CN108504862A - A method of it is extracted from cadmium and recycles cadmium in plant harvest object - Google Patents
A method of it is extracted from cadmium and recycles cadmium in plant harvest object Download PDFInfo
- Publication number
- CN108504862A CN108504862A CN201810114032.2A CN201810114032A CN108504862A CN 108504862 A CN108504862 A CN 108504862A CN 201810114032 A CN201810114032 A CN 201810114032A CN 108504862 A CN108504862 A CN 108504862A
- Authority
- CN
- China
- Prior art keywords
- cadmium
- ash
- lime
- pyrolysis
- plant harvest
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of methods for being extracted from cadmium and recycling cadmium in plant harvest object, first thermally decompose cadmium extraction plant harvest object, obtain pyrolysis lime-ash；The pyrolysis lime-ash is mixed with water, obtains pyrolysis lime-ash slurry；The pyrolysis lime-ash slurry is subjected to acidleach, then through filtering, obtains pickle liquor；The pickle liquor is mixed with zinc, is reacted into line replacement, obtains cadmium.The experimental results showed that the method for recycling cadmium provided by the invention, the purity of gained cadmium is 77.2 ~ 88.1%, and the rate of recovery of cadmium realizes the recycling of cadmium, while can cadmium be extracted plant harvest object minimizing up to 85%.
Description
Technical field
The present invention relates to heavy metal recovery processing technology fields, more particularly to a kind of extracted in plant harvest object from cadmium to recycle
The method of cadmium.
Background technology
Phytoremediation is a kind of emerging environmental improvement technology, it is to restrain oneself to be enriched with certain or certainization with excess with plant
Based on the theory for learning element, a kind of environmental renovation technology of the polluted heavy metals in soil is removed using plant.With it is traditional
Physics, technology of chemical engineering are compared, and phytoremediation has following features:When it is applied widely, it can be not only used for removing in soil
Heavy metal contaminants, it can also be used to remove air around contaminated soil, pollutant in water body；Second is that implement in-situ immobilization, it
It is not destroy ecological environment of soil, keeps the situation of soil texture and microbial activity to go down depollution object, soil can be increased
The content of organic matter improves soil texture, improves fertility, while the effect for having concurrently and conserving water and soil, beautify the environment；Third, throwing
Enter at low cost, manpower and materials less investment needed for phytoremediation is easily managed, while recyclable precious metal, there is certain economy
Benefit.Phytoremediation technology has above-mentioned low cost, environmentally protective advantage, has in the agricultural land soil of cadmium pollution is repaired wide
Wealthy application prospect.
Plant is based primarily upon two kinds of mechanism to the reparation of heavy-metal contaminated soil:First, plant is fixed, root system of plant is utilized
Suction-operated or secretory activity by root system, so that the heavy metal mobility in soil is reduced, biological effectiveness declines, and reduces
It is migrated and bio-toxicity, and heavy metal in soil content is not reduced, but form is changed；Second is that plant extract, utilizes
Heavy metal in special plant absorption soil, also referred to as plant extraction.The wherein phytoremediation skill based on plant extraction mechanism
Due to can extract heavy metal from soil the recycling of soil may be implemented, in Cd-polluted farmland soil in art
It has obtained being widely popularized implementation in reparation.
But with the popularization of the phytoremediation technology based on plant extraction mechanism, produce a large amount of cadmium extraction plant harvest
Object.The universal cadmium containing higher concentration of these cuttings, if mishandling can cause secondary pollution.Currently, cadmium extraction plant is received
The disposal technology for obtaining object mainly has landfill, compost, burning and pyrolysis etc..However, existing technology can not extract cadmium,
Realize the recycling of cadmium.
Invention content
The purpose of the present invention is to provide a kind of method for being extracted from cadmium and recycling cadmium in plant harvest object, this method can incite somebody to action
Cadmium is extracted in plant harvest object from cadmium and is extracted, and realizes the recycling of cadmium.
To achieve the above object, the present invention provides a kind of methods for being extracted from cadmium and recycling cadmium in plant harvest object, including
Following steps：
(1) cadmium extraction plant harvest object is thermally decomposed, obtains pyrolysis lime-ash；
(2) the pyrolysis lime-ash is mixed with water, obtains pyrolysis lime-ash slurry；
(3) the pyrolysis lime-ash slurry is subjected to acidleach, then through filtering, obtains pickle liquor；
(4) pickle liquor is mixed with zinc, is reacted into line replacement, obtains cadmium.
Preferably, the temperature of the thermal decomposition is 250~450 DEG C, and the time of the thermal decomposition is 45~60min.
Preferably, the temperature of the thermal decomposition is 300~350 DEG C.
Preferably, the thermal decomposition is carried out in nitrogen atmosphere.
Preferably, the mass ratio of the pyrolysis lime-ash and water is 1:4~6.
Preferably, the acidleach includes the following steps：The pyrolysis lime-ash slurry is heated to 70~90 DEG C, stops adding
Then heat adjusts the pH value of pyrolysis lime-ash slurry to 0.5~1, carries out acid extraction reaction.
Preferably, the time of the acid extraction reaction is 1~2h.
Preferably, the concentrated sulfuric acid that the acid used in the pH value for adjusting pyrolysis lime-ash slurry is a concentration of 95~98wt.%.
Preferably, the temperature of the displacement reaction is 30~70 DEG C, and the time of the displacement reaction is 0.5~2.5h.
Preferably, the ratio between the theoretical addition amount of the zinc and the amount of being actually added into of the zinc are 1:1.3~1.75.
The present invention provides a kind of methods for being extracted from cadmium and recycling cadmium in plant harvest object, and cadmium is extracted plant harvest first
Object is thermally decomposed, and pyrolysis lime-ash is obtained；The pyrolysis lime-ash is mixed with water, obtains pyrolysis lime-ash slurry；By the pyrolysis
Lime-ash slurry carries out acidleach, then through filtering, obtains pickle liquor；The pickle liquor is mixed with zinc, reacts, obtains into line replacement
Cadmium.The present invention thermally decomposes cadmium extraction plant harvest object, and the organic matter in cutting can be made to decompose, and cadmium extraction plant is received
Object loss of weight amount is obtained up to 91.8% (relative to cutting fresh weight), realizes the minimizing of cutting；Pyrolysis lime-ash is prepared into heat
Lime-ash slurry is solved, is conducive to subsequently carry out acidleach；Pyrolysis lime-ash slurry is subjected to acidleach, can will be pyrolyzed the cadmium compound in lime-ash
It is converted into water-soluble salt, through the pickle liquor containing cadmium salt is obtained by filtration；Pickle liquor is mixed with zinc, is reacted through displacement, it will
Cadmium is converted into simple substance, is precipitated, to obtain cadmium.The experimental results showed that method provided by the present invention, the purity of gained cadmium are
77.2~88.1%, the rate of recovery of cadmium is up to 85%.
Description of the drawings
The picture of cadmium prepared by Fig. 1 embodiments 1.
Specific implementation mode
The present invention provides a kind of methods for being extracted from cadmium and recycling cadmium in plant harvest object, include the following steps：
(1) cadmium extraction plant harvest object is thermally decomposed, obtains pyrolysis lime-ash；
(2) the pyrolysis lime-ash is mixed with water, obtains pyrolysis lime-ash slurry；
(3) the pyrolysis lime-ash slurry is subjected to acidleach, then through filtering, obtains pickle liquor；
(4) pickle liquor is mixed with zinc, is reacted into line replacement, obtains cadmium.
The present invention thermally decomposes cadmium extraction plant harvest object, obtains pyrolysis lime-ash.
The type that the present invention extracts the cadmium plant harvest object is not particularly limited, and can be that arbitrary cadmium extracts plant
Cutting；In embodiments of the present invention, cadmium extraction plant harvest object be preferably in feather cockscomb, black nightshade and Sedum alfredii Hance at least
A kind of cutting.
In the present invention, the water content of the cadmium extraction plant harvest object is preferably smaller than 25wt.%；The cadmium extracts plant
The grain size of cutting is preferably≤150 μm.
The source that the present invention extracts the cadmium plant harvest object is not particularly limited.In embodiments of the present invention, described
Cadmium extraction plant harvest object is preferably prepared via a method which to obtain：
Cadmium extraction plant is cleaned successively, dry, broken, obtain cadmium extraction plant harvest object.
The present invention is not particularly limited the mode of cleaning, and the soil that can be extracted cadmium on plant removes.
The present invention is not particularly limited the mode of the drying, and cadmium can be extracted to plant drying to constant weight.
In the embodiment of the present invention, the drying is preferably air dry oven drying；The temperature of the drying is preferably 60~80 DEG C, more excellent
It is selected as 70 DEG C；The time of the drying is preferably 20~28h, more preferably for 24 hours.
The present invention is not particularly limited the broken mode, can obtain the cadmium extraction plant harvest object of required grain size
.
In the present invention, the thermal decomposition is preferably carried out in nitrogen atmosphere；The flow velocity of the nitrogen is preferably 3~5L/
min.In the present invention, the nitrogen atmosphere ensure that thermal decomposition process is anoxybiotic environment, reduce cadmium flying dust He bioxin
Generation.
It after the present invention is preferably pressed into 5~10min of nitrogen, then is warming up to thermal decomposition required temperature and is thermally decomposed, to ensure
Air in thermal decomposition reactor is excluded completely.
In the present invention, the temperature of the thermal decomposition is preferably 250~450 DEG C, more preferably 300~350 DEG C；The heat
The time of decomposition is preferably 45~60min, more preferably 50~55min；The present invention thermally decomposes the liter of required temperature to being warming up to
Warm rate is not particularly limited, and can be arbitrary heating rate；The time of the thermal decomposition is preferably from being warming up to needed for thermal decomposition
Chronotherm rises.In the present invention, in the thermal decomposition process, the organic matter in cadmium extraction plant harvest object is decomposed into titanium dioxide
Carbon largely reduces the quality of cadmium extraction plant harvest object.
After the completion of thermal decomposition, thermal decomposition products therefrom is preferably cooled to room temperature by the present invention, obtains pyrolysis lime-ash.
The present invention is not particularly limited the rate of the cooling, can be arbitrary rate of temperature fall.In the embodiment of the present invention
In, the cooling is preferably Temperature fall.
After obtaining pyrolysis lime-ash, the present invention mixes the pyrolysis lime-ash with water, obtains pyrolysis lime-ash slurry.
In the present invention, the mass ratio of the pyrolysis lime-ash and water is preferably 1:4~6, more preferably 1:5.
The present invention is not particularly limited the mode of the mixing, can obtain uniformly being pyrolyzed lime-ash slurry.
In the embodiment of the present invention, the mixing is preferably mechanical agitation mixing；The rotating speed of the mixing is preferably 180~200r/min；
The time of the mixing is preferably 0.5~1h.
After obtaining pyrolysis lime-ash slurry, the pyrolysis lime-ash slurry is carried out acidleach by the present invention, then through filtering, obtains acid
Immersion liquid.In the present invention, the cadmium being pyrolyzed in lime-ash can be converted to water-soluble cadmium salt through acidleach, in extraction to pickle liquor.
In the present invention, the acidleach preferably includes following steps：The pyrolysis lime-ash slurry is heated to 70~90 DEG C,
Stop heating, then adjusts the pH value of pyrolysis lime-ash slurry to 0.5~1, carry out acid extraction reaction.In the present invention, pyrolysis ash
Cadmium in slag is mainly with alkali formula chloride Cd2(OH)3Cl and metal oxide CdMn2O4Equal crystal habits exist, and by the heat
Solution lime-ash slurry is heated to 70~90 DEG C, after stopping heating, using the waste heat of slurry, in acid condition, can promote above-mentionedization
The cadmium closed in object is converted to water-soluble cadmium salt, is conducive to the abundant extraction of cadmium.
The present invention is not particularly limited the rate of the heating, can be the arbitrary rate of heat addition.
In the present invention, the acid used in the pH value for adjusting pyrolysis lime-ash slurry is preferably a concentration of 95~98wt.%
The concentrated sulfuric acid.In the present invention, certain heat can be discharged in the concentrated sulfuric acid adition process, heat can be maintained within a certain period of time
The temperature of solution lime-ash slurry is maintained at 70~90 DEG C, is conducive to the extraction of cadmium.
In the present invention, the time of the acid extraction reaction is preferably 1~2h, more preferably 1.5h；The acid extraction is anti-
The time answered is preferably from meter when the pH value for being pyrolyzed lime-ash slurry is adjusted to 0.5~1.
In the present invention, 0.5~1h is preferably first stirred in the acid extraction reaction, is then allowed to stand 0.5~1h.In the present invention
In, after standing, the pyrolysis lime-ash natural subsidence through acidleach, pickle liquor is located at upper layer, and when filtering, pickle liquor can directly pass through filter
Film can quickly obtain pickle liquor.
The present invention is not particularly limited the mode of the filtering, is using filter type well known to those skilled in the art
It can.
The present invention preferably cleans filtering gained filter residue, and cleaning solution is merged with filtrate, obtains pickle liquor.This hair
The bright mode to the cleaning is not particularly limited, by the way of conventional cleaning filter residue；In embodiments of the present invention,
The cleaning preferably mixes filter residue with water, after washing by soaking, through filtering, obtains cleaning solution；The number of the cleaning is preferred
It is 3~5 times.
After obtaining pickle liquor, the present invention mixes the pickle liquor with zinc, is reacted into line replacement, obtains cadmium.In the present invention
In, it is more active than cadmium using zinc, cadmium can be cemented out from pickle liquor, obtains cadmium simple substance.
In the present invention, the zinc is preferably zinc metal sheet or spelter body, more preferably zinc metal sheet；In embodiments of the present invention, institute
State the preferably useless zinc metal sheet of zinc；It is reacted into line replacement using zinc metal sheet or spelter body, cadmium simple substance can be attached directly to zinc metal sheet or spelter body
On, the cadmium of sponge state is obtained, subsequently cadmium can directly be separated from zinc metal sheet or spelter body.
In the present invention, the temperature of the displacement reaction is preferably 30~70 DEG C, more preferably 40~60 DEG C；The displacement
The time of reaction is preferably 0.5~2.5h, more preferably 1~2h.
In the present invention, the ratio between the theoretical addition amount of the zinc and the amount of being actually added into of the zinc preferably 1:35~
1.75。
In the present invention, the theoretical addition amount of the zinc is the amount of the substance of the contained cadmium in pickle liquor.The present invention couple
The test method of the amount of the substance of cadmium is not particularly limited in the pickle liquor, in embodiments of the present invention, in the pickle liquor
The mole of cadmium preferably obtains as follows：It is surveyed using inductively coupled plasma atomic emission spectrometry (ICP-AES)
The cadmium content in pickle liquor is obtained, the cadmium content is then scaled mole, obtains the mole of cadmium in pickle liquor.
Displacement reaction after the completion of, the present invention preferably by it is described displacement reaction after product successively through being filtered, washed, drying,
Obtain cadmium；When the zinc is zinc metal sheet or spelter body, the present invention is preferably by the product after the displacement displacement reaction through filtering, zinc
Cadmium separation, washing, drying, obtain the cadmium of sponge state.
The present invention is not particularly limited the mode being filtered, washed, using the conventional filtration of those skilled in the art
With mode of washing.In embodiments of the present invention, the cleaning preferably mixes filter residue with water, after washing by soaking, passes through
Filter, obtains cleaning solution；The number of the cleaning is preferably 3~5 times.
Displacement reaction products therefrom is preferably placed in blender and is mixed with water by the zinc cadmium separation in the present invention, is carried out
Stirring obtains the cadmium and zinc metal sheet or spelter of sponge state；The rotating speed of the stirring is preferably 400~500r/min；The present invention is to institute
The dosage for stating water is not particularly limited, can be by displacement reaction products therefrom submergence.In the present invention, the sponge state
Cadmium is attached on zinc metal sheet or spelter, is stirred by being mixed with water, and in collision process, the cadmium of sponge state can be from zinc metal sheet or zinc
It is split away off on block, to realize that zinc cadmium detaches.
In the present invention, the drying is preferably dried in vacuo；The temperature of the drying is preferably 40~60 DEG C, more preferably
It is 50 DEG C；The vacuum degree of the drying is preferably -0.09~-0.1MPa；The present invention does not have special limit to the time of the drying
It is fixed, the product of constant weight can be obtained.In the present invention, the vacuum drying can prevent cadmium to again be oxidized.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
(1) by 100g feather cockscombs wash with water it is clean after at 70 DEG C of baking oven for 24 hours, dry to constant weight, obtaining moisture is
The feather cockscomb of 22.9wt%, is crushed with crusher, is sieved with 100 mesh sieve, and 22.5g feather cockscomb cuttings are obtained；Using inductive coupling etc.
It is 269.3mg/kg that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures cadmium content in feather cockscomb cutting,；
(2) the feather cockscomb cutting is put into porcelain boat, is placed in electric tube furnace heating region, led into stove with 3L/min flow velocitys
Enter nitrogen, after being continually fed into nitrogen 5min, is warming up to 350 DEG C, keeps the temperature 60min, thermally decomposed；After the completion of thermal decomposition, stop
Heating, is naturally cooling to room temperature, obtains 9.0g pyrolysis lime-ash；Using inductively coupled plasma atomic emission spectrometry (ICP-
AES it is 572.3mg/kg) to measure the cadmium content in pyrolysis lime-ash；It is computed, weight-loss ratio (i.e. (quality-pyrolysis of feather cockscomb of feather cockscomb
The quality of lime-ash)/feather cockscomb quality * 100%) be 91.0%；
(3) it is 1 by solid-liquid mass ratio by the pyrolysis Ash water to blender:5 are added water, stir to pulpous state, obtain
It is pyrolyzed lime-ash slurry, the rotating speed of the stirring is 180r/min；
(4) the pyrolysis lime-ash slurry is heated to 80 DEG C, solution ph is adjusted to 1 with 98% concentrated sulfuric acid, continue with
After the rotating speed stirring 0.5h of 180r/min, 0.5h is stood；Then through filtering, and make to wash with water filter residue three times, merging filtrate and
Cleaning solution obtains 70ml pickle liquors, and gained filter residue is as the processing of ordinary solid waste；It is sent out using inductively coupled plasma atom
It is 62.6mg/L to penetrate the cadmium content that spectroscopic methodology (ICP-AES) measures in pickle liquor；
(5) it is 1 according to the mass ratio of zinc metal sheet theory dosage and practical dosage:1.6 are added zinc into the pickle liquor
Piece, and solution temperature is controlled at 50 DEG C, reaction time 2h, obtaining load has the zinc metal sheet of sponge state cadmium；Using inductive coupling etc.
It is 3.6mg/L that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures the cadmium content in the pickle liquor after displacement, is computed cadmium
Replacement rate be 94.3%；
(6) sponge state cadmium and zinc metal sheet are detached, after washed, it is 50 DEG C to be placed in temperature, and vacuum degree is the true of -0.09MPa
Empty drying box drying, obtains 4.2mg cadmiums.
Gained cadmium is sponge state cadmium, as shown in Figure 1.
Energy depressive spectroscopy (EDS) is used to measure the purity of gained cadmium as 87.7%.
The rate of recovery for being computed cadmium is 81.5%.
Embodiment 2
(1) by 100g feather cockscombs wash with water it is clean after at 70 DEG C of baking oven for 24 hours, dry to constant weight, obtaining moisture is
The feather cockscomb of 22.9wt%, is crushed with crusher, is sieved with 100 mesh sieve, and 22.5g feather cockscomb cuttings are obtained；Using inductive coupling etc.
It is 269.3mg/kg that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures cadmium content in feather cockscomb cutting,
(2) the feather cockscomb cutting is put into porcelain boat, is placed in electric tube furnace heating region, led into stove with 5L/min flow velocitys
Enter nitrogen, after being continually fed into nitrogen 5min, is warming up to 350 DEG C, keeps the temperature 45min, thermally decomposed；After the completion of thermal decomposition, stop
Heating, is naturally cooling to room temperature, obtains 9.0g pyrolysis lime-ash；Using inductively coupled plasma atomic emission spectrometry (ICP-
AES it is 572.3mg/kg) to measure the cadmium content in pyrolysis lime-ash；It is computed, weight-loss ratio (i.e. (quality-pyrolysis of feather cockscomb of feather cockscomb
The quality of lime-ash)/feather cockscomb quality * 100%) be 91.0%；
(3) it is 1 by solid-liquid mass ratio by the pyrolysis Ash water to blender:5 are added water, stir to pulpous state, obtain
It is pyrolyzed lime-ash slurry, the rotating speed of the stirring is 180r/min；
(4) the pyrolysis lime-ash slurry is heated to 80 DEG C, solution ph is adjusted to 0.5 with 98% concentrated sulfuric acid, continue with
After the rotating speed stirring 0.5h of 180r/min, 0.5h is stood；Then through filtering, and make to wash with water filter residue three times, merging filtrate and
Cleaning solution obtains 70ml pickle liquors, and gained filter residue is as the processing of ordinary solid waste；It is sent out using inductively coupled plasma atom
It is 66.7mg/L to penetrate the cadmium content that spectroscopic methodology (ICP-AES) measures in pickle liquor；
(5) it is 1 according to the mass ratio of zinc metal sheet theory dosage and practical dosage:1.6 are added zinc into the pickle liquor
Piece, and solution temperature is controlled at 60 DEG C, reaction time 2h, obtaining load has the zinc metal sheet of sponge state cadmium；Using inductive coupling etc.
It is 3.9mg/L that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures the cadmium content in the pickle liquor after displacement, is computed cadmium
Replacement rate be 94.1%；
(6) sponge state cadmium and zinc metal sheet are detached, after washed, it is 50 DEG C to be placed in temperature, and vacuum degree is the vacuum of -0.1MPa
Drying box is dried, and 4.4mg cadmiums are obtained.
Energy depressive spectroscopy (EDS) is used to measure the purity of gained cadmium as 88.1%.
The rate of recovery for being computed cadmium is 85.3%.
Embodiment 3
(1) by 100g feather cockscombs wash with water it is clean after at 70 DEG C of baking oven for 24 hours, dry to constant weight, obtaining moisture is
The feather cockscomb of 22.9wt%, is crushed with crusher, is sieved with 100 mesh sieve, and 22.5g feather cockscomb cuttings are obtained；Using inductive coupling etc.
It is 269.3mg/kg that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures cadmium content in feather cockscomb cutting,；
(2) the feather cockscomb cutting is put into porcelain boat, is placed in electric tube furnace heating region, led into stove with 5L/min flow velocitys
Enter nitrogen, after being continually fed into nitrogen 5min, is warming up to 350 DEG C, keeps the temperature 45min, thermally decomposed；After the completion of thermal decomposition, stop
Heating, is naturally cooling to room temperature, obtains 9.0g pyrolysis lime-ash；Using inductively coupled plasma atomic emission spectrometry (ICP-
AES it is 572.3mg/kg) to measure the cadmium content in pyrolysis lime-ash；It is computed, weight-loss ratio (i.e. (quality-pyrolysis of feather cockscomb of feather cockscomb
The quality of lime-ash)/feather cockscomb quality * 100%) be 91.0%；
(3) it is 1 by solid-liquid mass ratio by the pyrolysis Ash water to blender:5 are added water, stir to pulpous state, obtain
It is pyrolyzed lime-ash slurry, the rotating speed of the stirring is 200r/min；
(4) the pyrolysis lime-ash slurry is heated to 80 DEG C, solution ph is adjusted to 1 with 98% concentrated sulfuric acid, continue with
After the rotating speed stirring 0.5h of 200r/min, 0.5h is stood；Then through filtering, and make to wash with water filter residue three times, merging filtrate and
Cleaning solution obtains 70ml pickle liquors, and gained filter residue is as the processing of ordinary solid waste；It is sent out using inductively coupled plasma atom
It is 62.5mg/L to penetrate the cadmium content that spectroscopic methodology (ICP-AES) measures in pickle liquor；
(5) it is 1 according to the mass ratio of zinc metal sheet theory dosage and practical dosage:1.6 are added zinc into the pickle liquor
Piece, and solution temperature is controlled at 70 DEG C, reaction time 2h, obtaining load has the zinc metal sheet of sponge state cadmium；Using inductive coupling etc.
It is 3.8mg/L that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures the cadmium content in the pickle liquor after displacement, is computed cadmium
Replacement rate be 93.9%；
(6) sponge state cadmium and zinc metal sheet are detached, after washed, it is 50 DEG C to be placed in temperature, and vacuum degree is the vacuum of -0.1MPa
Drying box is dried, and 4.1mg cadmiums are obtained.
Energy depressive spectroscopy (EDS) is used to measure the purity of gained cadmium as 86.7%.
The rate of recovery for being computed cadmium is 79.8%.
Embodiment 4
(1) by 100g feather cockscombs wash with water it is clean after at 70 DEG C of baking oven for 24 hours, dry to constant weight, obtaining moisture is
The feather cockscomb of 22.9wt%, is crushed with crusher, is sieved with 100 mesh sieve, and 22.5g feather cockscomb cuttings are obtained；Using inductive coupling etc.
It is 269.3mg/kg that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures cadmium content in feather cockscomb cutting,；
(2) the feather cockscomb cutting is put into porcelain boat, is placed in electric tube furnace heating region, led into stove with 5L/min flow velocitys
Enter nitrogen, after being continually fed into nitrogen 5min, is warming up to 350 DEG C, keeps the temperature 45min, thermally decomposed；After the completion of thermal decomposition, stop
Heating, is naturally cooling to room temperature, obtains 9.0g pyrolysis lime-ash；Using inductively coupled plasma atomic emission spectrometry (ICP-
AES it is 572.3mg/kg) to measure the cadmium content in pyrolysis lime-ash；It is computed, weight-loss ratio (i.e. (quality-pyrolysis of feather cockscomb of feather cockscomb
The quality of lime-ash)/feather cockscomb quality * 100%) be 91.0%；
(3) it is 1 by solid-liquid mass ratio by the pyrolysis Ash water to blender:5 are added water, stir to pulpous state, obtain
It is pyrolyzed lime-ash slurry, the rotating speed of the stirring is 200r/min；
(4) the pyrolysis lime-ash slurry is heated to 80 DEG C, solution ph is adjusted to 0.5 with 98% concentrated sulfuric acid, continue with
After the rotating speed stirring 0.5h of 200r/min, 1h is stood；Then through filtering, and make to wash with water filter residue three times, merging filtrate and clear
Washing lotion obtains 70ml pickle liquors, and gained filter residue is as the processing of ordinary solid waste；Using inductively coupled plasma atomic emissions
It is 66.7mg/L that spectroscopic methodology (ICP-AES), which measures the cadmium content in pickle liquor,；
(5) it is 1 according to the mass ratio of zinc metal sheet theory dosage and practical dosage:1.6 are added zinc into the pickle liquor
Piece, and solution temperature is controlled at 30 DEG C, reaction time 2.5h, obtaining load has the zinc metal sheet of sponge state cadmium；Using inductive coupling
It is 8.9mg/L that plasma atomic emission spectrometry (ICP-AES), which measures the cadmium content in the pickle liquor after displacement, is computed
The replacement rate of cadmium is 86.7%；
(6) sponge state cadmium and zinc metal sheet are detached, after washed, it is 50 DEG C to be placed in temperature, and vacuum degree is the vacuum of -0.1MPa
Drying box is dried, and 4.0mg cadmiums are obtained.
Energy depressive spectroscopy (EDS) is used to measure the purity of gained cadmium as 77.2%.
The rate of recovery for being computed cadmium is 78.6%.
Embodiment 5
(1) by 100g black nightshades wash with water it is clean after at 70 DEG C of baking oven for 24 hours, dry to constant weight, obtaining moisture is
The black nightshade of 22.5wt%, is crushed with crusher, is sieved with 100 mesh sieve, and 22.3g black nightshade cuttings are obtained；Using inductive coupling etc.
It is 206.3mg/kg that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures cadmium content in black nightshade cutting,；
(2) the feather cockscomb cutting is put into porcelain boat, is placed in electric tube furnace heating region, led into stove with 5L/min flow velocitys
Enter nitrogen, after being continually fed into nitrogen 5min, is warming up to 350 DEG C, keeps the temperature 45min, thermally decomposed；After the completion of thermal decomposition, stop
Heating, is naturally cooling to room temperature, obtains 8.7g pyrolysis lime-ash；Using inductively coupled plasma atomic emission spectrometry (ICP-
AES it is 449.5mg/kg) to measure the cadmium content in pyrolysis lime-ash；It is computed, weight-loss ratio (i.e. (quality-pyrolysis of feather cockscomb of feather cockscomb
The quality of lime-ash)/feather cockscomb quality * 100%) be 91.3%；
(3) it is 1 by solid-liquid mass ratio by the pyrolysis Ash water to blender:5 are added water, stir to pulpous state, obtain
It is pyrolyzed lime-ash slurry, the rotating speed of the stirring is 180r/min；
(4) the pyrolysis lime-ash slurry is heated to 80 DEG C, solution ph is adjusted to 1 with 98% concentrated sulfuric acid, continue with
After the rotating speed stirring 0.5h of 180r/min, 0.5h is stood；Then through filtering, and make to wash with water filter residue three times, merging filtrate and
Cleaning solution obtains 60ml pickle liquors, and gained filter residue is as the processing of ordinary solid waste；It is sent out using inductively coupled plasma atom
It is 55.4mg/L to penetrate the cadmium content that spectroscopic methodology (ICP-AES) measures in pickle liquor；
(5) it is 1 according to the mass ratio of zinc metal sheet theory dosage and practical dosage:1.6 are added zinc into the pickle liquor
Piece, and solution temperature is controlled at 50 DEG C, reaction time 2h, obtaining load has the zinc metal sheet of sponge state cadmium；Using inductive coupling etc.
It is 3.5mg/L that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures the cadmium content in the pickle liquor after displacement, is computed cadmium
Replacement rate be 93.6%；
(6) sponge state cadmium and zinc metal sheet are detached, after washed, it is 50 DEG C to be placed in temperature, and vacuum degree is the true of -0.09MPa
Empty drying box drying, obtains 3.1mg cadmiums.
Energy depressive spectroscopy (EDS) is used to measure the purity of gained cadmium as 86.3%.
The rate of recovery for being computed cadmium is 79.6%.
Embodiment 6
(1) by 40g cadmiums extract plant mixture (cadmium extraction plant mixture be feather cockscomb, black nightshade and Sedum alfredii Hance with
Mass ratio is 1:1:1 ratio mixes) wash with water it is clean after at 70 DEG C of baking oven for 24 hours, it is dry to constant weight, obtain moisture
The cadmium that content is 21.5wt% extracts plant mixture, is crushed, is sieved with 100 mesh sieve with crusher, obtains the extraction of 8.2g cadmiums and plants
Object cutting；Use inductively coupled plasma atomic emission spectrometry (ICP-AES) measure in black nightshade cutting cadmium content for
235.1mg/kg；
(2) the feather cockscomb cutting is put into porcelain boat, is placed in electric tube furnace heating region, led into stove with 5L/min flow velocitys
Enter nitrogen, after being continually fed into nitrogen 5min, is warming up to 350 DEG C, keeps the temperature 45min, thermally decomposed；After the completion of thermal decomposition, stop
Heating, is naturally cooling to room temperature, obtains 3.3g pyrolysis lime-ash；Using inductively coupled plasma atomic emission spectrometry (ICP-
AES it is 496.6mg/kg) to measure the cadmium content in pyrolysis lime-ash；It is computed, weight-loss ratio (i.e. (quality-pyrolysis of feather cockscomb of feather cockscomb
The quality of lime-ash)/feather cockscomb quality * 100%) be 91.8%；
(3) it is 1 by solid-liquid mass ratio by the pyrolysis Ash water to blender:5 are added water, stir to pulpous state, obtain
It is pyrolyzed lime-ash slurry, the rotating speed of the stirring is 200r/min；
(4) the pyrolysis lime-ash slurry is heated to 80 DEG C, solution ph is adjusted to 0.5 with 98% concentrated sulfuric acid, continue with
After the rotating speed stirring 0.5h of 200r/min, 0.5h is stood；Then through filtering, and make to wash with water filter residue three times, merging filtrate and
Cleaning solution obtains 30ml pickle liquors, and gained filter residue is as the processing of ordinary solid waste；It is sent out using inductively coupled plasma atom
It is 49.4mg/L to penetrate the cadmium content that spectroscopic methodology (ICP-AES) measures in pickle liquor；
(5) it is 1 according to the mass ratio of zinc metal sheet theory dosage and practical dosage:1.6 are added zinc into the pickle liquor
Piece, and solution temperature is controlled at 50 DEG C, reaction time 2h, obtaining load has the zinc metal sheet of sponge state cadmium；Using inductive coupling etc.
It is 3.0mg/L that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures the cadmium content in the pickle liquor after displacement, is computed cadmium
Replacement rate be 93.9%；
(6) sponge state cadmium and zinc metal sheet are detached, after washed, it is 50 DEG C to be placed in temperature, and vacuum degree is the vacuum of -0.1MPa
Drying box is dried, and 1.4mg cadmiums are obtained.
Energy depressive spectroscopy (EDS) is used to measure the purity of gained cadmium as 83.2%.
The rate of recovery for being computed cadmium is 85.1%.
Embodiment 7
By 100g feather cockscombs wash with water it is clean after at 70 DEG C of baking oven for 24 hours, dry to constant weight, obtaining moisture is
The feather cockscomb of 22.9wt%, is crushed with crusher, is sieved with 100 mesh sieve, and 22.5g feather cockscomb cuttings are obtained；Using inductive coupling etc.
It is 269.3mg/kg that plasma-atomic emission spectroscopic methodology (ICP-AES), which measures cadmium content in feather cockscomb cutting,
(2) the feather cockscomb cutting is put into porcelain boat, is placed in electric tube furnace heating region, led into stove with 5L/min flow velocitys
Enter nitrogen, after being continually fed into nitrogen 5min, is warming up to 250 DEG C, keeps the temperature 45min, thermally decomposed；After the completion of thermal decomposition, stop
Heating, is naturally cooling to room temperature, obtains 17.8g pyrolysis lime-ash；Using inductively coupled plasma atomic emission spectrometry (ICP-
AES it is 297.2mg/kg) to measure the cadmium content in pyrolysis lime-ash；It is computed, weight-loss ratio (i.e. (quality-pyrolysis of feather cockscomb of feather cockscomb
The quality of lime-ash)/feather cockscomb quality * 100%) be 82.2%；
(3) it is 1 by solid-liquid mass ratio by the pyrolysis Ash water to blender:5 are added water, stir to pulpous state, obtain
It is pyrolyzed lime-ash slurry, the rotating speed of the stirring is 200r/min；
(4) the pyrolysis lime-ash slurry is heated to 80 DEG C, solution ph is adjusted to 0.5 with 98% concentrated sulfuric acid, continue with
After the rotating speed stirring 0.5h of 200r/min, 1h is stood；Then through filtering, and make to wash with water filter residue three times, merging filtrate and clear
Washing lotion obtains 100ml pickle liquors, and gained filter residue is as the processing of ordinary solid waste；It is sent out using inductively coupled plasma atom
It is 47.9mg/L to penetrate the cadmium content that spectroscopic methodology (ICP-AES) measures in pickle liquor；
(5) it is 1 according to the mass ratio of zinc metal sheet theory dosage and practical dosage:1.6 are added zinc into the pickle liquor
Piece, and solution temperature is controlled at 30 DEG C, reaction time 2.5h, obtaining load has the zinc metal sheet of sponge state cadmium；Using inductive coupling
It is 2.9mg/L that plasma atomic emission spectrometry (ICP-AES), which measures the cadmium content in the pickle liquor after displacement, is computed
The replacement rate of cadmium is 94.0%；
(6) sponge state cadmium and zinc metal sheet are detached, after washed, it is 50 DEG C to be placed in temperature, and vacuum degree is the vacuum of -0.1MPa
Drying box is dried, and 4.5mg cadmiums are obtained.
Energy depressive spectroscopy (EDS) is used to measure the purity of gained cadmium as 77.8%.
The rate of recovery for being computed cadmium is 85.2%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of extracting the method for recycling cadmium in plant harvest object from cadmium, include the following steps：
(1) cadmium extraction plant harvest object is thermally decomposed, obtains pyrolysis lime-ash；
(2) the pyrolysis lime-ash is mixed with water, obtains pyrolysis lime-ash slurry；
(3) the pyrolysis lime-ash slurry is subjected to acidleach, then through filtering, obtains pickle liquor；
(4) pickle liquor is mixed with zinc, is reacted into line replacement, obtains cadmium.
2. according to claim 1 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the heat point
The temperature of solution is 250~450 DEG C, and the time of the thermal decomposition is 45~60min.
3. according to claim 2 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the heat point
The temperature of solution is 300~350 DEG C.
4. extracting the method for recycling cadmium in plant harvest object from cadmium according to claims 1 to 3 any one of them, feature exists
In the thermal decomposition is carried out in nitrogen atmosphere.
5. according to claim 1 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the pyrolysis
The mass ratio of lime-ash and water is 1:4~6.
6. according to claim 1 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the acidleach
Include the following steps：The pyrolysis lime-ash slurry is heated to 70~90 DEG C, stops heating, then adjusts pyrolysis lime-ash slurry
PH value carries out acid extraction reaction to 0.5~1.
7. according to claim 6 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the acid carries
It is 1~2h to negate the time answered.
8. according to claim 6 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the adjusting
It is pyrolyzed the concentrated sulfuric acid that the acid used in the pH value of lime-ash slurry is a concentration of 95~98wt.%.
9. according to claim 1 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the displacement
The temperature of reaction is 30~70 DEG C, and the time of the displacement reaction is 0.5~2.5h.
10. according to claim 1 extract the method for recycling cadmium in plant harvest object from cadmium, which is characterized in that the zinc
The ratio between the amount of being actually added into of theoretical addition amount and the zinc be 1:1.3~1.75.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810114032.2A CN108504862A (en) | 2018-02-05 | 2018-02-05 | A method of it is extracted from cadmium and recycles cadmium in plant harvest object |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810114032.2A CN108504862A (en) | 2018-02-05 | 2018-02-05 | A method of it is extracted from cadmium and recycles cadmium in plant harvest object |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108504862A true CN108504862A (en) | 2018-09-07 |
Family
ID=63374487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810114032.2A Pending CN108504862A (en) | 2018-02-05 | 2018-02-05 | A method of it is extracted from cadmium and recycles cadmium in plant harvest object |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108504862A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101513640A (en) * | 2009-03-18 | 2009-08-26 | 浙江大学 | Harmless fixed bed thermolysis system for zinc and cadmium super accumulator plant |
| CN101871046A (en) * | 2010-06-29 | 2010-10-27 | 青川县天运金属开发有限公司 | Method for recycling heavy metal pollution wastes |
| CN101974691A (en) * | 2010-11-10 | 2011-02-16 | 白银有色集团股份有限公司 | Method for recovering cobalt in cobalt-containing waste residues from zinc smelting |
| CN102277502A (en) * | 2011-04-28 | 2011-12-14 | 彭克俭 | Method for enrichment extraction of cadmium in polluted soil through herbaceous plant Chinese lobelia herb |
| CN102517455A (en) * | 2011-12-29 | 2012-06-27 | 株洲冶炼集团股份有限公司 | Method for recovering cadmium from copper cadmium residues |
| CN106939376A (en) * | 2017-04-01 | 2017-07-11 | 北京神源环保有限公司 | A kind of system and method for recycling super enriching plant cutting |
-
2018
- 2018-02-05 CN CN201810114032.2A patent/CN108504862A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101513640A (en) * | 2009-03-18 | 2009-08-26 | 浙江大学 | Harmless fixed bed thermolysis system for zinc and cadmium super accumulator plant |
| CN101871046A (en) * | 2010-06-29 | 2010-10-27 | 青川县天运金属开发有限公司 | Method for recycling heavy metal pollution wastes |
| CN101974691A (en) * | 2010-11-10 | 2011-02-16 | 白银有色集团股份有限公司 | Method for recovering cobalt in cobalt-containing waste residues from zinc smelting |
| CN102277502A (en) * | 2011-04-28 | 2011-12-14 | 彭克俭 | Method for enrichment extraction of cadmium in polluted soil through herbaceous plant Chinese lobelia herb |
| CN102517455A (en) * | 2011-12-29 | 2012-06-27 | 株洲冶炼集团股份有限公司 | Method for recovering cadmium from copper cadmium residues |
| CN106939376A (en) * | 2017-04-01 | 2017-07-11 | 北京神源环保有限公司 | A kind of system and method for recycling super enriching plant cutting |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106082646B (en) | The method for cooperateing with melting to prepare glass sand with domestic garbage incineration flyash using electroplating sludge | |
| CN101502838B (en) | Novel technique for harmless treatment of medical refuse burning flyash | |
| CN103978007B (en) | A kind of fluidized bed type chromium slag pyrolysis butanedionedioxime | |
| CN110240386A (en) | A kind of stalk cooperates with the devices and methods therefor of processing with sludge | |
| CN104070060B (en) | A kind of chromium-contaminatesoil soil remediation method | |
| CN107011933B (en) | preparation process of biological white carbon | |
| CN101690934B (en) | Method for stabilizing fly ash from refuse incineration by combination of complementary type medicaments | |
| CN106010542A (en) | Sludge charcoal for repairing heavy metal contaminated soil and preparation method of sludge charcoal | |
| CN103740372A (en) | Fixing agent for repairing arsenic-polluted soil, and preparation and application method thereof | |
| CN101905235A (en) | Method for extracting harmful heavy metal from incineration fly ash by using supercritical fluid | |
| CN103977529A (en) | Chromium slag pyrolysis treatment method with low tar emission amount | |
| CN101062783A (en) | Environment-friendly type technique for vanadium extraction of stone coal | |
| CN105776796A (en) | Method of reducing heavy metal bio-availability through pig manure pyrolysis and biochar application of pig manure | |
| CN103978006B (en) | A kind of efficient low-consume oligosaprobic chromium slag pyrolysis treating method | |
| CN100387734C (en) | Method of extracting radioactive uranium in fly ash | |
| CN104399222A (en) | Composite biomass charcoal waste incineration fly ash treatment stabilizer and preparation method thereof | |
| CN108927405B (en) | A kind of method of the repairing hexavalent chromium polluted soil of ferriferous oxide crystallisation | |
| CN106765159A (en) | A kind of industrial organic solid castoff burns the innoxious method for coexisting and putting with sludge high temperature | |
| CN109593964A (en) | The device and method of variable valency metal in dangerous solid waste is recycled in low-temperature reduction chlorination | |
| CN101928017A (en) | Method for producing potassium chloride by utilizing potassium-bearing waste residues from pesticide plants | |
| CN108504862A (en) | A method of it is extracted from cadmium and recycles cadmium in plant harvest object | |
| CN109848188B (en) | Method for pretreating household garbage incineration fly ash by kitchen garbage lactic acid fermentation liquor | |
| CN106824979A (en) | A kind of cooperative disposal method of Cr VI slag and biomass castoff | |
| CN107217147B (en) | A method of removing and absorption ciliate desert-grass heavy metal | |
| CN109576505A (en) | A kind of method that zinc cobalt efficiently separates |
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 |
Application publication date: 20180907 |
|
| RJ01 | Rejection of invention patent application after publication |