CN112321367A - A kind of method for removing heavy metal in traditional Chinese medicine dregs - Google Patents
A kind of method for removing heavy metal in traditional Chinese medicine dregs Download PDFInfo
- Publication number
- CN112321367A CN112321367A CN202011183997.0A CN202011183997A CN112321367A CN 112321367 A CN112321367 A CN 112321367A CN 202011183997 A CN202011183997 A CN 202011183997A CN 112321367 A CN112321367 A CN 112321367A
- Authority
- CN
- China
- Prior art keywords
- chinese medicine
- traditional chinese
- heavy metals
- thiobacillus ferrooxidans
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003814 drug Substances 0.000 title claims abstract description 82
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000029087 digestion Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000010802 sludge Substances 0.000 claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 21
- 238000000855 fermentation Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000007790 solid phase Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000000813 microbial effect Effects 0.000 claims abstract description 7
- 229910052793 cadmium Inorganic materials 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052745 lead Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000003337 fertilizer Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000003516 soil conditioner Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 abstract description 12
- 239000007787 solid Substances 0.000 abstract description 9
- 244000005700 microbiome Species 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000002207 metabolite Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 239000002893 slag Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 13
- 238000011081 inoculation Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229930013930 alkaloid Natural products 0.000 description 3
- 150000003797 alkaloid derivatives Chemical class 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000001079 digestive effect Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000120 microwave digestion Methods 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000003895 organic fertilizer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000009630 liquid culture Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229940126680 traditional chinese medicines Drugs 0.000 description 2
- 241000266272 Acidithiobacillus Species 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052564 epsomite Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/20—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation using specific microorganisms or substances, e.g. enzymes, for activating or stimulating the treatment
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/80—Separation, elimination or disposal of harmful substances during the treatment
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
- C05F5/006—Waste from chemical processing of material, e.g. diestillation, roasting, cooking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Environmental & Geological Engineering (AREA)
- Toxicology (AREA)
- Botany (AREA)
- Tropical Medicine & Parasitology (AREA)
- Soil Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本发明提供了一种去除中药渣中重金属的方法，属于中药渣处理技术领域，所述方法包括以下步骤：1)将中药渣、污泥和水混合，厌氧发酵30～50d获得厌氧消化物料；2)向所述厌氧消化物料中接种氧化亚铁硫杆菌，进行微生物淋滤培养8～12d后，固液分离，收集固相组分为去除重金属的中药渣。本发明所述的方法通过将中药渣、污泥与水混合厌氧消化后，以氧化亚铁硫杆菌进行微生物淋滤培养，氧化亚铁硫杆菌直接作用或其代谢产物的间接作用产生氧化、还原、络合、吸附和溶解等反应，使重金属由药渣固相溶出进入液相，再通过脱水达到去除中药渣中重金属的目的，操作简单，成本低，重金属去除率高。The invention provides a method for removing heavy metals in traditional Chinese medicine dregs, belonging to the technical field of traditional Chinese medicine dregs treatment. The method comprises the following steps: 1) mixing the traditional Chinese medicine dregs, sludge and water, and anaerobic fermentation for 30-50 days to obtain anaerobic digestion 2) Inoculate Thiobacillus ferrooxidans into the anaerobic digestion material, carry out microbial leaching and culture for 8-12 days, separate the solid and liquid, and collect the solid-phase component as the Chinese medicine residue for removing heavy metals. In the method of the invention, after anaerobic digestion of traditional Chinese medicine slag, sludge and water, the microorganism is leached and cultured with Thiobacillus ferrooxidans, and the direct effect of Thiobacillus ferrooxidans or the indirect effect of its metabolites produces oxidation, Reduction, complexation, adsorption, dissolution and other reactions make the heavy metals dissolve from the solid phase of the medicinal residues into the liquid phase, and then achieve the purpose of removing heavy metals in the traditional Chinese medicine residues through dehydration. The operation is simple, the cost is low, and the heavy metal removal rate is high.
Description
Technical Field
The invention belongs to the technical field of traditional Chinese medicine residue treatment, and particularly relates to a method for removing heavy metals in traditional Chinese medicine residue.
Background
In recent years, with the strong support of China to the pharmaceutical industry of China, Chinese medicine pharmaceutical enterprises are rapidly developing and growing, and meanwhile, the annual discharge amount of the Chinese medicine residues is also multiplied. According to statistics, the annual discharge amount of the traditional Chinese medicine residues reaches 3000 ten thousand tons. The traditional Chinese medicine residues have various sources, such as processing and concocting traditional Chinese medicine decoction pieces in hospitals and pharmacies, production of Chinese patent medicines, production of raw material medicines, processing of traditional Chinese medicines, production of light chemical products containing traditional Chinese medicines and the like in traditional Chinese medicine enterprises, wherein the traditional Chinese medicine residues produced by the Chinese patent medicines have the maximum amount which accounts for about 70 percent of the total amount of medicine residues.
The residual traditional Chinese medicine residues after industrial extraction are still rich in organic matters such as cellulose, polysaccharide, amino acid, protein, alkaloid and the like, and also rich in inorganic matters such as nitrogen, phosphorus, potassium and the like, so that the organic fertilizer is a good soil conditioner and a high-quality organic fertilizer, can improve the soil texture and increase the fertilizer efficiency, and can reduce the resource waste and environmental pollution caused by burning, burying, stacking and the like of the medicine residues, therefore, the organic fertilizer taking the traditional Chinese medicine residues as the raw materials is a main trend of future agricultural development.
Heavy metal contained in the traditional Chinese medicine residues is taken as a persistent toxic pollutant, only changes in chemical occurrence form are generated in most treatment processes, the heavy metal is not effectively removed, the heavy metal is accumulated and migrated in the environment, the heavy metal exceeds the standard, and finally enters a food chain to harm human health, which is one of main reasons for limiting the large-scale utilization of the residues.
At present, the removal of the heavy metals remained in the traditional Chinese medicine residues is a blank field. Generally speaking, the methods for removing heavy metals mainly include electrokinetic techniques, chemical leaching methods, supercritical fluid extraction methods, plant extraction methods and the like, but these methods have the problems of high treatment cost, possible secondary pollution and the like.
Disclosure of Invention
In view of the above, the present invention is directed to a method for removing heavy metals from herb residue, which is simple to operate and low in cost.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a method for removing heavy metals in traditional Chinese medicine residues, which comprises the following steps:
1) mixing the traditional Chinese medicine residues, sludge and water, and performing anaerobic fermentation for 30-50 days to obtain an anaerobic digestion material;
2) inoculating thiobacillus ferrooxidans into the anaerobic digestion material, performing microbial leaching culture for 8-12 days, performing solid-liquid separation, and collecting solid-phase components which are traditional Chinese medicine residues for removing heavy metals.
Preferably, the particle size of the traditional Chinese medicine residues is 0.5-1.5 cm.
Preferably, the mass ratio of the traditional Chinese medicine residues to the sludge to the water is 1: (0.8-1.2): (8-12).
Preferably, the temperature of the anaerobic fermentation is 30-40 ℃; the anaerobic fermentation is accompanied by intermittent oscillation; the oscillating speed is 85-95 rpm, and the oscillating time is 10-12 hours per day.
Preferably, the concentration of the Thiobacillus ferrooxidans in step 2) is 108～109cfu/mL。
Preferably, the inoculation amount of the thiobacillus ferrooxidans in the step 2) is 10-20% by volume percentage.
Preferably, after the thiobacillus ferrooxidans is inoculated into the anaerobic digestion material in the step 2), FeSO is added into the anaerobic digestion material4And a pH adjustment step, said FeSO4The final concentration of (A) is 6.0-10.0 g/L, and the pH value is adjusted to 4.0-7.0.
Preferably, the dissolved oxygen of the microorganism leaching culture is 3.0-5.0 mg/L, and the temperature of the microorganism leaching culture is 25-32 ℃.
Preferably, the heavy metal comprises one or more of Ni, Zn, Pb, Cu, Cd and Mn.
The invention provides application of the traditional Chinese medicine residue obtained by removing heavy metals and prepared by the method as a soil conditioner or a fertilizer.
The invention has the beneficial effects that: according to the method for removing the heavy metals in the traditional Chinese medicine residues, the sludge and the water are mixed for anaerobic digestion, and then the thiobacillus ferrooxidans is used for carrying out microorganism leaching culture, so that the thiobacillus ferrooxidans directly acts or indirectly acts on metabolites of the thiobacillus ferrooxidans to generate the effects of oxidation, reduction, complexation, adsorption, dissolution and the like, the heavy metals are dissolved out from the solid phase of the traditional Chinese medicine residues into the liquid phase, and the purpose of removing the heavy metals in the traditional Chinese medicine residues is achieved through dehydration, so that the further utilization of the traditional Chinese medicine residues is promoted, and the harm to the; the method disclosed by the invention is simple to operate, low in cost and high in heavy metal removal rate.
The method disclosed by the invention can effectively remove heavy metals in the Chinese medicine residues, and can reduce the harm of the Chinese medicine residues to soil and environment after composting; the method is environment-friendly and harmless treatment at normal temperature and normal pressure, can effectively utilize resources, avoid land occupation, fully utilize organic matters such as cellulose, polysaccharide, amino acid, protein and alkaloid in the traditional Chinese medicine residues and inorganic matters such as nitrogen, phosphorus and potassium as fertilizers, and can also avoid energy consumption and environmental pollution in the treatment process.
The method has the advantages of definite change rule of the heavy metal form in the Chinese medicine residue and stable heavy metal removal rate.
Drawings
FIG. 1 is a flow chart of the method for removing heavy metals in herb residue according to the present invention.
Detailed Description
The invention provides a method for removing heavy metals in traditional Chinese medicine residues, which comprises the following steps: 1) mixing the traditional Chinese medicine residues, sludge and water, and performing anaerobic fermentation for 30-50 days to obtain an anaerobic digestion material; 2) inoculating thiobacillus ferrooxidans into the anaerobic digestion material, performing microbial leaching culture for 8-12 days, performing solid-liquid separation, and collecting solid-phase components which are traditional Chinese medicine residues for removing heavy metals.
In the invention, the traditional Chinese medicine residues, the sludge and water are mixed, and anaerobic fermentation is carried out for 30-50 days to obtain the anaerobic digestion material.
In the invention, the traditional Chinese medicine dregs are preferably dried traditional Chinese medicine dregs, and the traditional Chinese medicine dregs are preferably crushed. In the invention, the particle size of the traditional Chinese medicine residues is preferably 0.5-1.5 cm, and more preferably 1 cm; in the present invention, before the traditional Chinese medicine residue is pulverized, the solid-liquid phase heavy metal content and the chemical form distribution are preferably quantitatively detected and analyzed, and in the present invention, the solid-liquid phase heavy metal content and the chemical form distribution are preferably performed by the following method: with HNO3And H2O2Digesting the traditional Chinese medicine residues by a microwave high-pressure digestion method, and detecting the heavy metal content of the digested traditional Chinese medicine residues by ICP-MS. The source of the herb residue is not particularly limited in the present invention, and conventional sources in the art can be adopted, for exampleIs derived from the dregs of a decoction in a pharmaceutical factory.
In the present invention, the sludge is preferably sludge derived from a sewage treatment plant, and more preferably mixed sludge collected from a thickener of a municipal sewage treatment plant. In the present invention, the sludge is preferably subjected to a pretreatment for mixing with herb residue to bioleaching (anaerobic fermentation) for removing heavy metals from the herb residue, the pretreatment comprising the steps of: heating the collected mixed sludge at 85-95 ℃ for 1-2 h under the condition of stirring, stopping stirring, settling for 3-5 h, and removing the supernatant to obtain sludge to be used; the heating temperature is more preferably 90 ℃, and the heating time is more preferably 4 h; the rotation speed of the stirring in the invention is preferably 4000-6000 rpm, and more preferably 5000 rpm. In the present invention, the solid content of the sludge to be used is preferably 4% to 6%, more preferably 5%.
In the present invention, the water is preferably distilled water. In the invention, the mass ratio of the traditional Chinese medicine dregs, the sludge and the water is preferably 1: (0.8-1.2): (8-12), more preferably 1: 1: 10. in the invention, the time for anaerobic fermentation is preferably 30-50 d, more preferably 35-45 d, and most preferably 40 d; the temperature of the anaerobic fermentation is preferably 30-40 ℃, more preferably 32-38 ℃, and most preferably 35 ℃; the anaerobic fermentation is preferably accompanied by intermittent shaking; the rotating speed of the oscillation is preferably 85-95 rpm, and more preferably 90 rpm; the time of oscillation is preferably 10-12 h per day, and more preferably 11h per day. In the invention, the solid content of the anaerobic fermentation substrate is preferably 6-10%, more preferably 7-9%, and most preferably 8%; in the invention, nitrogen is preferably filled into the anaerobic fermentation substrate to ensure an anaerobic environment, and the flow rate of the nitrogen is preferably 80-120 mL/min, and more preferably 100 mL/min; in the present invention, the anaerobic fermentation is preferably carried out in a water bath shaker. In the process of anaerobic fermentation, sampling detection is preferably carried out, the sampling time interval is preferably 2-3 d in the first 10 days of the anaerobic fermentation, and the sampling time interval is preferably 5-6 d after 10 days of the anaerobic fermentation.
After the anaerobic digestion material is obtained, thiobacillus ferrooxidans is inoculated into the anaerobic digestion material, the anaerobic digestion material is subjected to microorganism leaching culture for 8-12 days, solid-liquid separation is carried out, and solid-phase components, namely traditional Chinese medicine residues for removing heavy metals, are collected.
In the present invention, the concentration of the Thiobacillus ferrooxidans is preferably 108～109cfu/mL. The source of the thiobacillus ferrooxidans is not particularly limited, and commercially available thiobacillus ferrooxidans or thiobacillus ferrooxidans obtained by self-separation can be adopted. In the present invention, the thiobacillus ferrooxidans for inoculation is preferably obtained by the following method: inoculating Thiobacillus ferrooxidans in liquid culture medium, and culturing until thallus concentration reaches 108～109After cfu/mL, FeSO was added4The final concentration is 6.0-10.0 g/L, and the culture is carried out under stirring at 25-32 ℃. In the present invention, the liquid medium preferably includes the following components: solution A: (NH4)2SO4 3.0g/L，K2HPO4 0.5g/L，KCl 0.1g/L，MgSO4·7H2O 0.5g/L，Ca(NO3)20.01; deionized Water 800mL, H2SO4Adjusting pH to 2.0, and autoclaving at 121 deg.C for 20 min. And B, liquid B: FeSO4·7H2O44.78 g/L, deionized water 200mL, H2SO4Adjusting pH to 2.0, and filtering with 0.22 μm filter membrane for sterilization. Mixing the sterilized solution A and solution B, and packaging. In the present invention, the method for obtaining thiobacillus ferrooxidans by self-isolation is preferably as follows: mixing anaerobic digested sludge of an urban sewage treatment plant, a liquid culture medium and starch, and carrying out anaerobic culture at 31-33 ℃ for 15-20 days under the conditions of sealing and stirring to obtain the starch. In the present invention, the ratio of the anaerobically digested sludge, the liquid medium and the starch is preferably 8mL:1000mL:20 g.
In the present invention, the inoculation amount of the thiobacillus ferrooxidans is preferably 10% to 20%, more preferably 12% to 18%, and most preferably 15% by volume. In the present invention, after inoculating Thiobacillus ferrooxidans into the anaerobic digestion material, it is preferable to further include adding FeSO into the anaerobic digestion material4And a pH adjustment step, said FeSO4Is preferably at a final concentration of6.0-10.0 g/L, more preferably 7.0-9.0 g/L, and most preferably 8.0 g/L; the pH value is preferably adjusted to 4.0 to 7.0, more preferably 5.0 to 6.0. In the invention, the dissolved oxygen for the microorganism leaching culture is preferably 3.0-5.0 mg/L, more preferably 3.5-4.50 mg/L, and most preferably 4.00 mg/L; in the invention, the temperature for leaching and culturing the microorganisms is preferably 25-32 ℃, and more preferably 27-30 ℃; the time for the microbial leaching culture is preferably 9-11 days, and more preferably 10 days. After the microorganism leaching culture, the solid-liquid separation is carried out; the solid-liquid separation method is preferably centrifugation, and in the method, the solid-phase components are collected to be the traditional Chinese medicine residues for removing the heavy metals; collecting liquid phase components to measure the types and the contents of heavy metals in the liquid phase components.
In the present invention, the equations for producing the oxidation, reduction, complexation, adsorption and dissolution effects by using the direct action of Acidithiobacillus or the indirect action of its metabolites are as follows:
in the invention, the heavy metal comprises one or more of Ni, Zn, Pb, Cu, Cd and Mn.
The invention provides application of the traditional Chinese medicine residue obtained by removing heavy metals and prepared by the method as a soil conditioner or a fertilizer. The traditional Chinese medicine residue for removing heavy metals, which is prepared by the method, has low heavy metal content, and also contains rich organic matters such as cellulose, polysaccharide, amino acid, protein and alkaloid and inorganic matters such as nitrogen, phosphorus and potassium; is environment-friendly as a soil conditioner or a fertilizer.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
A method for removing heavy metals in traditional Chinese medicine residues comprises the following steps:
preparing a strain inoculation liquid: 8mL of anaerobic digestion sludge of an urban sewage treatment plant is taken, 1000mL of nutrient solution and 20g of starch are added, and anaerobic culture is carried out for 18 days at 32 ℃ under the conditions of sealing and stirring to prepare inoculation liquid.
Preparation of traditional Chinese medicine residues: taking 2kg of traditional Chinese medicine residues in a pharmaceutical factory, respectively carrying out quantitative detection and analysis on the solid-liquid phase heavy metal content and the chemical form distribution of the residues, drying the traditional Chinese medicine residues, and crushing the traditional Chinese medicine residues to be within 1.0 cm.
The detection method for the heavy metal content and the chemical form distribution of the solid-liquid phase of the decoction dregs comprises the following steps: taking 0.25g of the herb residue sample, adding 2mL of 30% hydrogen peroxide solution (H)2O2) 6mL of concentrated nitric acid (HNO)3) Digesting for 35min by using a microwave digestion instrument; after the digested liquid is filtered and diluted by a 0.45-micron water system membrane, the content of heavy metal is measured by an inductively coupled plasma mass spectrometer (ICP-MS), and the result is that: before removal, the contents of 5 heavy metals such as Ni, Cr, Pb, Cu, Cd and the like are respectively (mg/kg): 10.272, 1.251, 8.356, 0.093, 0.213; the contents of the 5 heavy metals such as Ni, Zn, Pb, Cu, Cd and the like after removal are respectively (mg/kg): 2.178, 0.173, 5.791, 0.028, 0.167.
Anaerobic digestion of the Chinese medicine residues: and mixing the obtained crushed Chinese medicine dregs, sludge and distilled water according to the ratio of 1: 1: 10, maintaining 8 percent of digestion substrate solid content, charging nitrogen to ensure anaerobic environment, sealing and digesting the connection air collecting bag, adjusting the temperature of a water bath oscillator to 35 ℃, the rotating speed of the oscillator to 90rpm, and oscillating for 12 hours every day. And taking the digestive juice every 2 days in the early reaction period for detection, and taking samples at an interval of 5 days in the later reaction period.
Biological leaching: inoculating the bacteria inoculation liquid into the dregs of a decoction according to the volume ratio of 20 percentAnaerobic digested material. Adding FeSO4Adjusting pH to 6.0 to 8.0g/L, controlling dissolved oxygen at 4.0mg/L, performing leaching culture at 30 deg.C for 10 days, centrifuging to separate solid and liquid to obtain solid phase with reduced heavy metal content and water phase rich in heavy metal.
The removal rates of 5 heavy metals such as Ni, Zn, Pb, Cu, Cd and the like in the solid phase are respectively as follows: 78.8%, 86.2%, 30.7%, 70.3%, 21.6%.
Example 2
A method for removing heavy metals in traditional Chinese medicine residues comprises the following steps:
preparing a strain inoculation liquid: 8mL of anaerobic digestion sludge of an urban sewage treatment plant is taken, 1000mL of nutrient solution and 20g of starch are added, and anaerobic culture is carried out for 20 days at 31 ℃ under the conditions of sealing and stirring to prepare inoculation liquid.
Preparation of traditional Chinese medicine residues: taking 2kg of traditional Chinese medicine residues in a pharmaceutical factory, respectively carrying out quantitative detection and analysis on the solid-liquid phase heavy metal content and the chemical form distribution of the residues, drying the traditional Chinese medicine residues, and crushing the traditional Chinese medicine residues to be within 1.0 cm.
The detection method for the heavy metal content and the chemical form distribution of the solid-liquid phase of the decoction dregs comprises the following steps: taking 0.25g of the herb residue sample, adding 2mL of 30% hydrogen peroxide solution (H)2O2) 6mL of concentrated nitric acid (HNO)3) Digesting for 35min by using a microwave digestion instrument; after the digested liquid is filtered and diluted by a 0.45-micron water system membrane, the content of heavy metal is measured by an inductively coupled plasma mass spectrometer (ICP-MS), and the result is that: before removal, the contents of 5 heavy metals such as Ni, Cr, Pb, Cu, Cd and the like are respectively (mg/kg): 8.784, 2.051, 9.432, 0.125, 0.267; the contents of the 5 heavy metals such as Ni, Zn, Pb, Cu, Cd and the like after removal are respectively (mg/kg): 1.774, 0.345, 6.253, 0.038 and 0.212.
Anaerobic digestion of the Chinese medicine residues: and mixing the obtained crushed Chinese medicine dregs, sludge and distilled water according to the ratio of 1: 1: 10, maintaining 8 percent of digestion substrate solid content, charging nitrogen to ensure anaerobic environment, sealing the digestion connection air collecting bag, adjusting the temperature of a water bath oscillator to 36 ℃, the rotating speed of the oscillator to 95rpm, and oscillating for 12 hours every day. And taking the digestive juice every 2 days in the early reaction period for detection, and taking samples at an interval of 5 days in the later reaction period.
Biological leaching: inoculating the bacteria inoculation liquid into the substance after anaerobic digestion of the dregs according to the volume ratio of 20%. Adding FeSO4Adjusting pH to 6.0 to 8.0g/L, controlling dissolved oxygen at 4.0mg/L, performing leaching culture at 30 deg.C for 10 days, centrifuging to separate solid and liquid to obtain solid phase with reduced heavy metal content and water phase rich in heavy metal.
The removal rates of 5 heavy metals such as Ni, Zn, Pb, Cu, Cd, Mn and the like in the solid phase are respectively as follows: 79.8%, 83.2%, 33.7%, 69.3%, 20.6%.
Example 3
A method for removing heavy metals in traditional Chinese medicine residues comprises the following steps:
preparing a strain inoculation liquid: 8mL of anaerobic digestion sludge of an urban sewage treatment plant is taken, 1000mL of nutrient solution and 20g of starch are added, and anaerobic culture is carried out for 19 days at 33 ℃ under the conditions of sealing and stirring to prepare inoculation liquid.
Preparation of traditional Chinese medicine residues: taking 2kg of traditional Chinese medicine residues in a pharmaceutical factory, respectively carrying out quantitative detection and analysis on the solid-liquid phase heavy metal content and the chemical form distribution of the residues, drying the traditional Chinese medicine residues, and crushing the traditional Chinese medicine residues to be within 1.0 cm.
The detection method for the heavy metal content and the chemical form distribution of the solid-liquid phase of the decoction dregs comprises the following steps: taking 0.25g of the herb residue sample, adding 2mL of 30% hydrogen peroxide solution (H)2O2) 6mL of concentrated nitric acid (HNO)3) Digesting for 35min by using a microwave digestion instrument; after the digested liquid is filtered and diluted by a 0.45-micron water system membrane, the content of heavy metal is measured by an inductively coupled plasma mass spectrometer (ICP-MS), and the result is that: before removal, the contents of 5 heavy metals such as Ni, Cr, Pb, Cu, Cd and the like are respectively (mg/kg): 10.781, 1.403, 8.055, 0.114, 0.193; the contents of the 5 heavy metals such as Ni, Zn, Pb, Cu, Cd and the like after removal are respectively (mg/kg): 2.124, 0.199, 7.668, 0.038, 0.157.
Anaerobic digestion of the Chinese medicine residues: and mixing the obtained crushed Chinese medicine dregs, sludge and distilled water according to the ratio of 1: 1: 10, maintaining 8 percent of digestion substrate solid content, charging nitrogen to ensure anaerobic environment, sealing and digesting the connection air collecting bag, adjusting the temperature of a water bath oscillator to be 34 ℃, the rotating speed of the oscillator to be 85rpm, and oscillating for 12 hours every day. And taking the digestive juice every 2 days in the early reaction period for detection, and taking samples at an interval of 5 days in the later reaction period.
Biological leaching: inoculating the bacteria inoculation liquid into the substance after anaerobic digestion of the dregs according to the volume ratio of 20%. Adding FeSO4Adjusting pH to 6.0 to 8.0g/L, controlling dissolved oxygen at 4.0mg/L, performing leaching culture at 30 deg.C for 10 days, centrifuging to separate solid and liquid to obtain solid phase with reduced heavy metal content and water phase rich in heavy metal.
The removal rates of 5 heavy metals such as Ni, Zn, Pb, Cu, Cd, Mn and the like in the solid phase are respectively as follows: 80.3%, 85.8%, 38.7%, 66.3%, 18.6%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for removing heavy metals in traditional Chinese medicine residues comprises the following steps:
1) mixing the traditional Chinese medicine residues, sludge and water, and performing anaerobic fermentation for 30-50 days to obtain an anaerobic digestion material;
2) inoculating thiobacillus ferrooxidans into the anaerobic digestion material, performing microbial leaching culture for 8-12 days, performing solid-liquid separation, and collecting solid-phase components which are traditional Chinese medicine residues for removing heavy metals.
2. The method according to claim 1, wherein the grain size of the herb residue is 0.5-1.5 cm.
3. The method according to claim 1, wherein the mass ratio of the traditional Chinese medicine dregs, the sludge and the water is 1: (0.8-1.2): (8-12).
4. The method according to claim 1, wherein the temperature of the anaerobic fermentation is 30-40 ℃; the anaerobic fermentation is accompanied by intermittent oscillation; the oscillating speed is 85-95 rpm, and the oscillating time is 10-12 hours per day.
5. The method according to claim 1, wherein the concentration of the Thiobacillus ferrooxidans in step 2) is 108～109cfu/mL。
6. The method according to claim 5, wherein the amount of the Thiobacillus ferrooxidans inoculated in the step 2) is 10-20% by volume.
7. The method of claim 5, wherein the step 2) further comprises adding FeSO to the anaerobically digested material after inoculating Thiobacillus ferrooxidans into the anaerobically digested material4And a pH adjustment step, said FeSO4The final concentration of (A) is 6.0-10.0 g/L, and the pH value is adjusted to 4.0-7.0.
8. The method according to any one of claims 5 to 7, wherein the dissolved oxygen in the microbial leaching culture is 3.0 to 5.0mg/L, and the temperature in the microbial leaching culture is 25 to 32 ℃.
9. The method of claim 1, wherein the heavy metal comprises one or more of Ni, Zn, Pb, Cu, Cd, and Mn.
10. Use of the traditional Chinese medicine residue obtained by the method of any one of claims 1 to 9 and used for removing heavy metals as a soil conditioner or a fertilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011183997.0A CN112321367A (en) | 2020-10-29 | 2020-10-29 | A kind of method for removing heavy metal in traditional Chinese medicine dregs |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011183997.0A CN112321367A (en) | 2020-10-29 | 2020-10-29 | A kind of method for removing heavy metal in traditional Chinese medicine dregs |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112321367A true CN112321367A (en) | 2021-02-05 |
Family
ID=74297414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011183997.0A Pending CN112321367A (en) | 2020-10-29 | 2020-10-29 | A kind of method for removing heavy metal in traditional Chinese medicine dregs |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112321367A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375553A (en) * | 2002-04-25 | 2002-10-23 | 南京农业大学 | Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith |
| CN101624300A (en) * | 2009-08-03 | 2010-01-13 | 安徽莱姆佳肥业有限公司 | Method for removing heavy metal in solid organic waste compost |
| US20170036967A1 (en) * | 2014-04-23 | 2017-02-09 | Konstantin Nikolaevich TOROP | Method for comprehensively processing brown coal and leonardite into humic fertilizers and preparations and into fuel briquettes, and mechanochemical reactor for processing highly-viscous media |
| CN111792971A (en) * | 2020-07-23 | 2020-10-20 | 山东胜伟盐碱地科技有限公司 | Organic microbial fertilizer harmless to environment |
-
2020
- 2020-10-29 CN CN202011183997.0A patent/CN112321367A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375553A (en) * | 2002-04-25 | 2002-10-23 | 南京农业大学 | Ferrous oxide theobacillus and sludge heavy-metal eliminating method therewith |
| CN101624300A (en) * | 2009-08-03 | 2010-01-13 | 安徽莱姆佳肥业有限公司 | Method for removing heavy metal in solid organic waste compost |
| US20170036967A1 (en) * | 2014-04-23 | 2017-02-09 | Konstantin Nikolaevich TOROP | Method for comprehensively processing brown coal and leonardite into humic fertilizers and preparations and into fuel briquettes, and mechanochemical reactor for processing highly-viscous media |
| CN111792971A (en) * | 2020-07-23 | 2020-10-20 | 山东胜伟盐碱地科技有限公司 | Organic microbial fertilizer harmless to environment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112007609A (en) | Preparation method and application of Fe-Mg/mulberry stem biochar composites | |
| CN108265017A (en) | A kind of biological prosthetic reagent and restorative procedure for promoting hyperaccumulative plant growth and strengthening extraction heavy metal-polluted soil | |
| CN102337299A (en) | Preparation method of bacillus flocculant | |
| CN106190871A (en) | A kind of method that compound thread fungal organism drip leaching with straw as carbon source processes heavy-metal contaminated soil | |
| CN105903757A (en) | Method for removing heavy metals in soil through combination of bioleaching and Fenton reaction | |
| CN113307377A (en) | Method for treating fermentation exhaust gas and wastewater by coupling active microalgae | |
| CN112972520B (en) | Method for improving active ingredient yield by deeply fermenting eucommia ulmoides leaves with inonotus obliquus liquid | |
| CN112403444B (en) | Modified biochar for reducing methyl mercury enrichment in rice and method | |
| CN101328089B (en) | A method for producing compound microbial phosphate fertilizer by utilizing low-grade phosphate rock powder | |
| CN107879485A (en) | A kind of biological adsorption recovery method of heavy metals in industrial wastewater | |
| CN107739835B (en) | Continuous leaching biological leaching device and method for red mud | |
| CN107236864A (en) | The method for extracting rare precious metals from flyash using Microorganism Leaching | |
| CN101392327B (en) | Method for leaching copper in waste printed circuit board by microbiology | |
| CN104817243A (en) | Bioleaching-Fenton-like oxidation combined bottom mud heavy metal removal and dehydration method | |
| CN112321367A (en) | A kind of method for removing heavy metal in traditional Chinese medicine dregs | |
| CN105112656A (en) | Method for increasing recovery rate of gold in mineral leaching system | |
| CN102992557A (en) | Method for effectively removing heavy metal from bottom mud | |
| CN106754562B (en) | Bacterial strain for high yield of bacterial polysaccharide and method for preparing polysaccharide by fermenting traditional Chinese medicine waste | |
| CN110759754A (en) | Harmless treatment and resource utilization method of glucosamine fermentation bacterium residues | |
| CN113980090B (en) | Method for recycling biological source protein by using biological medicine fermentation fungus dreg | |
| Meng et al. | UV induced mutations in Acidianus brierleyi growing in a continuous stirred tank reactor generated a strain with improved bioleaching capabilities | |
| CN112156416B (en) | Method for preparing fly ash heavy metal organic chelating agent by anaerobic fermentation of biogas slurry from kitchen waste | |
| CN207567313U (en) | A kind of the continuous of red mud leaches bioleaching device | |
| CN106984631A (en) | A kind of equipment for treating organic refuse | |
| CN101705359A (en) | Method for recovering silver in silver-containing waste water by biological method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |