CN100335418C - Method for preparing ferric chloride by spent pickling solution - Google Patents
Method for preparing ferric chloride by spent pickling solution Download PDFInfo
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- CN100335418C CN100335418C CNB2005101010656A CN200510101065A CN100335418C CN 100335418 C CN100335418 C CN 100335418C CN B2005101010656 A CNB2005101010656 A CN B2005101010656A CN 200510101065 A CN200510101065 A CN 200510101065A CN 100335418 C CN100335418 C CN 100335418C
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Abstract
The present invention discloses a method for preparing polymeric ferric chloride by using pickling waste liquid. The method comprises the steps that hydrochloric acid pickling waste liquid, aqua fortis and high concentration hydrochloric acid are added to a corrosion-resistant reactor; under the conditions of 1.0 to 3.0 standard atmospheric pressure, continuous oxygen supply and controlled temperature of 50 DEG C to 120 DEG C, the hydrochloric acid pickling waste liquid, the aqua fortis and the high concentration hydrochloric acid react for forty to ninety minutes, and thus, a polymeric ferric chloride product can be made. The polymeric ferric chloride prepared by the method has the advantages of good performance, stable quality, low production cost and short reaction time.
Description
Technical field
The present invention relates to belong to technical fields such as environmental chemical engineering, environment protection with the novel process of hydrochloric acid pickling waste liquor with catalytic oxidation legal system poly-ferric chloride.
Background technology
At iron and steel processing industry and whole electroplating industry, often need steel part surface and plated item surface to be cleaned, to remove its surperficial iron rust with hydrochloric acid lotion.In acid cleaning process, the hydrochloric acid in the hydrochloric acid lotion constantly is consumed, and ferrous ion wherein no longer has cleanup action to plating piece also constantly increasing along with the consumption of hydrochloric acid until this hydrochloric acid lotion simultaneously.This moment, the scrub raffinate that produced was spent pickle liquor, and wherein main component is a solution of ferrous chloride.This waste liquid quantity discharged in the cleanup acid treatment process of metallic surface is big, has greater environmental impacts if liquid waste disposal is improper.Every year will be discharged the spent pickle liquor of hundreds of ten thousand steres in the whole nation thus, and the raising that steel part plated item surface quality is required along with steel output and people, and the spent pickle liquor amount that is produced is also increasing.The characteristics of spent pickle liquor are that concentration height, waste liquid amount are big, temperature is also up to 50～100 ℃, therefore must handle it, otherwise will cause serious environmental to pollute, and influence the benefit of enterprise, in the industrial general employing and processing such as oxidation-precipitation method, ferrous sulfate crystalline deposit+oxidation neutralization precipitation method, deep-well facture, but complex process, facility investment is big, technical requirements is high, cost is high.
Poly-ferric chloride is a kind of inorganic polymer coagulant, since the eighties in 20th century is synthetic in Japan, enjoy people's attention with its good application performance, not only have safe lifeless matter toxicity, and have the alumen ustum macrostructure of formation closely knit, advantage such as consumption is few, sedimentation is fast, dehydration property is good.Especially have superiority for processing low temperature, low turbidity water.In the processing of domestic water, process water, municipal wastewater, trade effluent and petroleum waste water.Significant turbidity removal, oil removing, decolorizing effect are all arranged, the ability that reduces COD is also arranged, so wide market application prospect is arranged.
Though the existing at present report that utilizes hydrochloric acid pickling waste liquor crystallization iron protochloride and poly-ferric chloride.The technology that wherein prepares the crystallization iron protochloride is the direct evaporation condensing crystal, the preparation poly-ferric chloride then is to adopt direct oxidation method or catalytic oxidation, (prepare poly-ferric chloride and applied research thereof as Wuhan University's Wang Hongyu (Ph D dissertation) and Ceng Xiaojun from iron and steel pickling waste liquid, Chongqing Environmental Science, 2003,25 (12) 34-36), all be with sodium chlorate direct oxidation system poly-ferric chloride, though this technology is simple, facility investment is few, reaction is fast, but need to consume more and expensive sodium chlorate, products obtained therefrom cost height.In addition, the CN1266819A patent application also is to make catalyzer with sodium chlorate, and needs to add before reaction the higher phosphate stabilizer of price; Add the basicity that acid or alkali are regulated poly-ferric chloride the later stage in reaction.Complex process is arranged, the shortcoming of production cost height and poor stability.Qiu Huiqin [utilize hydrochloric acid pickler liquid to produce poly-ferric chloride. Treatment of Industrial Water, 1997,17 (6)] etc. the people has reported that with oxygen or air be oxygenant, Sodium Nitrite is the research of Preparation of Catalyst poly-ferric chloride, and its weak point is that production cost is higher, long reaction time (document is 2h), (basicity was greater than 4 o'clock for the product instability, deposit less than a week just separating out precipitation), and remain in nitrite in the water body to the toxic effect of biology, and easily make human body that carcinogenic pathology takes place.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing poly-ferric chloride with spent pickle liquor, not only solved the pollution problem of spent pickle liquor, inorganic water purification agent Chemicals have been made simultaneously with high added value, have less investment, instant effect, do not produce secondary pollution, really reached the purpose of " waste recycling is turned waste into wealth ".
For reaching the foregoing invention purpose, the present invention with the method that spent pickle liquor prepares poly-ferric chloride is: with Fe (II) concentration of 600 parts by volume is that hydrochloric acid pickling waste liquor, 8.8～19.8 parts by volume concentration of 80～170g/L are that 65～68% concentrated nitric acid and 37.3～83.4 parts by volume concentration are 36～38% concentrated hydrochloric acid, add in the corrosion resistant reactor, under the condition of 1.0～3.0 standard atmospheric pressures and lasting logical oxygen, controlled temperature is at 50～120 ℃, reacted 40～90 minutes, and made basicity and be 8～16% poly-ferric chloride product.
As a kind of preferred version, the concentration of Fe in the described hydrochloric acid pickling waste liquor (II) is 160～165g/L.
Described reactor can be reactor or reaction tower.When using reactor, be reflected under the stirring condition and carry out; When using reaction tower, can adopt jet-type or material filling type reaction tower, be beneficial to the gas-to-liquid contact face and increase.
Preferred pressure in the described reactor is 1.0～1.5 standard atmospheric pressures.
The optimum temps of reaction is about 90～95 ℃.
The best reaction times is about 60～70 minutes.
Compared with prior art, the present invention has following advantage:
1, having reduced the reaction later stage adds the step that acid or alkali are regulated the product basicity, has not only saved raw material, has reduced production cost, and saved slaking workshop section, has improved throughput, makes reaction times from a few hours reduce to 40～90 minutes.
2, because do not need with the high strong oxidizer of prices such as sodium chlorate, products obtained therefrom cost of the present invention is low, is about direct oxidation method and prepares 2/3rds of poly-ferric chloride cost.
3, compare with the Sodium Nitrite catalytic oxidation, the reaction times shortens greatly, and product stability strong (place and produced precipitation in 6 months) and lifeless matter toxicity have reduced cost.
4, this technology has the advantages that less investment, instant effect, throughput greatly, do not produce secondary pollution, by poly-ferric chloride excellent property, the steady quality of method gained of the present invention.
Embodiment
Embodiment 1
With Fe (II) content is that hydrochloric acid pickling waste liquor 600L, the 19.8L concentration of 165g/L is that 65～68% concentrated nitric acid and 80L concentration are that 36～38% concentrated hydrochloric acid adds in the corrosion resistant reactor, fully stir, under 1.0 normal atmosphere and lasting logical oxygen condition, controlled temperature is about 90 ℃, reaction 90min, making basicity is 8～16%, and total iron content is 13.8%, the poly-ferric chloride product of Fe (II)＜0.1% stable performance.
Embodiment 2
With Fe (II) content is that hydrochloric acid pickling waste liquor 600L, the 16L concentration of 145g/L is that 65～68% concentrated nitric acid and 70L concentration are that 36～38% concentrated hydrochloric acid adds in the corrosion resistant reactor, fully stir, under the condition of 1.2 normal atmosphere and lasting logical oxygen, controlled temperature is about 95 ℃, reaction 70min, making basicity is 8～16%, the poly-ferric chloride product of Fe (II)＜0.1% stable performance.
Embodiment 3
With Fe (II) content is that hydrochloric acid pickling waste liquor 600L, the 12L concentration of 110g/L is that 65～68% concentrated nitric acid and 50L concentration are that 36～38% concentrated hydrochloric acid adds in the corrosion resistant reactor, fully stir, under the condition of 1.5 normal atmosphere and lasting logical oxygen, controlled temperature is about 110 ℃, reaction 60min, making basicity is 8～16%, the poly-ferric chloride product of Fe (II)＜0.1% stable performance.
Embodiment 4
With Fe (II) content is that hydrochloric acid pickling waste liquor 600L, the 9L concentration of 80g/L is that 65～68% concentrated nitric acid and 41L concentration are that 36～38% concentrated hydrochloric acid adds in the corrosion resistant reactor, fully stir, under the condition of 2.5 normal atmosphere and lasting logical oxygen, controlled temperature is about 120 ℃, reaction 50min, making basicity is 8～16%, the poly-ferric chloride product of Fe (II)＜0.1% stable performance.
Embodiment 5
With Fe (II) content is that hydrochloric acid pickling waste liquor 600L, the 9.9L concentration of 90g/L is that 65～68% concentrated nitric acid and 42L concentration are that 36～38% concentrated hydrochloric acid adds in the corrosion resistant spray tower, under the condition of 1.0 normal atmosphere and lasting logical oxygen, controlled temperature is about 90 ℃, reaction 60min, making basicity is 8～16%, the poly-ferric chloride product of Fe (II)＜0.1% stable performance.
Embodiment 6
With Fe (II) content is that hydrochloric acid pickling waste liquor 600L, the 9.9L concentration of 90g/L is that 65～68% concentrated nitric acid and 42L concentration are that 36～38% concentrated hydrochloric acid adds in the corrosion resistant packing tower, under the condition of 3 normal atmosphere and lasting logical oxygen, controlled temperature is about 90 ℃, reaction 60min, making basicity is 8～16%, the poly-ferric chloride product of Fe (II)＜0.1% stable performance.
Claims (7)
1, a kind of method for preparing poly-ferric chloride with spent pickle liquor, it is characterized by: with Fe (II) concentration is that hydrochloric acid pickling waste liquor 600 parts by volume, 8.8～19.8 parts by volume concentration of 80～170g/L are that 65～68% concentrated nitric acid and 37.3～83.4 parts by volume concentration are that 36～38% concentrated hydrochloric acid adds in the corrosion resistant reactor, under the condition of 1.0～3.0 standard atmospheric pressures and lasting logical oxygen, controlled temperature is at 50～120 ℃, reacted 40～90 minutes, and made basicity and be 8～16% poly-ferric chloride product.
2, method according to claim 1 is characterized in that: described reactor is a reactor, is reflected in the stirring and carries out.
3, method according to claim 1 is characterized in that: described reactor is jet-type or material filling type reaction tower.
4, method according to claim 1 is characterized in that: the pressure in the described reactor is 1.0～1.5 standard atmospheric pressures.
5, method according to claim 1 is characterized in that: described temperature of reaction is 90-95 ℃.
6, method according to claim 1 is characterized in that: the described reaction times is 60-70 minute.
7, method according to claim 1 is characterized in that: the Fe of described hydrochloric acid pickling waste liquor (II) concentration is 160-165g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101010656A CN100335418C (en) | 2005-11-07 | 2005-11-07 | Method for preparing ferric chloride by spent pickling solution |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101010656A CN100335418C (en) | 2005-11-07 | 2005-11-07 | Method for preparing ferric chloride by spent pickling solution |
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| CN1789147A CN1789147A (en) | 2006-06-21 |
| CN100335418C true CN100335418C (en) | 2007-09-05 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671054B (en) * | 2009-09-28 | 2012-06-06 | 暨南大学 | Poly-ferric chloride purifying agent and preparation method and application thereof |
| CN102502747A (en) * | 2011-11-30 | 2012-06-20 | 东南大学 | Method for preparing polyferric chloride flocculant by a double catalytic oxidation process and application of flocculant |
| CN102603015A (en) * | 2012-03-20 | 2012-07-25 | 蓝保(厦门)水处理科技有限公司 | Method for producing polymerized iron chloride by utilizing acid-washing waste liquid of steel |
| CN105271435B (en) * | 2015-10-06 | 2017-08-25 | 聊城大学 | Seamless steel pipe pickle liquor prepares the production technology of polyaluminium ferric flocculant |
| CN110615485B (en) * | 2019-09-05 | 2022-03-25 | 中信环境技术（广州）有限公司 | Continuous production method and application of polyferric chloride |
| CN110756144A (en) * | 2019-10-31 | 2020-02-07 | 唐山达润达危废处理有限公司 | Production device and method of ferric trichloride |
| CN114249407B (en) * | 2021-12-28 | 2024-02-02 | 河北正润环境科技有限公司 | Recycling method of steel finishing pickling waste liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266819A (en) * | 1999-03-11 | 2000-09-20 | 中国科学院生态环境研究中心 | Flocculant of polyiron chloride prepared from waste hydrochloric acid as pickling liquid of iron and steel and its preparing process |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266819A (en) * | 1999-03-11 | 2000-09-20 | 中国科学院生态环境研究中心 | Flocculant of polyiron chloride prepared from waste hydrochloric acid as pickling liquid of iron and steel and its preparing process |
Non-Patent Citations (1)
| Title |
|---|
| 从钢铁酸性废液制备聚合氯化铁及其应用研究 曾小君，重庆环境科学，第12卷 2003 * |
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