CN100434162C - Biological matter pyrolysis gasifying detarring catalyst and preparing method - Google Patents
Biological matter pyrolysis gasifying detarring catalyst and preparing method Download PDFInfo
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- CN100434162C CN100434162C CNB2007100206216A CN200710020621A CN100434162C CN 100434162 C CN100434162 C CN 100434162C CN B2007100206216 A CNB2007100206216 A CN B2007100206216A CN 200710020621 A CN200710020621 A CN 200710020621A CN 100434162 C CN100434162 C CN 100434162C
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Abstract
The invention relates to a catalyst of taking off biomass Thermal Gasification tar,Dolomite concavo convex stone clay get the granular or columnar or ring catalyst through crushing,molding and activating, the special surface is 25-1252/g, pore volume is 0.3-0.4ml/g. the described activation after molding calcine 2 to 4 hours under 500-900deg.C. The catalyst tar removal rate reaches more than 90%.
Description
One, technical field:
The present invention relates to a kind of Catalysts and its preparation method, exactly is a kind of biological matter pyrolysis gasifying detarring catalyst and preparation method thereof.
Two, technical background
Annual about 1,000,000,000 tons of the various stalks of producing of China, agriculture and forestry product and be that the industrial enterprise of raw material also produces several hundred million tons residual processing thing with living beings.Biomass resource is a kind of reproducible clean energy resource, can realize CO
2Zero-emission alleviates greenhouse effects and environmental pollution greatly.With new and high technology development and utilization biomass energy, replace the mineral matter energy such as oil, coal, be one of important channel that solves the energy and environment problem.From present progress, the biomass pyrogenation gasification technology has the advantage that efficient is higher, adaptability to raw material is strong, equipment is simple, investment is lower, relatively be suitable for technology, the economic level of China rural area present stage and following regular period, and not limited by region, weather.Utilize in the technology in numerous living beings, biomass pyrogenation gasification is the most rising, by this technology, can produce valuable combustion gas for civilian and industrial use.
In biomass pyrogenation gasification technology, can contain a certain amount of tar inevitably.When being main purpose with process gas fuel, the existence of tar not only causes factor of created gase and the thermal efficiency to reduce, and also can be condensed into liquid state when low temperature, stops up and etching apparatus thereby be easy to combine with water and dust, causes the equipment can't operate as normal in the time of seriously.The water resource of water elution tar Technology Need consume valuable commonly used and very easily cause serious secondary pollution is difficult to tar in the combustion gas is removed clean simultaneously.Because the tar blockage problem is serious in the biomass gasification burning, the straw from village gasification central gas supply station majority that has built up at present can not run well, and existing small-sized household biomass gasifying furnace is ubiquity tar blockage problem also, and has constituted potential safety hazard.
At the problem that biomass gasification tar causes, Chinese scholars is being studied and is being adopted the catalytic cracking of tar method to solve.Catalytic cracking method be by catalyst at high temperature coke tar cracking be H
2, CH
4, reduce CO simultaneously
2Content, improve flammable composition ratio in the combustion gas.Ni-Al
2O
3, loaded with nano MgO has obligate catalytic action and effect preferably to coke tar cracking, and the catalytic pyrolysis temperature reduces (at 350-500 ℃) greatly, but catalyst cost height.The common white marble is as catalyst, because catalytic activity is low, catalysis detar efficient is low.Chinese patent publication number CN1686606A, title is biomass gasification catalyst and production method." a kind of biomass gasification catalyst and production method " disclosed.Described catalyst is by " Concave-convex clay rod, alumine, iron oxide, magnesia calcium oxide and anthracite are formed ".Above-mentioned catalyst makes goudron lysis rate more than 75%, and rate of gasification improves 15%, and fuel gases calorific value has improved 20%.
In Jiangsu and border land, Anhui abundant Concave-convex clay rod resource is arranged.The Concave-convex clay rod ore type is divided into four kinds: Concave-convex clay rod (attapulgite content is greater than 70%), montmorillonite Concave-convex clay rod (attapulgite content 20-50%, smectite content is greater than 50%), opal Concave-convex clay rod (containing more opal), dolomite Concave-convex clay rod (dolomite content is greater than 20%).Symbiosis has a large amount of dolomite Concave-convex clay rods in the Concave-convex clay rod ore deposit, and with the Concave-convex clay rod alternating layers output of other type.When the exploitation Concave-convex clay rod, the dolomite Concave-convex clay rod is used as abandoned mine and long-term the stacking.The dolomite Concave-convex clay rod is not well utilized at present, has not only increased the Concave-convex clay rod cost of winning, and because a large amount of the stacking caused serious environmental destruction.
Typical case's dolomite Concave-convex clay rod ore chemistry composition is: SiO
2, 33.14%; CaO, 15.9%; MgO, 15.7%; Fe
2O
3, 2.48%; Al
2O
3, 3.69%; TiO
2, 0.39%; Loss on ignition, 28.14%
The applicant discovers the dolomite Concave-convex clay rod with high-resolution-ration transmission electric-lens and ESEM, about the dolomite particle diameter 200nm in the dolomite Concave-convex clay rod, there is the growth or the corrosion step of several nanometers on the surface, and inside has abundant nanometer corrosion hole.This is the very rare nanostructured feature (Fig. 1,2) of nature that the applicant finds first.About attapulgite diameter 40 nanometers wherein, length 300～800 nanometers.The dolomite Concave-convex clay rod is the natural nano-material with unique mineral composition, microstructure and special performance.
Three, summary of the invention
The tar that produces when the present invention is intended to remove biomass pyrogenation gasification, technical problem to be solved are to use cracking catalyst tar.
The alleged detar catalyst of the present invention is that dolomite content is 20～70%, attapulgite content be 20～80% dolomite Concave-convex clay rod through pulverizing, moulding with under 500～900 ℃ of conditions, calcine column or ring-type or the granular catalyst that activation in 2～4 hours obtains, specific area is 25～125m
2/ g, pore volume are 0.3～0.4ml/g.
This Preparation of catalysts method, with the dolomite Concave-convex clay rod is raw material, wherein dolomite content is 20～70%, attapulgite content is 20～80%, comprise pulverizing, moulding and activation, it is characterized in that described activation promptly is to calcine 2～4 hours after the moulding, calcines 2～3 hours under preferred 600～750 ℃ of conditions under 500～900 ℃ of conditions.
The dolomite Concave-convex clay rod is after high-temperature calcination, and palygorskite nano crystal morphology and adsorption activity remain unchanged, and dolomite decomposes about 20 nanometers of generation nano-MgO particle, and loads on the attapulgite plane of crystal, constitutes the nano complex (see figure 4).This complex has very high specific area and to the absorption and the catalytic pyrolysis activity of tar.The MgO particle that the dolomite thermal activation produces in the dolomite Concave-convex clay rod is little more than the MgO particle that common dolime produces, and is close with the MgO granular size of artificial synthetic special load, has very high adsorption capacity and catalytic activity.
Through test shows that the tar clearance reaches more than 90% to the stalk gasifier catalytic cracking of tar.
This catalyst raw material cheapness, be easy to get, preparation technology is simple, and tar clearance height is easy to popularize.
Four, description of drawings
Fig. 1 catalyst raw material dolomite Concave-convex clay rod field emission scanning electron microscope image.Show that the mutual embedding of attapulgite (fibrous crystal) and dolomite (granular solid matter) is living, grow the space, show higher voidage, the about 200-300nm of DOLOMITE CRYSTALS particle diameter, be the dolomite of the particle diameter minimum of present nature discovery, it is active to have higher heat.
Fig. 2 catalyst raw material dolomite Concave-convex clay rod field emission scanning electron microscope image.Show that the DOLOMITE CRYSTALS in the dolomite Concave-convex clay rod contains the microstructure features of nanoscales such as abundant cavity, corrosion step.
Fig. 3 catalyst raw material dolomite Concave-convex clay rod high-resolution-ration transmission electric-lens image shows dolomite pattern in the clay, shows to have nano-mineral features such as nanometer particle size and nanometer cavity.
Fig. 4 the present invention prepares the high-resolution-ration transmission electric-lens image of catalyst, show that the nano-MgO crystal (20 nano-granular particle) that the dolomite thermal activation produces in the catalyst loads on the attapulgite plane of crystal, constitute nano complex, this complex has very high specific area and to the absorption and the catalytic pyrolysis activity of tar.
Five, the specific embodiment
(1) Preparation of catalysts
Now the dolomite Concave-convex clay rod ore with Jiangsu and border land, Anhui is an example as the raw material for preparing catalyst, wherein dolomite content is 60%, the content of attapulgite is 35%, and impure mineral content quartzy and feldspar is about 5%, and non-limiting examples is described below:
1. the fragmentation of dolomite Concave-convex clay rod, screening are obtained the granular material of 0.5～6mm,, promptly obtain graininess detar catalyst through 700 ℃ of calcinings 2 hours.
2. the dolomite Concave-convex clay rod is crushed to granularity≤0.1mm powder.Powder joined throw in the clothing machine, spraying adds an amount of water, and dolomite Concave-convex clay rod powder rolling balling obtains the particle of particle diameter 1～6mm, then 105 ℃ of dryings in baking oven.The particle of preparation was calcined 3 hours for 650 ℃, promptly obtained graininess detar catalyst.
3. the dolomite Concave-convex clay rod is crushed to granularity≤0.1mm powder.Powder and adhesive C MC and water are mixed the back mold pressing be diameter 1～6mm, long 8～10mm's is cylindric or circular, puts in the baking oven earlier to dehydrate, and calcining 2 hours in the time of 750 ℃ then promptly gets column or ring-type detar catalyst.
(2) detar test
The detar catalyst of preparation is loaded into catalytic reactor, is that the catalytic pyrolysis object carries out catalysis experiment with the stalk gasifier tar that condenses, and during 600 ℃ of catalytic reaction temperature, the tar clearance reaches more than 90%.
Claims (3)
1, a kind of biological matter pyrolysis gasifying detarring catalyst, it is characterized in that: this catalyst is that dolomite content is 20～70%, attapulgite content be 20～80% from the marble Concave-convex clay rod through pulverizing, moulding with under 500～900 ℃ of conditions, calcine graininess or column or the ring-type catalyst that activation in 2～4 hours obtains, specific area is 25～125m
2/ g, pore volume are 0.3～0.4ml/g.
2, the described Preparation of catalysts method of claim 1, this method is a raw material with the dolomite Concave-convex clay rod, wherein dolomite content is 20～70%, attapulgite content is 20～80%, this method comprises pulverizing, moulding and activation, it is characterized in that: described activation is to calcine 2～4 hours under 500～900 ℃ of conditions after the moulding.
3, preparation method according to claim 2 is characterized in that: described activation is to calcine 2～3 hours under 600～750 ℃ of conditions after the moulding.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102145298B (en) * | 2010-02-09 | 2013-04-17 | 广州金安源节能科技股份有限公司 | Catalytic conversion agent of tar in gas for biomass boiler |
| CN103801278A (en) * | 2014-02-25 | 2014-05-21 | 合肥工业大学 | Method for preparing nanometer magnesium oxide composite material through dolomite attapulgite thermal activation and application thereof |
| CN112246823A (en) * | 2020-09-08 | 2021-01-22 | 新奥生物质能(天津)有限公司 | High ash pyrolytic carbon utilization method and system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1667086A (en) * | 2005-02-25 | 2005-09-14 | 许庆华 | Purifying system for biomass gasifying oven |
| CN1686606A (en) * | 2005-02-25 | 2005-10-26 | 许庆华 | Biomass gasification catalyst and its production method |
| JP2006068723A (en) * | 2004-08-06 | 2006-03-16 | Takuma Co Ltd | Gasification catalyst, producing method therefor and gasification system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006068723A (en) * | 2004-08-06 | 2006-03-16 | Takuma Co Ltd | Gasification catalyst, producing method therefor and gasification system |
| CN1667086A (en) * | 2005-02-25 | 2005-09-14 | 许庆华 | Purifying system for biomass gasifying oven |
| CN1686606A (en) * | 2005-02-25 | 2005-10-26 | 许庆华 | Biomass gasification catalyst and its production method |
Non-Patent Citations (2)
| Title |
|---|
| 生物质焦油的催化裂解研究. 周劲松，王铁柱等.燃料化学学报，第31卷第2期. 2003 |
| 生物质焦油的催化裂解研究. 周劲松，王铁柱等.燃料化学学报，第31卷第2期. 2003 * |
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