CN100404135C - Method for preparing integral biomass gasified tarcracking catalyst - Google Patents
Method for preparing integral biomass gasified tarcracking catalyst Download PDFInfo
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- CN100404135C CN100404135C CNB2006101225807A CN200610122580A CN100404135C CN 100404135 C CN100404135 C CN 100404135C CN B2006101225807 A CNB2006101225807 A CN B2006101225807A CN 200610122580 A CN200610122580 A CN 200610122580A CN 100404135 C CN100404135 C CN 100404135C
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- cordierite
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- catalyst
- oxalic acid
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Abstract
The present invention provides a preparation method of integral type biomass tar cracking catalyst with high reaction intensity, high tar cracking rate and good selectivity. Said method includes the following steps: (1), using oxalic acid to treat carrier: placing the cordierite in the constant-boiling oxalic acid solution whose concentration is 30-40%, treating for 20-30 min, drying and calcining; (2),coating liquor coating: making nano-grade gamma-Al2O3 be mixed with ethyl alcohol and water, grinding them, placing the above-mentioned cordierite into the above-mentioned solution, soaking said cordierite, at the same time vacuum pumping for 40-60 min, taking out residue, ageing, drying, calcining and repeatedly coating to make the coating rate be reached to 8-15%; (3), soaking by using active component solution: preparing Ni(NO3)2 solution, soaking the above-mentioned cordierite in the above-mentioned solution, ageing, drying, calcining and repeatedly coating to make its coating rate be up to above 5%.
Description
Technical field
The present invention relates to chemical technology field, relate in particular to a kind of preparation method of integral biomass gasified tarcracking catalyst.
Technical background
The gasification of biomass thermal chemistry is a kind of advanced person's a biomass energy conversion regime, and its target is to obtain imflammable gas product as much as possible.By the difference of used gasifying agent, gasification of biomass can be divided into air gasification, steam gasification, oxygen-rich gasification etc.; By reactor used difference, can be divided into using downdraft furnaces gasification, updraft type furnace gas and fluidized gasification etc.No matter in which kind of gasification, coke and tar all are inevitable accessory substances.Wherein tar mixes with fuel gas fully owing to be gaseous state when high temperature, is condensed into liquid state and (generally be lower than 200 ℃) when low temperature, so its separation and processing are more difficult.The existence of tar has many-sided adverse effect to environment and gasification.Aspect gasification, tar reduces gasification efficiency, because the energy of tar product generally accounts for the 5-15% of gross energy in the gasification, this part energy is difficult to be utilized with fuel gas when low temperature, and major part is wasted; In addition, tar is condensed into liquid state when low temperature, and easy and water, coke etc. combine, and stop up air duct, makes the operation of equipment for gasification that difficulty take place.Aspect environment, because WATER-WASHING METHOD is the major way of oil processing of focusing at present, thereby can produce secondary pollution inevitably, environment is caused more serious harm.
Utilizing catalyst that tar is carried out catalytic pyrolysis is to reduce tar content, improves a kind of advanced method of gasification efficiency.Therefore, Biomass Catalytic Gasification has been carried out a large amount of experimental studies both at home and abroad.Catalyst system therefor is mainly natural crystal class catalyst, alkali metal class catalyst and nickel-base catalyst.No matter but which kind of catalyst, its form is pellet type catalyst basically.Owing to be subjected to the restriction of pellet type catalyst catalytic efficiency, technique for applying and cost, catalyst still stayed cool in the gasification of biomass of reality is used.
Therefore, compact, safe, the efficient and eco-friendly integral catalyzer of development is imperative.Integral catalyzer have pressure fall very low, remarkable advantage such as the surface area of unit reactor volume is big, catalyst efficiency is high, reaction selectivity significantly improves with enlarge-effect is little.This novel reactor has obtained commercial application in many fields, such as purifying automobile tail gas, thermal power plant tail gas and industrial discharged waste gas.Advanced person's catalyst preparation technology is applied to gasification of biomass and generation technology, is an effective way that promotes the gasification of biomass application level.
Summary of the invention
The preparation method who the purpose of this invention is to provide the good integral biomass tar cracking catalyst of a kind of response intensity height, goudron lysis rate height and selectivity.
For reaching above-mentioned purpose, preparation method of the present invention comprises the steps:
(1) carrier oxalic acid treatment
Place the 30-40% oxalic acid solution of azeotropic to process 20-30min cordierite, afterwards oven dry and roasting, sintering temperature is 300 ℃.
(2) coating liquid coating
With nanoscale γ-Al
2O
3Mix described γ-Al with the second alcohol and water
2O
3With the ratio of second alcohol and water be: the ethanol consumption is 8-12ml/g γ-Al
2O
3, water consumption is 4-8ml/g γ-Al
2O
3Be ground to γ-Al
2O
3Not having the wadding polymers occurs.After will placing through the cordierite that step (1) is processed mentioned solution dipping and while vacuum draw 40-60min, take out and blow raffinate.Blow in the cordierite air of most raffinate 60 ℃ of dry 6h behind the aging 24h, afterwards at 500 ℃ of roasting 6h.Coating is so that the coating rate reaches 8-15% repeatedly.
(3) active component solution dipping
Preparation 1mol/l Ni (NO
3)
2Solution vacuumizes dipping with it and processes the cordierite that obtains through step (2), and dry behind aging 12h, baking temperature is 60-100 ℃, then at 600-800 ℃ of roasting 6h.Apply so that the coating rate reaches more than 5% repeatedly.
Adopt the simulation biomass rough gas and naphthalene is carried out catalyst activity evaluation discovery as the tar model compound, than traditional graininess tar cracking catalyst, as dolomite, commercial nickel-base catalyst etc., the catalyst that the present invention prepares possesses following advantage: reaction velocity is big, catalytic activity is high, pressure drop is little, enlarge-effect is little, and practical application technology is simple.
The specific embodiment
Embodiment 1
Step (1): get 1 peplolite (external diameter 40mm, height 50mm) and place 100ml 35% oxalic acid solution to handle 20min, after the taking-up, 100 ℃ of oven dry 8h are then at 300 ℃ of following roasting 5h.
Step (2): with 10g γ-Al
2O
3, 90ml ethanol, 50ml water is mixed into mixed liquor, and mixed liquor is ground to no γ-Al in mortar
2O
3The wadding polymers occurs.To put to be dipped in the mixed liquor through the cordierite that step (1) is processed and flood, and behind the vacuum draw 50min, take out and blow raffinate simultaneously.With the cordierite that blows raffinate 60 ℃ of dry 6h behind the aging 24h in air, change afterwards roasting 6h in 500 ℃ of muffle furnaces over to.
Step (2) is 2-3 time repeatedly, reaches 8-15% and gets final product to γ-Al2O3 coating rate.
Step (3): the Ni (NO of preparation 1mol/l
3)
2, vacuumizing dip coating with it has Al
2O
3Cordierite carrier 40-60min, the aging laggard drying box drying of 12h in air, baking temperature is 80 ℃, changes then roasting 6h in 700 ℃ of muffle furnaces over to.
Step is (3) 3 times repeatedly, and the coating rate of last weighing nickel oxide reaches 6.3%.
Embodiment 2
Step (1): get 1 peplolite (external diameter 40mm, height 50mm) and place 120ml 30% oxalic acid solution to handle 30min, after the taking-up, 100 ℃ of oven dry 8h are then at 300 ℃ of following roasting 5h.
Step (2): with 10g γ-Al
2O
3, 100ml ethanol, 60ml water is mixed into mixed liquor, and mixed liquor is ground to no γ-Al in mortar
2O
3The wadding polymers occurs.To put to be dipped in the mixed liquor through the cordierite that step 1 is processed and flood, and behind the vacuum draw 40min, take out and blow raffinate simultaneously.With the cordierite that blows raffinate 60 ℃ of dry 6h behind the aging 24h in air, change afterwards roasting 6h in 500 ℃ of muffle furnaces over to.
Step (2) is 2-3 time repeatedly, reaches 8-15% and gets final product to γ-Al2O3 coating rate.
Step 3: the Ni (NO of preparation 1mol/l
3)
2, vacuumizing dip coating with it has Al
2O
3Cordierite carrier 50min, the aging laggard drying box drying of 12h in air, baking temperature is 90 ℃, changes then roasting 6h in 750 ℃ of muffle furnaces over to.
Step is (3) 3 times repeatedly, and the coating rate of last weighing nickel oxide reaches 7.1%.
Adopt the simulation biomass rough gas and naphthalene is carried out the catalyst activity evaluation as the tar model compound.The biomass rough gas flow is 300ml/min, consists of: V (H
2): V (CO): V (C
2H
4): V (CO
2): V (CH
4): V (N
2)=16.04: 12.10: 2.5: 21.95: 15.08: 32.33.Add a certain amount of naphthalene, 1.1g/m
3, as the model compound of tar in the biomass rough gas.Earlier the reducing gases with V (H2): V (N2)=5: 95 is warmed up to 750 ℃, leads to biomass rough gas behind the reductase 12 h and tests continuously.Reaction end gas carries out off-line analysis with GC9800 type gas chromatographicanalyzer.N
2, CO, CO
2, CH
4, H
2Adopt TCD to detect CH
4, C
2H
4Deng adopting FID to detect, pass through CH between the 2 detection data
4Related.Tar adopts GC-MS that the reformate of model compound naphthalene is carried out off-line analysis.
Embodiment 1 evaluating catalyst result is as shown in table 1:
Table 1 embodiment 1 evaluating catalyst result
| The material title | Retention time (min) | Concentration (μ g/m 3) |
| The 1-butylene | 4.76 | 148.26 |
| Benzene | 8.87 | 268.36 |
| Toluene | 11.78 | 40.21 |
| Ethylbenzene | 14.74 | 7.86 |
| Between ortho-xylene | 14.99 | 8.96 |
| Paraxylene | 15.72 | 4.98 |
| Styrene | 15.56 | 506.23 |
| Amount to | 984.86 | |
| Goudron lysis rate | 99.90% |
Embodiment 2 evaluating catalyst results are as shown in table 2:
Table 2 embodiment 2 evaluating catalyst results
| The material title | Retention time (min) | Concentration (μ g/m 3) |
| The 1-butylene | 4.76 | 139.45 |
| Benzene | 8.87 | 280.66 |
| Toluene | 11.78 | 38.45 |
| Ethylbenzene | 14.74 | 9.23 |
| Between ortho-xylene | 14.99 | 9.06 |
| Paraxylene | 1 5.72 | 5.31 |
| Styrene | 15.56 | 489.56 |
| Amount to | 971.72 | |
| Goudron lysis rate | 99.90% |
Claims (1)
1. the preparation method of an integral biomass gasified tarcracking catalyst is characterized in that comprising the steps:
(1) carrier oxalic acid treatment: place the 30-40% oxalic acid solution of azeotropic to handle 20-30min cordierite, oven dry and roasting afterwards, sintering temperature is 300 ℃;
(2) coating liquid coating: with nanoscale γ-Al
2O
3Mix described γ-Al with the second alcohol and water
2O
3With the ratio of second alcohol and water be: the ethanol consumption is 8-12ml/g γ-Al
2O
3, water consumption is 4-8ml/g γ-Al
2O
3Be ground to γ-Al
2O
3Not having the wadding polymers occurs, after will placing through the cordierite that step (1) is processed mentioned solution dipping and while vacuum draw 40-60min, taking-up blows raffinate, blow in the cordierite air of raffinate 60 ℃ of dry 6h behind the aging 24h, at 500 ℃ of roasting 6h, coating is so that the coating rate reaches 8-15% repeatedly afterwards;
(3) active component solution dipping: preparation 1mol/l Ni (NO
3)
2Solution vacuumizes dipping with it and processes the cordierite that obtains through step (2), and dry behind aging 12h, baking temperature is 60-100 ℃, then at 600-800 ℃ of roasting 6h; Repeatedly apply so that the coating rate reaches more than 5%.
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| CN100404135C true CN100404135C (en) | 2008-07-23 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798516B (en) * | 2009-02-09 | 2013-03-27 | 中源新能源(福建)有限公司 | Nano-base carrier synchronous multiple-effect cracking catalyst and preparation method thereof |
| CN101757919B (en) * | 2009-12-28 | 2012-12-26 | 中国科学院广州能源研究所 | Integral catalyst applied to biological oil reforming hydrogen production, preparation and application thereof |
| CN102634355B (en) * | 2011-12-20 | 2014-04-23 | 华北电力大学 | Method for cracking biomass pyrolytic tar catalytically using nickel-carrying carbon nano tube |
| CN103055882A (en) * | 2012-12-26 | 2013-04-24 | 中国科学院广州能源研究所 | Preparation method for multi-metal monolithic tar cracking catalyst |
| CN103263922A (en) * | 2013-05-15 | 2013-08-28 | 武汉工程大学 | Preparation method of high-dispersibility m-dinitrobenzene hydrogenation structuring catalyst |
| CN104549450B (en) * | 2015-01-14 | 2017-04-26 | 天津大学 | Method for preparing loaded molecular sieve catalyst by using catalytic cracking of biomass gasification tar |
| CN108970616A (en) * | 2017-05-30 | 2018-12-11 | 镇江杜微人才咨询有限公司 | A kind of preparation method of biomass tar cracking catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104846A (en) * | 1989-08-23 | 1992-04-14 | Viswanatha Sankaran | Molecular restructuring catalyst |
| JPH04237193A (en) * | 1991-01-22 | 1992-08-25 | Matsushita Electric Ind Co Ltd | Taped electronic component connection method and device |
| CN1404903A (en) * | 2002-10-29 | 2003-03-26 | 上海多灵环保工程设备有限公司 | Garbage-incineration smoke purifying agent and purifying apparatus |
| CN1686606A (en) * | 2005-02-25 | 2005-10-26 | 许庆华 | Biomass gasification catalyst and its production method |
-
2006
- 2006-09-30 CN CNB2006101225807A patent/CN100404135C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104846A (en) * | 1989-08-23 | 1992-04-14 | Viswanatha Sankaran | Molecular restructuring catalyst |
| JPH04237193A (en) * | 1991-01-22 | 1992-08-25 | Matsushita Electric Ind Co Ltd | Taped electronic component connection method and device |
| CN1404903A (en) * | 2002-10-29 | 2003-03-26 | 上海多灵环保工程设备有限公司 | Garbage-incineration smoke purifying agent and purifying apparatus |
| CN1686606A (en) * | 2005-02-25 | 2005-10-26 | 许庆华 | Biomass gasification catalyst and its production method |
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Effective date of registration: 20180228 Address after: 525011 Guangdong city of Maoming Province Petrochemical Industrial Park Road West Mining Maonan Patentee after: Maoming Hongyu Energy Technology Co., Ltd. Address before: Energy road Guangzhou City, Guangdong province 510640 Wushan Park No. 1 Guangzhou Institute of Energy Conversion.CAS Patentee before: Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences |
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Denomination of invention: Preparation method of integral biomass gasification tar cracking catalyst Effective date of registration: 20220225 Granted publication date: 20080723 Pledgee: Bank of China Limited by Share Ltd. Maoming branch Pledgor: Maoming Hongyu Energy Technology Co.,Ltd. Registration number: Y2022980001900 |
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