CN101219336A - Reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent and production method thereof - Google Patents
Reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent and production method thereof Download PDFInfo
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- CN101219336A CN101219336A CNA2007100096610A CN200710009661A CN101219336A CN 101219336 A CN101219336 A CN 101219336A CN A2007100096610 A CNA2007100096610 A CN A2007100096610A CN 200710009661 A CN200710009661 A CN 200710009661A CN 101219336 A CN101219336 A CN 101219336A
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Abstract
The invention provides a reproducible microbe metal oxide complex absorption desulfurizer and a preparation method thereof, which relates to a desulfurizer. The reproducible microbe metal oxide complex absorption desulfurizer has high absorption and can recycle sulfur dioxide through utilizing microbial cells and metal ions and the preparation method thereof. The desulfurizer consists of microbe, oxide and carrier of metallic copper and is marked as Bio-Cu/Al2O3, wherein, the Bio represents dry cell powder of microbe bacillus licheniformis, the carrier is Gamma-Al2O3 or Alpha-Al2O3. The carrier is process through baking and activating; Cu(NO3)2 and the activated carrier are isopyknic soaked before being stewed and dried; the carrier loaded with cupric ions is mixed with RO8 dry cell powder, then mixture obtained is stirred, stewed, filtered, washed and dried.
Description
Technical field
The present invention relates to a kind of desulfurizing agent, especially relate to a kind of reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent and preparation method who is used to remove sulfur dioxide of flue gases.
Background technology
Sulfur dioxide in the flue gas is one of primary pollution source of atmosphere pollution.Present industrial flue gas desulfurization is based on the wet desulphurization technology.The used desulfurizing agent of wet desulfurizing process mainly is to be representative with alkaline matters such as lime, ammonia, magnesia.When adopting these materials as desulfurizing agent, because the flue gas particularly flue gas emissions amount of coal-burning power plant is very big, one the 300000 kilowatts every h of unit can produce 1,500,000 mark cubic meter left and right sides flue gases, thereby alkaline sorbent consumption is huge, easily causes the secondary pollution of equipment corrosion and alkali solid thing.Chinese patent ZL01132142.3 discloses the method that a kind of seawater removes sulfur dioxide in flue gas, and it utilizes flyash and seawater eroding to carry out flue gas desulfurization afterwards, thereby reduces the consumption of alkaline matter.The use but flyash can not be regenerated still has a large amount of solid waste to produce.Reduce the consumption of alkaline matter, the discharging that reduces solid waste is the Wet Flue Gas Desulfurization Technique problem needing to overcome.
The applicant provides a kind of method that reclaims palladium with the bacterium thalline from the palladium ion waste liquid of low concentration in Chinese patent CN1388256, the bacterium of adopting is that this thalline of bacillus licheniformis (Bacillus licheniformis) has been stored in China Committee for Culture Collection of Microorganisms common micro-organisms center, that registers on the books is numbered 0503, strain R08.This method is that R08 somatic cells solution and the concentration of 0.4～2.0g/L is the Pd of 30～300mg/L with cell concentration
2+Aqueous solution, in 5～60 ℃, under the condition of pH2.0～3.5, the frequency of oscillation vibration 3～90min by 130 times/min filters Pd then
2+Thalline effect liquid is with the absorption Pd after filtering
2+Thalline under room temperature, place 6～48h, after behind 550～800 ℃ of calcination 1.5～3h Metal Palladium.
Summary of the invention
Purpose of the present invention aim to provide a kind of can high absorption by utilizing microbial cells and metal ion to form to have, reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent and the preparation method of recyclable sulfur dioxide.
The oxide that consists of microorganism, metallic copper and the carrier of reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent of the present invention are labeled as Bio-Cu/Al
2O
3Wherein Bio represents the dry bacterium powder of microorganism bacillus licheniformis (BacillusLicheniformis), this thalline is stored in China Committee for Culture Collection of Microorganisms common micro-organisms center, accession designation number is 0503, strain R08 (the Chinese patent CN1388256 that provides in the scape technology of passing away); Carrier is γ-Al
2O
3Or α-Al
2O
3Each component is counted Bio: Cu: Al in mass ratio
2O
3Be 60～100: 1～4: 99～96.
The preparation method of reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent of the present invention is as follows:
1) at first with carrier through 500～600 ℃ of following roasting 4～6h activation processing;
2) under 15～30 ℃, press Cu: Al
2O
3Mass ratio counts 1～4: Cu (NO is measured in 99～96 load
3)
2With leave standstill 12～16h behind the carrier incipient impregnation after the activation process, then at 105～120 ℃ of lower dry 12～16h;
3) carrier that load is had a copper ion is by 100: the mass ratio of (60～100) mixes with the R08 dry bacterium powder, and it is wetting to be with the pH value that 5.5～6.5 distilled water fully stirs, and leaves standstill effect 24～48h;
4) filtration washing at 75～85 ℃ of lower vacuum drying 6～8h, namely gets the microorganism metallic oxide adsorption desulfurizing agent Bio-Cu/Al of Biological preparation
2O
3
2%SO with flow 40ml/min
2Mixed flue gas passes into sulfur dioxide is absorbed, and forms to contain the aqueous solution that sulfur dioxide is 200～350mg/L.In 0.5～1.0g/L ratio 40～60 order microorganism metallic oxide adsorption desulfurizing agent inputs are contained in the aqueous solution of sulfur dioxide.At 15～30 ℃, under 300～400 rev/mins of stirrings, make the adsorbent and sulfur dioxide aqueous solution interaction 1.5～2.5h, suitable amount of sulfur dioxide is respectively C in the aqueous solution of absorption front and back by measuring
0, C, thus desulfurization degree X%=(C calculated
0-C)/C
0* 100%.
To be adsorbed saturated Bio-Cu/Al by sulfur dioxide
2O
3Put into distilled water by 2.5～5g/L, under nitrogen atmosphere protection, at 60～80 ℃, act on 3～4h under 300～400 rev/mins of stirrings, record till sulfur dioxide concentration no longer increases in the aqueous solution, accordingly Bio-Cu/Al
2O
3It is complete to regenerate.The aqueous solution that contains sulfur dioxide after the regeneration can obtain through the water vapour desorption method sulfur dioxide recovery utilization of high concentration.
The present invention utilizes microbial cells and metal ion to form the principle of complexing body, and thalline and the metal ion that loads on the carrier are interacted, and forms to have the microorganism metallic oxide complex desulfurizing agent that can adsorb sulfur dioxide.This complexing desulfurizing agent is efficient adsorbing and removing sulfur dioxide not only, but also the sulfur dioxide that adsorbed of desorption under certain condition obtains regeneration and reuses.The consumption of adsorbent can be significantly reduced like this, sulfur dioxide can also be reclaimed simultaneously.Its desulfurization degree average out to is more than 80%.
Description of drawings
Fig. 1 is the microorganism metallic oxide desulfurizing agent stereoscan photograph of the embodiment of the invention 1 preparation.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
With 0.6g γ-Al
2O
3Carry out activation process at 500 ℃ of roasting 6h, prepare Cu (NO with equi-volume impregnating by 1% bronze medal load capacity under the room temperature then
3)
2/ γ-Al
2O
3Leave standstill 12h, under 105 ℃ of conditions, carry out dry 12h, mix with the 0.36gR08 dry mycelium by 100: 60 mass ratioes (following all in mass ratio calculating), the distilled water of regulating pH=5.5 with dilute sulfuric acid is fully wetting, at 15 ℃, leaves standstill 24h, at 75 ℃ of lower vacuum drying 6h, obtain desulfurizing agent Bio-1%Cu/Al
2O
30.92g (Bio: Cu: Al
2O
3=60: 1: 99).
In the ratio of 0.5g/L with 80～100 order 0.2gBio-1%Cu/Al
2O
3Desulfurizing agent drops into 400ml and contains in the aqueous solution of 350mg/L sulfur dioxide.At 15 ℃, under 300 rev/mins of stirrings, make adsorbent and sulfur dioxide aqueous solution interaction 1.5h, measure content of sulfur dioxide C in the aqueous solution of absorption front and back at last
0, C is according to desulfurization degree X%=(C
0-C)/C
0* 100% to calculate desulfurization degree be 80.68%.From Fig. 1 a, can find out Bio-1%Cu/ γ-Al before not adsorbing sulfur dioxide
2O
3Upper microorganism R08 bacterium and load have the alumina phase mutual effect of copper ion that copper and the complexing of bacterium powder are integrated, after Fig. 1 b then shows absorption sulfur dioxide, sulfur dioxide and adsorbent take place to interact and adsorb from the teeth outwards, and the particle surface form obviously is different from Fig. 1 a.
With above-mentioned by the desulfurizing agent Bio-1%Cu/Al behind the sulfur dioxide saturated adsorption
2O
3, put into distilled water by 2.5g/L, under nitrogen atmosphere protection, at 60 ℃, act on 3h under 300 rev/mins of stirrings, record till sulfur dioxide concentration no longer increases in the aqueous solution, separate after filtration, desulfurizing agent obtains regeneration.With the Bio-1%Cu/Al after the regeneration
2O
3Carry out as stated above desulfurization in the Aqueous Solution of Sulfur Dioxide, the desulfurizing agent use of can repeatedly regenerating, the desulfurization degree after the regeneration is as shown in table 1.The aqueous solution that contains sulfur dioxide after the regeneration can obtain through the water vapour desorption method sulfur dioxide recovery utilization of high concentration.
Table 1 different Cu load capacity Bio-Cu/Al
2O
3Desulfurization performance after the regeneration
| Embodiment | The copper load capacity | Carrier | The once desulfurization rate | The secondary desulfuration rate | Three desulfurization degrees | Four desulfurization degrees |
| 1 | 1% | γ-Al 2O 3 | 80.68% | 79.23% | 77.62% | 75.29% |
| 2 | 1% | α-Al 2O 3 | 81.32% | 78.42% | 76.28% | 75.37% |
| 3 | 2% | γ-Al 2O 3 | 93.50% | 89.16% | 87.46% | 85.69% |
| 4 | 2% | α-Al 2O 3 | 91.37% | 88.05% | 87.27% | 85.34% |
| 5 | 3% | γ-Al 2O 3 | 88.56% | 84.67% | 81.65% | 78.85% |
| 6 | 3% | α-Al 2O 3 | 87.61% | 83.15% | 82.75% | 79.36% |
| 7 | 4% | γ-Al 2O 3 | 82.45% | 80.42% | 78.26% | 76.08% |
| 8 | 4% | α-Al 2O 3 | 81.94% | 79.54% | 77.43% | 76.40% |
Embodiment 2
With 0.8g α-Al
2O
3Carry out activation process at 600 ℃ of roasting 4h, prepare Cu (NO with equi-volume impregnating by 1% bronze medal load capacity under 30 ℃
3)
2/ α-Al
2O
3, leave standstill 16h, under 120 ℃ of conditions, carry out dry 16h, mass ratio by 100: 100 mixes with the 0.8gR08 dry mycelium, and the distilled water of regulating pH=6.5 with dilute sulfuric acid is fully wetting, leaves standstill 48h at 30 ℃, at 85 ℃ of lower vacuum drying 8h, obtain desulfurizing agent Bio-1%Cu/ α-Al
2O
31.54g (Bio: Cu: Al
2O
3=100: 1: 99).
In the 1.0g/L ratio with 0.6g80～100 order Bio-1%Cu/Al
2O
3Desulfurizing agent drops into 600ml and contains in the aqueous solution of 200mg/L sulfur dioxide, at 30 ℃, under 400 rev/mins of stirrings, make adsorbent and Aqueous Solution of Sulfur Dioxide interaction 2.5h, measure at last suitable amount of sulfur dioxide in the aqueous solution of absorption front and back, desulfurization degree 81.32%.With above-mentioned by the desulfurizing agent Bio-1%Cu/ α-Al behind the sulfur dioxide saturated adsorption
2O
3Put into distilled water by 5g/L, at 80 ℃, 400 rev/mins of revolutions stir lower effect 4h, separate after filtration under the nitrogen atmosphere protection, and desulfurizing agent obtains regeneration.With the Bio-1%Cu/ α-Al after the regeneration
2O
3Carry out as stated above desulfurization in the Aqueous Solution of Sulfur Dioxide, the desulfurizing agent performance is as shown in table 1 after the regeneration.
Embodiment 3
Prepare Cu (NO with equi-volume impregnating by 2% bronze medal load capacity
3)
2/ γ-Al
2O
30.7g all the other methods obtain desulfurizing agent Bio-2%Cu/ γ-Al with embodiment 1
2O
31.0g (Bio: Cu: Al
2O
3=60: 2: 98).Get desulfurizing agent 0.45g, record desulfurization degree 93.50% by embodiment 1 method, the renovation process of desulfurizing agent is with embodiment 1, and regeneration back desulfurizing agent performance is as shown in table 1.
Embodiment 4
Prepare Cu (NO with equi-volume impregnating 2% bronze medal load capacity
3)
2/ α-Al
2O
30.75g all the other methods obtain desulfurizing agent Bio-2%Cu/ α-Al with embodiment 2
2O
3(Bio: Cu: Al
2O
3=100: 2: 98) 1.4g.Get desulfurizing agent 0.55g, record desulfurization degree 91.37% by embodiment 2 methods, the renovation process of desulfurizing agent is with embodiment 2, and regeneration back desulfurizing agent performance is as shown in table 1.
Embodiment 5
Prepare Cu (NO with equi-volume impregnating by 3% bronze medal load capacity
3)
2/ γ-Al
2O
30.8g all the other methods obtain desulfurizing agent Bio-3%Cu/ γ-Al with embodiment 1
2O
3(Bio: Cu: Al
2O
3=60: 3: 97) 1.2g.Get desulfurizing agent 0.65g, record desulfurization degree 88.56% by the method for embodiment 1.The renovation process of desulfurizing agent is with embodiment 1, and regeneration back desulfurizing agent performance is as shown in table 1.
Embodiment 6
Prepare 0.75gCu (NO with equi-volume impregnating by 3% bronze medal load capacity
3)
2/ α-Al
2O
3, all the other methods get desulfurizing agent Bio-3%Cu/ α-Al with embodiment 2
2O
3(Bio: Cu: Al
2O
3=100: 3: 97) 1.6g.Get the method for desulfurizing agent 0.85g, record desulfurization degree 87.61% by embodiment 2.The renovation process of desulfurizing agent is with embodiment 2, and regeneration back desulfurizing agent performance is as shown in table 1.
Embodiment 7
Prepare 1.2gCu (NO with equi-volume impregnating by 4% bronze medal load capacity
3)
2/ γ-Al
2O
3, all the other methods get desulfurizing agent Bio-4%Cu/ γ-Al with embodiment 1
2O
3(Bio: Cu: Al
2O
3=60: 4: 96) 1.65g.Get the method for desulfurizing agent 0.75g, record desulfurization degree 82.45% by embodiment 1.The desulfurizing agent renovation process is with embodiment 1, and regeneration back desulfurizing agent performance is as shown in table 1.
Embodiment 8
Prepare 0.95gCu (NO with equi-volume impregnating by 4% bronze medal load capacity
3)
2/-Al
2O
3, all the other methods get desulfurizing agent Bio-4%Cu/ α-Al with embodiment 1
2O
3(Bio: Cu: Al
2O
3=100: 4: 96) 1.87g.Get desulfurizing agent 0.88g, press the method for embodiment 2, record desulfurization degree 81.94%.The desulfurizing agent renovation process is with embodiment 2, and regeneration back desulfurizing agent performance is as shown in table 1.
Claims (2)
1. reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent is characterized in that oxide and carrier that it consists of microorganism, metallic copper, is labeled as Bio-Cu/Al
2O
3, wherein Bio represents microorganism bacillus licheniformis (BacillusLicheniformis) dry bacterium powder, strain R08; Carrier is γ-Al
2O
3Or α-Al
2O
3Each component is counted Bio: Cu: Al in mass ratio
2O
3Be 60～100: 1～4: 99～96.
2. the preparation method of reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent as claimed in claim 1 is characterized in that may further comprise the steps:
1) at first with carrier through 500～600 ℃ of following roasting 4～6h activation processing;
2) under 15～30 ℃, press Cu: Al
2O
3Mass ratio counts 1～4: Cu (NO is measured in 99～96 load
3)
2With leave standstill 12～16h behind the carrier incipient impregnation after the activation process, then at 105～120 ℃ of lower dry 12～16h;
3) carrier that load is had a copper ion is by 100: the mass ratio of (60～100) mixes with the R08 dry bacterium powder, and it is wetting to be with the pH value that 5.5～6.5 distilled water fully stirs, and leaves standstill effect 24～48h;
4) filtration washing at 75～85 ℃ of lower vacuum drying 6～8h, namely gets the microorganism metallic oxide adsorption desulfurizing agent Bio-Cu/Al of Biological preparation
2O
3
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|---|---|---|---|
| CNB2007100096610A CN100525887C (en) | 2007-10-12 | 2007-10-12 | Reproducible microorganism metallic oxide complex adsorbing-desulphurizing agent and production method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101487004B (en) * | 2009-01-23 | 2011-03-30 | 厦门大学 | Reproducible dry-adsorption desulfurizing agent and preparation method thereof |
| CN102179167A (en) * | 2011-04-22 | 2011-09-14 | 天津工业生物技术研究所 | Microbial flue gas desulfurizer |
| CN107983108A (en) * | 2017-12-18 | 2018-05-04 | 常州思宇环保材料科技有限公司 | A kind of preparation method of the special sulphur-fixing agent of flue gas desulfurization |
-
2007
- 2007-10-12 CN CNB2007100096610A patent/CN100525887C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101487004B (en) * | 2009-01-23 | 2011-03-30 | 厦门大学 | Reproducible dry-adsorption desulfurizing agent and preparation method thereof |
| CN102179167A (en) * | 2011-04-22 | 2011-09-14 | 天津工业生物技术研究所 | Microbial flue gas desulfurizer |
| CN102179167B (en) * | 2011-04-22 | 2012-11-21 | 天津工业生物技术研究所 | Microbial flue gas desulfurizer |
| CN107983108A (en) * | 2017-12-18 | 2018-05-04 | 常州思宇环保材料科技有限公司 | A kind of preparation method of the special sulphur-fixing agent of flue gas desulfurization |
| CN107983108B (en) * | 2017-12-18 | 2021-02-12 | 秦皇岛鑫浩新材料科技有限公司 | Preparation method of special sulfur fixing agent for flue gas desulfurization |
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| Publication number | Publication date |
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