CN103934256A - Wet detoxification method for chromium slag and chromium-containing pollutants - Google Patents

Wet detoxification method for chromium slag and chromium-containing pollutants Download PDF

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CN103934256A
CN103934256A CN 201410161228 CN201410161228A CN103934256A CN 103934256 A CN103934256 A CN 103934256A CN 201410161228 CN201410161228 CN 201410161228 CN 201410161228 A CN201410161228 A CN 201410161228A CN 103934256 A CN103934256 A CN 103934256A
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chromium
slag
slurry
chromium slag
reducing agent
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CN 201410161228
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Chinese (zh)
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马强
廖书林
尹贞
张进峰
金慧宁
朱卫兵
李月中
浦燕新
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江苏维尔利环保科技股份有限公司
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Abstract

The invention relates to a wet detoxification method for chromium slag and chromium-containing pollutants. The wet detoxification method comprises the following steps: screening and crushing the chromium slag and the chromium-containing pollutants, performing wet milling on the chromium slag and the chromium-containing pollutants in a ball mill, adding a filtrate containing sulfate ions, leaching out acid-soluble calcium chromate in chromium slag slurry, adding the chromium slag slurry and a first reducing agent sequentially into a reaction tank, stirring and mixing the chromium slag slurry with the first reducing agent to perform reduction reaction, reducing the acid-soluble calcium chromate in chromium slag slurry to trivalent chromium, adding concentrated sulfuric acid and to stirring and mixing for regulating, adjusting pH value of the chromium slag slurry to be 7+/-0.5, then adding a second reducing agent into the reaction tank and stirring and mixing for reducing, stirring the reduced slag slurry to cure the reduced slag slurry, and converting hexavalent chromium in the chromium slag slurry to chromic hydroxide sediment; and separating solid and liquid of the cured chromium slag slurry. The wet detoxification method has the characteristics of low cost, no waste liquid, no slag returning phenomenon, good detoxification effect and capability of being applicable to the large-scale industrial production.

Description

铬渣及含铬污染物的湿法解毒方法 Chromium and chromium-containing wet detoxification methods contaminants

技术领域 FIELD

[0001] 本发明涉及一种铬渣及含铬污染物的湿法解毒方法,属于铬污染修复处理技术领域。 [0001] The present invention relates to a method for detoxification of chromium slag and wet chromium-containing contaminants, which belongs to the repair Technical Field Chromium contamination.

背景技术 Background technique

[0002] 铬渣及含铬污染物主要是指金属铬及铬盐生产企业,尤其是有钙焙烧生产工艺的生产企业在生产过程中产生的残渣及受该类残渣污染的土壤、岩石、建筑废弃物等,属于重金属危险废物,其中,六价铬的毒性要远远大于三价铬,六价铬具有较强的致癌和致突变特性,是EPA确认的129种重点污染物之一,不对其进行无害化处理则会严重影响周边生活人群的身体健康。 [0002] Chromium and chromium and chromium metal contaminants mainly refers manufacturer chromium salts, in particular calcium roasting residue is the production process, the company generated in the production process of such residues and by contaminated soil, rocks, construction waste, etc., belong to heavy metal hazardous waste, which is much larger than the toxicity of hexavalent chromium is trivalent chromium, hexavalent chromium having strong carcinogenic and mutagenic properties, is one of 129 kinds of major pollutants EPA recognized, not its treatment and disposal would severely affect the surrounding population living in good health.

[0003]目前,铬渣及含铬污染物的无害化处理工艺主要有干法解毒和湿法解毒两种,其中干法解毒工艺成本非常高且极易引起二次污染。 [0003] Currently, chromium slag and safe disposal process containing chromium pollutants mainly dry and wet detoxification two kinds of detoxification, detoxification process wherein the dry cost very high and can easily cause secondary pollution. 而湿法解毒中,大都采用碱浸溶工艺,经硫化钠湿法解毒工艺解毒后的铬渣及铬污染物稳定性比较差,放置半年后出现明显的返渣现象。 Detoxification and wet, mostly by alkali leaching process, contamination by chromium and chromium slag stability after the wet sulfide detoxification detoxification process relatively poor, significant back-residue phenomenon after standing for six months. 而硫酸亚铁湿法解毒工艺所需的硫酸亚铁量比较高,解毒过程中会产生大量废液,还需要对废液进行处理,在提高处理成本的同时也不利于实际生产操作。 Ferrous sulfate and higher wet detoxification process required ratio of ferrous sulfate, the detoxification process will produce a large number of liquid waste, also we need to waste processing, while improving process is not conducive to the actual production costs of the operation.

[0004] 还有一种铬渣及含铬污染物的湿法解毒方法,是综合了硫化钠湿法解毒工艺和硫酸亚铁湿法解毒工艺,是在对铬渣湿法球磨同时加入硫化钠进行混合研磨,然后对研磨后的浆料加入硫酸和硫酸亚铁进行还原反应的工艺流程。 [0004] Another method for detoxification of chromium slag and wet chromium-containing contaminants, is a combination of sodium sulfide and ferrous sulfate wet wet process detoxification detoxification process, in the wet milling of chromium residue was added sodium sulfide simultaneously performed mixing and grinding, then grinding the slurry after the addition of sulfuric acid and ferrous sulfate process for the reduction reaction. 但是这种解毒方法由于湿法球磨所采用的循环水中存在一定量亚铁离子,会与硫化钠反应产生硫化亚铁沉淀,造成了硫化钠的格外损耗,既增加了解毒成本,又降低了有效亚铁离子对铬的还原效果。 However, this method of detoxifying certain amount of ferrous ions due to the circulating water used in the wet milling, to produce sodium sulfide will react with the iron sulfide precipitates, particularly the loss of sodium sulfide resulting, not only increasing the cost of detoxification, but also reduces the effective reducing effect of ferrous ions of chromium. 此外硫离子还会与各污染物中含有的其他金属离子如钙离子等产生沉淀反应。 Also other metal ions also contains sulfur ions with calcium ions and other contaminants, such as precipitation reaction.

发明内容 SUMMARY

[0005] 本发明的目的是提供一种成本低、无废液、无返渣现象、解毒效果好,能适合于大规模工业化生产的铬渣及含铬污染物的湿法解毒方法。 [0005] The object of the present invention is to provide a low cost, without waste, without return residue phenomenon, detoxifying effect is good, it can be adapted to large-scale industrial production of chromium slag and wet detoxification of chromium-containing contaminants.

[0006] 本发明专利为达到上述目的的技术方案是:一种铬渣及含铬污染物的湿法解毒方法,其特征在于:按以下步骤进行: [0006] The present invention patent is a technical solution to achieve the above object is: chromium slag and wet methods of detoxification of chromium-containing contaminants, which is characterized in that: the following steps performed:

[0007] ⑴、对铬渣及含铬污染物进行筛分后送至颚式粉碎机粉碎处理,粉碎后的铬渣及铬污染物的粒径在0.2-lcm ; [0007] ⑴, chromium slag and the chromium-containing contaminants were sieved to the jaw crusher crushing process, chromium slag and the particle size after pulverization chromium contaminants in 0.2-lcm;

[0008] ⑵、对筛分粉碎后的铬渣及含铬污染物在球磨机中进行湿法球磨,加入含硫酸根离子的滤液,将铬渣料浆中的酸溶性铬酸钙浸出,铬渣料浆的颗径在120-200目,铬渣料浆的波美度室温下在30-50° Be ; [0008] ⑵, chromium slag and chromium contaminants sieved wet pulverized in a ball mill for milling, sulfate ion-containing filtrate is added, chromium slag slurry leach acid-soluble calcium chromate, chromium slag slurry particle diameter of 120-200 mesh, chromium slag temperature Baume slurry at 30-50 ° Be;

[0009] ⑶、将铬渣料浆加入反应罐内,加入第一还原剂搅拌混合进行第一次还原反应,还原反应时间在0.5-1.5小时,将铬渣料浆中的酸溶性铬酸钙还原成三价铬,按质量比,第一还原剂的投加量与铬渣料浆比为0.0005-0.001:1,所述的第一还原剂为硫化钠、焦亚硫酸钠、硫化钾或硫化钙的其中之一或两种以上任意组合物;[0010] (4)、向反应罐加入浓硫酸并进行搅拌混合进行调理,将铬渣料浆的pH值调节至7±0.5,铬渣料浆温度保持在50-70°C ; [0009] ⑶, chromium slag slurry is added to the reaction tank, a first reducing agent is added to stirred and mixed for the first time a reduction reaction, the reduction reaction time of 0.5-1.5 hours, the slurry of chromium slag acid soluble calcium chromate reduced to trivalent chromium, the mass ratio, a first dosage of the reducing agent and the ratio of chromium slag slurry 0.0005-0.001: 1, the first reducing agent is sodium sulfide, sodium metabisulfite, potassium sulfide or calcium sulfide wherein one or two or more of any composition; [0010] (4), concentrated sulfuric acid was added to the reaction tank and mixed with stirring for conditioning the pH of the slurry of chromium residue was adjusted to 7 ± 0.5, chromium slag slurry temperature was maintained at 50-70 ° C;

[0011] (5)、再向反应罐加入第二还原剂并搅拌混合进行第二次还原处理,按质量比,第二还原剂的投加量与铬渣料浆比为0.05-0.2:1,第二次还原反应时间在0.5-1.5小时,所述的第二还原剂为氯化亚铁、溴化亚铁、硫酸亚铁或硫酸亚铁铵的其中一种或任意两种以上的混合物; [0011] (5), the second reducing agent is added to the reaction tank and stirred and mixed for a second reduction process, the mass ratio, the dosage of the second reducing agent ratio of chromium slag slurry is 0.05 to 0.2: 1 , the second reduction in the reaction time from 0.5 to 1.5 hours, the second reducing agent is ferrous chloride, ferrous bromide, ferrous sulfate, or wherein a mixture of ferrous ammonium sulfate one or more of any two ;

[0012] (6)、对第二次还原反应后的渣料浆搅拌进行熟化处理,熟化处理时间在6-12小时,将铬渣料浆中的六价铬被转化为氢氧化铬沉淀物; [0012] (6), slag slurry after the second aging treatment for the reduction reaction with stirring, the aging treatment time is 6-12 hours, the chromium slag in the slurry is converted to hexavalent chromium hydroxide precipitate ;

[0013] (7)、对熟化处理后的铬渣料浆进行固液分离,分离后的滤液排至球磨机中,分离后的解毒铬渣排出,得到六价铬浸出毒性值低于0.5mg/L的解毒铬渣。 [0013] (7), the slurry of chromium slag after aging treatment for solid-liquid separation, the separated filtrate discharged into a ball mill, detoxification of chromium slag discharged after the separation, a value obtained leaching toxicity of hexavalent chromium is less than 0.5mg / L detoxification of chromium slag.

[0014] 本发明采用上述技术方案后具有以下优点: [0014] With the present invention, the above technical scheme has the following advantages:

[0015] 1、本发明采用颚式粉碎机对铬渣及含铬污染物进行粉碎,粉碎后渣料粒径为 [0015] 1, the present invention employs a jaw crusher chromium and chromium-containing contaminant residue was pulverized, crushed slag particle diameter

0.2-lcm,大大缩短了湿法球磨的时间,能提高球磨效率。 0.2-lcm, greatly reducing the time of wet milling, the milling efficiency can be improved.

[0016] 2、本发明在湿法球磨中加入固液分离后含有大量硫酸根离子的滤液,在球磨过程中,使滤液中的硫酸根离子对铬渣及含铬污染物中酸溶性铬酸钙浸出,故而增加了酸溶性铬酸钙的浸出率,避免了采用纯碱浸溶工艺,也使得整个生产工艺中不会产生废液外排的现象。 [0016] 2, the present invention is added after the solid-liquid separation in a wet ball mill contains a large amount of filtrate sulfate ions, in the milling process, so that the sulfate ions in the filtrate chromium slag and chromium contaminants of acid soluble chromic acid calcium leaching, the leaching rate increases and therefore the acid-soluble calcium chromate, avoid the use of soda leaching process, but also makes the whole production process does not produce waste outer discharge phenomenon. 本发明在湿法球磨时,硫酸根离子会与钙等离子生成沉淀物,可以去除浆料中会与硫离子等产生沉淀反应的各种离子,避免后续还原反应时硫化钠等还原剂的浪费。 The present invention is in a wet ball mill, a sulfate ion generated precipitate calcium ions, various ions in the slurry with the precipitation reaction of sulfur ions can be removed, to avoid wasting the subsequent reduction reaction the reducing agent is sodium sulfide and the like.

[0017] 3、采用了固液分离后的滤液对铬渣及含铬污染物进行湿法球磨循环利用的方式,一方面解决了滤液出路问题,减少了滤液处理工艺,降低了建设和运营成本;另一方面由于滤液中存在大量的硫酸根离子和一定量的亚铁离子,而硫酸根可以跟铬污染物中酸溶性铬酸钙等难溶性物质反应,生成硫酸钙沉淀和铬酸根离子,增加六价铬离子的溶出,也可以去除浆料中会与硫离子等产生沉淀反应的各种离子,避免后续还原反应时硫化钠等还原剂的浪费。 [0017] 3, using a solid-liquid separated filtrate embodiment of chromium and chromium slag contaminants wet milling recycling, the settlement of the filtrate outlet problem, the filtrate treatment process is reduced, reducing the construction and operating costs ; on the other hand due to the large amount of sulfate ions and ferrous ions in the filtrate, the sulfate can be followed by acid-soluble chromium pollutants soluble substance such as calcium chromate reaction, precipitate calcium sulfate and chromate ions, elution of hexavalent chromium ions increases, various ions can be removed in the slurry with the precipitation reaction of sulfur ions, such as sodium sulfide to avoid wasting the subsequent reduction reaction the reducing agent. 再则,本发明滤液中的亚铁离子还可以在湿法球磨时对六价铬进行一定程度的还原作用,充分利用了硫酸亚铁原料。 Furthermore, the ferrous ions in the filtrate of the present invention may also be a certain degree of hexavalent chromium reduction in a wet ball mill, full use of ferrous sulfate material. 本发明在充分溶解了六价铬、去除了亚铁和钙等离子的前提下,对湿法球磨后的料浆进行还原反应熟化处理,充分利用各种还原剂,减少不必要的附加化学反应,降低了原料投加量。 The present invention is sufficiently dissolved hexavalent chromium, in addition to the premise of ferrous and calcium ions to the slurry after wet milling reduction reaction aging treatment, make full use of various reducing agents, reducing unnecessary additional chemical reaction, reducing the dosage of raw materials.

[0018] 4、本发明将铬渣料浆加入至反应罐内,分别加入第一还原剂、pH值的调理及第二还原剂,进而实现还原解毒处理,通过浓硫酸既起到了调节铬渣料浆PH的作用,又可以为整个后部的还原反应及熟化处理提供必要的温度条件,增强熟化处理的效果,铬渣及含铬污染物处理工艺稳定,能适合于大规模工业化生产。 [0018] 4, the present invention is chromium slag slurry added to the reaction tank, a first reducing agent were added, and the pH of the conditioned second reducing agent, so as to realize reduction detoxification process, concentrated sulfuric acid by adjusting both played a chromium slag slurry PH effect, but also can provide a reduction reaction and the entire rear of the aging treatment the necessary temperature conditions, aging treatment to enhance the effect of chromium and chromium slag pollutant treatment process is stable, can be adapted to industrial production.

[0019] 5、本发明采用两步还原解毒处理,对铬渣料浆在各自适宜的反应环境投加不同的还原剂,第一次还原反应将铬渣料浆将铬渣料浆中的酸溶性铬酸钙还原成三价铬,第二还原反应则继续与六价铬产生还原反应而生成氢氧化铬沉淀,还可以使亚铁离子与硫离子生成硫化铁沉淀物,第二次还原反应后对料浆进行熟化处理,整个熟化处理过程严格控制铬渣料浆PH值,解决pH值太低会增加浓硫酸的投加量并且不利于三价铬形成沉淀,导致料浆总铬浓度超标,PH值太高,氢氧化铬又容易被空气中的氧气所氧化生成六价铬化合物,造成返渣的问题。 [0019] 5, the present invention employs a two-step reduction process detoxification of chromium slag in their respective slurry reaction environment a suitable reducing agent dosing different, the first reduction reaction of chromium slag slurry chromium slag slurry acid soluble calcium chromate is reduced to trivalent chromium, a second reduction reaction is continued to produce chromium hydroxide precipitate was produced and the reduction reaction of hexavalent chromium, may ferrous sulfide ions and iron sulfide precipitates, the second reduction reaction the slurry was aged after treatment, the entire aging process strictly controlled chromium pH value of slurry, solution pH is too low will increase the dosage of concentrated sulfuric acid and trivalent chromium is not conducive to formation of a precipitate, resulting in a total chromium concentration in excess slurry , PH value is too high, the chromium hydroxide and easy to be oxidized by oxygen in the air hexavalent chromium compounds, cause back problems slag. 本发明在熟化处理过程中铬渣料浆的控制PH值为7±0.5,通过熟化处理后铬渣料浆中的六价铬基本完全被转化为氢氧化铬沉淀物,渣料浆中的六价铬离子浓度小于0.5mg/L,保证了六价铬的解毒效果,且无返渣现象。 In the present invention, the aging process control Chromium PH value of the slurry 7 ± 0.5, chromium slag in the slurry is substantially completely converted to hexavalent chromium hydroxide precipitate after aging treatment, six slag in the slurry trivalent chromium ions concentration is less than 0.5mg / L, to ensure a detoxifying effect of hexavalent chromium, and no residue back phenomenon.

具体实施方式 detailed description

[0020] 本发明的铬渣及含铬污染物的湿法解毒方法,按以下步骤: [0020] Chromium present invention and the method of detoxifying a wet chromium-containing contaminants, the following steps:

[0021] ⑴、对铬渣及含铬污染物进行筛分后送至颚式粉碎机粉碎处理,粉碎后的铬渣及铬污染物的粒径0.2-lcm,如铬渣及铬污染物的粒径0.4-0.8cm,可通过分选去除铬渣及含铬污染物中的岩石、建筑废弃物等杂质,通过粉碎处理能大大提高湿法球磨的处理效率。 [0021] ⑴, chromium slag and the chromium-containing contaminants were sieved to the jaw crusher crushing treatment, the particle size of chromium and chromium slag pulverized contaminants 0.2-lcm, such as chromium, and chromium slag contaminants particle size of 0.4-0.8, can be removed by the sorting chromium slag and chromium contaminants rocks, construction waste and other impurities, can greatly improve the processing efficiency of the pulverization treatment by a wet ball mill.

[0022] ⑵、将对筛分粉碎后的铬渣及含铬污染物在球磨机中进行湿法球磨,加入含硫酸根离子的滤液,该滤液为本发明固液分离后的液体,将铬渣料浆中的酸溶性铬酸钙浸出,具有的反应方程式如下: [0022] ⑵, chromium slag will be sieved after grinding and wet milling chromium contamination in a ball mill, a sulfate ion added to the filtrate, the filtrate liquid after the solid-liquid separation of the present invention, chromium slag acid soluble calcium chromate leaching slurry, with reaction equation is as follows:

[0023] CaCr04+S042- = CrO42^CaSO4, [0023] CaCr04 + S042- = CrO42 ^ CaSO4,

[0024] 本发明渣料浆的颗径在120-200目,铬渣料浆的波美度室温下在30-50° Be,最好铬渣料浆的波美度室温下为35-45° Βέ,循环利用滤液中的硫酸根离子和滤液中亚铁离子,按质量百分比,滤液中硫酸根离子的浓度在0.5 - 3 %,滤液中亚铁离子的浓度在 [0024] The slurry of slag particles of the present invention, diameter of 120-200 mesh, chromium slag slurry Baume degree at room temperature 30-50 ° Be, preferably at room temperature Baume slurry Chromium 35-45 ° Βέ, sulfate ion and recycling of ferrous ions in the filtrate in the filtrate, by mass percent, the concentration of sulfate ion in the filtrate in 0.5 --3% and the concentration of ferrous ions in the filtrate

0.05-0.5%。 0.05-0.5%. 本发明铬渣料浆的波美度及铬渣料浆的颗径的具体参数见表1所示。 Specific parameters particle diameter of the slurry of chromium slag and chromium slag Baume slurry of the present invention shown in Table 1.

[0025]表1 [0025] TABLE 1

[0026] [0026]

Figure CN103934256AD00051

[0027] ⑶、将铬渣料浆加入反应罐内,并加入第一还原剂搅拌混合,搅拌速度在40-100rad/min,进行第一次还原反应,还原反应时间在0.5-1.5小时,将铬渣料浆中的酸溶性铬酸钙还原成三价铬,按质量比,第一还原剂的投加量与铬渣料浆比为0.0005-0.001:I,最好第一还原剂的投加量与铬渣料浆的质量比为0.0006-0.009:1,该反应方程式如下: [0027] ⑶, chromium slag slurry is added to the reaction tank, and stirring and mixing the reducing agent is added first, a reduction in stirring rate 40-100rad / min, for the first, the reduction in the reaction time of 0.5-1.5 hours, acid soluble calcium chromate chromium slag in the slurry is reduced to trivalent chromium, the mass ratio, a first dosage of the reducing agent and the ratio of chromium slag slurry 0.0005-0.001: I, the first reducing agent is preferably administered mass ratio of the amount of added chromium slag slurry is 0.0006-0.009: 1, the reaction equation is as follows:

[0028] 8Cr042>3S2>20H20 = 8Cr (OH) 3+3S0 广+160H' [0028] 8Cr042> 3S2> 20H20 = 8Cr (OH) 3 + 3S0 wide + 160H '

[0029] 本发明第一还原剂为硫化钠、焦亚硫酸钠、硫化钾或硫化钙的其中之一或两种以上任意组合物。 [0029] The first reducing agent is sodium sulfide present invention, one of sodium metabisulfite, potassium sulfide or calcium sulfide, or two or more of any composition. 本发明第一还原剂具体的投加量见表2所示。 First reductant specific dosage of the present invention shown in Table 2.

[0030] 表2 [0030] TABLE 2

[0031] [0031]

Figure CN103934256AD00052

⑷、向反应罐加入浓硫酸并进行搅拌混合进行调理,将铬渣料浆的pH值调节至 ⑷, concentrated sulfuric acid was added to the reaction tank and mixed with stirring for conditioning the pH of the slurry of chromium slag is adjusted to

7±0.5,使铬渣料浆温度保持在50_70°C,具体的反应方程式如下: 7 ± 0.5, chromium slag slurry temperature was maintained at 50_70 ° C, the specific reaction equation is as follows:

[0033] 4Cr042>3S2052>14H+ = 4Cr (OH) 3+6S0广+7H20 ; [0033] 4Cr042> 3S2052> 14H + = 4Cr (OH) 3 + 6S0 wide + 7H20;

[0034] Η++0Η- = H2O [0034] Η ++ 0Η- = H2O

[0035] 本发明的浓硫酸采用工业级质量浓度为98%浓硫酸,通过加入浓硫酸,一方面可以为还原反应提供氢离子,另一方面浓硫酸溶于水产生剧烈放热,可以将整个反应体系加热至50-70°C,有利于第二次还原反应和熟化处理的进行。 [0035] The present invention employs concentrated sulfuric industrial mass concentration of 98% concentrated sulfuric acid, by adding concentrated sulfuric acid, may be provided on the one hand to a reduction reaction of hydrogen ion, dissolved in water to produce sulfuric acid on the other hand is strongly exothermic, the entire the reaction was heated to 50-70 ° C, favor the reduction reaction and the second aging treatment. 本发明铬渣料浆的pH值见表3所示。 Chromium pH of the slurry of the present invention, the value is shown in Table 3.

[0036]表 3 [0036] TABLE 3

[0037] [0037]

Figure CN103934256AD00061

[0038] (5)、再向反应罐加入第二还原剂并进行搅拌混合进行第二次还原处理,搅拌速度在40-100rad/min,按质量比,第二还原剂的投加量与铬渣料浆比为0.05-0.2:1,最好第二还原剂的投加量与铬渣料浆的质量比为0.08-0.1.8:1,第二次还原反应时间在0.5-1.5小时,在第二次还原反应中,亚铁离子不仅可以继续与六价铬产生还原反应,生成氢氧化铬沉淀物,使得铬渣料浆中的六价铬得到充分解毒,同时还可以与料浆中的硫离子生成硫化亚铁沉淀,具体反应方程式如下: [0038] (5), the second reducing agent is added to the reaction tank and stirred and mixed for a second reduction process, the rate of stirring 40-100rad / min, the mass ratio, a second dosage of the reducing agent to chromium slag slurry ratio of 0.05 to 0.2: 1, mass ratio of the dosage of the second reducing agent is preferably chromium slag slurry is 0.08-0.1.8: 1, the second reduction in the reaction time from 0.5 to 1.5 hours, in the second reduction reaction, not only continue to produce ferrous ions and a reduction reaction of hexavalent chromium, chromium hydroxide precipitate slurry such that the chromium slag fully detoxification hexavalent chromium, but also with the slurry sulphide FeS generated precipitate, the specific reaction equation is as follows:

[0039] Fe2++S2_ = FeS [0039] Fe2 ++ S2_ = FeS

[0040] Fe2++Cr042>40H>4H20 = 3Fe (OH) 3+Cr (OH) 3 [0040] Fe2 ++ Cr042> 40H> 4H20 = 3Fe (OH) 3 + Cr (OH) 3

[0041] 本发明的第二还原剂为氯化亚铁、溴化亚铁、硫酸亚铁或硫酸亚铁铵的其中一种或任意两种以上的混合物,本发明第二还原剂具体的投加量见表4所示。 Ferrous chloride, ferrous bromide, wherein a mixture of any two or more [0041] of the present invention the second reducing agent is ferrous sulfate or ferrous ammonium sulfate, particularly the second reducing agent of the present invention is administered increase the amount shown in Table 4.

[0042]表 4 [0042] TABLE 4

[0043] [0043]

Figure CN103934256AD00062

[0044] 对第二次还原反应后的渣料浆搅拌进行熟化处理,搅拌速度在40_100rad/min,熟化处理时间在6-12小时,该熟化处理时间最好在8-10小时,将铬渣料浆中的六价铬被转化为氢氧化铬沉淀。 [0044] The slag slurry after the second aging treatment for the reduction reaction with stirring, the rate of stirring 40_100rad / min, the aging treatment time is 6-12 hours, the aging treatment time is preferably 8-10 hours, chromium slag the slurry is converted to hexavalent chromium is precipitated as chromium hydroxide.

[0045] (6)、对熟化处理后的铬渣料浆进行固液分离,可采用板框压滤机对反应罐中的熟化处理后的铬渣料浆进行脱水处理,板框压滤机的压力在0.8-1.8Mp,出渣含水率〈60%,对滤液进行检测,分离后的滤液排至球磨机中,分离后的解毒铬渣排出,得到六价铬浸出毒性值低于0.5mg/L的解毒铬渣。 [0045] (6), the slurry of chromium slag after aging treatment for solid-liquid separation, filter presses can be used for chromium slag slurry in the reaction tank after the aging treatment for dehydration treatment and frame filter pressure 0.8-1.8Mp, the residue water content <60%, and the filtrate is detected, discharging the separated filtrate to a ball mill, detoxification of chromium slag discharged after the separation, a value obtained leaching toxicity of hexavalent chromium is less than 0.5mg / L detoxification of chromium slag. 本发明还原反应和熟化处理的具体参数见表5。 Specific parameters of the invention the reduction reaction and aging treatment are shown in Table 5.

[0046]表 5 [0046] TABLE 5

[0047] [0047]

Figure CN103934256AD00071

[0048] 试验地块为原铬渣堆放的场地,由于受到铬渣的影响,待处理的受污染土壤受到严重的铬污染,土壤中总铬含量为102-7162mg/kg,六价铬含量为9.8_1940mg/kg。 [0048] a plot of the original site of chromium slag heap, due to the impact of chromium slag, contaminated soil to be treated severely chromium contaminated soil total chromium content is 102-7162mg / kg, an amount of hexavalent chromium 9.8_1940mg / kg.

[0049] 在需解毒的铬渣及铬污染土壤进行筛分后送至颚式粉碎机粉碎处理,送入球磨机进行湿磨,按表2中各实施例控制其铬渣料浆的波美度及铬渣料浆的颗径,按表2加入第一还原剂,进行第一次还原反应后,再在该反应罐搅拌边加入浓硫酸进行酸化,或用渣浆泵将铬渣料浆输送至另一反应罐边搅拌边加入浓硫酸进行酸化,至铬渣料浆的PH值稳定在表3中,再按表4加入第二还原剂,进行第二次还原反应后,再进行熟化处理,溶出的六价铬还原为三价铬,送入压滤机进行压滤脱水实现固液分离,滤液排出存放在存储罐内循环利用,或直接送至球磨机以循环利用,脱水解毒后的滤渣可以直接进入填埋场进行安全填埋,或进行资源化利用。 [0049] After screening the soil of chromium slag and the chromium contamination antidotes to the jaw crusher crushing process, into the wet-milled in a ball mill, according to the embodiments in Table 2 which controls chromium slag slurry Baume and chromium slag slurry particle diameter, according to table 2 was added after the first reducing agent, for the first time a reduction reaction, then acidifying the reaction vessel was stirred while adding concentrated sulfuric acid, or with a slurry pump to a slurry of chromium slag conveyor after the reaction tank to another of concentrated sulfuric acid was added with stirring acidified to PH value of the slurry stabilized chromium slag in table 3, table 4, then the second reducing agent is added, a second reduction reaction, and then aging treatment elution of hexavalent chromium to trivalent chromium, into the filter press filter press dewatering solid-liquid separation, the filtrate is stored in the storage tank is discharged recycled, or recycled directly to the ball mill, dehydrated cake detoxification direct access to the landfill for landfill, or resource utilization.

[0050] 检测用各实施例处理铬渣及铬污染物土壤后第7天和第28天滤渣中六价铬、总铬浸出浓度,具体的检测结果如表6所示。 After various embodiments of chromium and chromium slag treating the soil contaminants [0050] detection of residues 7 and day 28 of hexavalent chromium, the concentration of total chromium leached specific detection results shown in Table 6. 浸出液的制备参照HJ/T299-2007《固体废物浸出毒性浸出方法硫酸硝酸法》执行,六价铬浸出浓度按标准GBT15555.4-1995《固体废物六价铬的测定二苯碳酰二肼分光光度法》测定,总铬浸出浓度按标准GB15555.5-1995《固体废物总铬测定二苯碳酰二肼分光光度法》测定。 Referring leachate prepared HJ / T299-2007 "solid waste leaching toxicity of nitric acid sulfuric acid method" performing, hexavalent chromium concentration of the leaching standard GBT15555.4-1995 "solid waste chromium Diphenylcarbazide measured spectrophotometrically dihydrazide method "assay, the standard concentration of total chromium leached GB15555.5-1995" Determination of total chromium solid wastes Diphenylcarbazide dihydrazide Spectrophotometric "assay.

[0051]表 6 [0051] TABLE 6

[0052] [0052]

Figure CN103934256AD00072

[0053] 从表6可见,采用本发明湿法解毒方法具有非常好的处理效果,处理后得到的滤渣其浸出液中所含的六价铬低于0.27mg/L,总铬浓度低于0.37mg/L,可以有效铬渣及含铬污染物造成的污染。 [0053] can be seen from Table 6, the detoxification method of the present invention is wet with a very good treatment effect, hexavalent chromium contained in the filter cake obtained after processing of the leaching solution in less than 0.27mg / L, total chromium concentration less than 0.37mg / L, and chromium slag can be effectively pollution chromium pollutants.

Claims (5)

  1. 1.一种铬渣及含铬污染物的湿法解毒方法,其特征在于:按以下步骤进行: (1)、对铬渣及含铬污染物进行筛分后送至颚式粉碎机粉碎处理,粉碎后的铬渣及铬污染物的粒径在0.2-lcm ; (2)、对筛分粉碎后的铬渣及含铬污染物在球磨机中进行湿法球磨,加入含硫酸根离子的滤液,将铬渣料浆中的酸溶性铬酸钙浸出,铬渣料浆的颗径在120-200目,铬渣料浆的波美度室温下在30-50° Be ; ⑶、将铬渣料浆加入反应罐内,加入第一还原剂搅拌混合进行第一次还原反应,还原反应时间在0.5-1.5小时,将铬渣料浆中的酸溶性铬酸钙还原成三价铬,按质量比,第一还原剂的投加量与铬渣料浆比为0.0005-0.001:1,所述的第一还原剂为硫化钠、焦亚硫酸钠、硫化钾或硫化钙的其中之一或两种以上任意组合物; ⑷、向反应罐加入浓硫酸并进行搅拌混合进行调理,将铬渣料浆的PH值调 A method for detoxification of chromium slag and wet chromium-containing contaminants, which is characterized in that: the following steps performed: (1), the chromium and chromium-containing residue contaminants were sieved to the jaw crusher crushed , chromium slag and the particle size after pulverization chromium contaminants in 0.2-lcm; (2), the filtrate residue and chromium chromium pollutants sieved wet ball mill crushing in a ball mill, addition of sulfate ion-containing , chromium slag slurry leach acid-soluble calcium chromate, chromium slag slurry particle diameter of 120-200 mesh, chromium slag slurry Baume degree at room temperature 30-50 ° be; ⑶, chromium slag slurry was added to the reaction tank, a first reducing agent is added to stirred and mixed for the first time a reduction reaction, the reduction reaction time of 0.5-1.5 hours, the reduction of chromium slag in the slurry of acid-soluble calcium chromate to trivalent chromium by mass than, the first dosage of the reducing agent and the ratio of chromium slag slurry is 0.0005-0.001: 1, the first reducing agent is sodium sulfide, one of sodium metabisulfite, potassium sulfide or calcium sulfide or wherein two or more any combination thereof; ⑷, concentrated sulfuric acid was added to the reaction tank and mixed with stirring for conditioning, chromium slag slurry PH value adjustment 至7±0.5,铬渣料浆温度保持在50-70°C ; (5)、再向反应罐加入第二还原剂搅拌混合进行第二次还原处理,按质量比,第二还原剂的投加量与铬渣料浆比为0.05-0.2:1,第二次还原反应时间在0.5-1.5小时,所述的第二还原剂为氯化亚铁、溴化亚铁、硫酸亚铁或硫酸亚铁铵的其中一种或任意两种以上的混合物; (6)、对第二次还原反应后的渣料浆搅拌进行熟化处理,熟化处理时间在6-12小时,将铬渣料浆中的六价铬被转化为氢氧化铬沉淀物; (7)、对熟化处理后的铬渣料浆进行固液分离,分离后的滤液排至球磨机中,分离后的解毒铬渣排出,得到六价铬浸出毒性值低于0.5mg/L的解毒铬渣。 To 7 ± 0.5, chromium slag slurry temperature was maintained at 50-70 ° C; (5), the second reducing agent is added to the reaction tank for stirring and mixing a second reduction process, the mass ratio, a second reducing agent is administered plus the amount of chromium slag slurry ratio of 0.05 to 0.2: 1, the second reduction in the reaction time from 0.5 to 1.5 hours, the second reducing agent is ferrous chloride, ferrous bromide, ferrous sulfate, or sulfuric acid wherein one or any mixture of two or more kinds of ferrous ammonium; (6), slag slurry after the second aging treatment for the reduction reaction with stirring, the aging treatment time is 6-12 hours, the slurry of chromium slag hexavalent chromium is converted to chromium hydroxide precipitate; (7), the slurry of chromium slag after aging treatment for solid-liquid separation, the separated filtrate discharged into a ball mill, detoxification of chromium slag discharged after the separation, to obtain six chromium leaching toxicity values ​​below 0.5mg / L chromium slag detoxification.
  2. 2.根据权利要求1所述的铬渣及含铬污染物的湿法解毒方法,其特征在于:所述铬渣料浆的波美度室温下为35-45° Be0 The chromium slag claim 1 and wet methods of detoxification of chromium-containing contaminants claim, wherein: at room temperature the Baume degree chromium slag slurry is 35-45 ° Be0
  3. 3.根据权利要求1所述的铬渣及含铬污染物的湿法解毒方法,其特征在于:所述第一还原剂的投加量与铬渣料浆的质量比为0.0006-0.0009:1。 The chromium slag claim 1 and wet methods of detoxification of chromium-containing contaminants claim, wherein: the mass ratio of the dosage of the first reducing agent and chromium slag slurry is 0.0006-0.0009: 1 .
  4. 4.根据权利要求1所述的铬渣及含铬污染物的湿法解毒方法,其特征在于:所述第二还原剂的投加量与铬渣料浆的质量比为0.08-0.1.8:1。 The chromium slag claim 1 and wet methods of detoxification of chromium-containing contaminants claim, wherein: the mass ratio of the second dosage of the reducing agent and chromium slag slurry is 0.08-0.1.8 :1.
  5. 5.根据权利要求1所述的铬渣及含铬污染物的湿法解毒方法,其特征在于:按质量百分比,所述滤液中硫酸根离子的浓度在0.5-3%,滤液中亚铁离子的浓度在0.05-0.5%。 According to claim 1 chromium slag and wet methods of detoxification of chromium-containing contaminants claim, wherein: the percentage by mass of the filtrate concentration of sulfate ions in 0.5-3% of ferrous ions in the filtrate at a concentration of 0.05 to 0.5%.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105215051A (en) * 2015-11-10 2016-01-06 辽宁石油化工大学 Reduction-stabilization two-stage type remediating method for chromium-contaminated soil
CN105396872A (en) * 2015-12-15 2016-03-16 北京高能时代环境技术股份有限公司 Wet process detoxifying processing device and method for chromium slag and contaminated soil of chromium slag

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3937785A (en) * 1974-09-17 1976-02-10 Allied Chemical Corporation Treatment of chromium ore residues to suppress pollution
DE19546644A1 (en) * 1994-12-23 1996-06-27 Volkswagen Ag Redn. of chromium-(VI) cpds. to chromium-(III) cpds. in aq. soln.
CN1733373A (en) * 2004-08-13 2006-02-15 范玉瓒 Chromic slag immersion, reduction and detoxification technique
CN1799716A (en) * 2006-01-05 2006-07-12 赵建国 Harmless treatment process for waste chromium slag
WO2006105536A2 (en) * 2005-03-31 2006-10-05 The Trustees Of The Stevens Institute Of Technology Method of treatment, stabilization and heave control for chromite ore processing residues (copr) and chromium contaminated soils
CN101816829A (en) * 2010-04-09 2010-09-01 河南金谷环保工程设备有限公司 Chromium residue detoxifying process
CN102189093A (en) * 2010-03-09 2011-09-21 刘杰 Method for detoxicating chromium residues and comprehensive utilization of detoxicated chromium residues
CN102614620A (en) * 2012-03-15 2012-08-01 中国科学院过程工程研究所 Wet detoxification method of hexavalent chromium contained alkali waste residues

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3937785A (en) * 1974-09-17 1976-02-10 Allied Chemical Corporation Treatment of chromium ore residues to suppress pollution
DE19546644A1 (en) * 1994-12-23 1996-06-27 Volkswagen Ag Redn. of chromium-(VI) cpds. to chromium-(III) cpds. in aq. soln.
CN1733373A (en) * 2004-08-13 2006-02-15 范玉瓒 Chromic slag immersion, reduction and detoxification technique
WO2006105536A2 (en) * 2005-03-31 2006-10-05 The Trustees Of The Stevens Institute Of Technology Method of treatment, stabilization and heave control for chromite ore processing residues (copr) and chromium contaminated soils
CN1799716A (en) * 2006-01-05 2006-07-12 赵建国 Harmless treatment process for waste chromium slag
CN102189093A (en) * 2010-03-09 2011-09-21 刘杰 Method for detoxicating chromium residues and comprehensive utilization of detoxicated chromium residues
CN101816829A (en) * 2010-04-09 2010-09-01 河南金谷环保工程设备有限公司 Chromium residue detoxifying process
CN102614620A (en) * 2012-03-15 2012-08-01 中国科学院过程工程研究所 Wet detoxification method of hexavalent chromium contained alkali waste residues

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张国栋等: "pH值对含铬废水处理效果的影响研究", 《工业用水与废水》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105215051A (en) * 2015-11-10 2016-01-06 辽宁石油化工大学 Reduction-stabilization two-stage type remediating method for chromium-contaminated soil
CN105215051B (en) * 2015-11-10 2018-06-26 辽宁石油化工大学 Kind of reduction of chromium contaminated soil - stabilizing two-stage repair method
CN105396872A (en) * 2015-12-15 2016-03-16 北京高能时代环境技术股份有限公司 Wet process detoxifying processing device and method for chromium slag and contaminated soil of chromium slag

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