CN107824609A - One heavy metal species soil-repairing agent and preparation method and application - Google Patents
One heavy metal species soil-repairing agent and preparation method and application Download PDFInfo
- Publication number
- CN107824609A CN107824609A CN201710966298.5A CN201710966298A CN107824609A CN 107824609 A CN107824609 A CN 107824609A CN 201710966298 A CN201710966298 A CN 201710966298A CN 107824609 A CN107824609 A CN 107824609A
- Authority
- CN
- China
- Prior art keywords
- soil
- heavy metal
- stalk
- agent
- repairing agent
- 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
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002689 soil Substances 0.000 claims abstract description 123
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 113
- 238000009418 renovation Methods 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 53
- 239000002923 metal particle Substances 0.000 claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 17
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000001913 cellulose Substances 0.000 claims abstract description 15
- 229920002678 cellulose Polymers 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000007885 magnetic separation Methods 0.000 claims abstract description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000012216 screening Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000003466 welding Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000012545 processing Methods 0.000 claims description 20
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 11
- -1 iron ion Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 7
- 238000013532 laser treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims 1
- 239000011790 ferrous sulphate Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 18
- 238000005067 remediation Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003672 processing method Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 235000015759 Artemisia selengensis Nutrition 0.000 description 1
- 241001168877 Artemisia selengensis Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000749 chronicity Toxicity 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- 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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic 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
- C09K2101/00—Agricultural use
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to technical field of soil remediation, there is provided a heavy metal species soil-repairing agent and preparation method and application.This method is added in copperas solution after stalk is crushed first, and addition ammoniacal liquor interweaves with hydrogen peroxide generation ferric hydroxide gel with stalk cellulose, after standing, wash, filter, drying and grinding, obtains heavy metal soil-repairing agent.Renovation agent is scattered in soil and adsorbs heavy metal particles, it is bulky grain that then laser irradiation welding, which is reunited, then removes renovation agent through magnetic separation screening machine, you can realizes the permanent removing of heavy metal in soil.Compared with conventional method, the processing method of the present invention can effectively prevent secondary pollution, gained renovation agent adsorption capacity is strong, and efficiency high is applied widely, the heavy metal particles in soil can be made permanently to remove, whole process cost is low simultaneously, simple to operate, easy to control, it is pollution-free, there is good comprehensive benefit.
Description
Technical field
The invention belongs to technical field of soil remediation, there is provided a heavy metal species soil-repairing agent and preparation method and should
With.
Background technology
Soil not only provides mechanical support ability for plant growth, and water required for being provided for growth and development of plants,
The fertility key element such as fertilizer, air and heat.In recent years, due to population sharp increase, the continuous quickening of process of industrialization, mineral resources are not
Rational exploitation and its smelting discharge, the reasons such as sewage irrigation and sludge administration, the administration of chemical fertilizer and agricultural chemicals are carried out to soil for a long time,
Solid waste is constantly stacked and toppled over to soil surface, and harmful waste water constantly permeates into soil, pernicious gas in air and
Floating dust is also constantly dropped in soil with rainwater, causes increasingly severe soil contamination problem occurred.
Heavy metal pollution of soil numerous types, source is widely distributed, and can farming land crops be produced with harm, more serious
It is that some virose heavy metals have disguised, chronicity and irreversibility during to Sichuan.Soil
Earth heavy metal pollution has form changeable and is difficult two features of degraded.
At present, it is mainly physical-chemical process reparation to heavy metal pollution of soil recovery technique and biological prosthetic.Wherein physics
Chemical method includes chemosetting, Soil leaching and electro reclamation etc.；It is biological prosthetic including microorganism remediation and phytoremediation.Wherein
It is widely used to have chemosetting, microorganism remediation and phytoremediation.Chemosetting reparation is mainly to make the weight in soil
Precipitated metal absorption complexing chelating, there is important meaning to stabilizing heavy metal；Biological prosthetic is to utilize to have pollutant necessarily
The microorganism of resistance, in its physiology course, pollutant is degraded, converted and adsorbed；Phytoremediation is with Plant Tolerance
Based on some pollutants are accumulated, fixed using the plant absorption of growth naturally or heredity culture and remove heavy metal contaminants
Method.Domestic and international researcher has obtained certain achievement in terms of heavy metal pollution of soil reparation, and Hu et al. has invented one kind
The method for administering heavy-metal contaminated soil, this method are entered by vertical sampling and level sampling to the content of beary metal value in soil
Row more accurate measurement, animal bone powder heavy metal ion has good suction-operated, phosphoric acid in the heavy metal stabilizer of addition
Sodium dihydrogen, sodium lignin sulfonate, potassium chloride, hydroxyapatite comprehensive function can be made with the chemism of curing heavy metal ion
Absorbed after it is adsorbed with other biological nutriment by the rhizome of artemisia selengensis, soil improvement agent is added, in microorganism isoreactivity thing
Under matter effect, suppress the harmful bacteria in soil, liquid microbe fertilizer improves the fertility and growth activity of soil.Meanwhile
Zhong et al. has invented a kind of heavy metal-polluted soil renovation agent and preparation method thereof, and this heavy metal-polluted soil renovation agent includes macromolecule
Polymer and filler, high molecular polymer can form stable chelate with heavy metal ion, effectively will be free in soil
Heavy metal ion adsorbed fixation, heavy metal activity is reduced, prevent crop from absorbing, and control it to move by the suction-operated of filler
Move.However, the either biological fixation of above-mentioned technology or chemistry are fixed, all it is difficult to heavy metal being forever fixed, exists again
The secondary risk being lost in again because of environmental change into soil, and preparation process is complicated and cost is high, hinders heavy metal-polluted soil
The development of pollution amelioration.
The content of the invention
The defects of being difficult to be permanently fixed be present for existing heavy metal-polluted soil treatment technology, the present invention proposes a heavy metal species
Soil-repairing agent and preparation method and application.It is characterized in iron hydroxide and stalk being prepared into gel, then dries and formed by straw
The nano-pore sorbing material of stalk fiber element and iron hydroxide uniform interleaving, i.e. heavy metal soil-repairing agent.For except in de- soil
Heavy metal when, application method is that heavy metal soil-repairing agent is scattered in into soil, make heavy metal renovation agent fully adsorb a huge sum of money
Belong to ion, then weld the adsorbent of absorption heavy metal ion using laser irradiation and agglomerate into bulky grain, further pass through
Magnetic separation sub-sieve is by by the bulky grain adsorbent of absorption heavy metal ion, sub-sieve goes out from soil.Its significant advantage is to utilize absorption
The bulky grain of heavy metal accumulation is obtained with laser welding, and is screened out from soil, heavy metal is fundamentally solved and is lost in again
The problem of in soil.
The heavy metal soil-repairing agent of the present invention, can effectively solve the problems, such as heavy metal pollution of soil, prevent heavy metal
Again because environmental change is lost in the risk into soil again, and preparation process is relatively simple, and cost is low, is suitable for extensive
Promote.
To achieve the above object, the present invention adopts the following technical scheme that：
The preparation method of one heavy metal species soil-repairing agent, it is characterized in that being added after stalk is crushed in copperas solution, add
Ammonification water interweaves with hydrogen peroxide generation ferric hydroxide gel with stalk cellulose, after standing, wash, filter, drying and grinding,
Obtain heavy metal soil-repairing agent；Specific preparation method is as follows：
Stalk is crushed to obtain of length no more than 5mm stalk particle, then stalk particle is added in copperas solution, stirred
Mix uniformly, be placed in constant temperature water bath, and ammoniacal liquor and hydrogen peroxide are continuously added under stirring, until system ferrous ions
All be oxidized to iron ion, form ferric hydroxide gel, and with stalk cellulose uniform interleaving；After standing certain time, use
Distillation water washing simultaneously filters, heating, drying, and being milled in grinder in atmosphere, the obtained sorbing material with nano-pore
As heavy metal soil-repairing agent.
Preferably, the mass concentration of the copperas solution is 10 ~ 15%；
Preferably, the addition of the stalk particle is the 5 ~ 10% of copperas solution quality；
Preferably, the temperature of the water bath with thermostatic control is 70 ~ 90 DEG C；
Preferably, the time of repose is 10 ~ 12h；
Preferably, the drying temperature is 100 ~ 120 DEG C.
One heavy metal species soil-repairing agent, it is characterized in that fine with stalk by the ferric hydroxide gel that the above method is prepared
Dimension element interweaves, and has the sorbing material of nano-pore.It has excellent absorption fixation to the heavy metal put forward in allowing.
The application of one heavy metal species soil-repairing agent, it is characterized in that：The heavy metal soil remediation that the above method is prepared
Agent, heavy metal particles are adsorbed by being scattered in soil, it is bulky grain that then laser irradiation welding, which is reunited, then through magnetic separation screening machine
Remove renovation agent, you can realize the permanent removing of heavy metal in soil；Concrete application method is as follows：
The renovation agent of gained is mixed and is uniformly dispersed by certain mass ratio with soil, makes the nano aperture of renovation agent abundant
Effectively absorption heavy metal particles；Then mixed soil is placed in Laser room, opens continuous wave laser generator and spoke is carried out to it
According to processing, the renovation agent for adsorbing heavy metal particles welds under laser action, forms the bulky grain of reunion；Then will mixing
Soil is added in magnetic separation screening machine, and bulky grain renovation agent is screened from soil, you can by heavy metal from soil it is permanent
Property remove.
Preferably, the addition of the renovation agent is the 1 ~ 3% of soil quality；
Preferably, the frequency of the continuous wave laser is 4.5 ~ 6.5 × 1014Hz, power density are 2 ~ 8 × 105W/cm2；
Preferably, step（2）The time of the laser treatment is 2 ~ 4min.
In the present invention, in the preparation process of renovation agent, because iron hydroxide uses generated in-situ mode, therefore need to adopt
Take the mode of titration to determine reaction end, to avoid the presence of over oxidation or ferrous ion, the potassium ferricyanide and ferrous cyanogen can be used
Change potassium solution to be detected, it is ensured that the ferro element in system is changed into ferric ion and forms ferric hydroxide gel.Prepare
During should be stirred continuously, on the one hand in the presence of shearing force is stirred, rupture the outer wall of stalk particle, promote stalk particle
Expansion and cellulose effusion, on the other hand make the ammoniacal liquor of addition and hydrogen peroxide dispersed as early as possible in the mixture, favorably
In the formation speed for improving ferric hydroxide gel and prevent that addition is excessive.The heavy metal particles in using renovation agent absorption soil
When, renovation agent should be made to be uniformly dispersed in soil first, to prevent that absorption is uneven.In laser treatment, laser should be rationally controlled
Frequency and power density.Laser frequency is too low or power density is too small, and the welding of renovation agent is incomplete, is unfavorable for an absorption huge sum of money
The complete removing of the renovation agent of category.And laser frequency is too high or power density is excessive, it may simultaneously kill and be advantageous to plant in soil
The material that thing grows or soil property improves, causes soil quality to decline.
The invention provides a heavy metal species soil-repairing agent and preparation method and application, and compared with prior art, it is prominent
The characteristics of going out and excellent effect are：
1. the processing method of the present invention is without adding chemical reagent into soil, it is therefore prevented that secondary pollution.
2. the present invention prepares renovation agent, stalk is used as raw material, is formed and handed over using the cellulose in it and iron hydroxide
Structure is knitted, one side stalk source is wide, cost is cheap, on the other hand promotes the recycling of stalk, reduces stalk processing band
The environmental problem come.
3. renovation agent prepared by the present invention has the hole of nano-scale, adsorption capacity is strong, efficiency high.
It is bulky grain that 4. the present invention, which is reunited the renovation agent for adsorbing heavy metal particles by laser welding, then sieves removing,
The heavy metal particles in soil can be made permanently to remove, solve conventional treatment method easily because environmental change causes heavy metal again
The defects of loss enters soil.
5. preparation method cost of the present invention is low, simple to operate, easy to control, pollution-free, it is adapted to large-scale production, has good
Comprehensive benefit.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 3min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 0.5kg stalk particles are added
10kg mass concentrations are in 15% copperas solution, stir, are placed in 90 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 12h, using distillation water washing and filter, be heated to 100 DEG C of drying in atmosphere
8h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By obtained by 3kg
Renovation agent is mixed and is uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.Then
Mixed soil is placed in Laser room, continuous wave laser generator is opened and carries out radiation treatment to it, laser frequency is 6.5 ×
1014Hz, power density are 2 × 105W/cm2, processing time 4min, make the renovation agent of absorption heavy metal particles in laser action
It is lower to weld, form the bulky grain of reunion.Then mixed soil is added in magnetic separation screening machine, by bulky grain renovation agent from soil
Screened in earth, you can permanently remove heavy metal from soil.
The heavy metal soil-repairing agent prepared using the method for embodiment 1, use it for handling the soil of heavy metal pollution,
Heavy metal particles concentration before test processes and after processing, and compared with conventional treatment method, obtained data are as described in Table 1.
It can be seen that：Heavy metal soil-repairing agent prepared by the method for the present invention, has more preferable repairing effect, heavy metal in soil can be made residual
Rate is stayed to be less than 5%.
Embodiment 2
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 3min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 1kg stalk particles are added
10kg mass concentrations are in 10% copperas solution, stir, are placed in 70 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 10h, using distillation water washing and filter, be heated to 100 DEG C of drying in atmosphere
8h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By obtained by 2kg
Renovation agent is mixed and is uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.Then
Mixed soil is placed in Laser room, continuous wave laser generator is opened and carries out radiation treatment to it, laser frequency is 4.5 ×
1014Hz, power density are 8 × 105W/cm2, processing time 2min, make the renovation agent of absorption heavy metal particles in laser action
It is lower to weld, form the bulky grain of reunion.Then mixed soil is added in magnetic separation screening machine, by bulky grain renovation agent from soil
Screened in earth, you can permanently remove heavy metal from soil.
The heavy metal soil-repairing agent prepared using the method for embodiment 2, use it for handling the soil of heavy metal pollution,
Heavy metal particles concentration before test processes and after processing, and compared with conventional treatment method, obtained data are as described in Table 1.
It can be seen that：Heavy metal soil-repairing agent prepared by the method for the present invention, has more preferable repairing effect, heavy metal in soil can be made residual
Rate is stayed to be less than 5%.
Embodiment 3
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 2min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 0.8kg stalk particles are added
10kg mass concentrations are in 12% copperas solution, stir, are placed in 80 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 11h, using distillation water washing and filter, be heated to 110 DEG C of drying in atmosphere
9h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By 1.5kg institutes
Obtain renovation agent to mix and be uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.So
Mixed soil is placed in Laser room afterwards, continuous wave laser generator is opened and carries out radiation treatment to it, laser frequency is 5 ×
1014Hz, power density are 3 × 105W/cm2, processing time 3min, make the renovation agent of absorption heavy metal particles in laser action
It is lower to weld, form the bulky grain of reunion.Then mixed soil is added in magnetic separation screening machine, by bulky grain renovation agent from soil
Screened in earth, you can permanently remove heavy metal from soil.
The heavy metal soil-repairing agent prepared using the method for embodiment 3, use it for handling the soil of heavy metal pollution,
Heavy metal particles concentration before test processes and after processing, and compared with conventional treatment method, obtained data are as described in Table 1.
It can be seen that：Heavy metal soil-repairing agent prepared by the method for the present invention, has more preferable repairing effect, heavy metal in soil can be made residual
Rate is stayed to be less than 5%.
Embodiment 4
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 3min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 0.7kg stalk particles are added
10kg mass concentrations are in 15% copperas solution, stir, are placed in 70 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 10h, using distillation water washing and filter, be heated to 100 DEG C of drying in atmosphere
8h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By 2.5kg institutes
Obtain renovation agent to mix and be uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.So
Mixed soil is placed in Laser room afterwards, continuous wave laser generator is opened and carries out radiation treatment to it, laser frequency is 6 ×
1014Hz, power density are 4 × 105W/cm2, processing time 4min, make the renovation agent of absorption heavy metal particles in laser action
It is lower to weld, form the bulky grain of reunion.Then mixed soil is added in magnetic separation screening machine, by bulky grain renovation agent from soil
Screened in earth, you can permanently remove heavy metal from soil.
The heavy metal soil-repairing agent prepared using the method for embodiment 4, use it for handling the soil of heavy metal pollution,
Heavy metal particles concentration before test processes and after processing, and compared with conventional treatment method, obtained data are as described in Table 1.
It can be seen that：Heavy metal soil-repairing agent prepared by the method for the present invention, has more preferable repairing effect, heavy metal in soil can be made residual
Rate is stayed to be less than 5%.
Embodiment 5
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 2min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 0.5kg stalk particles are added
10kg mass concentrations are in 10% copperas solution, stir, are placed in 70 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 12h, using distillation water washing and filter, be heated to 110 DEG C of drying in atmosphere
10h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By obtained by 3kg
Renovation agent is mixed and is uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.Then
Mixed soil is placed in Laser room, continuous wave laser generator is opened and carries out radiation treatment to it, laser frequency is 4.8 ×
1014Hz, power density are 6 × 105W/cm2, processing time 2min, make the renovation agent of absorption heavy metal particles in laser action
It is lower to weld, form the bulky grain of reunion.Then mixed soil is added in magnetic separation screening machine, by bulky grain renovation agent from soil
Screened in earth, you can permanently remove heavy metal from soil.
The heavy metal soil-repairing agent prepared using the method for embodiment 5, use it for handling the soil of heavy metal pollution,
Heavy metal particles concentration before test processes and after processing, and compared with conventional treatment method, obtained data are as described in Table 1.
It can be seen that：Heavy metal soil-repairing agent prepared by the method for the present invention, has more preferable repairing effect, heavy metal in soil can be made residual
Rate is stayed to be less than 5%.
Embodiment 6
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 3min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 1kg stalk particles are added
10kg mass concentrations are in 15% copperas solution, stir, are placed in 90 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 10h, using distillation water washing and filter, be heated to 100 DEG C of drying in atmosphere
10h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By obtained by 2kg
Renovation agent is mixed and is uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.Then
Mixed soil is placed in Laser room, continuous wave laser generator is opened and carries out radiation treatment to it, laser frequency is 6.2 ×
1014Hz, power density are 7 × 105W/cm2, processing time 2.5min, the renovation agent of absorption heavy metal particles is made in laser
Welded with lower, form the bulky grain of reunion.Then by mixed soil add magnetic separation screening machine in, by bulky grain renovation agent from
Screened in soil, you can permanently remove heavy metal from soil.
The heavy metal soil-repairing agent prepared using the method for embodiment 6, use it for handling the soil of heavy metal pollution,
Heavy metal particles concentration before test processes and after processing, and compared with conventional treatment method, obtained data are as described in Table 1.
It can be seen that：Heavy metal soil-repairing agent prepared by the method for the present invention, has more preferable repairing effect, heavy metal in soil can be made residual
Rate is stayed to be less than 5%.
Embodiment 7
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 2min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 0.8kg stalk particles are added
10kg mass concentrations are in 13% copperas solution, stir, are placed in 80 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 10h, using distillation water washing and filter, be heated to 120 DEG C of drying in atmosphere
10h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By obtained by 1kg
Renovation agent is mixed and is uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.Then
Mixed soil is placed in Laser room, continuous wave laser generator is opened and carries out radiation treatment to it, laser frequency is 5.5 ×
1014Hz, power density are 5 × 105W/cm2, processing time 3.5min, the renovation agent of absorption heavy metal particles is made in laser
Welded with lower, form the bulky grain of reunion.Then by mixed soil add magnetic separation screening machine in, by bulky grain renovation agent from
Screened in soil, you can permanently remove heavy metal from soil.
The heavy metal soil-repairing agent prepared using the method for embodiment 7, use it for handling the soil of heavy metal pollution,
Heavy metal particles concentration before test processes and after processing, and compared with conventional treatment method, obtained data are as described in Table 1.
It can be seen that：Heavy metal soil-repairing agent prepared by the method for the present invention, has more preferable repairing effect, heavy metal in soil can be made residual
Rate is stayed to be less than 5%.
Comparative example 1
One heavy metal species soil-repairing agent and preparation method and application, it is prepared and the detailed process of rehabilitating soil is as follows：
Stalk crasher and its motor are arranged on made of angle steel on support, first dally 2min after startup, after confirming normally,
Stalk continuous dosing will be dried, is grinding to obtain of length no more than 5mm stalk particle.Then 0.8kg stalk particles are added
10kg mass concentrations are in 13% copperas solution, stir, are placed in 80 DEG C of constant temperature water bath, and in stirring shape
Ammoniacal liquor and hydrogen peroxide are continuously added under state, until system ferrous ions are all oxidized to iron ion, forms ferric hydroxide gel,
And with stalk cellulose uniform interleaving.After standing 10h, using distillation water washing and filter, be heated to 120 DEG C of drying in atmosphere
10h, and be milled in grinder, the obtained sorbing material with nano-pore is heavy metal soil-repairing agent；By obtained by 1kg
Renovation agent is mixed and is uniformly dispersed with 100kg soil, the nano aperture of renovation agent is fully effectively adsorbed heavy metal particles.Then
Mixed soil is added in magnetic separation screening machine, renovation agent is screened from soil.
Using the default laser treatment of comparative example 1, the heavy metal particles concentration before test processes and after processing, and with routine
Processing method compares, and obtained data are as described in Table 1.
Comparative example 2
Using the heavy metal in plant soil restoration, the reparation phase is a season.Repairing effect such as table 1.
Table 1：
By verification experimental verification, renovation agent of the present invention due to heavy metal with excellent adsorptivity, will be adsorbed by laser welding
Bulky grain is formed, and is isolated by magnetic separation, heavy metal is thoroughly separated from soil.Comparative example is due to default laser welding
Processing, adsorb heavy metal renovation agent separation it is not thorough, influence treatment effect.And conventional plant soil restoration, due to counterweight
Metal is selective, and long processing period, therefore repairing effect is substantially less than the present invention.
Claims (9)
1. the preparation method of a heavy metal species soil-repairing agent, it is characterized in that added after stalk is crushed in copperas solution,
Add ammoniacal liquor with hydrogen peroxide generation ferric hydroxide gel with stalk cellulose to interweave, through standing, washing, filtering, drying and grinding
Afterwards, heavy metal soil-repairing agent is obtained；Specific preparation method is as follows：
Stalk is crushed to obtain of length no more than 5mm stalk particle, then stalk particle is added in copperas solution, stirred
Mix uniformly, be placed in constant temperature water bath, and ammoniacal liquor and hydrogen peroxide are continuously added under stirring, until system ferrous ions
All be oxidized to iron ion, form ferric hydroxide gel, and with stalk cellulose uniform interleaving；After standing certain time, use
Distillation water washing simultaneously filters, heating, drying, and being milled in grinder in atmosphere, the obtained sorbing material with nano-pore
As heavy metal soil-repairing agent.
2. the preparation method of a heavy metal species soil-repairing agent according to claim 1, it is characterised in that：The ferrous sulfate
The mass concentration of solution is 10 ~ 15%.
3. the preparation method of a heavy metal species soil-repairing agent according to claim 1, it is characterised in that：The stalk particle
Addition be copperas solution quality 5 ~ 10%.
4. the preparation method of a heavy metal species soil-repairing agent according to claim 1, it is characterised in that：The water bath with thermostatic control
Temperature be 70 ~ 90 DEG C；The time of repose is 10 ~ 12h；Preferably, the drying temperature is 100 ~ 120 DEG C.
A 5. heavy metal species soil-repairing agent, it is characterized in that being prepared by any one of claim 1-4 methods described.
6. a kind of application of heavy metal soil-repairing agent as claimed in claim 5, it is characterized in that：Adsorbed by being scattered in soil
Heavy metal particles, it is bulky grain that then laser irradiation welding, which is reunited, then removes renovation agent through magnetic separation screening machine, you can realizes soil
The permanent removing of middle heavy metal；Concrete application method is as follows：
The renovation agent of gained is mixed and is uniformly dispersed by certain mass ratio with soil, makes the nano aperture of renovation agent abundant
Effectively absorption heavy metal particles；Then mixed soil is placed in Laser room, opens continuous wave laser generator and spoke is carried out to it
According to processing, the renovation agent for adsorbing heavy metal particles welds under laser action, forms the bulky grain of reunion；Then will mixing
Soil is added in magnetic separation screening machine, and bulky grain renovation agent is screened from soil, you can by heavy metal from soil it is permanent
Property remove.
7. apply according to claim 6, it is characterized in that：The addition of the renovation agent is the 1 ~ 3% of soil quality.
8. apply according to claim 6, it is characterized in that：The frequency of the continuous wave laser is 4.5 ~ 6.5 × 1014Hz, work(
Rate density is 2 ~ 8 × 105W/cm2。
9. apply according to claim 6, it is characterized in that：Step（2）The time of the laser treatment is 2 ~ 4min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710966298.5A CN107824609B (en) | 2017-10-17 | 2017-10-17 | Heavy metal soil remediation agent, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710966298.5A CN107824609B (en) | 2017-10-17 | 2017-10-17 | Heavy metal soil remediation agent, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107824609A true CN107824609A (en) | 2018-03-23 |
| CN107824609B CN107824609B (en) | 2021-06-11 |
Family
ID=61648309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710966298.5A Active CN107824609B (en) | 2017-10-17 | 2017-10-17 | Heavy metal soil remediation agent, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107824609B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484269A (en) * | 2019-08-20 | 2019-11-22 | 北京上水环境科技发展有限公司 | A kind of heavy-metal contaminated soil renovation agent and its preparation and application method |
| CN112916607A (en) * | 2021-01-26 | 2021-06-08 | 广东中科碧城环境技术有限公司 | Stabilization restoration method for heavy metal contaminated soil |
| CN115624955A (en) * | 2022-10-25 | 2023-01-20 | 广州怀特远科技有限公司 | Biochar soil heavy metal restoration agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593745A (en) * | 2004-07-05 | 2005-03-16 | 南开大学 | Ferrum carried spherical cellulose adsorbent, preparation and application thereof |
| CN104893732A (en) * | 2015-06-05 | 2015-09-09 | 中国地质科学院矿产资源研究所 | Remediation agent S-PbCd for remediating heavy metal Pb-Cd combined contaminated soil as well as preparation method and use method thereof |
| CN106336038A (en) * | 2016-09-22 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Treatment method for heavy metal-containing polluted wastewater |
-
2017
- 2017-10-17 CN CN201710966298.5A patent/CN107824609B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593745A (en) * | 2004-07-05 | 2005-03-16 | 南开大学 | Ferrum carried spherical cellulose adsorbent, preparation and application thereof |
| CN104893732A (en) * | 2015-06-05 | 2015-09-09 | 中国地质科学院矿产资源研究所 | Remediation agent S-PbCd for remediating heavy metal Pb-Cd combined contaminated soil as well as preparation method and use method thereof |
| CN106336038A (en) * | 2016-09-22 | 2017-01-18 | 东莞市联洲知识产权运营管理有限公司 | Treatment method for heavy metal-containing polluted wastewater |
Non-Patent Citations (1)
| Title |
|---|
| 虞钢: "《激光制造工艺力学》", 31 January 2012, 国防工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484269A (en) * | 2019-08-20 | 2019-11-22 | 北京上水环境科技发展有限公司 | A kind of heavy-metal contaminated soil renovation agent and its preparation and application method |
| CN112916607A (en) * | 2021-01-26 | 2021-06-08 | 广东中科碧城环境技术有限公司 | Stabilization restoration method for heavy metal contaminated soil |
| CN115624955A (en) * | 2022-10-25 | 2023-01-20 | 广州怀特远科技有限公司 | Biochar soil heavy metal restoration agent and preparation method thereof |
| CN115624955B (en) * | 2022-10-25 | 2024-05-28 | 李智强 | Biochar soil heavy metal restoration agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107824609B (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105013811B (en) | A kind of preparation and application of heavy metal chromium pollution soil remediation material | |
| CN106216379B (en) | Comprehensive leaching remediation method and system for heavy metal contaminated soil | |
| CN103894395B (en) | A kind of method that heavy-metal contaminated soil secondary is repaired | |
| CN103894407B (en) | A kind of method of restoration of soil polluted by heavy metal | |
| CN107116097A (en) | A kind of method for repairing As polluted soil | |
| CN110076185B (en) | Method for repairing heavy metal and polycyclic aromatic hydrocarbon combined contaminated soil | |
| CN105923961B (en) | A kind of smelly river bottom mud repairing and treating material of urban black and preparation method thereof | |
| CN106978185A (en) | A kind of heavy-metal contaminated soil repairs conditioner and its application | |
| CN104258809A (en) | Modified biomass charcoal and remediation method of heavy metal contaminated soil | |
| CN105131960A (en) | Preparation method and application of lead-polluted soil restoration material | |
| CN108315016A (en) | A kind of porous magnetic humic acid/charcoal particle and preparation method thereof for heavy metal reparation | |
| CN105419807A (en) | Curing agent for heavy metal and organic matter combined polluted soil, and preparation and application methods for curing agent | |
| CN103861866A (en) | Fixed enrichment method for city life compost heavy metals through modified nanocarbon | |
| CN109078972B (en) | Heavy metal contaminated soil remediation material and application method thereof | |
| CN103170501B (en) | Preparation method of in-situ repair material for soil polluted by heavy metal chromium and application of material | |
| CN109575929A (en) | The method of the agent of heavy-metal contaminated soil complex repairation and its rehabilitating soil | |
| Zhao et al. | Effect of nanohydroxyapatite on cadmium leaching and environmental risks under simulated acid rain | |
| CN107824609A (en) | One heavy metal species soil-repairing agent and preparation method and application | |
| CN109370596A (en) | A kind of in-situ passivation the reparation medicament, preparation method and application of cadmium arsenic combined pollution agricultural land soil | |
| CN107893064A (en) | The preparation method and applications of the fixed microalgae bead of charcoal polyvinyl alcohol joint | |
| CN109807164B (en) | Preparation method of high-molecular compound material crosslinked double-modified attapulgite and biomass charcoal filler | |
| CN107555414A (en) | A kind of garden waste biomass carbon and its production and use | |
| CN104772111A (en) | Hydroxyl calcium phosphate-active carbon composite material and application thereof | |
| CN110064369A (en) | A kind of preparation method and applications of charcoal supported nano-gold metal particles | |
| CN110305666A (en) | A kind of heavy metal lead pollution soil stabilizer and preparation 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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210526 Address after: 414000 Zhuguo formation, Wangqiao village, Xitang Town, Yueyang Economic and Technological Development Zone, Yueyang City, Hunan Province Applicant after: Hunan jinxiju Space Technology Co.,Ltd. Address before: 610091, Sichuan, Chengdu province Qingyang dragon industrial port, East Sea 4 Applicant before: CHENDU NEW KELI CHEMICAL SCIENCE Co.,Ltd. CHINA |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210902 Address after: 414000 Yueyang, Hunan economic and Technological Development Zone, Tonghai Road, sun bridge building materials market 8, 23-29 facade. Patentee after: Hunan Katie Engineering Technology Co.,Ltd. Address before: 414000 Zhuguo formation, Wangqiao village, Xitang Town, Yueyang Economic and Technological Development Zone, Yueyang City, Hunan Province Patentee before: Hunan jinxiju Space Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221019 Address after: Room 102, Joint Plant, No. 86, Xindian Road, Tianxin District, Changsha, Hunan 410000 Patentee after: Hunan Jiangshan Chunjin Technology Co.,Ltd. Address before: 414000 Yueyang, Hunan economic and Technological Development Zone, Tonghai Road, sun bridge building materials market 8, 23-29 facade. Patentee before: Hunan Katie Engineering Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230630 Address after: 414000 Yueyang, Hunan economic and Technological Development Zone, Tonghai Road, sun bridge building materials market 8, 23-29 facade. Patentee after: Hunan Katie Engineering Technology Co.,Ltd. Address before: Room 102, Joint Plant, No. 86, Xindian Road, Tianxin District, Changsha, Hunan 410000 Patentee before: Hunan Jiangshan Chunjin Technology Co.,Ltd. |