CN114804950A - Heavy metal soil conditioner and preparation method thereof - Google Patents
Heavy metal soil conditioner and preparation method thereof Download PDFInfo
- Publication number
- CN114804950A CN114804950A CN202210352882.2A CN202210352882A CN114804950A CN 114804950 A CN114804950 A CN 114804950A CN 202210352882 A CN202210352882 A CN 202210352882A CN 114804950 A CN114804950 A CN 114804950A
- Authority
- CN
- China
- Prior art keywords
- parts
- heavy metal
- humic acid
- soil conditioner
- metal soil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 67
- 239000003516 soil conditioner Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004021 humic acid Substances 0.000 claims abstract description 54
- 239000003337 fertilizer Substances 0.000 claims abstract description 53
- 230000000813 microbial effect Effects 0.000 claims abstract description 51
- 241000894006 Bacteria Species 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000012530 fluid Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000003077 lignite Substances 0.000 claims description 15
- 244000063299 Bacillus subtilis Species 0.000 claims description 14
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000011573 trace mineral Substances 0.000 claims description 14
- 235000013619 trace mineral Nutrition 0.000 claims description 14
- 241000192700 Cyanobacteria Species 0.000 claims description 12
- 238000000855 fermentation Methods 0.000 claims description 12
- 230000004151 fermentation Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical group C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 9
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 9
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002509 fulvic acid Substances 0.000 claims description 9
- 229940095100 fulvic acid Drugs 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920001661 Chitosan Polymers 0.000 claims description 7
- 229920000615 alginic acid Polymers 0.000 claims description 7
- 235000010443 alginic acid Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000010902 straw Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 241000589196 Sinorhizobium meliloti Species 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000004463 hay Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 244000179560 Prunella vulgaris Species 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000005272 common selfheal Nutrition 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 240000004658 Medicago sativa Species 0.000 claims 1
- 239000002364 soil amendment Substances 0.000 claims 1
- 230000004083 survival effect Effects 0.000 abstract description 19
- 230000035784 germination Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002689 soil Substances 0.000 description 36
- 230000012010 growth Effects 0.000 description 26
- 230000000694 effects Effects 0.000 description 17
- 244000005700 microbiome Species 0.000 description 17
- 241000196324 Embryophyta Species 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 241000219198 Brassica Species 0.000 description 10
- 235000003351 Brassica cretica Nutrition 0.000 description 10
- 235000003343 Brassica rupestris Nutrition 0.000 description 10
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 10
- 235000010460 mustard Nutrition 0.000 description 10
- 241000219823 Medicago Species 0.000 description 8
- 210000004215 spore Anatomy 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 230000008635 plant growth Effects 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000005067 remediation Methods 0.000 description 5
- 241000223259 Trichoderma Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 210000003608 fece Anatomy 0.000 description 4
- 239000010871 livestock manure Substances 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 244000178993 Brassica juncea Species 0.000 description 3
- 235000005855 Brassica juncea var. subintegrifolia Nutrition 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000195940 Bryophyta Species 0.000 description 2
- 208000035240 Disease Resistance Diseases 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001465752 Purpureocillium lilacinum Species 0.000 description 2
- 241000589180 Rhizobium Species 0.000 description 2
- 241000579741 Sphaerotheca <fungi> Species 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000003895 organic fertilizer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 241001464430 Cyanobacterium Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 210000004666 bacterial spore Anatomy 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 235000019508 mustard seed Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000003904 radioactive pollution Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/20—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation using specific microorganisms or substances, e.g. enzymes, for activating or stimulating the treatment
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
-
- 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
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/16—Soil-conditioning materials or soil-stabilising materials containing organic compounds only applied in a physical form other than a solution or a grout, e.g. as platelets or granules
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Soil Sciences (AREA)
- Health & Medical Sciences (AREA)
- Tropical Medicine & Parasitology (AREA)
- Materials Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a heavy metal soil conditioner and a preparation method thereof, which comprises the steps of adopting biological bacteria with high spore survival rate, and the preparation method comprises the steps of mixing humic acid and microbial fertilizer in a fluid state, and spraying the rest three fourths of humic acid on the surface of the fluid of the mixture until a layer of humic acid shell is formed. The invention has the advantages of high germination rate and high survival rate of the microbial spores.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a heavy metal soil conditioner and a preparation method thereof.
Background
The soil pollution includes chemical pollution, physical pollution, biological pollution and radioactive pollution, and the soil heavy metal pollution is more prominent. Heavy metals cannot be decomposed by soil microorganisms, are easy to accumulate in soil, and are converted into methyl compounds with higher toxicity. In the process of crop growth, heavy metals accumulated in soil can enter crop bodies along with root systems of crops, people eating such vegetables can cause harm to health, the pollution treatment difficulty of the heavy metals to the soil is large, and the pollution hazard is large.
The method for treating the heavy metal pollution of the soil mainly comprises three methods, namely a physical method, a chemical method and a biological method, and specifically comprises a soil dressing deep ploughing method, a solidification method, a heavy metal migration method and the like. However, the economic expenditure of the deep ploughing of the foreign soil is raised, the method is only suitable for treating the soil with serious pollution in small area, and the method of adding a curing agent to cure the heavy metal or adding a migration agent to migrate the heavy metal in the soil is the most common treatment method. The microbial fertilizer is a novel fertilizer biological product, is a pure natural, low-carbon, non-toxic, harmless and pollution-free organic biological agent, and can also be used as a modifier for repairing heavy metal polluted soil in the field of repairing heavy metal polluted soil.
At present, Chinese patent with publication number CN108977204A discloses a humic acid microbial fertilizer, which is prepared by taking coal as raw material to prepare potassium humate, then adding bacillus subtilis, paecilomyces lilacinus and trichoderma in a ratio of 1: 1, and finally granulating to obtain the humic acid potassium fertilizer.
Although the humic acid microbial fertilizer contains various microbial bacteria, the germination rate of spores of trichoderma in the fertilizer under alkaline conditions is extremely low, potassium humate is used as a main component in the fertilizer, and the potassium humate is an alkaline compound, so that the germination rate of the spores of the trichoderma is very low and the trichoderma cannot play a normal role when the potassium humate is mixed with the alkaline compound; in addition, the paecilomyces lilacinus is a microorganism developed by high-tech biotechnology, has short preservation time and high spore mortality, and hardly exerts the effect when being used as a fertilizer.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the heavy metal soil conditioner and the preparation method thereof, and the heavy metal soil conditioner has the advantages of high germination rate and high survival rate of microbial spores.
In order to achieve the purpose, the invention provides the following technical scheme:
a heavy metal soil conditioner comprises 200g/m of conditioner 2 ∶100mg/L·m 2 The mixture of the microbial fertilizer and humic acid is prepared from the following raw materials in parts by weight:
weathered coal 5 parts
10 portions of biological bacteria
50 portions of straw
20 portions of common selfheal fruit-spike
10 portions of water
5 portions of trace elements
5 parts of algin
2 portions of chitosan
By adopting the technical scheme, the heavy metal contaminated soil is repaired by using the mixture of the microbial fertilizer and the humic acid, the microbial fertilizer adopts alfalfa rhizobia and cyanobacteria which are not influenced under the alkaline condition, bacillus subtilis and Moses sacculus mildew which have high spore survival rate, the germination rate and the survival rate of biological bacteria spores in the microbial fertilizer can be improved, a large amount of organic matters are required to provide nutrients when the microbial fertilizer is used, so that the microbial mass propagation is promoted, the aim of repairing the heavy metal soil is fulfilled, the humic acid and the microbial fertilizer are mixed for use, the humic acid provides nutrients for the microbial fertilizer, and the survival rate of biological bacteria is improved. The microbial fertilizer can activate heavy metals, promote the absorption of plants to the heavy metals and the transportation and accumulation of the heavy metals in the plants. The humic acid is a green and environment-friendly material, functional groups of the humic acid can be chelated with metal ions to form stable compounds, and the compounds have a fixing effect on heavy metals in soil. The weathered coal, the straw, the hay, the algin and the chitosan are combined to form an organic part in the bacterial manure, the weathered coal has the characteristic of adsorbing heavy metals, and the organic part can promote the adsorption of the biological bacteria part on the heavy metals and provide nutrition for plant growth, so that the biological bacterial manure can be used as a fertilizer for promoting the plant growth and a modifier for repairing heavy metal pollution.
Further, the biological bacteria comprise alfalfa rhizobium/cyanobacterium/bacillus subtilis/sacculus mossambica in a mass ratio of 1: 3: 1: 2.
By adopting the technical scheme, the alfalfa rhizobia and cyanobacteria can fix free nitrogen in the air to prepare nitrogen compounds for the growth and development of plants, the bacillus subtilis secretes antibacterial substances to inhibit the growth of pathogenic bacteria, and simultaneously induces a plant defense system to resist the invasion of the pathogenic bacteria, so that the improvement of the disease resistance of the plants can be achieved. The fertilizer is added into the organic part of the microbial fertilizer according to the mass ratio of 1 alfalfa rhizobia to 3 cyanobacteria to 1 bacillus subtilis to 2 sacculus murexi, so that the effect of the fertilizer on promoting plant growth can be improved, meanwhile, the disease resistance of plants can be improved, and nutrients can be provided for plant growth.
Further, the formula of the trace elements is as follows: 0.6mg/L of manganese sulfate, 120mg/L of ferric sulfate and 0.6mg/L of ammonium molybdate.
By adopting the technical scheme, the trace elements are essential key substances for the growth and development of the microorganisms, and the trace elements such as manganese, iron, molybdenum and the like are all indispensable trace elements in the microbial propagation process, so that the propagation of the microorganisms can be promoted, and the utilization rate of the microorganisms on the trace elements is very high, so that the effect of promoting the propagation of the microorganisms can be achieved by applying a small amount of the trace elements.
Further, the humic acid is prepared from the following raw materials in parts by weight:
40 parts of lignite
12 parts of 3mol/L nitric acid solution
12 parts of 3mol/L mixed solution of sodium hydroxide and sodium carbonate
Catalyst 4 parts
By adopting the technical scheme, the lignite contains a large amount of free humic acid which is an excellent material for extracting humic acid, the degraded fulvic acid in the solution can be extracted by the nitric acid solution, and the fulvic acid can be extracted by the sodium hydroxide and sodium carbonate mixed solution.
Further, the catalyst was 3mol/L sodium hydroxide solution.
By adopting the technical scheme, the reaction path of lignite degradation can be changed by adding 3mol/L sodium hydroxide solution, so that the reaction speed is increased.
The preparation method of the heavy metal soil conditioner is characterized by comprising the following steps:
s1: mixing one fourth of humic acid with the microbial fertilizer in a fluid state, and controlling the pH of the mixture to be 6.8-7.5;
s2: dividing the mixture into fluids with the diameter of 1 g;
s3: and spraying the remaining three quarters of humic acid on the surface of the mixture fluid until a layer of humic acid shell is formed.
By adopting the technical scheme, the microbial fertilizer plays a role by depending on the microorganisms contained in the microbial fertilizer, in order to ensure the activity of the microorganisms, the microbial fertilizer in a fluid state is directly wrapped in the humic acid shells, the microorganisms are not dried and keep the activity, the humic acid provides nutrients, the microorganisms are ensured to be always in a proper propagation condition, and the survival rate of the microorganisms is improved.
Further, the preparation method of the microbial fertilizer at least comprises the following steps:
s01: weighing weathered coal, straw, hay, algin and chitosan according to parts by weight, and grinding;
s02: adding a certain weight part of water into the ground powder, and performing primary fermentation for 6 hours at the temperature of 20-25 ℃ and the pH value of 6-8;
s03: after the primary fermentation is finished, adjusting the temperature to 40 ℃, adjusting the pH to 7.1-7.5, and fermenting for 10 days;
s04: weighing alfalfa rhizobia, cyanobacteria, bacillus subtilis, mosses sacculus mildew and trace elements in parts by weight, and adding the alfalfa rhizobia, cyanobacteria, bacillus subtilis, mosses sacculus mildew and trace elements into the fermentation product.
By adopting the technical scheme, the weathered coal, the straws, the hay, the algin, the chitosan and other materials are subjected to primary fermentation, partial organic matters are converted into humus by the primary fermentation, cellulose and lignin in secondary fermentation products are decomposed to finally form a stable organic fertilizer, and biological bacteria and trace elements are added to obtain the microbial organic fertilizer.
Further, the preparation of humic acid at least comprises the following steps:
s11: weighing lignite according to parts by weight, grinding, placing the lignite in a reaction kettle, introducing mixed gas of oxygen and water vapor at the temperature of 180 ℃, and adding a catalyst for reaction;
s12: mixing and reacting the fully reacted lignite with 6 parts of nitric acid solution;
s13: filtering after the reaction is completed, wherein the filtrate is a fulvic acid solution;
s14: putting the filter residue into a mixed solution of sodium hydroxide and sodium carbonate for reaction;
s15: filtering after the reaction is completed to obtain filtrate;
s16: adding 6 parts of nitric acid solution into the filtrate to adjust the pH to be less than or equal to 2, and generating precipitate;
s17: and filtering out the precipitate, and drying to obtain solid humic acid.
By adopting the technical scheme, firstly, the lignite is degraded with oxygen and water vapor at the temperature of 180 ℃, a catalyst is added to accelerate the reaction, benzene rings and fat chains in the degraded lignite are broken, then nitric acid is used for extracting the degraded lignite, fulvic acid with lower molecular weight is extracted, then mixed solution of sodium hydroxide and sodium carbonate is used for extracting the material left after the fulvic acid is extracted, and finally fulvic acid and fulvic acid with higher molecular weight are extracted.
Detailed Description
The present invention will be described in further detail with reference to examples.
The preparation method of the heavy metal soil conditioner comprises the following steps:
s1: mixing one quarter of humic acid with the microbial fertilizer in a fluid state, and controlling the pH of the mixture to be between 6.8 and 7.5;
s2: dividing the mixture into fluids with the diameter of 1 g;
s3: and spraying the remaining three quarters of humic acid on the surface of the mixture fluid until a layer of humic acid shell is formed.
The preparation method of the microbial fertilizer at least comprises the following steps:
s01: weighing weathered coal, straw, hay, algin and chitosan according to parts by weight, and grinding;
s02: adding a certain weight part of water into the ground powder, and performing primary fermentation for 6 hours at the temperature of 20-25 ℃ and the pH value of 6-8;
s03: after the primary fermentation is finished, adjusting the temperature to 40 ℃, adjusting the pH to 7.1-7.5, and fermenting for 10 days;
s04: weighing alfalfa rhizobia, cyanobacteria, bacillus subtilis, Moses sacculus mould and trace elements in parts by weight, and adding the weighed materials into a fermentation product.
The preparation of humic acid at least comprises the following steps:
s11: weighing lignite according to parts by weight, grinding, placing the lignite in a reaction kettle, introducing mixed gas of oxygen and water vapor at the temperature of 180 ℃, and adding a catalyst for reaction;
s12: mixing and reacting the fully reacted lignite with 6 parts of nitric acid solution;
s13: filtering after the reaction is completed, wherein the filtrate is a fulvic acid solution;
s14: putting the filter residue into a mixed solution of sodium hydroxide and sodium carbonate for reaction;
s15: filtering after the reaction is completed to obtain filtrate;
s16: adding 6 parts of nitric acid solution into the filtrate to adjust the pH to be less than or equal to 2, and generating precipitate;
s17: and filtering out the precipitate, and drying to obtain solid humic acid.
TABLE 1 Mass ratio of Rhizobium meliloti/cyanobacteria/Bacillus subtilis/Sphaerotheca mossambica in the microbial manure
TABLE 2-listing of environmental materials and plant material types
Table 3-microbial fertilizer-mustard seed amount per square meter
Table 4-microbial fertilizer, humic acid-mustard seed Per sq.m dosage
| Humic acid | Microbial fertilizer | Mustard seed | |
| Example 33 | 25mg/L·m 2 | 200g/m 2 | 1g/m 2 |
| Example 34 | 50mg/L·m 2 | 200g/m 2 | 1g/m 2 |
| Example 35 | 100mg/L·m 2 | 200g/m 2 | 1g/m 2 |
| Example 36 | 150mg/L·m 2 | 200g/m 2 | 1g/m 2 |
| Example 37 | 200mg/L·m 2 | 200g/m 2 | 1g/m 2 |
Performance test
1. Survival rate of each strain when microbial fertilizer is used
TABLE 5 survival rates of various strains when microbial fertilizers were used
In combination with examples 1-9, and in combination with tables 1 and 5, it was found that when the mass ratio of Rhizobium meliloti/cyanobacteria/Bacillus subtilis/Sphaerotheca moserii is 1: 3: 1: 2, the survival rate of the strains can reach more than 90 percent, when the mass ratio is 0.5: 3: 1: 2 and the mass ratio is 1.5: 3: 1: 2, the survival rate of the alfalfa rhizobia is reduced, when the mass ratio is 1: 2 and the mass ratio is 1: 5: 1: 2, the survival rate of the cyanobacteria is reduced, when the mass ratio is 1: 3: 0.5: 2 and the mass ratio is 1: 3: 1.5: 2, the survival rate of the bacillus subtilis is reduced, when the mass ratio is 1: 3: 1 and the mass ratio is 1: 3: 1: 3, the survival rate of the sacculus moscillus is reduced, and in conclusion, the best choice is when the mass ratio of rhizobium meliitus/cyanobacteria/bacillus subtilis/sacculus mixicus is 1: 3: 1: 2.
2. Heavy metal enrichment coefficient and running coefficient in plant body after 1 year of restoration
GB15618-1995
TABLE 6 heavy metal enrichment and running coefficients in plants 1 year after remediation
In combination with examples 10 to 18 and comparative examples 1 to 3, and in combination with tables 2 and 6, it is understood that the effect of the agent for improving heavy metal soils is inferior to that of the agent for improving heavy metal soils when the plant material is used alone. After the heavy metal soil conditioner is added into the plant material, the enrichment and running effects of the mustard on the heavy metals are obviously improved. The microbial fertilizer is added into the plant material, so that the enrichment and operation effects of the plant material on heavy metals can be improved, the enrichment and operation effects of the plant material on the heavy metals can also be improved by adding humic acid, but the effect of adding the humic acid is poorer than that of adding the microbial fertilizer, the microbial fertilizer and the humic acid are combined with the mustard to restore the soil polluted by the heavy metals, the survival rate of the microorganisms is improved by the humic acid, the soil restoration efficiency is improved, the growth of plants is promoted, and therefore the heavy metal soil is restored by adopting the microbial fertilizer and the humic acid together.
TABLE 7-enrichment and running coefficients of heavy metals in mustard after 1 year of remediation by combination of microbial manure and mustard
In combination with examples 19 to 32 and tables 3 and 6, it is understood that when the number of plants is too small, the excessive growth of biological bacteria in the microbial fertilizer adversely affects the enrichment and operation of heavy metals, and the excessive growth of biological bacteria also affects the growth of biological bacteria, resulting in the decrease of the enrichment and operation of heavy metals. The dosage of the microbial fertilizer is 200g/m 2 When the fertilizer is used, the enrichment and the operation of the mustard to the heavy metals in the soil reach the peak, and the dosage of the microbial fertilizer is less than 200g/m 2 When the soil is in gradient decrease, the enrichment and the operation of the mustard to the heavy metals in the soil are also reduced, and the using amount of the microbial fertilizer is more than 200g/m 2 When the gradient rises, the enrichment and the running coefficient of the mustard to the heavy metals in the soil are maintained at about the highest value, and basically have no change, in conclusion, the dosage of the microbial fertilizer is 200g/m 2 Is the optimal choice.
TABLE 8 heavy metal enrichment and running coefficients in leaf mustard after 1 year of leaf mustard restoration with heavy metal soil conditioner
As can be seen from Table 4 and Table 8 in combination with examples 33 to 37, the amount of the microbial fertilizer to be used was 200g/m 2 The dosage of the leaf mustard seeds is 1g/m 2 In the case of adding humic acid, when the amount of humic acid is 100 mg/L.m 2 When the method is used, the mustard has the highest enrichment and running coefficient of heavy metals in soil, the propagation of microorganisms reaches the most suitable state, and the dosage of humic acid is less than 100 mg/L.m 2 When the content of humic acid is reduced, the survival rate of microorganisms is reduced, the enrichment and running coefficients of the mustard to heavy metals in soil are reduced, and the dosage of humic acid is more than 100 mg/L.m 2 When the concentration of the humic acid increases in a gradient way, the propagation of microorganisms is vigorous, the enrichment of the mustard to the heavy metals in the soil and the running coefficient are stabilized at the highest value and are basically unchanged, so the dosage of the humic acid is 100 mg/L.m 2 Is the optimal choice.
Example of growth
The examples 16 to 18, 25 to 26, 34 to 35 and 37 are selected as 8 growth examples, and the heavy metal contaminated soil of one square meter is respectively repaired as follows:
TABLE 9-soil heavy Metal content and pH Change after remediation
| Pb(mg/kg) | Cd(mg/kg) | Zn(mg/kg) | pH | |
| Growth example 1 | 843.57 | 220.34 | 1997.09 | 8.14 |
| Growth example 2 | 703.54 | 192.38 | 1754.87 | 7.37 |
| Growth example 3 | 856.16 | 219.75 | 2001.89 | 8.09 |
| Growth example 4 | 725.67 | 191.01 | 1749.65 | 7.49 |
| Growth example 5 | 714.35 | 193.98 | 1759.89 | 7.20 |
| Growth example 6 | 651.78 | 178.32 | 1625.67 | 6.89 |
| Growth example 7 | 638.12 | 159.74 | 1499.97 | 6.50 |
| Growth example 8 | 623.35 | 163.27 | 1509.56 | 6.48 |
TABLE 10 reduction of heavy metals after remediation
| Pb(％) | Cd(％) | Zn(％) | |
| Growth example 1 | 16.17 | 13.98 | 17.76 |
| Growth example 2 | 25.78 | 20.83 | 26.47 |
| Growth example 3 | 15.89 | 14.46 | 16.75 |
| Growth example 4 | 26.01 | 19.74 | 27.01 |
| Growth example 5 | 25.92 | 21.78 | 26.73 |
| Growth example 6 | 35.82 | 28.56 | 30.83 |
| Growth example 7 | 40.19 | 36.28 | 38.57 |
| Growth example 8 | 39.56 | 35.98 | 39.46 |
As is clear from tables 9 and 10 in combination with growth examples 1 to 8, 200g/m of microbial fertilizer was contained in the heavy metal soil conditioner 2 And humic acid 100 mg/L.m 2 At this time, the reduction rate of the heavy metal after the restoration is the highest, andthat is, the repairing effect on the heavy metal soil is the best, that is, the microorganisms can be propagated to the optimal amount and grow vigorously under the dosage. The microbial fertilizer and the humic acid are used together, so that the survival rate of biological bacterial spores in the microbial fertilizer is improved, the humic acid has the effect of fixing heavy metals, the effect of improving heavy metal soil is improved, meanwhile, the microbial fertilizer and the humic acid can better promote the enrichment of plants on the heavy metals, on the effects, the microbial fertilizer and the humic acid can supplement a large amount of organic matters and microorganisms after entering the soil, and the humic acid can adjust the pH value of the soil, so that the effect of improving the soil is better. The mixture of the microbial fertilizer and the humic acid is used for repairing the heavy metal contaminated soil, so that the survival rate and the germination rate of biological bacteria spores can be improved, the survival rate of the biological bacteria is improved, and a better repairing effect is achieved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. A heavy metal soil conditioner, characterized in that the conditioner comprises a mixture of microbial fertilizer and humic acid in the ratio of 200 g/m: 100 mg/L-m, wherein the microbial fertilizer comprises the following raw materials in parts by weight:
weathered coal 5 parts
10 portions of biological bacteria
50 portions of straw
20 portions of common selfheal fruit-spike
10 portions of water
5 portions of trace elements
5 parts of algin
And 2 parts of chitosan.
2. The heavy metal soil amendment of claim 1, wherein the biological bacteria comprise rhizobium meliloti/cyanobacteria/bacillus subtilis/sacculus moserii at a mass ratio of 1: 3: 1: 2.
3. The heavy metal soil conditioner as claimed in claim 1, wherein the formula of the trace elements is manganese sulfate 0.6mg/L, ferric sulfate 120mg/L, and ammonium molybdate 0.6 mg/L.
4. The heavy metal soil conditioner according to claim 1, wherein the humic acid is prepared from the following raw materials in parts by weight:
40 parts of lignite
12 parts of 3mol/L nitric acid solution
12 parts of 3mol/L mixed solution of sodium hydroxide and sodium carbonate
4 parts of a catalyst.
5. The heavy metal soil conditioner according to claim 4, wherein said catalyst is a 3mol/L sodium hydroxide solution.
6. The preparation method of the heavy metal soil conditioner is characterized by comprising the following steps:
s1, mixing one fourth of humic acid with the microbial fertilizer in a fluid state, and controlling the pH of the mixture to be between 6.8 and 7.5;
s2, dividing the mixture into fluids with the diameter of 1 g;
and S3, spraying the remaining three quarters of humic acid on the surface of the mixture fluid until a layer of humic acid shell is formed.
7. The preparation method of the heavy metal soil conditioner as claimed in claim 6, wherein the preparation method of the microbial fertilizer at least comprises the following steps:
s01, weighing weathered coal, straw, hay, algin and chitosan according to parts by weight, and grinding;
s02, adding a certain weight part of water into the ground powder, and performing primary fermentation for 6 hours at the temperature of 20-25 ℃ and the pH = 6-8;
s03, after the primary fermentation is finished, adjusting the temperature to 40 ℃, adjusting the pH to 7.1-7.5, and fermenting for 10 days;
s04, weighing alfalfa rhizobia, cyanobacteria, bacillus subtilis, Moses sacculus mildew and trace elements in parts by weight, and adding the weighed materials into the fermentation product.
8. The preparation method of the heavy metal soil conditioner according to claim 6, wherein the preparation of the humic acid at least comprises the following steps:
s11, weighing lignite according to parts by weight, grinding, placing in a reaction kettle, introducing mixed gas of oxygen and water vapor at the temperature of 180 ℃, and adding a catalyst for reaction;
s12, mixing and reacting the fully reacted lignite with 6 parts of nitric acid solution;
s13, filtering after the reaction is completed, wherein the filtrate is fulvic acid solution;
s14, putting the filter residue into a mixed solution of sodium hydroxide and sodium carbonate for reaction;
s15, filtering after the reaction is completed to obtain filtrate;
s16, adding 6 parts of nitric acid solution into the filtrate to adjust the pH to be less than or equal to 2, and generating precipitate;
s17, filtering the precipitate, and drying to obtain solid humic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210352882.2A CN114804950A (en) | 2022-03-31 | 2022-03-31 | Heavy metal soil conditioner and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210352882.2A CN114804950A (en) | 2022-03-31 | 2022-03-31 | Heavy metal soil conditioner and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114804950A true CN114804950A (en) | 2022-07-29 |
Family
ID=82532106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210352882.2A Pending CN114804950A (en) | 2022-03-31 | 2022-03-31 | Heavy metal soil conditioner and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114804950A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049412A (en) * | 2009-11-05 | 2011-05-11 | 南开大学 | Biological compound preparation for repairing soil heavy metal pollution |
| CN102219614A (en) * | 2011-04-12 | 2011-10-19 | 天津海林园艺环保科技工程有限公司 | Biological improving fertilizer special for saline-alkali soil and preparation method thereof |
| CN103450285A (en) * | 2013-08-26 | 2013-12-18 | 张予 | Preparation method of humic acid |
| CN103752281A (en) * | 2014-01-21 | 2014-04-30 | 南京林业大学 | Magnetic humic acid nano material as well as preparation method and application of magnetic humic acid nano material |
| CN104193559A (en) * | 2014-09-09 | 2014-12-10 | 天津海林园艺环保科技工程有限公司 | Seashore saline soil improving and conditioning agent and preparation method thereof |
| CN105152781A (en) * | 2015-09-27 | 2015-12-16 | 天津东升阳化肥股份有限公司 | Biological semi-organic fertilizer containing amino acid and making method thereof |
| CN105585381A (en) * | 2015-12-23 | 2016-05-18 | 成都新柯力化工科技有限公司 | Microbial water-soluble fertilizer and preparation method thereof |
| CN106748347A (en) * | 2017-03-30 | 2017-05-31 | 山西广宇通科技股份有限公司 | A kind of method that utilization fluid bed prepares humic acid complex micro organism fungicide |
-
2022
- 2022-03-31 CN CN202210352882.2A patent/CN114804950A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049412A (en) * | 2009-11-05 | 2011-05-11 | 南开大学 | Biological compound preparation for repairing soil heavy metal pollution |
| CN102219614A (en) * | 2011-04-12 | 2011-10-19 | 天津海林园艺环保科技工程有限公司 | Biological improving fertilizer special for saline-alkali soil and preparation method thereof |
| CN103450285A (en) * | 2013-08-26 | 2013-12-18 | 张予 | Preparation method of humic acid |
| CN103752281A (en) * | 2014-01-21 | 2014-04-30 | 南京林业大学 | Magnetic humic acid nano material as well as preparation method and application of magnetic humic acid nano material |
| CN104193559A (en) * | 2014-09-09 | 2014-12-10 | 天津海林园艺环保科技工程有限公司 | Seashore saline soil improving and conditioning agent and preparation method thereof |
| CN105152781A (en) * | 2015-09-27 | 2015-12-16 | 天津东升阳化肥股份有限公司 | Biological semi-organic fertilizer containing amino acid and making method thereof |
| CN105585381A (en) * | 2015-12-23 | 2016-05-18 | 成都新柯力化工科技有限公司 | Microbial water-soluble fertilizer and preparation method thereof |
| CN106748347A (en) * | 2017-03-30 | 2017-05-31 | 山西广宇通科技股份有限公司 | A kind of method that utilization fluid bed prepares humic acid complex micro organism fungicide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106905980B (en) | Heavy metal soil remediation agent, preparation method and application thereof in sludge digestion | |
| CN101284741B (en) | Ecological organic fertilizer | |
| CN108410470B (en) | Microbial soil conditioner for saline-alkali soil and preparation method thereof | |
| CN110734333A (en) | microbial soil remediation agent and preparation method thereof | |
| CN110950707A (en) | Sandy soil conditioner and preparation method thereof | |
| CN111849501B (en) | Soil conditioner for repairing soil nickel pollution and preparation method and use method thereof | |
| CN112553100B (en) | Composite microbial agent and method for soil fertility improvement and ecological restoration of heavy metal-containing field by using same | |
| EP3090994A1 (en) | Method of producing a biofertilizer comprising fermentation in the solid state, immobilization by means of allophane nanoparticles and renewed fermentation, and biofertilizer | |
| CN106905052A (en) | Heavy metal pollution alkaline land modifying agent and saline and alkali land improvement method comprising spent bleaching clay | |
| CN111792971A (en) | Organic microbial fertilizer harmless to environment | |
| CN111635276A (en) | Conditioner for soil remediation and using method thereof | |
| CN106905982A (en) | Using the heavy metal pollution alkaline land modifying agent and saline and alkali land improvement method of spent bleaching clay | |
| CN113480364B (en) | Organic fertilizer for treating heavy metal pollution and preparation method thereof | |
| CN114804950A (en) | Heavy metal soil conditioner and preparation method thereof | |
| CN115677403A (en) | Microbial composite release and control fertilizer and application thereof | |
| CN111819946B (en) | Comprehensive improvement method for rice field soil ecological environment | |
| CN115465851A (en) | Synergistic application method for conditioning red soil by modified biomass carbon/humus/chemical fertilizer | |
| CN115448800A (en) | Bio-organic fertilizer and preparation method and application thereof | |
| CN113897200A (en) | Microbial soil remediation agent and preparation method thereof | |
| CN113416110A (en) | Preparation method of organic-inorganic environment-friendly pollution-free fertilizer | |
| CN112322303A (en) | Organic biological cadmium-reducing soil conditioner containing fish protein and preparation method thereof | |
| CN112522248A (en) | Preparation method and application of coated enterobacter cloacae Y16 solid microbial inoculum | |
| CN110746229A (en) | Microbial fertilizer for improving soil hardening condition | |
| Radwan | Evaluation of elemental sulphur application with Rhizobia inoculation on peanut yield and its quality grown in sandy soil at Egypt | |
| CN111247895A (en) | Cadmium-polluted rice field restoration method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220729 |