CN107029680A - A kind of bioxin handles the preparation method and applications of material - Google Patents
A kind of bioxin handles the preparation method and applications of material Download PDFInfo
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- CN107029680A CN107029680A CN201710260189.1A CN201710260189A CN107029680A CN 107029680 A CN107029680 A CN 107029680A CN 201710260189 A CN201710260189 A CN 201710260189A CN 107029680 A CN107029680 A CN 107029680A
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- bioxin
- handles
- iron
- containing molybdenum
- mixture
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The present invention handles the preparation method and applications of material for a kind of bioxin.With discarded object of the iron content containing molybdenum, zeolite, expanded vermiculite etc. for stock, a kind of bioxin is prepared by the step such as pretreatment, immersion, dry, roasting, mixing, polymerization and handles material.Processing of the bioxin material available for the purified treatment that bioxin gases are produced after waste incineration, and sour gas and VOCs pollutants.The present invention prepares bioxin processing material using tailing waste thing, not only solves puzzlement mine tailing accumulation problem, and can reduce air pollution emission total amount with the treatment of wastes with processes of wastes against one another.
Description
Technical field
Recycled the present invention relates to mine tailing, slag and flue gas of refuse burning processing Material Field, in particular for mine tailing, steel
Slag recycling recycling prepares the technology that bioxin handles material.
Background technology
With the continuous expansion of city size, growing and living standards of the people the continuous improvement of urban population,
The yield of domestic waste is gradually increasing.Early in 1996, the Chinese municipal refuse amount of clearing just reached 100,000,000
Ton, and increased every year with 8%~10% speed.The volume of cargo in storage over the years of rubbish reaches more than 60 hundred million tons, and there is more than 200 city in the whole nation
City is absorbed among the encirclement of rubbish, and rubbish stores up the land area occupied up to more than 500,000,000 square metre.Garbage disposal has become system
The about major issue of Chinese city environment.
The main method of urban garbage disposal has the processing methods such as landfill, compost and burning.Sanitary landfills was once for I
State handles the main method of rubbish, and advantage is that Installed capital cost is relatively low, operation cost is relatively low, technology maturation, rubbish is wanted
Ask relatively low, but have the disadvantage to take a large amount of land resources, percolate processing cost compared with high, risk of leakage greatly, easily cause secondary pollution；
Garbage compost is built upon on the basis of separate waste collection, and the rubbish of China is mainly composting, is not suitable for direct heap
Fertilizer, therefore the technology is difficult to promote, treatment plant's quantity is also constantly being reduced.
Waste incineration can quickly handle the rubbish for being piled into mountain, effectively reduce the volume 50%-90% of rubbish, lead to simultaneously
Burning electricity generation is crossed, occupation of land, the pollution problem of garbage loading embeading has both been solved, the cleaning that the energy is realized again is recycled.According to《State
Family's reply climate change (2014-2020) planning》, to the year two thousand twenty, national biomass power generation installed capacity reaches 30,000,000
Thousand, be 2.3 times of 2015 (13,000,000 kilowatts), wherein domestic garbage burning electricity generation as biomass power generation one kind.It is based on
Data above, it is contemplated that waste incineration and generating electricity will realize fast development during China " 13 ", following 3-5 will burn as rubbish
Burn the golden period of development of power industry.
Burning city domestic garbage can produce the harmful substances such as sour gas, ash content, heavy metal and chlorinated organics.Wherein
Dioxins materials are the pollutants of public's common concern.Usually said bioxin is really Zhi bioxin (Dioxins＆
Furam) material, they are many chloro dibenzodioxin English (PCDDs) and many chloro dibenzo furans (PCDFs)) general name.Er Evil
English is listed in international cancer research institute and endeavours one of strong carcinogen of research, is listed in a class carcinogenic substance, is also a kind of fatal
Carcinogen.The method of conventional control bioxin includes：Optimize burning process, flying dust trapping and charcoal absorption etc., but pin
Material of the Dui bioxin research and development with a variety of functions such as catalytic adsorption removing toxic substances is also rarely reported.
Mine tailing refers to the waste residue slag that bargh discharges after the completion of ore dressing, more to be arranged outside slurry form, accumulates over a long period
Form Tailings Dam.Tailings Dam floor space is big, and great potential safety hazard, the beneficiation reagent mine tailing being rich in addition in Tailings Dam
Water penetration to underground, great pollution will also result in environment, underground water.Therefore milltailings processing is pendulum in mining production
A big problem in face of person.According to statistics, before 2000, the mine tailing total amount of China's mine output is 50.26 hundred million tons, wherein, iron
Ore deposit mine tailing amount is 26.14 hundred million tons, and the mine tailing amount of main non-ferrous metal is 21.09 hundred million tons, and gold tailings amount is 2.72 hundred million tons, other
0.31 hundred million tons.
The content of the invention
The present invention is to solve providing a kind of method that utilization mine tailing and inorganic mineral prepare bioxin processing material, profit
Bioxin processing material is prepared with tailing waste thing, puzzlement mine tailing accumulation problem is not only solved, and can subtract with the treatment of wastes with processes of wastes against one another
Few air pollution emission total amount.
The present invention prepares bioxin by following steps and handles material：
A kind of bioxin handles the preparation method of material, comprises the following steps：
A, pretreatment：Zeolite and expanded vermiculite is taken to cross the sieve of 200 mesh respectively, screenings is with zeolite:Expanded vermiculite mass ratio
For 5~7:3~5 mix 25~30 minutes in three-dimensional mixer, obtain mixture 1；
B, immersion：Mixture 1 is put into acrylic acid and N, N '-methylene-bisacrylamide is leaching in the aqueous solution of solute
Bubble 30~50 minutes；
C, drying：The solution obtained after immersion is put into baking oven, dried under the conditions of 105 DEG C to moisture content be 10% with
Under；
D, roasting：Material after drying is put into high temperature furnace, vapor or CO is passed through2, roasted under the conditions of 300~500 DEG C
The product of roasting for burning 1~2 hour powdered；
E, mixing：Powdered product of roasting is taken out, is mixed with iron-contained waste material and discarded object containing molybdenum, obtains mixture
2, product of roasting described in mixture 2, iron-contained waste material, the mass ratio of the discarded object containing molybdenum are：10~15:1~5:1~3；
F, polymerization：It is put into after 0.1%~1% di-cyclohexylperoxy di-carbonate will be added in mixture 2 in reactor, plus
Heat keeps 1.0~1.5MPa pressure to 80~100 DEG C, reacts product after being heated for 2~2.5 hours；
G, product after heating takes out to be dried to moisture content under the conditions of 80~100 DEG C in an oven be less than 10%, obtain described
Bioxin handles material.
Further, acrylic acid and N, N in step B '-methylene-bisacrylamide mass ratio be 1~3:5~10；Third
Olefin(e) acid and N, N '-methylene-bisacrylamide quality and account for the 5%~20% of aqueous solution gross mass.
Further, the vapor or CO being passed through in step D2Account for 80%~90% of volume of gas in high temperature furnace.
Further, the iron-contained waste material is one kind or several in iron tailings, iron-bearing water extraction slag, iron content grinding slag
The mixture planted；The discarded object containing molybdenum is molybdic tailing, the extraction of water containing molybdenum slag, grinds one or more of mixed in slag containing molybdenum powder
Compound.
Bioxin handles the application of material：The bioxin material produces the net of bioxin gases after being used for waste incineration
Change is handled.
Further, the bioxin processing material is placed in flue gas bag-type dust, can substitute activated carbon and flue dust is inhaled
It is attached, and the degraded of Cuiization bioxin.
Bioxin handles the application of material：The bioxin processing material is used for handling sour gas and the pollution of VOCs classes
Thing.
The principle of product treatment bioxin is：Acrylic acid plays scion grafting effect, N, N '-methylene-bisacrylamide plays friendship
Connection is acted on, and zeolite and expanded vermiculite scion grafting are linked to together；Carried out using scion grafting and cross-linking agent confrontation inorganic mineral material
It is modified, the layered poros structure of inorganic mineral material is increased, high temperature bakees the intensity for adding material, it is ensured that flue gas is passed through
When endurance quality, iron tailings and molybdic tailing provide divalent and trivalent cation, interlayer is carried negative electrical charge, adds between stratiform
The inside and outside osmotic pressure of gap, di-cyclohexylperoxy di-carbonate promotes the progress of polymerisation so that stratified material and iron tailings
With combining closely for molybdic tailing cationic.
The present invention has advantages below and effect：
1) adsorption capacity of stratified material is increased：It is modified using scion grafting and cross-linking agent confrontation inorganic mineral material,
The layered poros structure of inorganic mineral material is increased, absorption property is improved；
2) strength of materials is improved：The method bakeed using high temperature, adds the intensity of material, improves anti-sweep of gases
Performance, it is ensured that durability when flue gas is passed through；
3) in the raw material used, mine tailing, slag are solid waste, realize the treatment of wastes with processes of wastes against one another, reduce secondary pollution
Risk.
Embodiment
A kind of bioxin handles the preparation method of material, comprises the following steps：
A, pretreatment：Zeolite and expanded vermiculite is taken to cross the sieve of 200 mesh respectively, screenings is with zeolite:Expanded vermiculite mass ratio
For 5~7:3~5 mix 25~30 minutes in three-dimensional mixer, obtain mixture 1；
B, immersion：Mixture 1 is put into acrylic acid and N, N '-methylene-bisacrylamide is leaching in the aqueous solution of solute
Bubble 30~50 minutes；Acrylic acid and N, N '-methylene-bisacrylamide mass ratio be 1~3:5~10；Acrylic acid and N, N '-
The quality of methylene-bisacrylamide and account for the 5%~20% of aqueous solution gross mass；
C, drying：The solution obtained after immersion is put into baking oven, dried under the conditions of 105 DEG C to moisture content be 10% with
Under；
D, roasting：Material after drying is put into high temperature furnace, vapor or CO is passed through2, roasted under the conditions of 300~500 DEG C
The product of roasting for burning 1~2 hour powdered；The vapor or CO being passed through2Account for volume of gas in high temperature furnace 80%~
90%；
E, mixing：Powdered product of roasting is taken out, is mixed with iron-contained waste material and discarded object containing molybdenum, obtains mixture
2, product of roasting described in mixture 2, iron-contained waste material, the mass ratio of the discarded object containing molybdenum are：10~15:1~5:1~3；It is described
Iron-contained waste material is one or more of mixtures in iron tailings, iron-bearing water extraction slag, iron content grinding slag；It is described useless containing molybdenum
Gurry is molybdic tailing, the extraction of water containing molybdenum slag, grinds one or more of mixtures in slag containing molybdenum powder；
F, polymerization：It is put into after 0.1%~1% di-cyclohexylperoxy di-carbonate will be added in mixture 2 in reactor, plus
Heat keeps 1.0~1.5MPa pressure to 80~100 DEG C, reacts product after being heated for 2~2.5 hours；
G, product after heating takes out to be dried to moisture content under the conditions of 80~100 DEG C in an oven be less than 10%, obtain described
Bioxin handles material.
The bioxin material is used for after waste incineration the purified treatment for producing bioxin gases；Bioxin handles material
It is placed in flue gas bag-type dust, activated carbon can be substituted flue dust is adsorbed, and Cuiization bioxin is degraded.
The bioxin processing material can also be used to processing sour gas and VOCs pollutants.
Embodiment 1
Pretreatment：Zeolite and expanded vermiculite are crossed to the sieve of 200 mesh respectively, screenings is with 5:3 ratio is in three-dimensional mixer
Middle mixing 25 minutes, obtains mixture 1；Mixture 1 is put into 5% acrylic acid and N, N '-methylene-bisacrylamide solution
Middle immersion 30 minutes, wherein：Acrylic acid and N, N '-methylene-bisacrylamide ratio be 3:5；The solution that will be obtained after immersion
Baking oven is put into, it is less than 10% to be dried at 105 DEG C to moisture content；Material after drying is put into high temperature furnace, volume is passed through and contains
Measure the vapor for 80%, be calcined 2 hours at 500 DEG C；Obtained product taking-up will be calcined, be mixed with iron tailings and molybdic tailing,
Mixture is obtained, wherein：Mixed proportion between three is 15:5:3, obtain mixture 2；The mistake of addition 1% in mixture 2
Two dicyclohexyl carbonates are aoxidized, are added in reactor, 100 DEG C are heated to, and keep 1.5MPa pressure, are reacted 2 hours；Will production
It is less than 10% that thing, which takes out and moisture content is dried in 100 DEG C of baking oven, just obtains finished material.After this material, compared to
Activated carbon, absorption property improves 20%；The strength of materials improves 1.5 times of , bioxin process performances and improves more than 60%.
Embodiment 2
Pretreatment：Zeolite and expanded vermiculite are crossed to the sieve of 200 mesh respectively, screenings is with 7:5 ratio is in three-dimensional mixer
Middle mixing 30 minutes, obtains mixture 1；Mixture 1 is put into 10% acrylic acid and N, N '-methylene-bisacrylamide solution
Middle immersion 25 minutes, wherein：Acrylic acid and N, N '-methylene-bisacrylamide ratio be 1:10；It is molten by what is obtained after immersion
Liquid is put into baking oven, and it is less than 10% to be dried at 105 DEG C to moisture content；Material after drying is put into high temperature furnace, volume is passed through
Content for 90% vapor, be calcined 2 hours at 500 DEG C；Obtained product taking-up will be calcined, slag is extracted and containing molybdenum with iron-bearing water
Grinding slag is mixed, and obtains mixture, wherein：Mixed proportion between three is 10:1:1, obtain mixture 2；In mixture 2
The di-cyclohexylperoxy di-carbonate of middle addition 0.5%, adds in reactor, is heated to 100 DEG C, and keep 1.0MPa pressure
Power, reacts 2 hours；It is less than 10% product to be taken out moisture content is dried in 100 DEG C of baking oven, just obtains finished material.Adopt
After this material, compared to activated carbon, absorption property improves 30%；The strength of materials improves 1.8 times of , bioxin process performances
Improve more than 70%.
Embodiment 3
Pretreatment：Zeolite and expanded vermiculite are crossed to the sieve of 200 mesh respectively, screenings is with 5:5 ratio is in three-dimensional mixer
Middle mixing 25 minutes, obtains mixture 1；Mixture 1 is put into 20% acrylic acid and N, N '-methylene-bisacrylamide solution
Middle immersion 30 minutes, wherein：Acrylic acid and N, N '-methylene-bisacrylamide ratio be 3:10；It is molten by what is obtained after immersion
Liquid is put into baking oven, and it is less than 10% to be dried at 105 DEG C to moisture content；Material after drying is put into high temperature furnace, volume is passed through
Content is 80% CO2, be calcined 1.5 hours at 400 DEG C；Obtained product taking-up will be calcined, slag is extracted and containing molybdenum with iron-bearing water
Grinding slag is mixed, and obtains mixture, wherein：Mixed proportion between three is 15:5:3, obtain mixture 2；In mixture 2
The di-cyclohexylperoxy di-carbonate of middle addition 0.4%, adds in reactor, is heated to 100 DEG C, and keep 1.0MPa pressure
Power, reacts 2.5 hours；It is less than 10% product to be taken out moisture content is dried in 100 DEG C of baking oven, just obtains finished material.
After this material, compared to activated carbon, absorption property improves 40%；The strength of materials improves 2 times of , bioxin process performances
Improve more than 75%.
Claims (7)
1. a kind of bioxin handles the preparation method of material, it is characterised in that：Comprise the following steps：
A, pretreatment：Zeolite and expanded vermiculite is taken to cross the sieve of 200 mesh respectively, screenings is with zeolite:Expanded vermiculite mass ratio be 5 ~
7:3 ~ 5 mix 25 ~ 30 minutes in three-dimensional mixer, obtain mixture 1；
B, immersion：Mixture 1 is put into acrylic acid and N, N '-methylene-bisacrylamide is soaks 30 in the aqueous solution of solute
~ 50 minutes；
C, drying：The solution obtained after immersion is put into baking oven, it is less than 10% to be dried under the conditions of 105 DEG C to moisture content；
D, roasting：Material after drying is put into high temperature furnace, vapor or CO is passed through2, 1 ~ 2 is calcined under the conditions of 300 ~ 500 DEG C small
When obtain powdered product of roasting；
E, mixing：Powdered product of roasting is taken out, is mixed with iron-contained waste material and discarded object containing molybdenum, obtains mixture 2, is mixed
Product of roasting described in compound 2, iron-contained waste material, the mass ratio of the discarded object containing molybdenum are：10~15:1~5:1~3；
F, polymerization：It is put into after 0.1% ~ 1% di-cyclohexylperoxy di-carbonate will be added in mixture 2 in reactor, it is heated to 80 ~
100 DEG C, and 1.0 ~ 1.5MPa pressure is kept, react product after being heated for 2 ~ 2.5 hours；
It G, will take out that to be dried to moisture content under the conditions of 80 ~ 100 DEG C in an oven be less than 10% by product after heating, and obtain the bioxin
Handle material.
2. bioxin according to claim 1 handles the preparation method of material, it is characterised in that：In step B acrylic acid with
N, N '-methylene-bisacrylamide mass ratio be 1 ~ 3:5~10；Acrylic acid and N, N '-methylene-bisacrylamide quality and
Account for the 5% ~ 20% of aqueous solution gross mass.
3. bioxin according to claim 1 handles the preparation method of material, it is characterised in that：The water being passed through in step D
Steam or CO2Account for 80% ~ 90% of volume of gas in high temperature furnace.
4. bioxin according to claim 1 handles the preparation method of material, it is characterised in that：Iron content described in step E
Discarded object is one or more of mixtures in iron tailings, iron-bearing water extraction slag, iron content grinding slag；The discarded object containing molybdenum
One or more of mixtures in slag are ground for molybdic tailing, the extraction of water containing molybdenum slag, containing molybdenum powder.
5. bioxin described in any one handles the application of material in claim 1 ~ 4, it is characterised in that：The bioxin
Material is used for after waste incineration the purified treatment for producing bioxin gases.
6. bioxin handles the application of material according to claim 5, it is characterised in that：The bioxin processing material is placed on
In flue gas bag-type dust, activated carbon can be substituted flue dust is adsorbed, and Cuiization bioxin is degraded.
7. bioxin described in any one handles the application of material in claim 1 ~ 4, it is characterised in that：The bioxin
Processing material is used for handling sour gas and VOCs pollutants.
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Citations (5)
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| CN103055919A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Structured catalyst of propylene by steam cracking |
| CN103055920A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst with neat structure for propylene production through cracking of oil vapor containing olefin and sulfur hydrocarbon |
| CN104258897A (en) * | 2014-07-24 | 2015-01-07 | 中国石油大学(华东) | Core-shell molecular sieve-coated catalyst and preparation method thereof |
| WO2014174375A3 (en) * | 2013-04-24 | 2015-04-16 | Saudi Basic Industries Corporation | High productivity catalyst for alkane oxidation to unsaturated carboxylic acids and alkenes |
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2017
- 2017-04-20 CN CN201710260189.1A patent/CN107029680A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090143221A1 (en) * | 2007-11-30 | 2009-06-04 | Steven Bolaji Ogunwumi | Zeolite-Based Honeycomb Body |
| CN103055919A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Structured catalyst of propylene by steam cracking |
| CN103055920A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst with neat structure for propylene production through cracking of oil vapor containing olefin and sulfur hydrocarbon |
| WO2014174375A3 (en) * | 2013-04-24 | 2015-04-16 | Saudi Basic Industries Corporation | High productivity catalyst for alkane oxidation to unsaturated carboxylic acids and alkenes |
| CN105209167A (en) * | 2013-04-24 | 2015-12-30 | 沙特基础工业公司 | High productivity catalyst for alkane oxidation to unsaturated carboxylic acids and alkenes |
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Application publication date: 20170811 |