CN110302756A - A method of heavy metal ion is removed using industrial residue modification biological charcoal - Google Patents
A method of heavy metal ion is removed using industrial residue modification biological charcoal Download PDFInfo
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- CN110302756A CN110302756A CN201910602464.2A CN201910602464A CN110302756A CN 110302756 A CN110302756 A CN 110302756A CN 201910602464 A CN201910602464 A CN 201910602464A CN 110302756 A CN110302756 A CN 110302756A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of methods using industrial residue modification biological charcoal removing heavy metal ion, specifically include the pretreatment of (1) raw material；(2) activation of industrial residue；(3) mixing of activated industrial residue and processed organic waste；(4) pyrolysis of uniformly mixed sample；(5) removing of the pyrolysis residue to heavy metal in the aqueous solution by heavy metal pollution；(6) calculating of Analysis of Heavy Metal Ions and removal efficiency.The present invention is using cheap industrial residue as heat transfer carrier and activator, in charcoal forming process, improve the aromatic hydrocarbons extent of polymerization in charcoal, improve charcoal physical chemistry micro-structure, pollution components in industrial residue are fixed in pyrolytic process, alkalinity reduces, and realizes the energy of organic waste, materialized innoxious, resource utilization with industrial residue.
Description
Technical field
The present invention relates to solid waste processing and Carbon Materials application field, it is specifically related to a kind of change using industrial residue
Property charcoal removing heavy metal ion method.
Background technique
Wood wastes are slowly pyrolyzed one kind of (700 DEG C of typical temperature <) generation under anaerobic or limited oxygen condition through high temperature
Indissoluble, stable, aromatization carbon rich material matter, referred to as charcoal.Charcoal is initially considered as the very high " black earth of fertility
Earth " can help plant growth, can be applied to agricultural use and carbon is collected and storage uses.In recent years, it ground both at home and abroad
Study carefully the result shows that charcoal is improving crop yield, improvement soil property, improving tunning fertilizer efficiency, repairing heavy metal pollution soil
Earth and control carbon emission etc. play positive effect.
Charcoal is prepared using wood wastes pyrolysis, high temperature pyrolysis gas incendivity is energized to meet the energy of preparation process
Amount demand, by-product wood vinegar can be used as insecticide, while can also prepare the charcoal product of high value, to reach wooden useless
The purpose that gurry reduction rate is 100%.However, wood wastes are directly pyrolyzed the charcoal of generation compared with active carbon, specific surface
Long-pending and hole holds that size gap is larger, so heavy metal, organic pollutant adsorption function on also have larger difference.In order to mention
Absorption of the high charcoal to toxic contaminants component needs to be modified charcoal using different activation methods.It is common at present
Activation method be broadly divided into physical method and chemical method, physical method energy consumption is high, less effective；Chemical activation method has activation temperature
Low, high-efficient advantage, but reagent is easy to cause to corrode to equipment, generates a large amount of liquid product, and reagent price is also relatively more high
It is expensive.
Industrial residue refers in the industrial production, give off it is toxic, inflammable, mordant, have chemical reaction
The solid waste of property, specifically includes aluminium making residue, steel-making waste residue, copper slag, catalyst of failure etc., in the prior art,
The processing mode of such waste residue is usually directly filled, but the long-term stockpiling of the harmful waste residue of industry, it does not only take up a large amount of
Land resource, by sleet leaching, the soluble ingredient in slag permeates downwards with water from earth's surface, converts to soil mobility, enrichment
Harmful substance makes stockyard soil property acidification nearby, alkalization, hardening, or even the pollution of huge sum of money genotype occurs.
In order to protect environment for human survival, innoxious, the resource utilization of industrial residue are further increased, it is necessary to seek
New industrial waste residue disposal method is found through detection, calcium, aluminium, potassium, sodium, silicon isoreactivity element is rich in waste residue, to biomass
Cracking reaction has catalytic action, using these industrial residues as the activator of charcoal preparation process, in pyrolytic process, with
Organic component forms fused matter, and heavy metal therein can be made to be fixed in charcoal, and alkalinity reduces；Meanwhile by physical method
It is combined with chemical method, the surface characteristic of charcoal can be improved in pyrolysis source.
Summary of the invention
It is an object of the invention to solve deficiency in the prior art, using cheap industrial residue as heat transfer carrier with
Activator reduces tar yield in pyrolytic process, improves energy gas yield, in charcoal forming process, improves charcoal
In aromatic hydrocarbons extent of polymerization, improve charcoal physical chemistry micro-structure, pollution components in industrial residue are in pyrolytic process
To fixation, alkalinity is reduced, and realizes the energy of organic waste, materialized innoxious, resource utilization with industrial residue.
The technical solution of the present invention is as follows: a kind of method using industrial residue modification biological charcoal removing heavy metal ion, tool
Steps are as follows for body
(1) pretreatment of raw material: the organic waste by moisture lower than 10% is crushed to 3 mm of partial size hereinafter, saving backup；
(2) activation of industrial residue: industrial residue is put into heating furnace, under the conditions of 500-700 DEG C, carries out 2 h of thermal activation；
(3) the processed organic waste that industrial residue activated made from step (2) and step (1) obtain is pressed into quality
It is uniformly mixed than 0:1-1:1；
(4) sample mixed in proportion that step (3) obtain is respectively put into pyrolysis reactor pyrolysis, is passed through certain nitrogen
Gas, flow rate of carrier gas are 0.08 ~ 0.1 L/min, are warming up to 400 ~ 900 DEG C with the heating rate of 8-12 DEG C/min, pyrolytic reaction 40-
90 min；
(5) pyrolysis residue for obtaining pyrolytic reaction is placed in the aqueous solution of heavy metal pollution, stirring 60-90 min, centrifugation 15-
30 min；
(6) it takes supernatant to carry out Analysis of Heavy Metal Ions, is compared with blank test, calculate removal efficiency.
Further, the organic waste specifically includes agriculture and forestry organic waste material, organic component and dress in biologic garbage
Repair one of wooden clast in rubbish or a variety of.
Further, the industrial residue is aluminium making residue, steel-making waste residue, copper slag, the discharge of non-ferrous metal smelter
Industrial sludge and failure one of catalyst or a variety of.
The invention has the benefit that
(1) this method utilizes industrial residue, in conjunction with physically activated and chemical activation method, improves charcoal in pyrolysis source
Performance has energy-saving advantage；
(2) with during organic solid waste cooperative disposal, the pollution components in industrial residue are effectively suppressed industrial residue, organic
The energy utilization rate of solid waste improves, and solves the problems, such as that wood waste arbitrarily banks up waste of resource, also solves industrial residue and fill out
Buried strap carrys out the problem of secondary pollution, makes its innoxious use；
(3) in pyrolysis source, industrial residue is added as activator, can not only reduce in charcoal activation process energy consumption and at
This, and obtained charcoal specific surface area increases 50-100%, average pore size increases 50% or more；
(4) after industrial residue being added in pyrolytic process, obtained charcoal is applied to heavy metal ion adsorbed in aqueous solution, removing
Rate can achieve 95% or more；
(5) charcoal after heavy metal ion is adsorbed, identifies that heavy metal is in charcoal by standard HJ/T 299-2007 method
In can effectively fix.
Detailed description of the invention
Fig. 1 is the implementing procedure of the method disclosed by the invention that heavy metal ion is removed using industrial residue modification biological charcoal
Figure；
Wherein, the organic solid waste of 1-, 2- is broken, 3- industrial residue, 4- calcining, 5- premix, 6- pyrolysis reactor, 7- charcoal, 8-
Absorption, 9- ecological risk assessment, 10- pyrolysis gas, 11- liquid product.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where essence of the present invention, to modification made by the method for the present invention, step or condition and replaces, belong to model of the invention
It encloses.
Comparative example:
It is 3 mm hereinafter, into being pyrolyzed in pyrolysis reactor that organic solid waste by moisture lower than 10%, which is crushed to partial size, is passed through nitrogen
As protection gas, flow rate of carrier gas is 0.08-0.1 L/min, is warming up to 700 DEG C with the heating rate of 8-12 DEG C/min, pyrolysis adds
Heat keeps 60 min, generates pyrolysis gas, liquid product and pyrolytic carbon.Wherein, gas yield 35%, tar yield 27% are raw
Object charcoal yield is 23%, and thermolysis water yield 15%, the specific surface area of charcoal is in 110-140 m2/ g, average pore size is in 1-3
nm.It takes 1 g charcoal to be placed in the hexavalent chromium solution of 3 mg/L and carries out adsorption test, stir 60-90 min, be centrifuged 15-
30 min take supernatant liquor to carry out sexavalence chromium analysis, are computed, and hexavalent chromium removal efficiency is 8.04%.Adsorb chromium ion
Charcoal carries out ecological risk assessment it is found that the chromium ion after absorption is in life after drying, through standard HJ/T 299-2007 method
It can effectively be fixed in object charcoal.
Embodiment
It is 3 mm hereinafter, industrial residue used is aluminium metallurgy in the present embodiment that organic solid waste by moisture lower than 10%, which is crushed to partial size,
Waste residue after 550 DEG C of 2 h of calcining, mixes in premixing system with organic solid waste 1:1 in mass ratio, into hot in pyrolysis reactor
Solution is passed through nitrogen as protection gas, and flow rate of carrier gas is 0.08-0.1 L/min, is warming up to the heating rate of 8-12 DEG C/min
700 DEG C, pyrolysis heating keeps 60 min, generates pyrolysis gas, liquid product and pyrolytic carbon, gas yield 38%, tar yield and is
22%, charcoal yield 29%, thermolysis water yield 11%, the specific surface area of charcoal is in 220-280 m2/ g, average pore size exist
2-10 nm.It takes 1 g charcoal to be placed in the hexavalent chromium solution of 3 mg/L and carries out adsorption test, stir 60-90 min, from
Heart 15-30 min takes supernatant liquor to carry out sexavalence chromium analysis, is computed, and hexavalent chromium removal efficiency is 95.11%.Adsorption of Chromium
The charcoal of ion after drying, through standard HJ/T 299-2007 method carry out ecological risk assessment it is found that absorption after chromium from
Son can be fixed effectively in charcoal.
Compared with the comparative example of no addition industrial residue, the present embodiment is disclosed de- using industrial residue modification biological charcoal
The method of removing heavy metals ion mainly includes two processes, first is that the pollution components in industrial residue pass through 700 DEG C of pyrolysis,
Heavy metal is most of gradually to be converted to residual form from transferable state, has been fixed on inside charcoal in charcoal forming process,
Pollution components are effectively suppressed, and alkalinity reduces, and at the same time, the tar yield decline in product, energy gas yield improves,
And the specific surface area and average pore size of the pyrolysis charcoal of preparation increase；Second is that going to adsorb using the modification biological charcoal prepared
Chromium ion makes chromium ion in conjunction with charcoal and a series of physical-chemical reaction occurs therewith, to be fixed in charcoal
To calculate modification biological charcoal to the removal efficiency of heavy metal and the solidification effect of heavy metal ion.
After drying, carrying out ecological risk assessment through standard HJ/T 299-2007 method can for the charcoal of absorption chromium ion
Know, the chromium ion after absorption can be fixed effectively in charcoal.
Basic principles and main features and advantage of the invention have been shown and described above.But the foregoing is merely this hairs
Bright specific embodiment, technical characteristic of the invention are not limited thereto, and any those skilled in the art is not departing from this hair
The other embodiments obtained under bright technical solution should all cover within the scope of the patent of the present invention.
Claims (6)
1. a kind of method using industrial residue modification biological charcoal removing heavy metal ion, which is characterized in that specific step is as follows:
(1) pretreatment of raw material: the organic waste by moisture lower than 10% is crushed to 3 mm of partial size hereinafter, saving backup；
(2) activation of industrial residue: industrial residue is put into heating furnace and is activated；
(3) in proportion by industrial residue activated made from step (2) and the processed organic waste of step (1) acquisition
It is uniformly mixed；
(4) sample mixed in proportion that step (3) obtain is respectively put into pyrolysis reactor pyrolysis, is passed through certain nitrogen
It is protected；
(5) pyrolysis residue for obtaining pyrolytic reaction is placed in the aqueous solution of heavy metal pollution, stirring 60-90 min, centrifugation 15-
30 min；
(6) it takes supernatant to carry out Analysis of Heavy Metal Ions, is compared with blank test, calculate removal efficiency.
2. a kind of method using industrial residue modification biological charcoal removing heavy metal ion as described in claim 1, feature
It is, the mixing mass ratio of industrial residue and organic waste in step (3) is 0:1-1:1.
3. a kind of method using industrial residue modification biological charcoal removing heavy metal ion as described in claim 1, feature
It is, the activation temperature of the industrial residue in step (2) is 500-700 DEG C, and activation time is 2 h.
4. a kind of method using industrial residue modification biological charcoal removing heavy metal ion as described in claim 1, feature
It is, the flow rate of carrier gas of nitrogen is 0.08 ~ 0.1 L/min in step (4), and pyrolytic reaction condition is with the heating of 8-12 DEG C/min
Rate is warming up to 400 ~ 900 DEG C, pyrolytic reaction 40-90 min.
5. a kind of method using industrial residue modification biological charcoal removing heavy metal ion as described in claim 1, feature
It is, the organic waste includes agriculture and forestry organic waste material, the wooden clast in organic component and decoration garbage in biologic garbage
One of or it is a variety of.
6. a kind of method using industrial residue modification biological charcoal removing heavy metal ion as described in claim 1, feature
Be, the industrial residue be aluminium making residue, steel-making waste residue, copper slag, non-ferrous metal smelter discharge industrial sludge and
One of catalyst of failure is a variety of.
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Cited By (3)
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| CN110976487A (en) * | 2019-12-24 | 2020-04-10 | 江苏筑原生物科技研究院有限公司 | Method for improving hydrogen yield by catalytic pyrolysis of organic solid waste by using industrial waste residues |
| CN112588261A (en) * | 2020-11-23 | 2021-04-02 | 常州大学 | Preparation method of carbon-aluminum composite material |
| CN113842879A (en) * | 2021-09-26 | 2021-12-28 | 北京建工资源循环利用投资有限公司 | Method for preparing organic matter adsorbent by utilizing decoration garbage sorting waste, application of organic matter adsorbent and sewage treatment system |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110976487A (en) * | 2019-12-24 | 2020-04-10 | 江苏筑原生物科技研究院有限公司 | Method for improving hydrogen yield by catalytic pyrolysis of organic solid waste by using industrial waste residues |
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| CN113842879A (en) * | 2021-09-26 | 2021-12-28 | 北京建工资源循环利用投资有限公司 | Method for preparing organic matter adsorbent by utilizing decoration garbage sorting waste, application of organic matter adsorbent and sewage treatment system |
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