CN105854815A - Flue gas adsorbent with large adsorption capacity - Google Patents

Flue gas adsorbent with large adsorption capacity Download PDF

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Publication number
CN105854815A
CN105854815A CN201610423147.0A CN201610423147A CN105854815A CN 105854815 A CN105854815 A CN 105854815A CN 201610423147 A CN201610423147 A CN 201610423147A CN 105854815 A CN105854815 A CN 105854815A
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flue gas
parts
flyash
gas adsorbent
deionized
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王春保
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MAANSHAN SHUNDA ENVIRONMENT PROTECTION EQUIPMENT CO Ltd
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MAANSHAN SHUNDA ENVIRONMENT PROTECTION EQUIPMENT CO Ltd
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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
    • 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
    • B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes

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  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a flue gas adsorbent with a large adsorption capacity. The flue gas adsorbent is prepared from, by weight, 40-50 parts of fly ash, 4-5 parts of ferric nitrate, 3-4 parts of manganese acetate, 13-15 parts of glass fibers, 5-7 parts of sodium silicate, 6-7 parts of calcium carbonate, 3-4 parts of jade powder, 4-5 parts of vanadium pentoxide, 0.3-0.5 part of boric acid ester coupling agent and an appropriate amount of deionized water. The flue gas adsorbent is simple in preparation method, low in cost, capable of effectively adsorbing mercury in flue gas and capable of reducing emission of coal burning mercury pollutants, therefore, large-scale utilization of biomass resources is formed, and the economic benefit, environmental benefit and social benefit of biomass utilization are achieved.

Description

The flue gas adsorbent that a kind of adsorption capacity is big
Technical field
The present invention relates to technical field of absorbent, particularly relate to the flue gas adsorbent that a kind of adsorption capacity is big.
Background technology
In recent years, the metallic element that coal produces in combustion causes the concern of various circles of society, and environment can be caused the biggest impact, hydrargyrum to be exactly wherein one of poisonous metal by these metallic elements after being discharged in air.Mercury element has the character of continuous enrichment with in food chain in vivo, the nervous system of human body can be caused the injury that can not be cured for a long time, in daily commercial production, smelting industry, Chi Kuang exploitation, manufacture of cement, biomass combustion, fired coal combustion etc. all can produce a certain amount of mercury emissions in air, and wherein fire coal is the most maximum polluter.In order to solve the most serious coal-fired flue-gas mercury pollution problem, people are devoted to the many effective catalyst of exploitation, flue activated carbon spraying technique is a kind of ideal technology, owing to having higher adsorption effect, use in many power plant, but owing to activated carbon is expensive, limited large-scale application, especially as developing country Chinese, replace activated carbon with greater need for a kind of cost-effective adsorbent.
Flyash has a certain amount of unburned carbon, content is typically between 2% to 12%, at present, in order to control the discharge of nitrogen oxides, many coal-burning power plants use the emissions requirements that low NO meets nitrogen oxides, hypothermia and hypoxia condition in low nitrogen burning makes the phosphorus content in flyash substantially increase, and makes the phosphorus content of flyash even increase to 20% the highest.The unburned carbon of flyash has certain absorbability to Elemental Mercury, replaces, with the unburned carbon in flyash, the hydrargyrum that activated carbon adsorbs in flue gas and can yet be regarded as a kind of economically viable method.Absorption and the oxidation of hydrargyrum are also had certain effect by the abundant metallic element contained in flyash.Flyash has certain absorbability to pollutant, but adsorption effect is the most not ideal enough, in order to make the absorption property of flyash be improved, flyash is modified studying the emphasis being to study.
Summary of the invention
The object of the invention is contemplated to make up the defect of prior art, it is provided that the flue gas adsorbent that a kind of adsorption capacity is big.
The present invention is achieved by the following technical solutions:
The flue gas adsorbent that a kind of adsorption capacity is big, is made up of the raw material of following weight portion: flyash 40-50, ferric nitrate 4-5, manganese acetate 3-4, glass fibre 13-15, sodium silicate 5-7, calcium carbonate 6-7, jade powder 3-4, vanadic anhydride 4-5, boric acid ester coupler 0.3-0.5, deionized water are appropriate；
The flue gas adsorbent that described a kind of adsorption capacity is big, is made up of step in detail below:
(1) flyash is washed with deionized for several times, under 120 ° of C, is dried 4-5h, by the flyash nitric acid dousing 2-3h of 2 times amount after cooling, water-bath 1h in the water-bath of 60 ° of C afterwards the most in an oven, then is washed with deionized to neutrality, dry for standby；
(2) deionized water dissolving of ferric nitrate and manganese acetate mixing 3-4 times amount is stirred, again flyash prepared by step (1) is added in mixed liquor, in magnetic stirring apparatus, heated and stirred is to dry, it is then placed in exsiccator under 120 ° of C being dried 3-4h, finally it is ground to thin, and put in Muffle furnace under 400-600 ° of C, to calcine 0.5-1h, cross 100 mesh sieves after cooling standby；
(3) wash after glass fibre being soaked 20min with the suds of 2 times amount, after drying, under 50 ° of C, soak 30-40min with the hydrochloric acid of 10%, standby after being then washed with deionized drying；
(4) glass chopped rear and calcium carbonate, jade powder, vanadic anhydride, boric acid ester coupler mixed grinding are uniformly dispersed, sodium silicate is dissolved in water and makes the solution that concentration is 40-60%, mixture is added in sodium silicate aqueous solution to be heated to 50-60 ° of C stir formation slurry, being added in slurry by modified coal ash prepared by step (2), the spray drying that stirs can be prepared by again.
nullThe invention have the advantage that fly ash grain smooth surface，The most coarse with acid oxidase rear surface，Increase specific surface area，Again after manganese and Fe2O3 doping，Reunite on its surface，Hydrargyrum is had good catalytic performance，Can be by mercury oxidation and firmly adsorb on flyash surface，And self also can reoxidation，The activity making adsorbent keeps stable continuation to play adsorption，Flyash is possibly together with abundant metallic element，There is in terms of the adsorption and oxidation of hydrargyrum certain advantage，The present invention also selects resistant to elevated temperatures glass fibre to be modified increasing specific surface area raising load effect，Thus play the adsorptivity of sharpest edges，The glass fibre added not only has good controlling to the fine particle in flue gas，Also there is good sulfur resistance，The calcium carbonate added、Jade powder、Vanadic anhydride three's synergism enhances the adsorption capacity of adsorbent greatly、The rate of adsorption、The performance such as wearability and antibiotic property，The adsorbent preparation method of the present invention is simple、Low cost、Can active adsorption mercury in flue gas，Can emission-reducing coal mercury contaminants，The scale forming biomass resource utilizes，Realize the economic benefit of biomass economy、Environmental benefit and social benefit.
Detailed description of the invention
The flue gas adsorbent that a kind of adsorption capacity is big, is made up of the raw material of following weight portion: flyash 40, ferric nitrate 4, manganese acetate 3, glass fibre 13, sodium silicate 5, calcium carbonate 6, jade powder 3, vanadic anhydride 4, boric acid ester coupler 0.3, deionized water are appropriate；
The flue gas adsorbent that described a kind of adsorption capacity is big, is made up of step in detail below:
(1) flyash is washed with deionized for several times, under 120 ° of C, is dried 4h, by the flyash nitric acid dousing 2h of 2 times amount after cooling, water-bath 1h in the water-bath of 60 ° of C afterwards the most in an oven, then is washed with deionized to neutrality, dry for standby；
(2) ferric nitrate and manganese acetate mixing are stirred with the deionized water dissolving of 3 times amount, again flyash prepared by step (1) is added in mixed liquor, in magnetic stirring apparatus, heated and stirred is to dry, it is then placed in exsiccator under 120 ° of C being dried 3h, finally it is ground to thin, and put in Muffle furnace under 400 ° of C, to calcine 0.5h, cross 100 mesh sieves after cooling standby；
(3) wash after glass fibre being soaked 20min with the suds of 2 times amount, after drying, under 50 ° of C, soak 30min with the hydrochloric acid of 10%, standby after being then washed with deionized drying；
(4) glass chopped rear and calcium carbonate, jade powder, vanadic anhydride, boric acid ester coupler mixed grinding are uniformly dispersed, sodium silicate is dissolved in water and makes the solution that concentration is 40%, mixture is added in sodium silicate aqueous solution to be heated to 50 ° of C stir formation slurry, being added in slurry by modified coal ash prepared by step (2), the spray drying that stirs can be prepared by again.
The adsorbent of preparation being used for demercuration performance grading experimental provision test, simulated flue gas flow is 1L/min, import mercury concentration 3mg/ m3, air velocity is 34000 h-1Experiment condition under, the removal efficiency of hydrargyrum is up to 85%, and denitration rate is up to 38%.

Claims (2)

1. the flue gas adsorbent that an adsorption capacity is big, it is characterized in that, be made up of the raw material of following weight portion: flyash 40-50, ferric nitrate 4-5, manganese acetate 3-4, glass fibre 13-15, sodium silicate 5-7, calcium carbonate 6-7, jade powder 3-4, vanadic anhydride 4-5, boric acid ester coupler 0.3-0.5, deionized water are appropriate.
The flue gas adsorbent that a kind of adsorption capacity is big, it is characterised in that be made up of step in detail below:
(1) flyash is washed with deionized for several times, under 120 ° of C, is dried 4-5h, by the flyash nitric acid dousing 2-3h of 2 times amount after cooling, water-bath 1h in the water-bath of 60 ° of C afterwards the most in an oven, then is washed with deionized to neutrality, dry for standby；
(2) deionized water dissolving of ferric nitrate and manganese acetate mixing 3-4 times amount is stirred, again flyash prepared by step (1) is added in mixed liquor, in magnetic stirring apparatus, heated and stirred is to dry, it is then placed in exsiccator under 120 ° of C being dried 3-4h, finally it is ground to thin, and put in Muffle furnace under 400-600 ° of C, to calcine 0.5-1h, cross 100 mesh sieves after cooling standby；
(3) wash after glass fibre being soaked 20min with the suds of 2 times amount, after drying, under 50 ° of C, soak 30-40min with the hydrochloric acid of 10%, standby after being then washed with deionized drying；
(4) glass chopped rear and calcium carbonate, jade powder, vanadic anhydride, boric acid ester coupler mixed grinding are uniformly dispersed, sodium silicate is dissolved in water and makes the solution that concentration is 40-60%, mixture is added in sodium silicate aqueous solution to be heated to 50-60 ° of C stir formation slurry, being added in slurry by modified coal ash prepared by step (2), the spray drying that stirs can be prepared by again.
CN201610423147.0A 2016-06-16 2016-06-16 Flue gas adsorbent with large adsorption capacity Pending CN105854815A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108828141A (en) * 2018-04-26 2018-11-16 宁波诺丁汉新材料研究院有限公司 A kind of heavy metal adsorption performance test methods of mussel shell material
CN109248688A (en) * 2018-10-26 2019-01-22 山东省科学院能源研究所 A method of coal-biomass carbon production base NOx occlusion reduction catalyst is prepared in situ
CN110368894A (en) * 2019-07-03 2019-10-25 合山市春旭环保科技有限责任公司 A kind of high performance agent for removing fluorin and preparation method thereof removing fluorinion in waste water

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103521164A (en) * 2013-10-18 2014-01-22 东南大学 Flue gas demercuration, desulfurization and denitration adsorbent and preparation method thereof
CN103691263A (en) * 2013-12-12 2014-04-02 芜湖中路实业有限责任公司 Industrial quick flue gas desulfurizing agent and preparation method thereof
CN104602806A (en) * 2012-06-11 2015-05-06 卡尔冈碳素公司 Sorbents for removal of mercury
CN105148840A (en) * 2015-09-01 2015-12-16 安徽省含山县天顺环保设备有限公司 Coal ash flue gas demercuration adsorbent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104602806A (en) * 2012-06-11 2015-05-06 卡尔冈碳素公司 Sorbents for removal of mercury
CN103521164A (en) * 2013-10-18 2014-01-22 东南大学 Flue gas demercuration, desulfurization and denitration adsorbent and preparation method thereof
CN103691263A (en) * 2013-12-12 2014-04-02 芜湖中路实业有限责任公司 Industrial quick flue gas desulfurizing agent and preparation method thereof
CN105148840A (en) * 2015-09-01 2015-12-16 安徽省含山县天顺环保设备有限公司 Coal ash flue gas demercuration adsorbent

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108828141A (en) * 2018-04-26 2018-11-16 宁波诺丁汉新材料研究院有限公司 A kind of heavy metal adsorption performance test methods of mussel shell material
CN109248688A (en) * 2018-10-26 2019-01-22 山东省科学院能源研究所 A method of coal-biomass carbon production base NOx occlusion reduction catalyst is prepared in situ
CN109248688B (en) * 2018-10-26 2021-03-02 山东省科学院能源研究所 Method for in-situ preparation of carbon-based NOx adsorption reduction catalyst from coal-biomass
CN110368894A (en) * 2019-07-03 2019-10-25 合山市春旭环保科技有限责任公司 A kind of high performance agent for removing fluorin and preparation method thereof removing fluorinion in waste water
CN110368894B (en) * 2019-07-03 2022-09-13 合山市春旭环保科技有限责任公司 Efficient fluorine removal agent for removing fluorine ions in wastewater and preparation method thereof

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Application publication date: 20160817