CN110872570A - Solution formula for efficiently producing sulfide by utilizing different soils and method for preparing sulfide - Google Patents
Solution formula for efficiently producing sulfide by utilizing different soils and method for preparing sulfide Download PDFInfo
- Publication number
- CN110872570A CN110872570A CN201911008499.XA CN201911008499A CN110872570A CN 110872570 A CN110872570 A CN 110872570A CN 201911008499 A CN201911008499 A CN 201911008499A CN 110872570 A CN110872570 A CN 110872570A
- Authority
- CN
- China
- Prior art keywords
- sulfide
- component
- soil
- reaction
- liquid
- 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.)
- Granted
Links
- 239000002689 soil Substances 0.000 title claims abstract description 147
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 93
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 84
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 56
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001540 sodium lactate Substances 0.000 claims abstract description 44
- 229940005581 sodium lactate Drugs 0.000 claims abstract description 44
- 235000011088 sodium lactate Nutrition 0.000 claims abstract description 44
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 42
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 42
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 42
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 42
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 42
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 28
- 239000001110 calcium chloride Substances 0.000 claims abstract description 19
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 19
- 229910052564 epsomite Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 250
- 238000006243 chemical reaction Methods 0.000 claims description 140
- 238000012544 monitoring process Methods 0.000 claims description 67
- 238000003860 storage Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000009472 formulation Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 64
- 241000894006 Bacteria Species 0.000 abstract description 21
- 230000019086 sulfide ion homeostasis Effects 0.000 abstract description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 13
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002068 microbial inoculum Substances 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 description 75
- 239000004033 plastic Substances 0.000 description 52
- 229910052799 carbon Inorganic materials 0.000 description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 38
- 230000009467 reduction Effects 0.000 description 30
- 229910052760 oxygen Inorganic materials 0.000 description 28
- 239000001301 oxygen Substances 0.000 description 28
- 229910052742 iron Inorganic materials 0.000 description 19
- 238000007789 sealing Methods 0.000 description 18
- 229910001385 heavy metal Inorganic materials 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000002985 plastic film Substances 0.000 description 13
- 150000004763 sulfides Chemical class 0.000 description 12
- 239000002054 inoculum Substances 0.000 description 11
- 230000001954 sterilising effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000002344 surface layer Substances 0.000 description 9
- 238000005273 aeration Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 206010027146 Melanoderma Diseases 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940046892 lead acetate Drugs 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007836 KH2PO4 Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000000245 forearm Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000012138 yeast extract Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/38—Chemical stimulation of growth or activity by addition of chemical compounds which are not essential growth factors; Stimulation of growth by removal of a chemical compound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/02—Form or structure of the vessel
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/26—Conditioning fluids entering or exiting the reaction vessel
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/30—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration
- C12M41/34—Means for regulation, monitoring, measurement or control, e.g. flow regulation of concentration of gas
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/20—Bacteria; Culture media therefor
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
Abstract
The invention discloses a solution formula for efficiently producing sulfide by using different soils and a method for preparing sulfide, wherein the solution formula is K2HPO4、NH4Cl、Na2SO4Anhydrous CaCl2、MgSO4·7H2O, sodium lactate and ascorbic acid; each liter of the aqueous solution contains K2HPO40.30～0.70g，NH4Cl 0.50～1.10g，Na2SO40.40-0.60 g of anhydrous CaCl20.04～0.06g，MgSO4·7H29.0 to 21.0g of O, 4.0 to 9.0mL of sodium lactate, and 0.05 to 0.13g of ascorbic acid. The invention provides a solution formula for efficiently producing sulfide by using different soils, which can activate the sulfide production activity of sulfate reducing bacteria in the soil, is suitable for efficiently producing sulfide by using different soils, has wide applicability of used soil inoculants, can produce sulfide by using local materials, has low cost and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of sulfide production equipment, in particular to a sulfide efficient generation device and a method for preparing sulfide.
Background
In recent years, environmental pollution caused by heavy metals has become increasingly serious. Heavy metals can be finally accumulated in human bodies through a food chain, and heavy metal pollution poses serious threats to agricultural product safety, human health and the like. Heavy metals have poor mobility in soil, long residence time, difficult degradation and great treatment difficulty. At present, the heavy metal polluted soil is repaired mainly by adopting two technologies of extraction and fixation. The immobilization method relies on weakening the migration ability of heavy metals to achieve the goal of reducing their biotoxicity. Among them, the microorganism immobilization technology has become a research hotspot of the soil heavy metal biological immobilization method due to the characteristics of high efficiency and low cost. Sulfate Reducing Bacteria (SRB) metabolize SO4 2-Conversion to S2-And S is2-Can form metal sulfide with extremely low solubility with heavy metal, such as CuS, PbS, CdS and ZnS, with solubility product constant of 1.3 × 10-36、9.0×10-29、7.9×10-27And 1.6X 10-24. The characteristics of the sulfide enable the sulfide to be quite suitable for the field of heavy metal pollution treatment of water and soilThe application value of (2). The addition of sulfides to the contaminated water can precipitate the heavy metals, which are removed from the water. The addition of sulfide to the contaminated soil can change the chemical form of heavy metals and reduce the biological toxicity. In fact, soil is the major cause of microorganisms, and sulfate-reducing bacteria are widely present in soil as an important decomposer in the soil ecosystem. If sulfate reducing bacteria originally existing in soil are activated, sulfides produced by the sulfate reducing bacteria can be used as remediation agents for heavy metal pollution treatment. However, because of the lack of carbon sources, the stress of oxygen and other factors, the sulfate reducing bacteria in the soil are always in a dormant state, and if the sulfate reducing bacteria in the soil can be activated, sulfides can be produced at low cost, and the activated sulfate reducing bacteria can be used in the field of heavy metal pollution remediation, so that the method has a broad prospect. At present, research on reducing sulfate bacteria is mainly in the field of petrochemical industry, and as the reducing sulfate bacteria generally exist in oil field operation and propagate in large quantities, serious harm is brought to a reinjection water system of an oil field, and the reducing sulfate bacteria are one of main reasons causing corrosion of oil field pipelines, main research on the reducing sulfate bacteria focuses on how to inhibit or eliminate SRB corrosion; for example, chinese patent 201310047630.X discloses novel biological inhibitors that inhibit the activity of oil well sulfate-reducing bacteria; chinese patent CN200810238979.0 discloses a nutrient for inhibiting sulfate reducing bacteria in oil field water; chinese patent CN201310019812.6 discloses the preparation of SRB biological inhibitor and the method for inhibiting SRB in crude oil. Only one patent CN201611241717.0 discloses a sulfate-reducing bacteria activator, but the environment is oil field and not soil. At present, methods and generating devices suitable for activating sulfate reducing bacteria in different types of soil to produce sulfides are lacking.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art, and provides a solution formula for efficiently producing sulfides by using different soils.
It is another object of the present invention to provide a method for preparing sulfides using the solution formulation.
It is still another object of the present invention to provide an apparatus for preparing sulfide using the above method.
The above object of the present invention is achieved by the following technical solutions:
a solution formula for high-efficient production of sulfide from different soils is prepared from K2HPO4、NH4Cl、Na2SO4Anhydrous CaCl2、MgSO4·7H2O, sodium lactate and ascorbic acid; each liter of the aqueous solution contains K2HPO40.30～0.70g，NH4Cl 0.50～1.10g，Na2SO40.40-0.60 g of anhydrous CaCl20.04～0.06g，MgSO4·7H29.0 to 21.0g of O, 4.0 to 9.0mL of sodium lactate, and 0.05 to 0.13g of ascorbic acid.
In the solution formulation of the invention, K2HPO4Providing phosphorus element required by sulfide generation reaction; NH (NH)4Cl provides nitrogen element required by sulfide generation reaction; na (Na)2SO4Anhydrous CaCl2Na and Ca elements required for the growth of sulfate-reducing bacteria in the sulfide-producing reaction are provided. MgSO (MgSO)4·7H2O provides the required sulfate electron acceptor for the sulfide-producing reaction. Sodium lactate provides the carbon source for the sulfide-producing reaction. Ascorbic acid provides a reducing environment for sulfide production. After the reaction is started, the sulfate reducing bacteria in the soil transfer electrons to sulfate by using a carbon source, so that sulfide is reduced to generate, and the reaction for producing sulfide continuously occurs in the reaction container under the condition of continuously supplying reaction liquid. The solution formula of the invention is suitable for efficiently producing sulfides in different soils, the used soil inoculum has wide applicability, and the sulfides can be produced by local materials.
The reaction solution can be suitable for activating sulfides in different soils to generate active high-efficiency sulfides; preferably, the invention also provides formulas I to VIII aiming at different soil types on the basis of the reaction solution, and when the formulas are specially selected for treatment, the reduction efficiency can be further improved, and the sulfide yield can be improved. The pH value of soil for inoculation in the formulas I to VIII is 6.5 to 7.8, and the soil is divided into high-oxygen state soil (0 to 20cm) contacting with surface atmosphere and low-oxygen state soil below 20cm of the ground surface according to the position of a soil layer in which the soil is located. The soil with the water-soluble organic carbon content higher than or equal to 400mg/L is high water-soluble organic carbon soil, and the soil with the water-soluble organic carbon content lower than the high water-soluble organic carbon soil is low water-soluble organic carbon soil. The water-soluble sulfate content is higher than or equal to 1.0g/L, and the soil is high sulfate soil, and the soil is low sulfate soil below the water-soluble sulfate content.
Preferably, the soil used for inoculation has a pH of 7.2, which is 30cm below the surface of the earth. The content of water-soluble organic carbon in the soil is 400 mg/L. The content of water-soluble sulfate is 1.0 g/L.
Formula I is used for high-oxygen and high-water-solubility organic carbon and high-sulfate soil, and is prepared from K2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.30 to 0.50g, (component B) NH4Cl 0.50-0.70 g, (component C) Na2SO40.40-0.60 g of anhydrous CaCl (component D)20.04-0.06 g, (component E) MgSO4·7H29.0-11.0G of O, 4.0-6.0 mL of sodium lactate (component F), and 0.10-0.14G of ascorbic acid (component G).
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.40g, (component B) NH4Cl 0.60g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H2O10.0G, sodium lactate 5.0mL (component F), and ascorbic acid 0.12G (component G).
Formulation II for high oxygen, low water soluble organic carbon, high sulfate soils, from2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.50 to 0.70g, (component B) NH4Cl 0.90-1.10 g, (component C) Na2SO40.40 to 0.60g, (component D) noneCaCl in water20.04-0.06 g, (component E) MgSO4·7H29.0-11.0G of O, 7.0-9.0 mL of sodium lactate (component F), and 0.11-0.13G of ascorbic acid (component G).
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.60g, (component B) NH4Cl 1.00g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H2O10.0G, sodium lactate 8.0mL (component F), ascorbic acid 0.12G (component G).
Formula III is used for high-oxygen and high-water-solubility organic carbon and low-sulfate soil, and is prepared from K2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.30 to 0.50g, (component B) NH4Cl 0.50-0.70 g, (component C) Na2SO40.40-0.60 g of anhydrous CaCl (component D)20.04-0.06 g, (component E) MgSO4·7H219.0-21.0G of O, 3.0-5.0 mL of sodium lactate (component F), and 0.11-0.13G of ascorbic acid (component G).
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.40g, (component B) NH4Cl 0.60g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H220.0G of O, 4.0mL of sodium lactate (component F), and 0.12G of ascorbic acid (component G).
Formulation IV for high oxygen, low water soluble organic carbon, low sulfate soils, from2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.50 to 0.70g, (component B) NH4Cl 0.90-1.10 g, (component C) Na2SO40.40-0.60 g of anhydrous CaCl (component D)20.04-0.06 g, (component E) MgSO4·7H219.0 to 21.0g of O, 7.0 to 9.0mL of sodium lactate (component F),(component G) ascorbic acid 0.11-0.13G.
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.60g, (component B) NH4Cl 1.00g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H220.0G of O, 8.0mL of sodium lactate (component F), and 0.12G of ascorbic acid (component G).
Formulation V for low-oxygen, highly water-soluble organic carbon, high-sulfate soil, from2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.30 to 0.50g, (component B) NH4Cl 0.50-0.70 g, (component C) Na2SO40.40-0.60 g of anhydrous CaCl (component D)20.04-0.06 g, (component E) MgSO4·7H29.0-11.0G of O, 4.0-6.0 mL of sodium lactate (component F), and 0.05-0.07G of ascorbic acid (component G).
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.40g, (component B) NH4Cl 0.60g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H2O,10.0G, (component F) sodium lactate 5.0mL, and (component G) ascorbic acid 0.06G.
Formulation VI for low oxygen, low water soluble organic carbon, high sulfate soils, from2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.50 to 0.70g, (component B) NH4Cl 0.90-1.10 g, (component C) Na2SO40.40-0.60 g of anhydrous CaCl (component D)20.04-0.06 g, (component E) MgSO4·7H29.0-11.0G of O, 7.0-9.0 mL of sodium lactate (component F), and 0.05-0.07G of ascorbic acid (component G).
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.60g, (component B) NH4Cl 1.00g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H2O10.0G, sodium lactate 8.0mL (component F), and ascorbic acid 0.06G (component G).
Formulation VII for low oxygen, high water soluble organic carbon, low sulfate soil, from2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.30 to 0.50g, (component B) NH4Cl 0.50-0.70 g, (component C) Na2SO40.40-0.60 g of anhydrous CaCl (component D)20.04-0.06 g, (component E) MgSO4·7H219.0-21.0G of O, 3.0-5.0 mL of sodium lactate (component F), and 0.05-0.07G of ascorbic acid (component G).
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.40g, (component B) NH4Cl 0.60g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H220.0G of O, 4.0mL of sodium lactate (component F), and 0.06G of ascorbic acid (component G).
Formulation VIII for low-oxygen, low-water-soluble organic carbon, low-sulfate soil, from K2HPO4，NH4Cl，Na2SO4Anhydrous CaCl2，MgSO4·7H2O, sodium lactate and ascorbic acid. Each liter of aqueous solution comprises (component A) K2HPO40.50 to 0.70g, (component B) NH4Cl 0.90-1.10 g, (component C) Na2SO40.40-0.60 g of anhydrous CaCl (component D)20.04-0.06 g, (component E) MgSO4·7H219.0-21.0G of O, 7.0-9.0 mL of sodium lactate (component F), and 0.05-0.07G of ascorbic acid (component G).
Preferably, each liter of aqueous solution comprises (component A) K2HPO40.60g, (component B) NH4Cl 1.00g, (component C) Na2SO40.50g of anhydrous CaCl (component D)20.05g, (component E) MgSO4·7H220.0G of O, 8.0mL of sodium lactate (component F), and 0.06G of ascorbic acid (component G).
In the present invention, (component A) K2HPO4(component B) NH4Cl, (component C) Na2SO4(component D) anhydrous CaCl2(component E) MgSO4·7H2O, (component F) sodium lactate, and (component G) ascorbic acid are used in analytical or chemical purity. The sodium lactate (component F) is liquid, the other various medicament components are solid powder, the dosage and the proportion are different according to the application range of 8 types of formulas, and the content of each component needs to be added according to the concentration range of the formula. The reaction solution can efficiently generate sulfides aiming at different soils, is used for treating heavy metal polluted water bodies or soils, and has a wide application prospect.
A method for preparing sulfide by using the solution formula comprises the steps of uniformly mixing the sterilized solution formula with soil, placing the mixture in a reaction device, deoxidizing, and sealing to react to produce sulfide.
Preferably, the soil content is 10.0-20.0 g (preferably 20g), and the water content is 20-50% (preferably 50%); the volume of the solution formula is 10-20L, and the reaction lasts for more than 120 h.
The sulfide generating device for the preparation of the sulfide by the method comprises a storage container, a reaction container, a receiving container and a controller, wherein the storage container is used for storing the reaction solution reacted with the soil, the reaction container is used for reacting the soil with the reaction solution, and the receiving container is used for receiving the sulfide solution generated by the reaction; a liquid inlet and a liquid outlet are respectively arranged on the reaction container; the storage container is connected with a liquid inlet of the reaction container through a liquid inlet pipe, and a liquid inlet pump is arranged on the liquid inlet pipe; the liquid outlet of the reaction container is connected with the receiving container through a liquid outlet pipe, and a liquid outlet pump is arranged on the liquid outlet pipe; the reactor can be sealed and opened, and the top of the reactor is provided with a small protruded hole capable of ventilating; the controller comprises a box body, a relay and an expandable and contractible structure positioned in the box body, the box body is fixed at the top of the reactor, and the expandable and contractible structure is hermetically connected with a small protruding hole on the reaction container; the box body is provided with a T-shaped rod which can move relative to the box body, the upper part of the T-shaped rod is arranged outside the box body, the bottom of the T-shaped rod penetrates through the box body to be contacted with the expandable and contractible structure in the box body, and two ends of the upper part of the T-shaped rod are respectively fixed with a conducting strip; the relay is provided with 2 switches which respectively control the liquid inlet pump and the liquid outlet pump, each switch extends out of 1 set of positive and negative wire connectors, and the conducting strips at the two ends of the T-shaped rod respectively correspond to 1 set of positive and negative wire connectors.
The preparation container in the sulfide generating device is used for storing a reaction solution reacted with soil, the reaction container is used for reacting the soil with the reaction solution, and the receiving container is used for receiving the sulfide solution generated by the reaction; when sulfide is prepared, soil and reaction liquid are added into a reaction container for reaction, a certain amount of reaction liquid is stored in a storage container, along with the progress of the reaction, when the air pressure in a U-shaped reaction container rises, the volume of an expandable and contractible structure can be increased, a T-shaped rod is pushed to move upwards, conductive sheets at two ends of the top of the T-shaped rod can respectively contact two sets of positive and negative electric wires, a relay is switched on, a liquid inlet pump is started to supply sulfide reaction solution, a liquid outlet pump is started to discharge sulfide liquid, after the gas and the sulfide reaction liquid in the reactor are discharged to a certain volume, the pressure in the reactor is reduced, the volume of the expandable and contractible structure is decreased, the T-shaped rod is reset, the relay is switched off, the liquid inlet pump and the liquid outlet pump stop working, the sulfide production reaction is continued, and automatic liquid.
Preferably, the reaction vessel is a U-shaped reaction vessel, and a liquid inlet and a liquid outlet are respectively arranged on two short arms of the U-shaped reaction vessel. The U-shaped reaction container can ensure that liquid entering from the liquid inlet can not be discharged from the liquid outlet under a certain flow velocity state, and the reaction liquid can be discharged after reacting with a substrate in the intermediate container through the intermediate container.
Preferably, the top of the short arm of the U-shaped reactor provided with the liquid inlet is sealed and provided with a small protruded hole capable of ventilating, and the box body is fixedly arranged above the small protruded hole and used for exhausting gas in the reactor; the top of the short arm provided with the liquid outlet can be sealed and opened and closed, and is used for adding reaction raw materials (soil) into the reactor.
Preferably, the two short arms of the U-shaped reaction vessel are the same in height, and the relay is fixed on the plane at the top end of the short arm provided with the liquid inlet and is opposite to the box body.
Preferably, a monitoring mechanism for monitoring the change of the concentration of the sulfide is arranged in the reaction vessel. Specifically, monitoring mechanism is the monitoring strip, and the monitoring strip is pasted and can be sealed the short arm top cap inboard that opens and shuts. The monitoring strip is lead acetate test paper, a black spot appears on the monitoring strip to indicate that the sulfide begins to generate, and most or all of the monitoring strip turns black to indicate that the sulfide concentration is higher.
Preferably, the inflatable and deflatable structure is a balloon.
Preferably, the liquid inlet pipe and the liquid outlet pipe are silicone tubes.
As a preferred implementation mode, the storage container is cylindrical or square, consists of a bottle body and a gauze top cover, has the volume of 4-10L, is provided with the gauze top cover at the top end, prevents foreign matter pollution, and is made of PVC or glass or organic glass.
Preferably, the storage container is square, has a volume of 4L and is made of glass.
As a preferable mode, the U-shaped reaction vessel is composed of a left short arm, a right short arm, a liquid inlet and a middle vessel; the bottom of the U-shaped container is 40-60 cm in length and 8-12 cm in width, the outer side heights of the two short arms are 25-35 cm, the inner side heights of the two short arms are 15-25 cm, and the width of the two short arms is 8-12 cm; the top of the left short arm is sealed, and the top of the right short arm can be opened.
Preferably, the bottom of the U-shaped container has a length of 50cm and a width of 10cm, and the two short arms have an outer height of 30cm, an inner height of 20cm and a width of 10 cm.
As a preferable implementation mode, the liquid inlet has a diameter of 0.40-0.60 cm, is positioned outside the left short arm of the U-shaped container, is 4-6 cm away from the upper end of the left short arm and is 4-6 cm away from the outer side of the left short arm 3, and the length of the liquid inlet 5 extending out of the left short arm is 1-3 cm. The liquid inlet 5 is connected with one end of a constant-current liquid inlet pump through a silicone tube, the outer diameter of the silicone tube is 0.40-0.60 cm, the liquid flow rate is 1.0-5.0 ml/min, the other end of the constant-current liquid inlet pump is connected with the bottle body 1 of the storage container through the silicone tube, and the opening of the silicone tube 8 is positioned below the liquid level.
Preferably, the diameter of the liquid inlet is 0.50cm, the distance from the liquid inlet to the upper end of the short arm is 5cm, the distance from the liquid inlet to the outer side of the short arm is 5cm, and the length of the liquid inlet extending out of the short arm is 2 cm. The outer diameter of the silicone tube was 0.5cm, and the liquid flow rate was 2.0 ml/min.
As a preferable implementation mode, the diameter of the liquid outlet is 0.40-0.60 cm, the liquid outlet is positioned outside the right short arm of the U-shaped container and is 4-6 cm away from the upper end of the short arm, and the length of the liquid outlet extending out of the short arm is 1-3 cm. The liquid outlet is connected with one end of the constant-current liquid outlet pump through a silicone tube, the outer diameter of the silicone tube is 0.40-0.60 cm, the flow rate of liquid is 1.0-5.0 ml/min, the other end of the constant-current liquid outlet pump is connected to a receiving container through the silicone tube, the size and the shape of the receiving container are unlimited, and the receiving container is used for receiving sulfide liquid produced in the reaction process for further use.
Preferably, the diameter of the liquid outlet is 0.50cm, the distance from the upper end of the short arm is 5cm, and the length of the liquid outlet extending out of the short arm is 2 cm. The outer diameter of the silicone tube was 0.5cm, and the liquid flow rate was 2.0 ml/min.
As a preferable implementation mode, the control device consists of a square box, a small protruding hole, a balloon, a rubber ring, a small bottom hole, a top cover, a movable clamp, a small top cover hole, a T-shaped plastic rod, a plastic sheet, a thin iron sheet, a relay and an electric wire. The control device is fixed on the top of the left short arm.
As a preferable implementation mode, the length of the shell of the square box ranges from 4cm to 6cm, the width ranges from 4cm to 6cm, the height ranges from 4cm to 6cm, and the square box is located at one corner of the plane above the left short arm. A small hole with the diameter of 0.8-1.2 cm is formed above the left short arm, the outer wall of the small hole protrudes out of the upper portion of the short arm by 0.8-1.2 cm, the small hole is located at one corner of the plane above the short arm, and the distance between the small hole and the two sides of the outer edge of the short arm is 2-3 cm. The small hole is sealed by a balloon, the diameter of the air inlet of the balloon is 0.8-1.2 cm, the air inlet of the balloon is sleeved on the protruding part of the small hole, and then the small hole is sealed by a rubber ring with the diameter of 0.8-1.2 cm.
Preferably, the housing of the square box is 5cm in length, 5cm in width and 5cm in height, a small hole with the diameter of 1cm is formed above the left short arm, the outer wall of the small hole protrudes 1cm above the short arm, and the distance between the outer wall of the small hole and the two sides of the outer edge of the short arm is 2.5 cm. The diameter of the balloon air inlet is 1cm, and the small hole is sealed by a rubber ring with the diameter of 1 cm.
As a preferred implementation mode, the balloon is placed in a square box, the shell of the square box is made of transparent organic glass, a small hole is formed in the center of the bottom of the shell, the diameter of the small hole is 0.9-1.3 cm, and the small hole is directly buckled on the outer wall of the small protruding hole of the left short arm. The top cover of the square box shell can be opened, the outside of the square box shell is fixed by a movable clamp, a small hole is formed in the center of the top cover, the diameter of the small hole is 0.3-0.5 cm, a T-shaped plastic rod is inserted into the small hole, the diameter of the T-shaped plastic rod is 0.2-0.4 cm, the bottom end of the T-shaped plastic rod is a small plastic wafer, the diameter of the small plastic wafer is 0.4-0.6 cm, the top end of the T-shaped plastic rod passes through the small hole of the top cover. The rectangular plastic sheet has a width of 0.8-1.2 cm, a length of 4-6 cm and a thickness of 0.1 cm. Two ends of the plastic sheet are respectively fixed with a thin iron sheet, the width of the iron sheet is 0.8-1.2 cm, the length of the iron sheet is 1.8-2.2 cm, and the thickness of the iron sheet is 0.1 cm. One part of the T-shaped plastic rod is arranged in the square box shell, and the other part of the T-shaped plastic rod is arranged outside the square box shell.
Preferably, the bottom of the shell is provided with a small hole with the diameter of 1.1 cm. The center of the top cover of the square box is provided with a small hole, the diameter of the small hole is 0.4cm, the diameter of the T-shaped plastic rod is 0.3cm, the bottom end of the square box is provided with a small plastic wafer, the diameter of the small plastic wafer is 0.5cm, the width of the rectangular plastic sheet is 1cm, the length of the rectangular plastic sheet is 5cm, and the thickness of the rectangular plastic sheet is 0.1. Two ends of the plastic sheet are respectively fixed with a thin iron sheet, the width of the iron sheet is 1cm, the length of the iron sheet is 2cm, and the thickness of the iron sheet is 0.1 cm.
As a preferred implementation mode, the electromagnetic relay is fixed on the top plane of the left short arm, opposite to the square box, the electromagnetic relay is provided with 2 switches, each switch extends out of 1 set of positive and negative wire connectors, the thin iron sheet at one end of the plastic sheet corresponds to the positive and negative electrodes of 1 set of wires respectively, and the wires are connected with the electromagnetic relay to control the liquid inlet pump and the liquid outlet pump. When sulfide is produced in the reaction process, the air pressure in the U-shaped container rises, the balloon expands to push the T-shaped plastic rod, the top end of the plastic rod rises, the thin iron sheets at the two ends respectively contact two sets of positive and negative electric wires, the electromagnetic relay is switched on, the liquid inlet pump is started to supply a reaction substrate for producing sulfide, and the liquid outlet pump is started to discharge sulfide liquid.
As a preferred practical mode, the top of the right short arm of the U-shaped reaction vessel is provided with a top cover with a sealing strip and a movable clamp which can be opened and closed. The monitoring strip is pasted on the inner side of the top cover of the short arm. The monitoring strip is lead acetate test paper, a black spot appears on the monitoring strip to indicate that the sulfide begins to generate, and most or all of the monitoring strip turns black to indicate that the sulfide concentration is higher.
The invention also claims a method for preparing sulfide by using any one of the devices, which comprises the steps of placing soil into a reaction container, adding the prepared solution into the reaction container, deoxidizing the reaction container, sealing the reaction container, injecting the reaction solution into a storage container, reacting to produce sulfide, and controlling the flow rate of liquid sample introduction and sample discharge to be 1.0-5.0 ml/min.
Preferably, the water content of the soil is 20-50%.
As a preferable possible embodiment, the method for producing a sulfide according to the present invention using the above reaction apparatus comprises the steps of:
(1) according to the condition of soil inoculum, selecting corresponding formula.
(2) Taking 10.0-20.0 g of soil with the water content of 20-50%, opening the top cover of the right short arm 4, and uniformly placing the soil at the bottom of the U-shaped reaction container.
Preferably, 20.0g of soil with 50% water content is taken.
(3) Preparing 2.0-6.0L of solution according to a formula, sterilizing for 20min at 121 ℃, and then introducing N2Aerating for 20-30 min, injecting the obtained solution into the reaction container through the opening of the right short arm of the U-shaped reactor, adhering the monitoring strip on the inner side of the top cover, closing the top cover, fastening the movable clamp and sealing. Filling N into the reaction vessel through the liquid inlet2Keeping for 10-20 min. Then seal the liquid inlet, the liquid inlet and the small protruding holes of the left short arm by a rubber tube and a clamp, stand for more than 120h, regularly observe the monitoring strip, and indicate the reaction to start when the monitoring strip is black.
Preferably, 6.0L of solution is prepared according to the formula, sterilized at 121 ℃ for 20min, and then N is introduced2Aerating for 30min, injecting the obtained solution into the reaction container through the opening of the right short arm, closing the top cover, and tightening the movable clamp and sealing. Filling N into the reaction vessel through the liquid inlet2Keeping for 20 min. Then the liquid inlet, the liquid inlet and the small protruding holes of the short arms are sealed by a rubber tube and a clamp,standing for 120 h.
(4) And opening the top cover of the right short arm, adding 4.0-8.0L of the sterilized and aerated formula solution into the reaction container, ensuring that the water level does not exceed the liquid inlet and the liquid inlet, and replacing a new monitoring strip. Preferably, 4.0L of the sterilized and aerated formulation solution is added to the reaction vessel.
(5) The small protruding hole of the left short arm is opened, the balloon air inlet is fixed to the small protruding hole, the square box is buckled above the left short arm, the small hole in the bottom of the square box is aligned to the small protruding hole of the short arm, and then the square box is sealed through the rubber ring. And inserting the lower end of the T-shaped plastic rod into the small hole of the square box top cover, and closing the square box top cover to ensure that the T-shaped plastic rod is perpendicular to the upper part of the balloon.
(6) The electromagnetic relay is fixed on the top of the left short arm, and 2 sets of extended positive and negative electrodes are respectively aligned to two ends of the T-shaped plastic rod. The other end of the electromagnetic relay is respectively connected with the liquid inlet pump and the liquid outlet pump.
(7) And (3) connecting a liquid inlet with a silicone tube, extending the other end of the silicone tube to pass through a liquid inlet pump, then placing the silicone tube into a storage container, adding 4-10L of solution prepared according to the corresponding formula into the storage container, wherein an inlet of the silicone tube is positioned below the liquid level of the storage solution, and controlling the flow rate of the liquid to be 1.0-5.0 ml/min. And (5) manually starting the liquid inlet pump, and checking whether the equipment is normal.
Preferably, 5L of the solution prepared according to the formula is added into the storage container, and the flow rate of the liquid is controlled to be 2.0 ml/min.
(8) And (3) connecting a silicone tube with the liquid inlet, enabling the other end of the silicone tube to pass through the liquid outlet pump, then placing the silicone tube into a receiving container, injecting water into the receiving container to submerge the outlet of the silicone tube, and controlling the flow rate of the liquid to be 1.0-5.0 ml/min. And (5) manually starting the liquid outlet pump to check whether the equipment is normal.
Preferably, the liquid flow rate is controlled to be 2.0 ml/min.
(9) Standing for more than 120h, periodically observing the monitoring strip, and simultaneously collecting the sulfide liquid in the receiving container.
Preferably, the observation is carried out after standing for 120 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a solution formula for efficiently producing sulfide by using different soils, which can activate the sulfide production activity of sulfate reducing bacteria in the soil, is suitable for efficiently producing sulfide by using different soils, has wide applicability of soil inoculants used for activating the sulfide activity, can produce sulfide by using local materials, has low cost and has larger application prospect. Meanwhile, the invention is matched with a continuous reaction device with automatic water inlet and automatic water outlet, and the generation of sulfides is efficiently realized. The high-concentration sulfide liquid obtained by the method can be diluted or directly used for treating heavy metal polluted water or soil, and the operation is simple and convenient.
Drawings
FIG. 1 is a schematic view of an automatic sulfide generator according to the present invention.
FIG. 2 is a detailed view of the gas control assembly of the auto-sulphiding apparatus of the present invention.
FIG. 3 is a graph showing the relationship between the initial solution volume of the auto-sulphiding apparatus of the present invention and the sulphide generation time and the apparatus start-up time.
FIG. 4 shows the sulfide production and sulfate reduction of a high oxygen, high organic carbon, high sulfate soil initiation reaction.
FIG. 5 shows the sulfide production and sulfate reduction of the start-up reaction for high oxygen, low organic carbon, high sulfate soils.
FIG. 6 shows the sulfide production and sulfate reduction of high oxygen, high organic carbon, low sulfate soil initiation reactions.
FIG. 7 shows the sulfide production and sulfate reduction of the high oxygen, low organic carbon, low sulfate soil start-up reaction.
FIG. 8 shows the sulfide production and sulfate reduction events for the low oxygen, high organic carbon, high sulfate soil initiation reactions.
FIG. 9 shows the sulfide production and sulfate reduction events for the low oxygen, low organic carbon, high sulfate soil initiation reaction.
FIG. 10 shows the sulfide production and sulfate reduction of the low oxygen, high organic carbon, low sulfate soil initiation reaction.
FIG. 11 shows the sulfide production and sulfate reduction of the low oxygen, low organic carbon, low sulfate soil initiation reaction.
FIG. 12 is a comparison of sulfide concentration and sulfate reduction efficiency of the inventive formulation versus the conventional formulation.
Drawing notes: 1-bottle body, 2-gauze top cover, 3-left short arm, 4-right short arm, 5-liquid inlet, 6-liquid outlet, 7-middle container, 8-liquid inlet silicone tube, 9-constant-current liquid inlet pump, 10-liquid outlet silicone tube, 11-constant-current liquid outlet pump, 12-receiving container, 13-control device, 14-square box, 15-bulge small hole, 16-balloon, 17-rubber ring, 18-bottom small hole, 19-top cover, 20-movable clamp, 21-top cover small hole, 22-T-shaped plastic rod, 23-plastic sheet, 24-thin iron sheet, 25-electromagnetic relay, 26-wire, 27-top cover, 28-clamp and 29-monitoring strip.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The agents in the following examples are represented by K2HPO4、NH4Cl、Na2SO4Anhydrous CaCl2、MgSO4·7H2O, sodium lactate and ascorbic acid, and the medicament is produced by Guangzhou chemical reagent factories. The present invention is also applicable to other conventional brands, and is only for convenience of description and not for limiting the scope of the invention.
Example 1
As shown in fig. 1 and 2: a sulfide generating device comprises a storage container, a liquid inlet pump, a reaction container, a control device, a monitoring strip, a liquid outlet pump and a receiving container.
The storage container is cylindrical, comprises bottle 1 and gauze top cap 2, and the volume is 5L, and the top is furnished with the gauze top cap, prevents the foreign matter pollution, and the material is glass.
The reaction vessel is U-shaped and comprises a left short arm 3, a right short arm 4, a liquid inlet 5 and a liquid outlet 6. The bottom of the U-shaped container is 50cm in length and 10cm in width, the outer side of the two short arms is 30cm in height, the inner side of the two short arms is 20cm in height, and the width of the two short arms is 10 cm. The top of the left short arm 3 is sealed, and the top of the right short arm 4 can be opened.
The liquid inlet 5 is 0.50cm in diameter, is positioned on the outer side of the left short arm 3 of the U-shaped container and is 5cm away from the upper end of the left short arm 3, and the length of the liquid inlet 5 extending out of the left short arm 3 is 2 cm. The liquid inlet 5 is connected with one end of a constant-current liquid inlet pump 9 through a silicone tube 8, the outer diameter of the silicone tube is 0.50cm, the liquid flow rate is 2.0ml/min, the other end of the constant-current liquid inlet pump 9 is connected with the bottle body 1 of the storage container through the silicone tube 8, and the opening of the silicone tube 8 is positioned below the liquid level.
The diameter of the liquid outlet 6 is 0.50cm, the liquid outlet is positioned outside the right short arm 4 of the U-shaped container and is 5cm away from the upper end of the right short arm 4, and the length of the liquid outlet 6 extending out of the right short arm 4 is 2 cm. The liquid outlet 6 is connected with one end of a constant-current liquid outlet pump 11 through a silicone tube 10, the outer diameter of the silicone tube is 0.50cm, the liquid flow rate is 2.0ml/min, the other end of the constant-current liquid outlet pump 11 is connected to a receiving container 12 through the silicone tube 10, the size and the shape of the receiving container are unlimited, and the receiving container is used for receiving sulfide liquid produced in the reaction process for further use.
The control device 13 is composed of a square box 14, a small bulge hole 15, a balloon 16, a rubber ring 17, a small bottom hole 18, a top cover 19, a movable clamp 20, a small top cover hole 21, a T-shaped plastic rod 22, a plastic sheet 23, a thin iron sheet 24, a relay 25 and an electric wire 26. The control device 13 is fixed on the top of the left short arm 3.
The housing of the square box 14 is 5cm in length, 5cm in width and 5cm in height, and is located at one corner of the plane above the left short arm 3. A small hole 15 with the diameter of 1cm is arranged above the left short arm 3, the outer wall of the small hole 15 protrudes out of the upper part of the left short arm 3 by 1.0cm, the small hole 15 is positioned at one corner of the plane above the left short arm 3, and the distance between the small hole 15 and the two sides of the outer edge of the left short arm 3 is 2.5 cm. The small hole 15 is sealed by a balloon 16, the diameter of an air inlet of the balloon 16 is 1.0cm, the air inlet of the balloon 16 is sleeved on the protruding part of the small hole 15, and then a rubber ring 17 with the diameter of 1.0cm is used for sealing the small hole 15.
The balloon 16 is arranged in the square box 14, the shell of the square box 14 is made of transparent organic glass, a small hole 18 with the diameter of 1.1cm is formed in the center of the bottom of the shell, and the small hole is directly buckled on the outer wall of the small protruding hole 15 of the left short arm 3. The top cover 19 of the square box shell can be opened, the outside of the square box shell is fixed by a movable clamp 20, a small hole 21 is formed in the center of the top cover, the diameter of the small hole is 0.4cm, a T-shaped plastic rod 22 is inserted into the small hole, the diameter of the T-shaped plastic rod is 0.3cm, a small plastic wafer is arranged at the bottom end of the T-shaped plastic rod, the diameter of the small plastic wafer is 0.5cm, the top end of the T-shaped plastic rod passes through the small hole 21 of the top. The rectangular plastic sheet has a width of 1.0cm, a length of 5cm and a thickness of 0.1 cm. Two ends of the plastic sheet are respectively fixed with a thin iron sheet 24, the width of the iron sheet is 1.0cm, the length of the iron sheet is 2.0cm, and the thickness of the iron sheet is 0.1 cm. One portion of the T-shaped plastic bar 22 is inside the square box housing and the other portion is outside the square box housing.
Electromagnetic relay 25 is fixed in 3 top planes of left forearm, and is relative with square box 14, and electromagnetic relay 25 possesses 2 switches, and every switch extends 1 set positive negative wire connector, and the thin iron sheet 24 of plastic sheet one end corresponds 1 set of positive negative pole of electric wire 26 respectively, and electromagnetic relay 25, control feed liquor pump 9 and play liquid pump 11 are connected to electric wire 26. When sulfide is produced in the reaction process, the air pressure in the U-shaped container rises, the balloon 16 expands to push the T-shaped plastic rod 22, the top end of the plastic rod 22 rises, the thin iron sheets 24 at the two ends respectively contact two sets of positive and negative electric wires 26, the electromagnetic relay 25 is switched on, the liquid inlet pump 9 is started to supply sulfide reaction substrates, and the liquid outlet pump 11 is started to discharge sulfide liquid.
The top of the right short arm 4 is provided with a top cover 27 with a sealing strip and a movable clamp 28 which can be opened and closed. The monitoring strip 29 is affixed to the inside of the top cover of the right short arm 4. The monitoring strip is lead acetate test paper, a black spot appears on the monitoring strip to indicate that the sulfide begins to generate, and most or all of the monitoring strip turns black to indicate that the sulfide concentration is higher.
When the method is used, soil is placed in a reaction container, then a reaction solution capable of activating sulfate reducing bacteria in the soil to produce sulfide is added into the reaction container, the reaction container is sealed, nitrogen is introduced for keeping for 10-20 min, and meanwhile the reaction solution is injected into a storage container to react to produce sulfide.
After the device is adopted, the correlation exists between the blackening time of the monitoring test paper and the volume of the initial solution, and the blackening time of the monitoring test paper is shortened along with the increase of the volume of the initial solution. Meanwhile, the time for starting the constant flow pump to automatically feed liquid and discharge liquid and the initial volume of the constant flow pump are related, the initial solution volume is increased, the gas production is faster, the starting time of the control device is relatively shortened (figure 3), and the starting time caused by the volumes is obviously different.
Example 2
Collecting soil with surface layer of 5cm, wherein the soil has physical and chemical properties of pH 6.9, water-soluble organic carbon content of 400mg/L and water-soluble sulfate content of 1.0g/L, and the soil is high-oxygen, high-organic-carbon and high-sulfate soil, and selecting formula I as soil inoculum.
Formulation I comprises per liter of aqueous solution (component A) K2HPO40.50g, (component B) NH4Cl 0.70g, (component C) Na2SO40.40g of (component D) anhydrous CaCl20.06g, (component E) MgSO4·7H2O9.0G, sodium lactate 6.0mL (component F), and ascorbic acid 0.14G (component G).
Obtaining a sulfide liquid according to the following steps:
(1) taking 18g of soil, opening the top cover of the right short arm 4, and uniformly placing the obtained inoculated soil in a U-shaped reaction container.
(2) Preparing the prepared formula I into 5.0L solution, sterilizing at 121 ℃ for 20min, and introducing N2Aerating for 20min, directly injecting the formula solution into the U-shaped reaction vessel, adhering the monitoring strip 29 on the top cover 27, closing the top cover, tightening the movable clamp and sealing. Introducing N into the reaction vessel through a liquid inlet 52Keeping for 10 min. And then sealing the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3 by using a rubber tube and a clamp, standing for more than 120h, regularly observing the monitoring strip 29, opening the top cover of the right short arm 4 after the monitoring strip is black, adding 4.0L of sterilized and aerated formula solution into the reaction vessel, and replacing a new monitoring strip.
(3) The small protruding hole 15 of the left short arm 3 is opened, the air inlet of the balloon 16 is fixed on the small hole 15, then the square box 14 is buckled above the left short arm 3, the small hole at the bottom of the square box is aligned with the small protruding hole 15 of the left short arm 3, and then the square box is sealed by the rubber ring 17. The lower end of the T-shaped plastic rod 22 is inserted into the square box top cover small hole 21, and the square box top cover 19 is closed, so that the T-shaped plastic rod 22 is vertical to the upper part of the balloon 16.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 extended sets of positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod 22. The other end of the electromagnetic relay is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) A silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube 8 extends through a liquid inlet pump 9 and then is placed in a storage container, 5.0L of solution prepared according to the corresponding formula is added into the storage container, the inlet of the silicone tube 8 is positioned below the liquid level of the storage solution, and the flow rate of the liquid is controlled to be 1.0 ml/min.
(6) A silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube passes through a liquid outlet pump 11 and then is placed in a receiving container, water is injected into the receiving container and overflows the outlet of the silicone tube 10, and the flow rate of the liquid is controlled to be 1.0 ml/min.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time to reach 16mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 95 percent (figure 4).
Example 3
Collecting soil with the surface layer of 10cm, wherein the soil physical and chemical properties are pH 6.7, water-soluble organic carbon is 334mg/L, the content of water-soluble sulfate is 1.50g/L, the soil is high-oxygen, low-organic carbon and high-sulfate soil, and selecting a formula II as a soil inoculum.
Formulation II comprises (component A) K per liter of aqueous solution2HPO40.70g, (component B) NH4Cl 1.10g, (component C) Na2SO40.60g of anhydrous CaCl (component D)20.06g, (component E) MgSO4·7H2O11.0G, sodium lactate 9.0mL (component F), and ascorbic acid 0.13G (component G).
Obtaining a sulfide liquid according to the following steps:
(1) taking 15g of soil, opening the top cover of the right short arm 4, and uniformly placing the obtained inoculated soil in a U-shaped reaction container.
(2) Preparing the prepared formula II into 4.0L solution, sterilizing at 121 ℃ for 20min, and introducing N2The resulting solution was directly injected into the reaction vessel with aeration for 25min, the monitoring strip 29 was attached to the top cover 27, the top cover 27 was closed, and the movable clamp 28 was tightened and sealed. N is injected into the reaction vessel through a liquid inlet 52Keeping for 15 min. Then, sealing the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3 by using a rubber tube and a clamp, standing for more than 120h, regularly observing the monitoring strip 29, opening the top cover 27 of the right short arm 4 after the monitoring strip is black, adding 5.0L of sterilized and aerated formula solution into the reaction vessel, and replacing a new monitoring strip.
(3) The small protruded hole 15 of the left short arm 3 is opened, the air inlet 16 of the balloon is fixed on the small hole 15, then the square box 14 is buckled above the left short arm 3, the small hole 18 at the bottom of the square box is aligned with the small protruded hole of the left short arm 3, and then the square box is sealed by a rubber ring 17. The lower end of the T-shaped plastic rod 22 is inserted into the small hole 21 of the square box top cover, and the square box top cover 19 is closed, so that the T-shaped plastic rod 22 is vertical to the upper part of the balloon.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 extended sets of positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod 22. The other end of the electromagnetic relay is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) A silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube 8 extends through a liquid inlet pump 9 and then is placed in a storage container, 8.0L of solution prepared according to the corresponding formula is added into the storage container, the inlet of the silicone tube 8 is positioned below the liquid level of the storage solution, and the flow rate of the liquid is controlled to be 2.0 ml/min.
(6) A silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube 10 passes through a liquid outlet pump 11 and then is placed in a receiving container, water is injected into the receiving container to submerge the outlet of the silicone tube 10, and the flow rate of the liquid is controlled to be 2.0 ml/min.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time to reach 18mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 95 percent (figure 5).
Example 4
Collecting soil with the surface layer of 15cm, wherein the soil physical and chemical properties are pH 7.5, the water-soluble organic carbon content is 640mg/L, the water-soluble sulfate content is 0.87g/L, the soil is high-oxygen high-organic carbon and low-sulfate soil, and selecting a formula III as a soil inoculum.
Formulation III comprises (component A) K per liter of aqueous solution2HPO40.50g, (component B) NH4Cl 0.70g, (component C) Na2SO40.60g of anhydrous CaCl (component D)20.06g, (component E) MgSO4·7H2O21.0G, sodium lactate 5.0mL (component F), and ascorbic acid 0.13G (component G).
Obtaining a sulfide liquid according to the following steps:
(1) 20g of soil is taken, the top cover 27 of the right short arm 4 is opened, and the obtained inoculated soil is uniformly placed in a U-shaped reaction container.
(2) Preparing the prepared formula III into 5.0L solution, sterilizing at 121 ℃ for 20min, and introducing N2The resulting solution was directly injected into the reaction vessel with aeration for 25min, the monitoring strip 29 was attached to the top cover 27, the top cover 27 was closed, and the movable clamp 28 was tightened and sealed. N is injected into the reaction vessel through a liquid inlet 52Keeping for 15 min. Then, sealing the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3 by using a rubber tube and a clamp, standing for more than 120h, regularly observing the monitoring strip 29, opening the top cover 27 of the right short arm 4 after the monitoring strip is black, adding 3.0L of sterilized and aerated formula solution into the reaction vessel, and replacing a new monitoring strip.
(3) The small protruding hole 15 of the left short arm 3 is opened, the air inlet of the balloon 16 is fixed on the small hole 15, then the square box 14 is buckled above the left short arm 3, the small hole 18 at the bottom of the square box is aligned with the small protruding hole of the left short arm 3, and then the square box is sealed by the rubber ring 17. The lower end of the T-shaped plastic rod 22 is inserted into the square box top cover small hole 21, and the square box top cover 19 is closed, so that the T-shaped plastic rod 22 is vertical to the upper part of the balloon 16.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 sets of extended positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod. The other end of the electromagnetic relay 25 is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) The silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube 8 extends through the liquid inlet pump and then is placed in a storage container, 6.0L of solution prepared according to the corresponding formula is added into the storage container, the inlet of the silicone tube 8 is positioned below the liquid level of the storage solution, and the flow rate of the liquid is controlled to be 5.0 ml/min.
(6) A silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube passes through a liquid outlet pump 11 and then is placed in a receiving container, water is injected into the receiving container and overflows the outlet of the silicone tube 10, and the flow rate of the liquid is controlled to be 5.0 ml/min.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time to reach 24mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 98 percent (figure 6).
Example 5
Collecting soil with surface layer of 20cm, wherein the soil has physical and chemical properties of pH 6.6, water-soluble organic carbon content of 300mg/L and water-soluble sulfate content of 0.62g/L, and the soil is high-oxygen, low-organic carbon and low-sulfate soil, and selecting formula IV as soil inoculum.
Formulation IV comprises (component A) K per liter of aqueous solution2HPO40.50g, (component B) NH4Cl 0.90g, (component C) Na2SO40.40g of (component D) anhydrous CaCl20.04g, (component E) MgSO4·7H219.0G of O, 7.0mL of sodium lactate (component F), and 0.11G of ascorbic acid (component G).
Obtaining a sulfide liquid according to the following steps:
(1) the soil 18g is taken, the top cover 27 of the right short arm 4 is opened, and the obtained inoculated soil is uniformly placed in a U-shaped reaction container.
(2) Preparing the prepared formula IV into 4.0L solution, sterilizing at 121 ℃ for 20min, and introducing N2The resulting solution was directly injected into the reaction vessel by aeration for 30min, the monitoring strip 29 was adhered to the top cover 27, the top cover 27 was closed, and the movable clamp 28 was tightened and sealed. N is injected into the reaction vessel through a liquid inlet 52Keeping for 15 min. Then using a rubber tube andthe clamp seals the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3, stands for 120h, regularly observes the monitoring strip 29, opens the top cover 27 of the right short arm 4 after the monitoring strip is black, adds 3.0L of sterilized and aerated formula solution into the reaction vessel, and replaces the new monitoring strip 29.
(3) The small protruding hole 15 of the left short arm 3 is opened, the air inlet of the balloon 16 is fixed on the small hole 15, then the square box 14 is buckled above the left short arm 3, the small hole 18 at the bottom of the square box is aligned with the small protruding hole 15 of the left short arm 3, and then the square box is sealed by the rubber ring 17. The lower end of the T-shaped plastic rod 22 is inserted into the square box top cover small hole 21, and the square box top cover 19 is closed, so that the T-shaped plastic rod 22 is vertical to the upper part of the balloon 16.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 extended sets of positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod 22. The other end of the electromagnetic relay 25 is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) A silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube extends through a liquid inlet pump and then is placed in a storage container, 10L of solution prepared according to the corresponding formula is added into the storage container, the inlet of the silicone tube 8 is positioned below the liquid level of the storage solution, and the flow rate of the liquid is controlled to be 2.0 ml/min.
(6) A silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube passes through a liquid outlet pump and then is placed in a receiving container, water is injected into the receiving container to submerge the outlet of the silicone tube 10, and the flow rate of the liquid is controlled to be 2.0 ml/min.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time, and reaches more than 21mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 96 percent (figure 7).
Example 6
Collecting 25cm of soil on the surface layer, wherein the soil has the physical and chemical properties of pH 6.8, water-soluble organic carbon of 674mg/L and water-soluble sulfate of 1.80g/L, is low-oxygen, high-organic-carbon and high-sulfate soil, and selecting a formula V as a soil inoculum.
Formulation V comprises (component A) K per liter of aqueous solution2HPO40.50g, (component B) NH4Cl 0.70g, (component C) Na2SO40.60g of anhydrous CaCl (component D)20.06g, (component E) MgSO4·7H211.0G of O, 6.0mL of sodium lactate (component F), and 0.07G of ascorbic acid (component G).
Obtaining a sulfide liquid according to the following steps:
(1) the soil 16g is taken, the top cover 27 of the right short arm 4 is opened, and the obtained inoculated soil is uniformly placed in a U-shaped reaction container.
(2) Preparing the prepared formula V into 4.0L solution, sterilizing at 121 ℃ for 20min, and then introducing N2The resulting solution was directly injected into the reaction vessel by aeration for 20min, the monitoring strip 29 was attached to the top cover 27, the top cover 27 was closed, and the movable clamp 28 was tightened and sealed. N is injected into the reaction vessel through a liquid inlet 52Keeping for 10 min. Then, a rubber tube and a clamp are used for sealing the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3, standing is carried out for 120 hours, the monitoring strip 29 is observed periodically, the top cover 27 of the right short arm 4 is opened after the monitoring strip is black, 3.0L of sterilized and aerated formula solution is added into the reaction vessel, and a new monitoring strip is replaced.
(3) The small protruding hole 15 of the left short arm 3 is opened, the air inlet of the balloon 16 is fixed on the small hole, then the square box 14 is buckled above the left short arm 3, the small hole 18 at the bottom of the square box is aligned with the small protruding hole 15 of the left short arm 3, and then the rubber ring is used for sealing 17. The lower end of the T-shaped plastic rod 22 is inserted into the square box top cover aperture and the square box top cover 19 is closed so that the T-shaped plastic rod 22 is perpendicular to the balloon 16.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 extended sets of positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod 22. The other end of the electromagnetic relay 25 is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) A silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube extends through a liquid inlet pump 9 and then is placed in a storage container, 6.0L of solution prepared according to the corresponding formula is added into the storage container, and an inlet of the silicone tube 8 is positioned below the liquid level of the storage solution.
(6) The silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube passes through the liquid outlet pump 11 and then is placed in the receiving container, and water is injected into the receiving container and then flows through the outlet of the silicone tube.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time, and reaches more than 25mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 92 percent (figure 8).
Example 7
Collecting 25cm of soil on the surface layer, wherein the soil has the physical and chemical properties of pH 7.2, water-soluble organic carbon of 226mg/L and water-soluble sulfate of 1.80g/L, is low-oxygen, low-organic carbon and high-sulfate soil, and selecting a formula VI as a soil inoculum.
Formulation VI comprises per liter of aqueous solution (component A) K2HPO40.70g, (component B) NH4Cl 0.90g, (component C) Na2SO40.60g of anhydrous CaCl (component D)20.04g, (component E) MgSO4·7H29.0G of O, 9.0mL of sodium lactate (component F), and 0.07G of ascorbic acid (component G).
Obtaining a sulfide liquid according to the following steps:
(1) taking 10g of soil, opening the top cover 27 of the right short arm 4, and uniformly placing the obtained inoculated soil in a U-shaped reaction container.
(2) Preparing the prepared formula VI into 5.0L solution, sterilizing at 121 ℃ for 20min, and then introducing N2The resulting solution was directly injected into the reaction vessel by aeration for 20min, the monitoring strip 29 was attached to the top cover 27, the top cover 27 was closed, and the movable clamp 28 was tightened and sealed. N is injected into the reaction vessel through a liquid inlet 52Keeping for 10 min. Then, sealing the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3 by using a rubber tube and a clamp, standing for 120h, regularly observing the monitoring strip 29, opening the top cover 27 of the right short arm 4 after the monitoring strip is black, adding 4.0L of sterilized and aerated formula solution into the reaction vessel, and replacing a new monitoring strip.
(3) The small protruding hole 15 of the left short arm 3 is opened, the air inlet of the balloon 16 is fixed on the small hole 15, then the square box 14 is buckled above the left short arm 3, the small hole 18 at the bottom of the square box is aligned with the small protruding hole 15 of the left short arm 3, and then the square box is sealed by the rubber ring 17. The lower end of the T-shaped plastic rod 22 is inserted into the square box top cover small hole 21, and the square box top cover 19 is closed, so that the T-shaped plastic rod 22 is vertical to the upper part of the balloon 16.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 sets of extended positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod. The other end of the electromagnetic relay 25 is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) A silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube extends through the liquid inlet pump and then is placed in a storage container, 4.0L of solution prepared according to the corresponding formula is added into the storage container, and an inlet of the silicone tube 8 is positioned below the liquid level of the storage solution.
(6) The silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube passes through the liquid outlet pump and then is arranged in the receiving container, and water is injected into the receiving container and then flows through the outlet of the silicone tube 10.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time, and reaches more than 22mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 92 percent (figure 9).
Example 8
Collecting soil with surface layer of 28cm, wherein the soil has physical and chemical properties of pH 6.8, water-soluble organic carbon 758mg/L and water-soluble sulfate content 0.80g/L, and is low-oxygen, high-organic-carbon and low-sulfate soil, and selecting formula VII as soil inoculum.
Formulation VII contains (component A) K per liter of aqueous solution2HPO40.50g, (component B) NH4Cl 0.50g, (component C) Na2SO40.60g of anhydrous CaCl (component D)20.06g, (component E) MgSO4·7H2O21.0G, sodium lactate 5.0mL (component F), ascorbic acid 0.05G (component G).
Obtaining a sulfide liquid according to the following steps:
(1) the soil 16g is taken, the top cover 27 of the right short arm 4 is opened, and the obtained inoculated soil is uniformly placed in a U-shaped reaction container.
(2) Preparing the prepared formula VII into 5.0L solution, sterilizing at 121 ℃ for 20min, and introducing N2The resulting solution was directly injected into the reaction vessel by aeration for 20min, the monitoring strip 29 was attached to the top cover 27, the top cover 27 was closed, and the movable clamp 28 was tightened and sealed. N is injected into the reaction vessel through a liquid inlet 52Keeping for 12 min. And then sealing the small protruded holes of the liquid inlet 5, the liquid outlet 6 and the left short arm 3 by using a rubber tube and a clamp, standing for 120h, regularly observing the monitoring strip 29, opening the top cover 27 of the right short arm 4 after the monitoring strip is black, adding 4.0L of sterilized and aerated formula solution into the reaction vessel, and replacing a new monitoring strip.
(3) The small protruding hole 15 of the left short arm 3 is opened, the air inlet of the balloon 16 is fixed on the small hole 15, then the square box 14 is buckled above the left short arm 3, the small hole 18 at the bottom of the square box is aligned with the small protruding hole 15 of the left short arm 3, and then the square box is sealed by the rubber ring 17. The lower end of the T-shaped plastic rod 22 is inserted into the square box top cover small hole 21, and the square box top cover 19 is closed, so that the T-shaped plastic rod 22 is vertical to the upper part of the balloon 16.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 extended sets of positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod 22. The other end of the electromagnetic relay is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) A silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube extends through a liquid inlet pump 9 and then is placed in a storage container, 8.0L of solution prepared according to the corresponding formula is added into the storage container, and an inlet of the silicone tube 8 is positioned below the liquid level of the storage solution.
(6) The silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube passes through the liquid outlet pump 11 and then is placed in the receiving container, and water is injected into the receiving container and then flows through the outlet of the silicone tube 10.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time, and can reach more than 21mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 97 percent (figure 10).
Example 9
Collecting soil with the surface layer of 28cm, wherein the soil physical and chemical properties are pH 7.7, the water-soluble organic carbon content is 210mg/L, the water-soluble sulfate content is 0.60g/L, the soil is low-oxygen, low-organic-carbon and low-sulfate soil, and the formula VIII is selected as a soil inoculum.
Formulation VIII comprises per liter of aqueous solution (component A) K2HPO40.70g, (component B) NH4Cl 1.10g, (component C) Na2SO40.60g of anhydrous CaCl (component D)20.06g, (component E) MgSO4·7H2O21.0G, sodium lactate 9.0mL (component F), and ascorbic acid 0.07G (component G).
Obtaining a sulfide liquid according to the following steps:
(1) the soil 18g is taken, the top cover 27 of the right short arm 4 is opened, and the obtained inoculated soil is uniformly placed in a U-shaped reaction container.
(2) Preparing the prepared formula VIII into 4.0L solution, sterilizing at 121 ℃ for 20min, and introducing N2Aerating for 25min, directly injecting the obtained solution into the reaction vessel, adhering the monitoring strip 29 on the top cover 27, closing the top cover 27, tightening the movable clamp and sealing. N is injected into the reaction vessel through a liquid inlet 52Keeping for 15 min. Then, a rubber tube and a clamp are used for sealing the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3, the mixture is kept stand for 120 hours, the monitoring strip 29 is observed periodically, the top cover 27 of the right short arm 4 is opened after the monitoring strip is black, 5.0L of sterilized and aerated formula solution is added into the reaction vessel, and a new monitoring strip is replaced.
(3) The small protruding hole 15 of the left short arm 3 is opened, the air inlet of the balloon 16 is fixed on the small hole 15, then the square box 14 is buckled above the left short arm 3, the small hole 18 at the bottom of the square box is aligned with the small protruding hole 15 of the left short arm 3, and then the square box is sealed by the rubber ring 17. The lower end of the T-shaped plastic rod 22 is inserted into the square box top cover small hole 21, and the square box top cover 19 is closed, so that the T-shaped plastic rod 22 is vertical to the upper part of the balloon 16.
(4) An electromagnetic relay 25 is fixed on the top of the left short arm 3, and 2 extended sets of positive and negative electrodes 26 are respectively aligned with two ends of the T-shaped plastic rod 22. The other end of the electromagnetic relay 25 is respectively connected with the liquid inlet pump 9 and the liquid outlet pump 11, and the equipment is in a power-off state during connection.
(5) A silicone tube 8 is connected with the liquid inlet 5, the other end of the silicone tube extends through a liquid inlet pump 9 and then is placed in a storage container, 5.0L of solution prepared according to the corresponding formula is added into the storage container, and an inlet of the silicone tube 8 is positioned below the liquid level of the storage solution.
(6) The silicone tube 10 is connected with the liquid outlet 6, the other end of the silicone tube passes through the liquid outlet pump 11 and then is placed in the receiving container, and water is injected into the receiving container and then flows through the outlet of the silicone tube 10.
(7) The vessel was allowed to stand for 120 hours or more, and the monitoring strip 29 was periodically observed while collecting the sulfide liquid in the receiving vessel.
The concentration of the sulfide in the liquid obtained by the method is gradually increased along with the time, and can reach 24mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches more than 96 percent (figure 11).
Comparative example 1
Collecting 25cm of soil on the surface layer, wherein the soil has the physical and chemical properties of pH 6.8, water-soluble organic carbon of 674mg/L and water-soluble sulfate of 1.80g/L, is low-oxygen, high-organic-carbon and high-sulfate soil, and selecting a formula V as a reaction formula of a soil inoculum.
Formulation V comprises (component A) K per liter of aqueous solution2HPO40.50g, (component B) NH4Cl 0.70g, (component C) Na2SO40.60g of anhydrous CaCl (component D)20.06g, (component E) MgSO4·7H211.0G of O, 6.0mL of sodium lactate (component F), and 0.07G of ascorbic acid (component G).
Obtaining a sulfide liquid according to the following steps:
(1) the U-shaped reaction containers A and B are taken for experiments, and the formula and the traditional formula are compared.
(2) Taking 16g of soil, opening a top cover 27 of the right short arm 4 of the U-shaped reaction container A, and uniformly placing the obtained inoculated soil in the U-shaped reaction container A.
(3) Preparing the prepared formula V into 4.0L solution, sterilizing at 121 ℃ for 20min, and then introducing N2Aerating for 20min, directly injecting the obtained solution into the reaction vessel, closing the top cover 27, tightening the movable clamp 28 and sealing. N is injected into the reaction vessel through a liquid inlet 52Keeping for 10 min. Then the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3 are sealed by a rubber tube and a clamp, and the mixture is kept stand for 120 hours.
(4) Taking 16g of soil, opening a top cover 27 of the right short arm 4 of the U-shaped reaction container A, and uniformly placing the obtained inoculated soil in the U-shaped reaction container B.
(5) Preparing 4.0L solution according to the formula of the traditional sulfate reducing bacteria Postgate C, sterilizing at 121 ℃ for 20min, and introducing N2Aerating for 20min, and directly injecting the obtained solution into the U-shaped reaction vessel B. The formula of Postgate C comprises KH2PO40.5g/L，NH4Cl 1.0g/L，CaCl2·2H2O 0.06g/L，Na2SO44.5g/L，MgSO4·7H20.06g/L of O, 3.5mL/L of sodium lactate, 1.0g/L of yeast extract and FeSO4·7H2O 0.01g/L，NaHCO32.0 g/L. The medicament is all chemically pure. The cap 27 is closed and the movable clamp 28 is tightened and sealed. N is injected into the reaction vessel through a liquid inlet 52Keeping for 10 min. Then the liquid inlet 5, the liquid outlet 6 and the small protruding hole 15 of the left short arm 3 are sealed by a rubber tube and a clamp, and the mixture is kept stand for 120 hours.
Samples were taken periodically from the U-shaped reaction vessels A and B and the sulfate reduction rate and sulfide concentration were determined.
The concentration of the sulfide in the liquid obtained by adopting the formula of the invention is gradually increased along with the time and reaches more than 8mg/L, the reduction rate of the sulfate is gradually increased, and the reduction efficiency reaches 95 percent (figure 12). The concentration of sulfide generated by the formula of the invention is far higher than that of sulfide generated by the traditional formula, and the reduction rate of sulfate is obviously higher than that of the traditional formula.
Claims (10)
1. A solution formula for efficiently producing sulfide by utilizing different soils is characterized in that K is used2HPO4、NH4Cl、Na2SO4No water is neededCaCl2、MgSO4·7H2O, sodium lactate and ascorbic acid; each liter of the aqueous solution contains K2HPO40.30～0.70g，NH4Cl 0.50～1.10g，Na2SO40.40-0.60 g of anhydrous CaCl20.04～0.06g，MgSO4·7H29.0 to 21.0g of O, 4.0 to 9.0mL of sodium lactate, and 0.05 to 0.13g of ascorbic acid.
2. A method for preparing sulfide by using the solution formulation as claimed in claim 1, wherein the sterilized solution formulation is mixed with soil, and the mixture is placed in a reaction device, deoxygenated, and sealed to react to produce sulfide.
3. A sulfide generating apparatus used in claim 2, comprising a reserve container for reserving a reaction solution reacting with soil, a reaction container for reacting the soil with the reaction solution, a receiving container for receiving a sulfide solution generated by the reaction, and a controller; a liquid inlet and a liquid outlet are respectively arranged on the reaction container; the storage containers are connected with a liquid inlet of the reaction container through a liquid inlet pipe, and a liquid inlet pump is arranged on the liquid inlet pipe; the liquid outlet of the reaction container is connected with the receiving container through a liquid outlet pipe, and a liquid outlet pump is arranged on the liquid outlet pipe; the reactor can be sealed and opened, and the top of the reactor is provided with a small protruded hole capable of ventilating; the controller comprises a box body, a relay and an expandable and contractible structure positioned in the box body, the box body is fixed at the top of the reactor, and the expandable and contractible structure is hermetically connected with a small protruding hole on the reaction container; the box body is provided with a T-shaped rod which can move relative to the box body, the upper part of the T-shaped rod is arranged outside the box body, the bottom of the T-shaped rod penetrates through the box body to be contacted with the expandable and contractible structure, and two ends of the upper part of the T-shaped rod are respectively fixed with a conducting strip; the relay is provided with 2 switches which respectively control the liquid inlet pump and the liquid outlet pump, each switch extends out of 1 set of positive and negative wire connectors, and the conducting strips at the two ends of the T-shaped rod respectively correspond to 1 set of positive and negative wire connectors.
4. The apparatus for generating sulfides according to claim 3, wherein the reaction vessel is a U-shaped reaction vessel, and the two short arms of the U-shaped reaction vessel are respectively provided with a liquid inlet and a liquid outlet.
5. The sulfide generating device according to claim 4, wherein the short arm of the U-shaped reactor is provided with a liquid inlet, the top of the short arm is sealed and is provided with a small protruded hole capable of ventilating, and the box body is fixedly arranged above the small protruded hole; the top of the short arm provided with the liquid outlet can be sealed and opened.
6. The sulfide generating apparatus according to claim 5, wherein the two short arms of the U-shaped reaction vessel are the same in height, and the relay is fixed to a plane at the top end of the short arm provided with the liquid inlet and is opposite to the box body.
7. A sulfide generating apparatus according to claim 5, wherein a monitoring means for monitoring a change in sulfide concentration is provided in the reaction vessel.
8. The sulfide generating device of claim 3, wherein the inflatable and deflatable structure is a balloon.
9. A method for producing sulfides by using the apparatus of claim 3, wherein the soil is placed in a reaction vessel, the solution formulation of claim 1 is then added to the reaction vessel, the reaction vessel is deaerated, the reaction vessel is closed, and the solution formulation of claim 1 is simultaneously poured into a storage vessel to carry out the reaction to produce sulfides.
10. The method according to claim 9, wherein the moisture content of the soil is 20 to 50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911008499.XA CN110872570B (en) | 2019-10-22 | 2019-10-22 | Solution formula for efficiently producing sulfide by utilizing different soils and method for preparing sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911008499.XA CN110872570B (en) | 2019-10-22 | 2019-10-22 | Solution formula for efficiently producing sulfide by utilizing different soils and method for preparing sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110872570A true CN110872570A (en) | 2020-03-10 |
| CN110872570B CN110872570B (en) | 2024-03-19 |
Family
ID=69717845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911008499.XA Active CN110872570B (en) | 2019-10-22 | 2019-10-22 | Solution formula for efficiently producing sulfide by utilizing different soils and method for preparing sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110872570B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029328A (en) * | 2006-11-30 | 2007-09-05 | 白莉 | Sulfate-reducing bacteria testing fluid and testing bottle |
| CN101745529A (en) * | 2008-11-28 | 2010-06-23 | 中国科学院成都生物研究所 | Method for treating radioactive strontium-90 polluted soil |
| US20110104776A1 (en) * | 2008-02-12 | 2011-05-05 | Bioteq Environmental Technologies Inc. | Processes for producing h2s using sulphur-reducing bacteria |
| JP2016014193A (en) * | 2015-09-02 | 2016-01-28 | 住友金属鉱山株式会社 | Equipment and method for producing sulfide |
| CN106834166A (en) * | 2016-12-29 | 2017-06-13 | 中国石油天然气股份有限公司 | A kind of sulfate reducing bacteria activator and its application in microbe oil production |
| CN107138520A (en) * | 2017-05-02 | 2017-09-08 | 东华理工大学 | The processing method of uranium contaminated soil is repaired in a kind of utilization sulfate Mixed Microbes reduction |
| CN107971336A (en) * | 2017-12-11 | 2018-05-01 | 西南科技大学 | A kind of Lead Pollution in Soil biology in situ renovation method |
| CN110093275A (en) * | 2019-05-14 | 2019-08-06 | 桂林电子科技大学 | A kind of acclimation method of resistance to cadmium sulfate-reducing activity sludge |
| CN211689073U (en) * | 2019-10-22 | 2020-10-16 | 广东第二师范学院 | Sulfide generating device |
-
2019
- 2019-10-22 CN CN201911008499.XA patent/CN110872570B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029328A (en) * | 2006-11-30 | 2007-09-05 | 白莉 | Sulfate-reducing bacteria testing fluid and testing bottle |
| US20110104776A1 (en) * | 2008-02-12 | 2011-05-05 | Bioteq Environmental Technologies Inc. | Processes for producing h2s using sulphur-reducing bacteria |
| CN101745529A (en) * | 2008-11-28 | 2010-06-23 | 中国科学院成都生物研究所 | Method for treating radioactive strontium-90 polluted soil |
| JP2016014193A (en) * | 2015-09-02 | 2016-01-28 | 住友金属鉱山株式会社 | Equipment and method for producing sulfide |
| CN106834166A (en) * | 2016-12-29 | 2017-06-13 | 中国石油天然气股份有限公司 | A kind of sulfate reducing bacteria activator and its application in microbe oil production |
| CN107138520A (en) * | 2017-05-02 | 2017-09-08 | 东华理工大学 | The processing method of uranium contaminated soil is repaired in a kind of utilization sulfate Mixed Microbes reduction |
| CN107971336A (en) * | 2017-12-11 | 2018-05-01 | 西南科技大学 | A kind of Lead Pollution in Soil biology in situ renovation method |
| CN110093275A (en) * | 2019-05-14 | 2019-08-06 | 桂林电子科技大学 | A kind of acclimation method of resistance to cadmium sulfate-reducing activity sludge |
| CN211689073U (en) * | 2019-10-22 | 2020-10-16 | 广东第二师范学院 | Sulfide generating device |
Non-Patent Citations (3)
| Title |
|---|
| RONGLIANG QIU等: "Sulfate reduction and copper precipitation by a Citrobacter sp. isolated from a mining area", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 164, no. 2 * |
| 刘辰等: "混合硫酸盐还原菌的筛选及其生理特性研究", 《铀矿冶》, vol. 36, no. 3 * |
| 陈明翔等: "硫酸盐还原菌的脱硫性能和铁还原性能", 《河北大学学报(自然科学版)》, vol. 34, no. 6 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110872570B (en) | 2024-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ferrag‐Siagh et al. | Tetracycline degradation and mineralization by the coupling of an electro‐Fenton pretreatment and a biological process | |
| Uberoi et al. | Interactions among sulfate reducers, acetogens, and methanogens in anaerobic propionate systems | |
| JP5027649B2 (en) | Female hormone substance-degrading microorganism and use thereof | |
| CN101798130A (en) | Wastewater treatment method based on electro-Fenton reaction | |
| CN101417848A (en) | Apparatus and method for processing parachlorophenol-containing waste water and recovering electric energy | |
| CN104690084A (en) | Electrochemical and microbial synergetic restoration integrated equipment for organic contaminated soil and restoration method thereof | |
| Yang et al. | Biomass, oleate, and other possible substrates for chloroethene reductive dehalogenation | |
| CN103787490B (en) | A kind of for the treatment of the bio-electrochemical reactor of waste water from organic fluorine industry and the treatment process of waste water from organic fluorine industry | |
| KR20130065891A (en) | Method for treating organic wastes | |
| CN110756041A (en) | Electro-bio-trickling filter for treating volatile organic compounds | |
| CN106479935A (en) | A kind of preparation method of use in waste water treatment denitrification denitrogenation microbial inoculum | |
| CN116177716A (en) | Experimental device and method for treating tetracycline wastewater through electro-Fenton reaction of cathode of microbial fuel cell | |
| JP5186169B2 (en) | Purification method of soil and groundwater in aquifer | |
| CN110872570A (en) | Solution formula for efficiently producing sulfide by utilizing different soils and method for preparing sulfide | |
| CN110937679A (en) | System and method for producing hydrogen by recovering nitrogen and phosphorus in sewage through bioelectrochemistry and synchronously fixing carbon | |
| CN211689073U (en) | Sulfide generating device | |
| CN1332898C (en) | Sludge stabilizing electrochemical treating process | |
| KR20130112064A (en) | Method for treating 1,4-dioxane-containing wastewater, and treatment device | |
| CN109013689A (en) | A kind of restorative procedure of As polluted soil | |
| CN201296687Y (en) | Device for treating wastewater containing chlorophenol while recycling electric energy | |
| JP3176849B2 (en) | Microorganism treatment method for soil contaminated with organochlorine compounds | |
| CN113149342A (en) | Device and method for efficiently degrading bisphenol A by illumination coupling of electroactive biomembrane | |
| CN215479925U (en) | Water treatment device | |
| CN216890489U (en) | Advanced oxidation treatment device for desulfurization wastewater of oil and gas field | |
| CN110903950B (en) | BES-anaerobic digestion coupling device and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |