CN107010805B - Process for removing heavy metals in livestock and poultry manure - Google Patents
Process for removing heavy metals in livestock and poultry manure Download PDFInfo
- Publication number
- CN107010805B CN107010805B CN201710251670.4A CN201710251670A CN107010805B CN 107010805 B CN107010805 B CN 107010805B CN 201710251670 A CN201710251670 A CN 201710251670A CN 107010805 B CN107010805 B CN 107010805B
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- China
- Prior art keywords
- livestock
- manure
- heavy metal
- poultry
- heavy metals
- Prior art date
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 99
- 239000010871 livestock manure Substances 0.000 title claims abstract description 88
- 210000003608 fece Anatomy 0.000 title claims abstract description 56
- 244000144977 poultry Species 0.000 title claims abstract description 44
- 244000144972 livestock Species 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000003463 adsorbent Substances 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 3
- 230000009920 chelation Effects 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 230000005389 magnetism Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 description 20
- 239000010949 copper Substances 0.000 description 20
- 229910052725 zinc Inorganic materials 0.000 description 17
- 239000011701 zinc Substances 0.000 description 17
- 241001465754 Metazoa Species 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000009395 breeding Methods 0.000 description 5
- 230000001488 breeding effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000271566 Aves Species 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005276 aerator Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
Abstract
A process for removing heavy metals in livestock and poultry manure belongs to the technical field of heavy metal treatment and comprehensive recycling. The method comprises the oxidation of the livestock manure and the removal process of heavy metals in the livestock manure; the invention can be oxidized by high-temperature air, can release heavy metal chelated with organic functional groups in the excrement of the livestock and poultry, and improves the proportion of the effective heavy metal; the invention adopts the magnetic heavy metal adsorbent to remove heavy metals, can efficiently, quickly and thoroughly remove the heavy metals in the livestock and poultry manure, and can realize the recovery and the reutilization of the adsorbent. The invention can achieve the aim of removing heavy metals in the livestock and poultry manure with low cost, rapidness, high efficiency and thoroughness.
Description
Technical Field
The invention relates to a process for removing heavy metals in livestock manure, belongs to the technical field of heavy metal treatment and comprehensive recycling, and can be used for treating the livestock manure containing the heavy metals.
Background
With the development of modern agriculture, the livestock and poultry breeding industry of many countries has the characteristics of regional, large-scale, specialized and intensive operation, and China also becomes an intensive breeding large country. With the rapid development of livestock and poultry breeding industry in China, a large amount of livestock and poultry excrement is produced. The livestock manure contains a large amount of elements such as nitrogen, phosphorus and the like for promoting the growth of crops, is an organic fertilizer source with great potential, and can be used for agricultural production after being treated, so that the soil fertility is improved, and the ecological environment is purified.
With the development of science and technology, the feed becomes a main nutrient source of the livestock manure in the modern breeding industry, and the feed is suitable for a general phenomenon in large-scale breeding. In order to promote the growth and development of livestock and poultry, at present, most domestic enterprises generally add heavy metal elements such as copper, zinc, selenium, arsenic and the like into feed at high dose, wherein the copper content in the feed generally reaches 200-300 mg/kg, the selenium content in the feed generally reaches 0.30-0.50 mg/kg, and the feed is taken as a concentrated feed with Chinese characteristics, wherein the copper content in the feed can reach 1000-1500 mg/kg, and the copper content in 1% of premix can reach 2000-3000 mg/kg. A large amount of heavy metal elements such as copper, zinc and the like are circulated through metabolism, a part of the heavy metal elements are deposited in animal tissues, and 90 percent of the heavy metal elements are discharged out of the body and remain in the excrement of the livestock and poultry. Heavy metals enter a human food chain through a way of feed addition, livestock absorption, livestock excretion, fertilization soil and crop absorption, so that the heavy metals are absorbed by human and influence human health. At present, compost is a better method for treating livestock manure, but only can deposit heavy metals, and the heavy metals in the manure cannot be removed. In the article of the current situation of heavy metal pollution of livestock and poultry manure and the research progress of passivation measures thereof (comparison document 1), volume 14, 3, 2014, of Chinese agricultural science and technology, it is reported that in the composting process, heavy metal is passivated by adding a heavy metal passivator, however, the measure cannot achieve the effect of removing heavy metal, the passivated heavy metal still remains in the livestock and poultry manure, and after a period of time, the heavy metal is released, and the ecological environment is still polluted.
Disclosure of Invention
In order to solve the problem of heavy metal in the livestock and poultry manure, the invention provides the heavy metal treatment process which is effective, short in treatment period and good in treatment effect and can remove the heavy metal in the livestock and poultry manure, and the heavy metal adsorbent used in the process can be recycled.
The technical scheme adopted by the invention for solving the problems comprises a livestock manure oxidation and heavy metal removal process,
the oxidation process of the livestock manure adopts high-temperature air oxidation to release heavy metals chelated with organic functional groups in the livestock manure;
the process for removing heavy metals in the livestock and poultry manure adopts a mode of adding a magnetic heavy metal adsorbent and stirring to remove the heavy metals.
Further, the livestock manure oxidation process comprises the following steps:
1) crushing the livestock manure for 2-10 times by using a crusher;
2) putting the livestock manure in the step 1) into a container, and continuously stirring the livestock manure by mechanical stirring;
3) under the condition of the step 2), heating the livestock manure in the step 2) to 40-80 ℃ by using a water bath kettle;
4) aerating the livestock and poultry manure for 4-10 hours by using an aeration device under the condition of the step 3);
further, the process for removing heavy metals in the livestock and poultry manure comprises the following steps:
1) after stopping heating and aeration, adding a magnetic heavy metal adsorbent into the oxidized livestock and poultry manure;
2) continuously stirring the livestock and poultry manure in the step 1) for 2-4 hours by using mechanical stirring;
3) and (3) recovering the magnetic heavy metal adsorbent in the livestock and poultry manure in the step 2) by using a magnetic separation device.
Further, the heavy metal adsorbent used in the process for removing the heavy metal in the livestock and poultry manure is internally coated with Fe3O4SiO of (2)2The particles are used as a core-shell structure and are modified on the SiO layer of the shell layer through the surface2Introducing amino group thereon, and carboxymethylation on the amino group to obtain-CH2CH2-N-(CH2COO-)2. Of the surface thereof, -CH2CH2-N-(CH2COO-)2The functional group can generate chelation with heavy metal in the livestock manure, and adsorb the heavy metal in the livestock manure. Fe coated inside magnetic heavy metal adsorbent3O4Have magnetism, can utilize the magnetic separation device to separate out from birds animal manure the heavy metal adsorbent after will adsorbing the heavy metal to reach the heavy metal that gets rid of in the birds animal manure, the heavy metal that adsorbs on the heavy metal adsorbent is eluted to accessible pickling simultaneously, thereby realizes heavy metal adsorbent's reuse. The magnetic heavy metal adsorbent is adopted, so that the heavy metal in the livestock and poultry manure can be removed, the treatment effect is good, the treatment period is short, and the heavy metal can be recycled.
The technical scheme adopted by the invention mainly has the following effects:
1) the high-temperature air oxidation is adopted, so that heavy metal chelated with organic functional groups in the livestock manure can be released, the proportion of effective heavy metal in the livestock manure is increased, and the heavy metal can be removed easily;
2) the invention can realize the removal of heavy metals in the livestock manure, thereby fundamentally solving the pollution of the heavy metals in the livestock manure to the ecological environment;
3) the invention adopts air oxidation, thus reducing the cost and avoiding the introduction of chemical reagents;
4) the process adopted by the invention has short treatment period and better removal effect on heavy metals in the livestock and poultry manure;
5) the invention can repeatedly utilize the magnetic heavy metal adsorbent and improve the resource utilization rate.
Detailed Description
The present invention will be further described with reference to the following specific embodiments
Example one
1. Oxidation of poultry and animal manure
1) Taking 1000g of pig manure, and grinding the pig manure for 2 times by using a pulping machine;
2) adding 300g of ground pig manure into a three-neck flask, putting the three-neck flask into a water bath kettle, and heating in a water bath to 40 ℃;
3) rapidly stirring the pig manure in the three-neck flask by using a mechanical stirring device;
4) the three-necked flask was aerated with an aerator at 40 ℃ for 4 hours while stirring.
2. Removal of heavy metals from animal dung
5) Stopping heating and aerating, pouring the oxidized pig manure into a beaker, and weighing 8g of magnetic heavy metal adsorbent to be added into the beaker;
6) continuously stirring the livestock manure in the step 5) for 2 hours by using mechanical stirring;
7) and (3) recovering the magnetic heavy metal adsorbent in the pig manure in the step 6) by using a magnet.
Example two
1. Oxidation of poultry and animal manure
1) Taking 1000g of pig manure, and grinding the pig manure for 10 times by using a pulping machine;
2) adding 300g of ground pig manure into a three-neck flask, putting the three-neck flask into a water bath kettle, and heating in a water bath to 80 ℃;
3) rapidly stirring the pig manure in the three-neck flask by using a mechanical stirring device;
4) the three-necked flask was aerated with an aerator at 80 ℃ for 10 hours while stirring.
2. Removal of heavy metals from animal dung
The procedure is the same as in steps 5) to 7) of example 1.
EXAMPLE III
1. Oxidation of poultry and animal manure
The procedure is the same as in steps 1) to 4) of example 2;
2. removal of heavy metals from animal dung
5) Stopping heating and aerating, pouring the oxidized pig manure into a beaker, and weighing 8g of magnetic heavy metal adsorbent to be added into the beaker;
6) continuously stirring the livestock manure in the step 5) for 4 hours by using mechanical stirring;
7) and (3) recovering the magnetic heavy metal adsorbent in the pig manure in the step 6) by using a magnet.
Results of the experiment
Detecting the total amount and effective state of Cu and Zn in the pig manure oxidized in the example 1, wherein the total amount of Cu and Zn is 1000mg/kg and 2000mg/kg respectively, and the effective state is 400mg/kg and 1000mg/kg respectively; the total amount of Cu and Zn in pig manure after the heavy metal removal in example 1 was measured, the total amount of Cu and Zn was 900mg/kg and 1600mg/kg, respectively, and the removal rates of Cu and Zn were 10% and 20%, respectively.
The total amount and effective state of Cu and Zn in the pig manure oxidized in the example 2 are tested, the total amount of Cu and Zn is 1000mg/kg and 2000mg/kg respectively, and the effective state is 900mg/kg and 1700mg/kg respectively; the total amount of Cu and Zn in pig manure after the heavy metal removal in example 2 was measured, and the total amount of Cu and Zn was 750mg/kg and 1300mg/kg, respectively, and the removal rates of Cu and Zn were 25% and 35%, respectively.
The total amount and effective state of Cu and Zn in the pig manure oxidized in the embodiment 3 are tested, the total amount of Cu and Zn is 1000mg/kg and 2000mg/kg respectively, and the effective state is 900mg/kg and 1700mg/kg respectively; the total amount of Cu and Zn in pig manure after the removal of heavy metals in example 3 was measured, and the total amount of Cu and Zn was 600mg/kg and 1000mg/kg, respectively, and the removal rates of Cu and Zn were 40% and 50%, respectively.
Some organic functional groups in the poultry and livestock manure can be oxidized through air oxidation, so that heavy metal originally chelated by the organic functional groups in the poultry and livestock manure is released, the content of effective state of the heavy metal is improved, after the magnetic heavy metal adsorbent is added, the adsorbent is combined with the effective state heavy metal, and the heavy metal in the poultry and livestock manure is removed through recycling the adsorbent.
It should be understood that the above-mentioned embodiments are merely preferred embodiments of the present invention, and not intended to limit the scope of the invention, therefore, all equivalent changes in the principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A process for removing heavy metals in livestock and poultry manure is characterized by comprising the following steps: a poultry excrement oxidation process and a heavy metal removal process in the poultry excrement;
the oxidation process of the livestock manure adopts high-temperature air oxidation to release heavy metals chelated with organic functional groups in the livestock manure;
the process for removing heavy metals in the livestock and poultry manure adopts a mode of adding a magnetic heavy metal adsorbent and stirring to remove heavy metals;
the oxidation process of the livestock manure comprises the following steps:
1) crushing the livestock manure for 2-10 times by using a crusher;
2) putting the livestock manure in the step 1) into a container, and continuously stirring the livestock manure by mechanical stirring;
3) under the condition of the step 2), heating the livestock manure in the step 2) to 40-80 ℃ by using a water bath kettle;
4) continuously aerating the livestock and poultry manure for 4-10 hours by using an aeration device under the condition of the step 3);
the process for removing heavy metals in the livestock and poultry manure comprises the following steps:
5) after stopping heating and aeration, adding a magnetic heavy metal adsorbent into the oxidized livestock and poultry manure;
6) continuously stirring the livestock manure in the step 5) for 2-4 hours by using mechanical stirring;
7) and (3) recovering the magnetic heavy metal adsorbent in the livestock and poultry manure in the step 6) by using a magnetic separation device.
2. Root of herbaceous plantThe process for removing heavy metals from livestock and poultry manure according to claim 1, wherein the magnetic heavy metal adsorbent is coated with Fe3O4SiO of (2)2The particles are used as a core-shell structure and are modified on the SiO layer of the shell layer through the surface2Introducing amino group thereon, and carboxymethylation on the amino group to obtain-CH2CH2-N-(CH2COO-)2。
3. The process for removing heavy metals from excrements of livestock and poultry as claimed in claim 2, wherein the surface of the excrements contains-CH2CH2-N-(CH2COO-)2The functional group has chelation with heavy metal in the livestock manure, and adsorbs the heavy metal in the livestock manure.
4. The process for removing heavy metals in the feces of livestock and poultry as claimed in claim 2, wherein the interior of the process is coated with Fe3O4The magnetic heavy metal adsorbent has magnetism, and the heavy metal adsorbent after adsorbing heavy metals is separated from livestock and poultry manure by using a magnetic separation device, so that the heavy metals in the livestock and poultry manure are removed.
5. The process for removing heavy metals from livestock and poultry manure according to claim 2, wherein the heavy metals adsorbed on the heavy metal adsorbent are eluted by acid washing, thereby realizing recycling of the heavy metal adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710251670.4A CN107010805B (en) | 2017-04-18 | 2017-04-18 | Process for removing heavy metals in livestock and poultry manure |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710251670.4A CN107010805B (en) | 2017-04-18 | 2017-04-18 | Process for removing heavy metals in livestock and poultry manure |
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| CN107010805A CN107010805A (en) | 2017-08-04 |
| CN107010805B true CN107010805B (en) | 2020-08-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107724057A (en) * | 2017-09-30 | 2018-02-23 | 莆田学院 | A kind of magnetic hydrogen peroxide bleaching stabilizer preparation method and its application in bleaching process |
| CN113004090B (en) * | 2021-04-27 | 2023-02-10 | 新至农业生态科技有限公司 | Soil conditioner prepared from livestock and poultry manure and preparation method thereof |
| CN113511926A (en) * | 2021-04-28 | 2021-10-19 | 新至农业生态科技有限公司 | Method for comprehensively utilizing livestock and poultry manure resources and returning to field |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105036834A (en) * | 2015-09-02 | 2015-11-11 | 张岩 | Organic waste and animal excrement harmless treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101575164B (en) * | 2009-06-05 | 2011-10-12 | 朱世友 | Multi-function high-efficiency livestock and poultry excrement treating device |
| CN204220614U (en) * | 2014-11-11 | 2015-03-25 | 武汉都市环保工程技术股份有限公司 | Organic matter and thermal sensitivity heavy-metal contaminated soil thermal desorption prosthetic device |
| CN105817469A (en) * | 2015-01-09 | 2016-08-03 | 武汉中地金盾环境科技有限公司 | Magnetic separation purifying treatment technology for removing heavy metal pollution of soil |
| CN105170620B (en) * | 2015-09-30 | 2018-07-03 | 江苏省中成建设工程总公司 | A kind of method of magnetic active carbon collaboration activator restoration of soil polluted by heavy metal |
| CN205152093U (en) * | 2015-10-26 | 2016-04-13 | 孔玉 | Equipment with innoxious fermenting organic fertilizer of animal manure |
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| CN105036834A (en) * | 2015-09-02 | 2015-11-11 | 张岩 | Organic waste and animal excrement harmless treatment method |
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