CN105771636B - A kind of preparation method of flue gas desulfurization pulvis - Google Patents

A kind of preparation method of flue gas desulfurization pulvis Download PDF

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CN105771636B
CN105771636B CN201610252905.7A CN201610252905A CN105771636B CN 105771636 B CN105771636 B CN 105771636B CN 201610252905 A CN201610252905 A CN 201610252905A CN 105771636 B CN105771636 B CN 105771636B
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CN105771636A (en
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王莉萍
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Beijing Qingxin Environmental Engineering Technology Co ltd
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Yancheng Qingxin Environmental Technology Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
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    • B01D—SEPARATION
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    • B01D53/46—Removing components of defined structure
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    • B01D53/50—Sulfur oxides
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    • 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
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • 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
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    • 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
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • 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
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    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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Abstract

The invention belongs to environmental technology fields, disclose a kind of preparation method of flue gas desulfurization pulvis, include the following steps：Step 1）Stirring and heating, step 2）Crushing, ball milling and immersion, step 3）Grinding and mixing, step 4）Calcining, step 5）It is mixed.The preparation method of flue gas desulfurization pulvis of the present invention is simple, is suitble to industrialized production.

Description

A kind of preparation method of flue gas desulfurization pulvis
Technical field
The invention belongs to environmental technology fields, disclose a kind of preparation method of flue gas desulfurization pulvis.
Background technology
In recent years, the industrial revolution is grown rapidly, and environmental technology field lags far behind.China is an Industrial Boiler production With use big country, coal-burned industrial boiler situation makes people worried, and Industrial Boiler coal-fired flue-gas in 2010 discharges sulfur dioxide about 1000 Ten thousand tons.Development clean combustion technique is a war of the atmosphere polluting problem based on China's solution primary energy combustion product gases pollution Slightly countermeasure is to realize the important technology direction that economy, social sustainable development and economy, energy environment develop in harmony；Clean combustion The core of technology is the burning of primary energy high cleaning, and the emission reduction that sulphur is a suitable China's national situation is consolidated in wherein primary energy desulfurization SO2One of technical measures.
Under such national conditions, novel desulphurization pulvis is studied, there will be extremely strong vitality, it can be in metallurgical, power generation, water The flue gas desulfurization in the fields such as mud, Industrial Boiler uses, and has popularity, advance and generality.At present, more company opens Begin set about research can simultaneous SO_2 and NO removal preparation, there are also launch sale；There are costs for most of desulfurization preparation Relatively high, adsorbance is smaller, and stability is not high, in large-scale application there are it is certain the defects of.In recent years, in environmental problem And in the case of energy crisis getting worse, both at home and abroad gradually by goal in research be transferred to exploitation it is relatively inexpensive, effective New material prepares desulfurization preparation, such as different kind organism material and mineral material.
Invention content
Invention content
For overcome the deficiencies in the prior art, the present invention provides a kind of preparation method of flue gas desulfurization pulvis, this method Simple possible, the desulfurization powder desulfurization effect of preparation is good, capacity is high, can be applied to various flue gas desulfurizations.
The present invention is realized by following scheme：
A kind of preparation method of flue gas desulfurization pulvis, includes the following steps：
Step 1）Stirring and heating, step 2）Crushing, ball milling and immersion, step 3）Grinding and mixing, step 4）Calcining, step Rapid 5）It is mixed；
Specifically, include the following steps：
Step 1）Stirring and heating：Calcium oxide, activated carbon, calcirm-fluoride and dicalcium silicate are added to mixing agitator In, 500 turns/min stirring 6min spray soya-bean oil, after stirring, are heated to 80 DEG C, keep the temperature 3min, mixed while stirring Expect A；Wherein, the mass ratio of activated carbon, calcium oxide, calcirm-fluoride, dicalcium silicate and soya-bean oil is 15:10:3:3:1；
Step 2）Crushing, ball milling and immersion：Monticellite, mullite and shepardite are used into crusher in crushing respectively, Then it mixes, then puts into vibrator, grain size to be milled to is 100-200um, stops ball milling, discharging, then with dense It spends and is impregnated 6 hours for the sodium hydrate aqueous solution of 1M, last 50 DEG C of drying obtain mixture B；Wherein, monticellite, Mo Lai The mass ratio of stone, shepardite and sodium hydrate aqueous solution is 3:2:2:5；
Step 3）Grinding and mixing：Soybean stalk with pulverizer is crushed, is then ground to the powder of 300-500um, most It is mixed afterwards with nano silicon dioxide, obtains mixture C；Wherein, the mass ratio of soybean stalk and nano silicon dioxide is 5:1；
Step 4）Calcining：By dolomite and diatomite according to 2:1 mass ratio mixing, is subsequently placed in and is calcined in calcining furnace 2h, calcination temperature are 1000 DEG C, take out, are cooled to room temperature, crushing obtains mixture D；
Step 5）It is mixed：By mixture A, mixture B, mixture C and mixture D according to 15-25:10-15:4- 7:The mass ratio of 2-3 be mixed evenly to get.
Preferably, the grain size of nano silicon dioxide is 200-500nm.
The advantageous effect that the present invention obtains mainly includes the following aspects：
The preparation method of flue gas desulfurization pulvis of the present invention is simple, is suitble to industrialized production, low raw-material cost, the powder of preparation Agent is environment friendly and pollution-free, can be widely applied to all kinds of flue gas desulfurizations.
Pulvis material combination prepared by the present invention is reasonable, and desulfurization effect is good, and sulfur capacity is high, shortens the vulcanization reaction time.
The present invention is mostly using the raw material and agricultural wastes derived from a wealth of sources so that waste becomes the new energy, solves Environmental protection of enterprise pressure, realizing turns waste into wealth.
The present invention is increased adsorption effect, is played good catalytic action using dolime and diatomaceous technique.
Present invention employs discarded soybean stalks, and grain size is big, form certain pore structure, improve adsorption effect.
The present invention is by spraying soya-bean oil and heating so that pulvis surface forms protective film, improves the holding time of pulvis And desulfuration efficiency.
The present invention improves dispersion effect, expands adsorbent capacity by adding nanometer particle.
Specific embodiment
In order to make those skilled in the art better understand the technical solutions in the application, have below in conjunction with the application Body embodiment more clearly and completely describes the present invention, it is clear that described embodiment is only the application one Divide embodiment, instead of all the embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not making All other embodiments obtained under the premise of creative work should all belong to the scope of protection of the invention.
Embodiment 1
A kind of preparation method of flue gas desulfurization pulvis, includes the following steps：
Step 1）Stirring and heating, step 2）Crushing, ball milling and immersion, step 3）Grinding and mixing, step 4）Calcining, step Rapid 5）It is mixed；
Specifically, include the following steps：
Step 1）Stirring and heating：Calcium oxide, activated carbon, calcirm-fluoride and dicalcium silicate are added to mixing agitator In, 500 turns/min stirring 6min spray soya-bean oil, after stirring, are heated to 80 DEG C, keep the temperature 3min, mixed while stirring Expect A；Wherein, the mass ratio of activated carbon, calcium oxide, calcirm-fluoride, dicalcium silicate and soya-bean oil is 15:10:3:3:1；
Step 2）Crushing, ball milling and immersion：Monticellite, mullite and shepardite are used into crusher in crushing respectively, Then it mixes, then puts into vibrator, grain size to be milled to is 100um, stops ball milling, discharging, then with a concentration of The sodium hydrate aqueous solution of 1M impregnates 6 hours, and last 50 DEG C of drying obtain mixture B；Wherein, monticellite, mullite, The mass ratio of shepardite and sodium hydrate aqueous solution is 3:2:2:5；
Step 3）Grinding and mixing：Soybean stalk with pulverizer is crushed, is then ground to the powder of 300um, finally with Nano silicon dioxide mixes, and obtains mixture C；Wherein, the mass ratio of soybean stalk and nano silicon dioxide is 5:1；
Step 4）Calcining：By dolomite and diatomite according to 2:1 mass ratio mixing, is subsequently placed in and is calcined in calcining furnace 2h, calcination temperature are 1000 DEG C, take out, are cooled to room temperature, crushing obtains mixture D；
Step 5）It is mixed：By mixture A, mixture B, mixture C and mixture D according to 15:10:4:2 matter Amount than be mixed evenly to get.
Wherein, the grain size of nano silicon dioxide is 200nm.
Embodiment 2
A kind of preparation method of flue gas desulfurization pulvis, includes the following steps：
Step 1）Stirring and heating, step 2）Crushing, ball milling and immersion, step 3）Grinding and mixing, step 4）Calcining, step Rapid 5）It is mixed；
Specifically, include the following steps：
Step 1）Stirring and heating：Calcium oxide, activated carbon, calcirm-fluoride and dicalcium silicate are added to mixing agitator In, 500 turns/min stirring 6min spray soya-bean oil, after stirring, are heated to 80 DEG C, keep the temperature 3min, mixed while stirring Expect A；Wherein, the mass ratio of activated carbon, calcium oxide, calcirm-fluoride, dicalcium silicate and soya-bean oil is 15:10:3:3:1；
Step 2）Crushing, ball milling and immersion：Monticellite, mullite and shepardite are used into crusher in crushing respectively, Then it mixes, then puts into vibrator, grain size to be milled to is 200um, stops ball milling, discharging, then with a concentration of The sodium hydrate aqueous solution of 1M impregnates 6 hours, and last 50 DEG C of drying obtain mixture B；Wherein, monticellite, mullite, The mass ratio of shepardite and sodium hydrate aqueous solution is 3:2:2:5；
Step 3）Grinding and mixing：Soybean stalk with pulverizer is crushed, is then ground to the powder of 500um, finally with Nano silicon dioxide mixes, and obtains mixture C；Wherein, the mass ratio of soybean stalk and nano silicon dioxide is 5:1；
Step 4）Calcining：By dolomite and diatomite according to 2:1 mass ratio mixing, is subsequently placed in and is calcined in calcining furnace 2h, calcination temperature are 1000 DEG C, take out, are cooled to room temperature, crushing obtains mixture D；
Step 5）It is mixed：By mixture A, mixture B, mixture C and mixture D according to 25:15:7:3 matter Amount than be mixed evenly to get.
Wherein, the grain size of nano silicon dioxide is 500nm.
Embodiment 3
The flue gas containing sulfur dioxide is simulated, into the desulphurization reaction room of the desulfurization powder prepared containing embodiment 2, flue gas speed Spend for 0.5m/min, flue-gas temperature is 100 DEG C, be set separately desulfurization time for 10,20,30,60min, measure desulfurization degree, specifically It is shown in Table 1：
Table 1
Desulfurization time min Inlet concentration mg/m3 Exit concentration mg/m3 Desulfurization degree %
10 748.5 189.3 74.71
20 761.3 167.6 77.99
30 759.1 133.5 82.41
60 753.8 129.6 82.81
Conclusion：Inventive desulfurization powder desulfurization rate can reach more than 80%；After reaction, desulfurization powder work is had detected 30min is to the adsorbance of sulfur dioxide：The adsorbable sulfur dioxide 58.7mg of every gram of adsorbent, adsorption capacity is good, and the reaction time is short.
Above in association with specific embodiment, invention has been described, it will be appreciated by those skilled in the art that this A little descriptions are all exemplary, and are not limiting the scope of the invention.Those skilled in the art can be according to the present invention Spirit and principle various variants and modifications are made to the present invention, these variants and modifications are also within the scope of the invention.

Claims (2)

1. a kind of preparation method of flue gas desulfurization pulvis, which is characterized in that the preparation method includes the following steps：
Step 1）Stirring and heating：Calcium oxide, activated carbon, calcirm-fluoride and dicalcium silicate are added in mixing agitator, 500 Turn/min stirring 6min, spray soya-bean oil while stirring, after stirring, be heated to 80 DEG C, keep the temperature 3min, obtain mixture A；Its In, activated carbon, calcium oxide, calcirm-fluoride, dicalcium silicate and soya-bean oil mass ratio be 15:10:3:3:1；
Step 2）Crushing, ball milling and immersion：Monticellite, mullite and shepardite are used into crusher in crushing respectively, then Mixing, then put into vibrator, grain size to be milled to is 100-200um, stops ball milling, discharging, then with a concentration of The sodium hydrate aqueous solution of 1M impregnates 6 hours, and last 50 DEG C of drying obtain mixture B；Wherein, monticellite, mullite, The mass ratio of shepardite and sodium hydrate aqueous solution is 3:2:2:5；
Step 3）Grinding and mixing：Soybean stalk with pulverizer is crushed, is then ground to the powder of 300-500um, finally with Nano silicon dioxide mixes, and obtains mixture C；Wherein, the mass ratio of soybean stalk and nano silicon dioxide is 5:1；
Step 4）Calcining：By dolomite and diatomite according to 2:1 mass ratio mixing, is subsequently placed in calcining furnace and calcines 2h, Calcination temperature is 1000 DEG C, takes out, is cooled to room temperature, and crushing obtains mixture D；
Step 5）It is mixed：By mixture A, mixture B, mixture C and mixture D according to 15-25:10-15:4-7:2- 3 mass ratio be mixed evenly to get.
2. preparation method according to claim 1, which is characterized in that the grain size of the nano silicon dioxide is 200- 500nm。
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CN111672269A (en) * 2020-06-28 2020-09-18 潮州市中乾环境科技有限公司 Environment-friendly waste gas treatment device with adsorption function
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JPH0299137A (en) * 1988-10-05 1990-04-11 Mitsubishi Heavy Ind Ltd Desulfurizing agent
CN101074402A (en) * 2006-05-17 2007-11-21 陈钧 Efficient sulfur-fixing agent and its usage
CN103495403A (en) * 2013-08-30 2014-01-08 蚌埠首创滤清器有限公司 Modified activated carbon adsorption desulfurization agent and its preparation method
CN103566879A (en) * 2013-09-26 2014-02-12 蚌埠华纺滤材有限公司 Expanded perlite modified activated carbon automobile exhaust desulfurizing agent, and preparation method thereof
CN103566880A (en) * 2013-09-29 2014-02-12 安徽金叶炭素科技有限公司 Rice hull modified active carbon adsorption desulfurizing agent and preparation method thereof
CN104479792A (en) * 2014-12-29 2015-04-01 李康 Preparation method for desulfurizing agent for boiler coal combustion

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