferrous sulfate hydrate, main component is that the mixed powder of the spathic iron ore of iron protocarbonate is one of main raw material, ferrous sulfate and spathic iron ore are carried out powder mix be broken to the 5-325 order, weight proportion is: ferrous sulfate hydrate 10-95 part, main component is spathic iron ore 90-5 part of iron protocarbonate, the properties-correcting agent phosphate radical, aluminum ion, one or several mixtures 0-10 part in the organic polymer aqueous solution, described phosphate radical refers to Na3PO4, soluble phosphates commonly used such as HPO4 Sodium hexametaphosphate 99; Aluminum ion refers to aluminum soluble salts such as Tai-Ace S 150, aluminum chloride, aluminum nitrate, aluminium hydroxide; The organic polymer aqueous solution refers to materials such as low molecular weight polycaprolactone olefin(e) acid, polymaleic acid.
With above-mentioned powder packed in the absorption tower, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1 in sulfurous gas and the air: 1-1: between 10, guarantee that oxygen is excessive and make in the absorption tower pressure greater than a normal atmosphere, control reaction temperature is between 20-90 degree centigrade, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously, in this reaction, spathic iron ore has played stable pH value carries out catalyzed reaction smoothly; Absorb side reaction product sulfuric acid and make product remain on the bodied ferric sulfate state, generate of the effect of the loose material of carbon dioxide to avoid the raw material conglomeration to stop up.
At the absorption tower direct draught, the bodied ferric sulfate that reaction generates is dissolved in the crystal water that the ferrous sulfate hydrate oxidation separates out and forms highly concentrated solution, partially mixed with the gas that can not absorb, filter sand layer by the bottom, absorption tower is come out by press filtration, be the finished product THE HIGH CONCENTRATION OF POLYMERIZED FERRIC SULFATE, the product basicity is controlled between 0-25%, also can carry out subsequent disposal to enhance product performance to product, discharge in the gas and contain micro-sulfurous gas, the alkali absorb method of available routine or ferrous sulfate absorption process are removed.
This technology is continuous reaction process, and speed of response is fast, do not have pollution problem, but owing to has used spathic iron ore therefore to need useless white residue in the periodic cleaning absorption tower in order to avoid filtering layer is blocked up.Introducing purposes such as phosphate radical, aluminum ion, the organic polymer aqueous solution in the raw material is that the product bodied ferric sulfate is carried out modification to improve flocculence and stability, because raw material uses nature mineral spathic iron ore, the industry byproduct ferrous sulfate, sulfuric acid industry raw materials for production sulfurous gas and air, equipment is comparatively simple, product is again the cheap THE HIGH CONCENTRATION OF POLYMERIZED FERRIC SULFATE of trucking costs simultaneously, therefore production cost is lower than existing the whole bag of tricks during scale operation, has the possibility of eliminating existing all the other polymeric ferric sulfate flocculant production technique.
Embodiment
Embodiment 1
The raw material powder mix of following parts by weight is broken to powder: 95 parts of ferrous sulfate hydrates and 5 parts of spathic iron ores are carried out powder mix be broken to 50 orders, the sodium hexametaphosphate solution that adds 5 part 30%, contain 50.3% iron protocarbonate in the described spathic iron ore, with above-mentioned moist powder packed in the absorption tower, packing height is absorption tower 1/4, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1: 2 in sulfurous gas and the air, and make that pressure is about 1.5 normal atmosphere in the absorption tower, control reaction temperature is between 20-90 degree centigrade, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously, and this moment, the reaction of by product and spathic iron ore generated bodied ferric sulfate.At the absorption tower direct draught, the bodied ferric sulfate that reaction generates is dissolved in the crystal water that the ferrous sulfate hydrate oxidation separates out and forms highly concentrated solution, partially mixed with the gas that can not absorb, filter sand layer by the bottom, absorption tower is come out by press filtration, be the finished product THE HIGH CONCENTRATION OF POLYMERIZED FERRIC SULFATE, the product basicity is about 2%, be red-brown, can introduce iron protocarbonate regulates basicity, also can carry out subsequent disposal to enhance product performance to product, discharge in the gas and contain micro-sulfurous gas, the alkali absorb method of available routine or ferrous sulfate absorption process are removed.
Embodiment 2
The raw material powder mix of following parts by weight is broken to powder: 85 parts of ferrous sulfate hydrates and 15 parts of spathic iron ores are carried out powder mix be broken to 200 orders, mix for 5 parts, contain 50.3% iron protocarbonate in the described spathic iron ore with the aluminum nitrate saturated solution.With above-mentioned moist powder packed in the absorption tower, packing height is 1/6 of an absorption tower height, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1: 5 in sulfurous gas and the air, guarantee that oxygen is excessive and make that pressure is 2 normal atmosphere in the absorption tower, control reaction temperature is 30-60 degree centigrade, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously, in this reaction, spathic iron ore has played stable pH value carries out catalyzed reaction smoothly; Absorb side reaction product sulfuric acid and make product remain on the bodied ferric sulfate state, generate of the effect of the loose material of carbon dioxide to avoid the raw material conglomeration to stop up.At the absorption tower direct draught, the bodied ferric sulfate that reaction generates is dissolved in the crystal water that the ferrous sulfate hydrate oxidation separates out and forms highly concentrated solution, partially mixed with the gas that can not absorb, filter sand layer by the bottom, absorption tower is come out by press filtration, be the finished product THE HIGH CONCENTRATION OF POLYMERIZED FERRIC SULFATE, the product basicity also can carry out subsequent disposal to enhance product performance to product between 8-10%, discharge in the gas and contain micro-sulfurous gas, the alkali absorb method of available routine or ferrous sulfate absorption process are removed.
Embodiment 3
The raw material powder mix of following parts by weight is broken to powder: 60 parts of ferrous sulfate hydrates and 40 parts of spathic iron ores are carried out powder mix be broken to 325 orders, mix with 10 parts of properties-correcting agent, contain 50.3% iron protocarbonate in the described spathic iron ore, described formula of modifier is as follows: 0.5 part of the polyacrylic acid of 3 parts of 60% phosphoric acid, the polymerization degree 100,000,1.5 parts in aluminum oxide, 5 parts in water.With above-mentioned moist powder packed in the absorption tower, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1: 6 in sulfurous gas and the air, pressure is between 1.5-3 normal atmosphere in the control absorption tower, control reaction temperature is at 20-80 degree centigrade, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously, in this reaction, spathic iron ore has played stable pH value carries out catalyzed reaction smoothly; Absorb side reaction product sulfuric acid and make product remain on the bodied ferric sulfate state, generate of the effect of the loose material of carbon dioxide to avoid the raw material conglomeration to stop up.At the absorption tower direct draught, the bodied ferric sulfate that reaction generates is dissolved in the crystal water that the ferrous sulfate hydrate oxidation separates out and forms highly concentrated solution, partially mixed with the gas that can not absorb, filter sand layer by the bottom, absorption tower is come out by press filtration, be the finished product THE HIGH CONCENTRATION OF POLYMERIZED FERRIC SULFATE, product is the dark brown red viscous solution, and the product basicity is 15-22%, discharge in the gas and contain micro-sulfurous gas, the alkali absorb method of available routine or ferrous sulfate absorption process are removed.
Claims (4)
1, sulfurous gas reverse absorption tower method CR production polyaluminum sulfate iron process, with the industrial by-products ferrous sulfate hydrate is raw material, it is characterized in that: the mixed powder of ferrous sulfate hydrate and spathic iron ore is broken to the 5-325 order for carrying out powder mix, described raw material weight proportioning is: ferrous sulfate hydrate 10-95 part, spathic iron ore 90-5 part, contain 50.3% iron protocarbonate in the described spathic iron ore, above-mentioned powder mixes with properties-correcting agent 0-10 part, be filled in the absorption tower, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1 in sulfurous gas and the air: 1-1: between 10, make in the absorption tower pressure greater than a normal atmosphere, control reaction temperature is between 20-90 ℃, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, and the ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously; At the absorption tower direct draught, the bodied ferric sulfate that reaction generates is dissolved in the crystal water that the ferrous sulfate hydrate oxidation separates out and forms highly concentrated solution, partially mixed with the gas that can not absorb, filter sand layer by the bottom, absorption tower is come out by press filtration, be the finished product THE HIGH CONCENTRATION OF POLYMERIZED FERRIC SULFATE, the product basicity is controlled between 0-25%.
2, sulfurous gas reverse absorption tower method CR production polyaluminum sulfate iron process according to claim 1, it is characterized in that: 95 parts of ferrous sulfate hydrates and 5 parts of spathic iron ores are carried out powder mix be broken to 50 orders, the sodium hexametaphosphate solution that adds 5 part 30%, with above-mentioned moist powder packed in the absorption tower, packing height is absorption tower 1/4, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1: 2 in sulfurous gas and the air, and make that pressure is about 1.5 normal atmosphere in the absorption tower, control reaction temperature is between 20-90 degree centigrade, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously, this moment, the reaction of by product and spathic iron ore generated bodied ferric sulfate, and the product basicity is about 2%.
3, sulfurous gas reverse absorption tower method CR production polyaluminum sulfate iron process according to claim 1, it is characterized in that: 85 parts of ferrous sulfate hydrates and 15 parts of spathic iron ores are carried out powder mix be broken to 200 orders, mix for 5 parts with the aluminum nitrate saturated solution, with above-mentioned moist powder packed in the absorption tower, packing height is 1/6 of an absorption tower height, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1: 5 in sulfurous gas and the air, guarantee that oxygen is excessive and make that pressure is 2 normal atmosphere in the absorption tower, control reaction temperature is 30-60 degree centigrade, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously, this moment, the reaction of by product and spathic iron ore generated bodied ferric sulfate, and the product basicity is between 8-10%.
4, sulfurous gas reverse absorption tower method CR production polyaluminum sulfate iron process according to claim 1, it is characterized in that: 60 parts of ferrous sulfate hydrates and 40 parts of spathic iron ores are carried out powder mix be broken to 325 orders, mix with 10 parts of properties-correcting agent, described formula of modifier is as follows: 3 parts of 60% phosphoric acid, 0.5 part of the polyacrylic acid of the polymerization degree 100,000,1.5 parts in aluminum oxide, 5 parts in water, with above-mentioned moist powder packed in the absorption tower, feed sulfurous gas and Air mixing gas from top, absorption tower, the effective content of oxygen ratio is 1: 6 in sulfurous gas and the air, pressure is between 1.5-3 normal atmosphere in the control absorption tower, control reaction temperature is at 20-80 degree centigrade, this moment is under the ferrous sulfate katalysis, oxygen reaction generates sulfuric acid in sulfurous gas and the air, ferrous ion from ferrous sulfate hydrate and spathic iron ore is oxidized into iron ion simultaneously, this moment, the reaction of by product and spathic iron ore generated bodied ferric sulfate, and the product basicity is 15-22%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274507A (en) * | 2013-05-17 | 2013-09-04 | 中南大学 | Biological flocculant for processing fluorine and calcium in wastewater and preparation and application methods thereof |
| CN108911073A (en) * | 2018-07-16 | 2018-11-30 | 湖北文理学院 | A kind of flocculant and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274507A (en) * | 2013-05-17 | 2013-09-04 | 中南大学 | Biological flocculant for processing fluorine and calcium in wastewater and preparation and application methods thereof |
| CN108911073A (en) * | 2018-07-16 | 2018-11-30 | 湖北文理学院 | A kind of flocculant and preparation method thereof |
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