CN1785824A - Refining method of metallugical acid washing iron oxide red - Google Patents
Refining method of metallugical acid washing iron oxide red Download PDFInfo
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- CN1785824A CN1785824A CN 200510019659 CN200510019659A CN1785824A CN 1785824 A CN1785824 A CN 1785824A CN 200510019659 CN200510019659 CN 200510019659 CN 200510019659 A CN200510019659 A CN 200510019659A CN 1785824 A CN1785824 A CN 1785824A
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- metallugical
- iron oxide
- oxide red
- acid washing
- washing iron
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Abstract
The present invention relates to a method for producing high-quality metallurgical pickling iron red by using metallurgical pickling iron red as raw material. Said method includes the following steps: uniformly mixing metallurgical pickling iron red and water with identical weight, adding them into fixed chromatographic column or elution bed, when the water layer of upper end of metallurgical pickling iron red in the chromatographic column or elution bed is quickly flowed off soon, supplementing water for 3-4 times until the liquor flowed out from lower end of chromatographic column is approaching to chlorineless neutrality, then taking out metallurgical pickling iron red slurry, so that the high-quality metallurgical pickling iron red can be obtained.
Description
Technical field
The present invention relates to a kind of is the metallugical acid washing iron oxide red method of raw material production high-quality with metallugical acid washing iron oxide red.
Background technology
Metallugical acid washing iron oxide red is the by product that Steel Plant reclaim the hydrochloric acid process, and being the spent pickle liquor that produces in the steel plate acid-washing process produces when high-temperature spray roasting (salt acid recovery), and its output is big.When reclaiming hydrochloric acid, section H Cl, Cl are always arranged
-Remain in metallugical acid washing iron oxide red in.Because HCl, Cl
-, impurity such as silicon existence, limited metallugical acid washing iron oxide red application greatly, in order to enlarge its use range, need carry out purification to it, remove HCl, Cl
-, Ca
2-, Na
+, impurity such as silicon.
At present, metallugical acid washing iron oxide red method of purification has: in high-temperature heat treatment method, water washing+high-temperature heat treatment method, the alkali and washing+high-temperature heat treatment method etc.Simple high-temperature heat treatment method is very serious to environmental influence, and back two kinds of methods are quite a lot of relatively, but because what use is general washing methods, dechlorination effect and degree are undesirable, still need remove remaining Cl by means of high-temperature heat treatment
-, therefore, environment is still had bigger influence.
Existing method comprises washing and high-temperature heat treatment two big steps substantially, and wherein method for washing is earlier metallugical acid washing iron oxide red and a certain amount of water to be mixed, stir, anhydrates and press filtration again.Every washing once treats that the removal of impurity is (as, Cl
-) between liquid-solid phase, set up once balance, again since metallugical acid washing iron oxide red be that the high temperature torch firing forms, it is the coacervate of forming by many subparticles, specific surface area is very big, adsorptive power is strong especially, even if also have only very a spot of soluble impurity to enter water when reaching dissolution equilibrium, in addition can not reach dissolution equilibrium in the actual production, by such once washing, the effect of removal of impurities is very limited.The particularly reduction that contains along with impurity, this washing impurity-removing difficulty that just becomes more, often through after the washing many times, the cl content in metallugical acid washing iron oxide red also maintains on the higher level.Therefore, single use this water washing method, not only time-consuming, effort, produce a large amount of waste water, and the effect of removal of impurities is very undesirable.In order further to reduce the cl content in metallugical acid washing iron oxide red, only by means of 800-900 ℃ high-temperature heat treatment.Someone adopts first alkali neutralization, the method for washing+high-temperature heat treatment again.This method is metallugical acid washing iron oxide red elder generation to be neutralized with alkaline matters such as lime on the basis in water washing+high-temperature heat treatment method, washing again, and high-temperature heat treatment though this method alleviates environmental influence to some extent than out-of-date methods, also has considerable influence to environment.This is because lime is difficult to make the acidic substance in metallugical acid washing iron oxide red thoroughly to be neutralized and changes into high stability compound, and the existence of compounds such as FeOCl is arranged, simultaneously, the amount that adds alkali is unsuitable again too many, otherwise, will have a strong impact on its application in magneticsubstance.Solving environmental issue is main, the most basic problem that prior art faces.For solving the problem of environmental pollution in producing, increase complicated HCl recovery system usually, like this, not only increase facility investment, but also increased production and operation cost greatly.In addition, the corrosive power of hydrochloric acid is strong especially under the high temperature, requires equipment to have very high resistance to corrosion, carries out a step and strengthens facility investment, in the work-ing life of having reduced equipment, has increased the maintenance cost of equipment.
At present for this reason, also there is not a kind of cost low, the effective ways of environmental sound.
Summary of the invention
The purpose of this invention is to provide a kind of use metallugical acid washing iron oxide red be raw material production high purity, the metallugical acid washing iron oxide red metallugical acid washing iron oxide red process for purification of high reactivity high-quality.
The implementation of the object of the invention is, metallugical acid washing iron oxide red process for purification, with weight ratio is 1: after the chloride metallugical acid washing iron oxide red and water of 0.8-1.5 mixes evenly, join in fixed chromatography column or the wash-out bed, treat to add make up water three to four times when metallugical acid washing iron oxide red upper end water layer is intact soon in chromatography column or the wash-out bed, till the approaching neutral no chlorine of the effluent liquid of chromatography column lower end, take out metallugical acid washing iron oxide red slip.
Though method of the present invention is similar to existing WATER-WASHING METHOD, wash-out mechanism is essentially different.Present method is metallugical acid washing iron oxide red to be not move, and rests in the wash-out bed with stationary phase, and water is that moving phase is carried out wash-out by stationary phase, foreign ion (as, Cl
-) between stationary phase and moving phase, set up absorption and dissolution equilibrium many times, be equivalent to common washing many times, therefore, can remove the impurity (cl content reaches below 0.1%) of solvable (or even slightly soluble) in metallugical acid washing iron oxide red effectively.
Adopt the present invention, metallugical acid washing iron oxide red can directly production without high-temperature heat treatment reduced energy consumption and facility investment, reduced the environmental pollution that the thermal treatment removal of impurities is brought.Simultaneously, owing to there is not a pyroprocessing, metallugical acid washing iron oxide red after institute make with extra care has higher chemically reactive, understands better with the magnetic material mass of its production.Therefore, the present invention has that operational path is simple, good impurity removing effect, low equipment investment, the metallugical acid washing iron oxide red active advantages of higher of, product little to environmental influence.
Description of drawings
Fig. 1 is for to clean synoptic diagram with chromatography column
Fig. 2 is for cleaning synoptic diagram with the wash-out bed
Embodiment
The present invention be with metallugical acid washing iron oxide red and water mixed evenly after, join in fixed chromatography column or the wash-out bed, clean for several times with clear water again, to the lower end effluent liquid near neutral no chlorine till, take out metallugical acid washing iron oxide red slip.
Chromatography column used in the present invention as shown in Figure 1, the clear water 1 metallugical acid washing iron oxide red chromatography column 2 of flowing through among the figure, chromatography column diameter 40mm, high 600mm, there are filtration mediums 3 such as glass fibre, cotton the chromatography column lower end, the chromatography column lower end links to each other with the filtrate bottle.For accelerating elution speed, the filtrate bottle can link to each other with vacuum, or adds certain pressure in the chromatography column upper end.
Wash-out bed used in the present invention as shown in Figure 2, the wash-out bed 4 that clear water 1 is flowed through metallugical acid washing iron oxide red among the figure, the long 1900mm of wash-out bed, wide 900mm, high 600mm, there is filter cloth 5 wash-out bed lower end, wash-out bed lower end links to each other with vacuum system.
For quickening elution speed, tensio-active agent and flocculation agent can be added, in chromatography column or wash-out bed as OP-10, polyacrylamide.After adding flocculation agent and tensio-active agent, reduce, increase the velocity of flow of intergranular voidage and water by metallugical acid washing iron oxide red particulate reunion and water surface tension.Surfactivity that other market is common and flocculation agent also can use mostly.
For accelerating elution speed, can flow out end at elutriant and adopt measures to reduce stresses, or add certain pressure at chromatography column or wash-out bed upper end.
With weight ratio is 1: after the chloride metallugical acid washing iron oxide red and water of 0.8-1.5 mixes evenly, add alkali to solution, to be weakly alkaline solution again adds in chromatography column or the wash-out bed, like this, make the elution speed can be faster, the elutriant environmental protection treatment is more or less freely, also can avoid the loss of iron, reduces the corrosion to equipment.Employed alkali can with various can with iron form the indissoluble thing alkali or other material, as sodium hydroxide, yellow soda ash, calcium hydroxide, calcium oxide or bicarbonate of ammonia.
If before wash-out with the metallugical acid washing iron oxide red 20-40% sodium-hydroxide treatment of using, to remove the silicon in metallugical acid washing iron oxide red.Sodium hydroxide makes the silicon-dioxide in metallugical acid washing iron oxide red be converted into soluble glass, just can remove wherein silicon through elution technique again, makes the metallugical acid washing iron oxide red specification of quality of producing soft magnetic ferrite that reaches, and realizes higher added value (as following example 6).
The auspicious the present invention of stating below gives an example:
Example 1, with 500 gram chloride 2.65% metallugical acid washing iron oxide red and 500 gram water mixed evenly after, join in the chromatography column of internal diameter 40mm, high 60mm, treat to add when metallugical acid washing iron oxide red upper end water layer is intact soon in the post make up water 220ml, three to four times like this, approaching neutral to chromatography column lower end effluent liquid, take out metallugical acid washing iron oxide red slip, the cl content during the mensuration bottom is metallugical acid washing iron oxide red, cl content is 0.09%.This routine elutant is the chloride soln of iron, and stronger corrodibility is arranged, and requires equipment that corrosion stability is preferably arranged.
Example 2, with example 1, different is, after the metallugical acid washing iron oxide red and 500 gram water of 500 grams chloride 2.65% mix evenly, add sodium hydroxide to solution and be weakly alkaline, add in the chromatography column again, treat to add make up water 220ml when metallugical acid washing iron oxide red upper end water layer is intact soon in the post, two to three times like this, measure the metallugical acid washing iron oxide red cl content 0.076% in bottom.
Example 3, with example 2, different is, add sodium hydroxide to solution and be weakly alkaline, add 1.0 again and restrain polyacrylamide and the 0.5 gram tensio-active agent OP-10 that swelling is in advance crossed, add the make up water 220ml that contains 0.1%OP-10 when metallugical acid washing iron oxide red upper end water layer is intact soon in the chromatography column, measuring the metallugical acid washing iron oxide red cl content in bottom is 0.08%.
Example 4, with example 3, different is, metallugical acid washing iron oxide red and 500 gram water 500 grams are chloride 2.65%, silicon 0.20% mixed evenly after, add 150 gram sodium hydroxide in 90 ℃ of stirring reactions 2 hours, add 1.0 after the cooling again and restrain polyacrylamide and the 0.5 gram tensio-active agent OP-10 that swelling is in advance crossed, add make up water four to five times, silicon wherein changes into soluble silicon and removes, measure chlorine, the silicone content of bottom in metallugical acid washing iron oxide red, cl content is 0.056%, silicone content is 0.008%.
Example 5, after mixing 600 kilograms chloride 6.50% metallugical acid washing iron oxide red and 500 kg water evenly, add sodium hydroxide and be neutralized to weakly alkaline for 7.5 kilograms, add 0.24 kg polypropylene acid amides (swelling is crossed in advance) and 0.5 kilogram of tensio-active agent OP-10 again, transfer to long 1900mm then, wide 900mm, in the elution pool of high 600mm, treat to add when metallugical acid washing iron oxide red surface water is closely dried in the pond 350 kilograms in clear water, allow it flow through metallugical acid washing iron oxide red immovable bed, after water is done, moisturizing is 350 kilograms again, so continue, effluent liquid is approaching neutral until wash-out bed bottom, silicon wherein changes into soluble silicon and removes, and detects till the no chlorion cl content 0.056%.
Claims (5)
1, metallugical acid washing iron oxide red process for purification, it is characterized in that with weight ratio be 1: after the chloride metallugical acid washing iron oxide red and water of 0.8-1.5 mixes evenly, join in fixed chromatography column or the wash-out bed, treat to add make up water three to four times when metallugical acid washing iron oxide red upper end water layer is intact soon in chromatography column or the wash-out bed, till the approaching neutral no chlorine of the effluent liquid of chromatography column lower end, take out metallugical acid washing iron oxide red slip.
2, metallugical acid washing iron oxide red process for purification according to claim 1, it is characterized in that with weight ratio be 1: after the chloride metallugical acid washing iron oxide red and water of 0.8-1.5 mixes evenly, add alkali to solution, will be weakly alkaline solution again and add in chromatography column or the wash-out bed.
3, metallugical acid washing iron oxide red process for purification according to claim 3 is characterized in that employed alkali is various alkali or other materials that can form the indissoluble thing with iron, as sodium hydroxide, yellow soda ash, calcium hydroxide, calcium oxide or bicarbonate of ammonia.
4, metallugical acid washing iron oxide red process for purification according to claim 1 is characterized in that adding tensio-active agent and flocculation agent in chromatography column or wash-out bed, as OP-10, polyacrylamide.
5, production method according to claim 1 is characterized in that before wash-out the metallugical acid washing iron oxide red 20-40% of using sodium-hydroxide treatment, to remove the silicon in metallugical acid washing iron oxide red.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100196592A CN100393627C (en) | 2005-10-25 | 2005-10-25 | Refining method of metallugical acid washing iron oxide red |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100196592A CN100393627C (en) | 2005-10-25 | 2005-10-25 | Refining method of metallugical acid washing iron oxide red |
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|---|---|
| CN1785824A true CN1785824A (en) | 2006-06-14 |
| CN100393627C CN100393627C (en) | 2008-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100196592A Expired - Fee Related CN100393627C (en) | 2005-10-25 | 2005-10-25 | Refining method of metallugical acid washing iron oxide red |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603013A (en) * | 2012-03-20 | 2012-07-25 | 湖北全阳磁性材料制造有限公司 | Novel method for dechlorinating acid-washing iron oxide red |
| CN102674470A (en) * | 2011-03-10 | 2012-09-19 | 本溪环宇磁业有限公司 | Method for purifying ferric oxide red by wet method |
| CN113943152A (en) * | 2021-09-06 | 2022-01-18 | 横店集团东磁股份有限公司 | Method for preparing permanent magnetic ferrite from high-chlorine iron oxide red and permanent magnetic ferrite |
| CN114031385A (en) * | 2021-10-22 | 2022-02-11 | 浙江安特磁材股份有限公司 | Method for preparing permanent magnetic ferrite material from high-chlorine iron oxide red |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU268399A1 (en) * | 1968-07-08 | 1975-10-15 | Московский Ордена Ленина Химикотехнологический Институт Им.Д.И.Менделеева | Method for chromatographic separation of iron isotopes |
| CN1119661A (en) * | 1994-09-30 | 1996-04-03 | 冀天宝 | Method for synthesizing iron oxide red by using refined iron powder |
| CN1163415C (en) * | 2000-09-19 | 2004-08-25 | 张美焦 | High-purity iron oxide red producing process with iron ore powder and other iron-bearing material |
-
2005
- 2005-10-25 CN CNB2005100196592A patent/CN100393627C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674470A (en) * | 2011-03-10 | 2012-09-19 | 本溪环宇磁业有限公司 | Method for purifying ferric oxide red by wet method |
| CN102674470B (en) * | 2011-03-10 | 2015-04-08 | 本溪环宇磁业有限公司 | Method for purifying ferric oxide red by wet method |
| CN102603013A (en) * | 2012-03-20 | 2012-07-25 | 湖北全阳磁性材料制造有限公司 | Novel method for dechlorinating acid-washing iron oxide red |
| CN113943152A (en) * | 2021-09-06 | 2022-01-18 | 横店集团东磁股份有限公司 | Method for preparing permanent magnetic ferrite from high-chlorine iron oxide red and permanent magnetic ferrite |
| CN114031385A (en) * | 2021-10-22 | 2022-02-11 | 浙江安特磁材股份有限公司 | Method for preparing permanent magnetic ferrite material from high-chlorine iron oxide red |
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|---|---|
| CN100393627C (en) | 2008-06-11 |
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