CN101173177A - Method and device for on-line catalytic pyrolysis fine purification of biomass - Google Patents
Method and device for on-line catalytic pyrolysis fine purification of biomass Download PDFInfo
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- CN101173177A CN101173177A CNA2007100472182A CN200710047218A CN101173177A CN 101173177 A CN101173177 A CN 101173177A CN A2007100472182 A CNA2007100472182 A CN A2007100472182A CN 200710047218 A CN200710047218 A CN 200710047218A CN 101173177 A CN101173177 A CN 101173177A
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Abstract
The invention discloses a refining method and a device for online catalytic cracking of bio-oil. The technical proposal of the method is that: the biomass materials are fast paralyzed; catalytic cracking are directly performed to the acquired product in the form of gas, and then the bio-oil is acquired by condensation, wherein the product after the fast paralysis is catalyzed and paralyzed after solid particles are removed by gas-solid separation. Therefore, the fast cracking reactor and the catalytic cracking reactor in prior fast cracking units are connected into one body in present invention, and a gas-solid separation device is arranged in between. The invention has the advantages of reducing energy consumption and investment operating cost, and obviously displaying excellences of biomass energy.
Description
Technical field
The present invention relates to the biomass energy field, particularly the device of a kind of method of on-line catalytic pyrolysis fine purification of biomass and use.
Background technology
Along with expanding economy, the global energy demand increases year by year.Act as a fuel and the transition exploitation of limited resources such as the coal of organic chemistry product main raw material, oil and natural gas has made energy problem more and more severeer.As a kind of renewable energy source of cleaning, effective utilization of biomass energy has caused people's extensive concern.
Biomass can be passed through various cleavage methods, as prepare liquid fuel---bio-oils such as quick cracking, vacuum cracking, microwave crackings, wherein cracking technique enjoys people to pay close attention to owing to having wide industrial prospect fast, becomes one of gordian technique of biomass utilization exploitation.Biomass flash pyrolysis adopts superelevation heating rate (10
2～10
4K/s), the ultrashort product residence time (0.2～3s) and moderate cracking temperature, make the organic polymer molecule in the biomass under the condition of secluding air, be fractured into short chain molecule rapidly, make coke and product gas drop to bottom line, thereby obtain liquid product to greatest extent.In quick cracking technology, the secondary reaction of split product is reduced to minimum, and many functional groups of biomass are retained, so, though fast pyrogenation can obtain higher bio oil output, be that the content of oxygen element the process of bio oil is little from Wood Adhesives from Biomass.By the bio-oil that quick cracking makes, it is low to exist oil product, the viscosity height, and volatility is low, the oxygen level height, calorific value is low, has shortcomings such as corrodibility, and its poor heat stability touches air and is easy to the hardening that bonds, and causes bio-oil to store problems such as transportation is difficult, development and use difficulty.
Bio-oil will substitute petrochemical material, must make with extra care it.At present the method that bio oil is carried out refinement treatment mainly contains 2 kinds: 1. shortening, 2. catalytic pyrolysis.Shortening generally be face the hydrogen high pressure (under 10～20MPa) conditions and hydrogen supply dissolvent in the presence of, on catalyzer, the bio-oil that makes is carried out hydrotreatment, remove the labile factor of bio oil---oxygen.Though the bio-oil quality behind the hydrogenation is significantly improved, the hydrotreatment cost is higher, equipment is complicated, often run into the phenomenon of reactor plugs and catalyst deactivation in the operating process.Therefore shortening is considered to and is uneconomical.
Catalytic pyrolysis is considered to economic alternative method, thereby is widely adopted in the bio oil treating process.Catalytic pyrolysis is to have under catalyzer existence, middle temperature, the condition of normal pressure by catalytic cracking reaction, can be with the oxygen element in the biomass cracked oil by using with CO, and CO
2, H
2The form of O is removed, and the unsettled chemical substance in the bio-oil that makes is converted into material stable under the normal temperature, make it to be converted under the normal temperature stable, oil quality is high, energy density is high, can direct applied liquid fuel.
At present, according to the raw material feed state, the catalytic pyrolysis of bio-oil can be divided into two kinds: non-online catalytic pyrolysis and online catalytic pyrolysis.Refining being meant by quick cracking of non-online catalytic pyrolysis produced liquid bio-oil, is that raw material carries out the refining modification of catalytic pyrolysis again with the oil phase.Online catalytic pyrolysis is refining to be meant product after the quick cracking without condensation, and it is refining directly with the gaseous product to be that raw material carries out catalytic pyrolysis.Though non-online catalytic pyrolysis can carry out under normal pressure, do not need reducing gas hydrogen yet, its coking rate height, catalyst life is short.Simultaneously, non-online catalytic pyrolysis charging need be used volume pump, and because bio-oil viscosity is big, needs to add solvent cut, could guarantee the charging of steady and continuous.In non-online catalytic pyrolysis process, need protection of inert gas and very high energy expenditure.In addition, the use of solvent has also increased the consumption of energy, and has increased operations such as subsequent disposal, and the reaction process complexity has reduced economy.Present stage, HZSM-5 is that the non-online catalytic pyrolysis of catalyzer is refining, and liquid yield is between 40～60%, and the coking rate on the catalyzer is greater than 30% (CN 1432625A; Guo Xiaoya, Yan Yongjie, Li Tingchen, Ren Zhengwei, Yuan Chuanmin, process engineering journal, in February, 2003, the 3rd the 1st phase of volume).
Online refining mainly be the splitting gas that makes by quick cracking without condensation, directly enter the catalytic cracking reaction device and carry out catalytic pyrolysis, bio-oil is made with extra care.It does not need extra feeding unit and extra inertia protection gas, does not more need to add solvent.Compare with non-online catalytic pyrolysis, technology is simplified, and has reduced energy expenditure to a great extent.In addition, be gaseous feed because online catalytic pyrolysis is made with extra care, reduced the bio-oil vaporescence of non-online catalytic pyrolysis.This has not only reduced the consumption of energy, and has reduced pyrolysis and condensation reaction in the vaporizing liquid process, and then has reduced coking rate.Adopt online method that bio-oil is made with extra care the oil product that not only can improve bio-oil, more can energy efficient, increase the comprehensive utilization ratio of biomass energy.Document (Paul T.Williams, Patrick A.Home.Journal of Analytical and Applied Pyrolysis 31 (1995) 39-61.) has been reported the online catalytic pyrolysis of bio-oil.With the biomass material hopper of packing into, entering under the effect of carrier gas with the silica sand is that the fluidized-bed reactor of fluidizing medium carries out quick cracking.The suspension zone of this fluidized-bed reactor is provided with fixed bed catalytic reactor, and quick splitting gas upwards leads to catalyticreactor and carries out online catalytic pyrolysis under the effect of carrier gas.Enter multi-stage condensing device condensation separation product liquid after catalytically cracked gas comes out from the catalyticreactor top, the noncondensable gas product is discarded.But still in quick cracking reactor, along with the lengthening of time, the solid product that rests in the medium will be unfavorable for conducting heat its solid product, influence quick scission reaction; Being suspended in solid product in the bed will speed up split product and carries out second pyrolysis; Inorganic salt in the solid product help biomass gasification reaction simultaneously, will cause the increase of gaseous product, and then reduce liquid yield; In addition,, will increase systemic resistance, increase the residence time of split product, increase the second pyrolysis reaction, reduce liquid yield if solid product accumulates on the catalytic cracking reaction device.
Summary of the invention
The technical problem to be solved in the present invention is in order to overcome the shortcoming of above-mentioned prior biological matter on-line catalytic pyrolysis fine purification method, and the method for the successional on-line catalytic pyrolysis fine purification of biomass of a kind of raising that helps liquid yield and experiment is provided.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: it comprises biomass material is carried out quick cracking, the product of gained directly carries out catalytic pyrolysis with the gasiform form, condensation obtains bio-oil again, it is characterized in that described quick split product after gas solid separation is removed solid particulate, carries out catalytic pyrolysis again.
According to the present invention, in the method for described on-line catalytic pyrolysis fine purification of biomass, the processing condition and the catalyzer of cracking fast, catalytic pyrolysis and condensation all can adopt prior art.
Preferably, the key step of bio-oil purified method of the present invention comprises:
With the biomass material hopper of packing into, under the effect of carrier gas, entering with quartz sand by feeding screw is that the fluidized-bed reactor of fluidizing medium carries out quick cracking, and cracking temperature is 450～600 ℃ fast, preferred 470～530 ℃; Gauge pressure pressure is 10～1000mmH
2O, preferred 30～100mmH
2O; The residence time of raw material in fluidized-bed is 0.5～10s, preferred 1.0～4.0s; The splitting gas residence time is 0.1～5.0s, preferred 0.5～3.0s.
Split product is brought cyclonic separator into by fluidized gas fast, and after solid product was separated, quick splitting gas led to the fixed-bed reactor that catalyzer is housed and carries out online catalytic pyrolysis, and online catalytic pyrolysis temperature is 300～550 ℃, preferred 380～500 ℃; Gauge pressure pressure is 10～100mmH
2O, preferred 20～50mmH
2O; Mass space velocity is 0.5～7.0h
-1, preferred 2～4h
-1, catalytic pyrolysis takes place in catalyticreactor, catalytic reforming reaction etc.
Gaseous product behind the catalytic pyrolysis enters condensing works and carries out condensation, be generally B-grade condensation, water-phase product and heavy bio-oil are collected in one-level condensing temperature to 100～200 ℃, the B-grade condensation temperature is collected product liquid and is mainly the purified bio-oil to room temperature.
It is a kind of for implementing the custom-designed device of aforesaid method that the present invention also provides, and its quick cracking reactor and catalytic cracking reaction device that will have now in the quick cracker of biomass material fuses, and is provided with gas-solid separating device betwixt.Therefore, apparatus of the present invention comprise hopper, feeder, quick cracking reactor, gas-solid separating device, catalytic cracking reaction device and the condensing works that connects successively, and the carrier gas steel cylinder that is connected with hopper and quick cracking reactor respectively.
According to the present invention, the preferred cyclonic separator of described gas-solid separating device, its below has the solid of reception ash bucket.
Described catalytic cracking reaction device is the atmospheric fixed bed reactor of downstriker preferably.
Described feeder is the adjustable feeding screw of rotating speed preferably.
Described quick cracking reactor can be normal pressure bubbling fluidized bed gasifier preferably.
Biomass of the present invention comprise agricultural wastes, as: stalk, shell, fruit stone, the waste of agricultural byproducts such as corn cob; Forestry waste, as: fuel wood, fallen leaves, bark, tree root and forestry processing waste; Waterplant, as: algae, duckweed, Herba Eichhorniae, jacinthe etc.; Energy crop, as: oil crops and the plant of being rich in hydrocarbon polymer; And other growth of biomass remaining residue after acid hydrolysis or enzymic hydrolysis.
Compare with existing non-online catalytic pyrolysis purified method, the quick split product of the present invention directly enters the catalytic cracking reaction device without condensation and carries out catalytic cracking reaction, it does not need to experience the bio-oil vaporescence, and this has just weakened the influence of pyrolysis and condensation reaction; It does not need extra feeding unit and extra inertia protection gas; more do not need to add a large amount of solvents, these have simplified technology, have improved liquid yield; and all to a great extent minimizing energy consumption and investment running cost, given prominence to the advantage of biomass energy more.
Compare with existing online catalytic pyrolysis purified method, the present invention separates quick cracking reactor and catalytic cracking reaction device, and add cleaning apparatus therebetween, so quick cracked solid product will be fluidized the band of gas and go out reactor, and it is separated before catalytic cracking reaction, no longer influence the reaction of back, help the continuity of the raising and the experiment of liquid yield.
Description of drawings
Fig. 1 is the structural representation of on-line catalytic pyrolysis fine purification of biomass device of the present invention.Wherein: 1-nitrogen steel cylinder; The 2-hopper; The 3-feeding screw; The 4-fluidized-bed reactor; The 5-grid distributor; The 6-cyclonic separator; The 7-ash bucket; The 8-fixed-bed reactor; The 9-first-stage condenser; The 10-secondary condenser; The 11-gas meter.
Embodiment
The invention will be further described below in conjunction with accompanying drawing, but the present invention is not limited.
See Fig. 1, the device of on-line catalytic pyrolysis fine purification of biomass of the present invention comprises hopper 2, feeding screw 3, normal pressure bubbling fluidized bed gasifier 4, cyclonic separator 6, the atmospheric fixed bed reactor 8 of downstriker, first-stage condenser 9 and the secondary condenser 10 that connects successively, and the nitrogen steel cylinder 1 that is connected with hopper 2 tops and normal pressure bubbling fluidized bed gasifier 4 belows; Wherein normal pressure bubbling fluidized bed gasifier 4 middle and lower parts also are provided with gas distribution grid 5, and cyclonic separator 6 belows are provided with ash bucket 7.In addition, nitrogen steel cylinder 1 respectively with hopper 2 and path that normal pressure bubbling fluidized bed gasifier 4 links to each other on, and the exhaust line of second condenser, 10 rear ends is provided with the gas meter 11 that has variable valve, control the raw material and the residence time of split product in reactor with this, and the pressure in the reactor.
Will be less than the wood chip (main component sees Table 1) of 0.38mm, speed with 3 kilograms/hour (kg/h) after oven dry removes its outside water in 105 ℃ of baking ovens adds in the material bin 2, from nitrogen steel cylinder 1 nitrogen as balance gas, enter by the hopper top, make to keep certain pressure in the hopper, and balance each other, prevent that split product from entering into hopper with pressure in the fluidized-bed reactor, influence charging, it can also discharge the air in the hopper simultaneously.Under the effect of balance gas, the biomass material in the hopper 2 enters into normal pressure bubbling fluidized bed gasifier 4 through feeding screw 3 and carries out quick scission reaction, and temperature of reaction is 500 ℃, pressure (gauge pressure) 50mmH
2O.The rotating speed of feeding screw 3 is adjustable, can control input speed.Place quartz sand on the fluidized bed gas grid distributor 5 and make fluidizing medium., enter from normal pressure bubbling fluidized bed gasifier 4 bottoms earlier as fluidized gas from the nitrogen of nitrogen steel cylinder 1, enter the reaction zone of normal pressure bubbling fluidized bed gasifier 4 again through gas distribution grid 5, fluidizing medium is carried out fluidisation.The residence time of biomass material in normal pressure bubbling fluidized bed gasifier 4 is 3 seconds, and the residence time of split product in normal pressure bubbling fluidized bed gasifier 4 is 2 seconds fast.Split product is brought cyclonic separator 6 into by fluidized gas fast, and most of solid particulate separates with gaseous product, and solid particulate enters in the ash bucket 7.The gained gaseous product directly enters the atmospheric fixed bed reactor 8 of downstriker, and catalytic pyrolysis takes place the molecular sieve catalyst catalysis in beds wherein, catalytic reforming reaction etc., and temperature of reaction is 300～550 ℃, pressure (gauge pressure) 30mmH
2O, catalyzer are HZSM-5 (Changfeng Chemical Plant, Shanghai produces, and character sees Table 2), and mass space velocity is 2 (kg wood chip h
-1/ kg catalyzer).Catalytic pyrolysis gas enters first-stage condenser 9 then, enters secondary condenser 10 after being condensed to 100～200 ℃, continues to be condensed to room temperature, isolates non-condensable gas.Last solid product is collected in the ash bucket, and product liquid is collected in the condensed in two stages device, and gas products is by the collection of gas collection bag and carry out non-online detection.
Calculate quick cracking liquid yield, gas yield and solid productive rate routinely, and liquid yield, gas yield and solid productive rate (coking rate) behind the online catalytic pyrolysis.
Change into the bio oil is that raw material calculates, liquid yield behind liquid yield=online catalytic pyrolysis/quick cracking liquid yield * 100%, gas yield=(gas yield behind the online catalytic pyrolysis-quick cracked gas productive rate)/fast cracking liquid yield * 100%, solid productive rate (coking rate)=100%-liquid yield-gas yield.
Table 1. wood chip elementary composition
| Composition | C | H | O [a] | Ash content |
| Content (%) | 43.17 | 6.27 | 48.89 | 1.67 |
[a] ignored the sulphur nitrogen content, by the content to oxygen element of minusing calculating.
Table 2.HZSM-5 molecular sieve catalyst character
| BET surface-area (m 2/g) | Mean pore size (nm) | Pore volume PVHg (cm 3/g) | Acidity [b] |
| 381.6 | 1.53 | 0.1927 | +0.8＜H 0＜+3.3 |
[b] acidity is measured with the special indicator method of Harmer.
The result:
The cracking liquid yield is 63.4% fast, and gas yield is 18.6%, solid productive rate 18.0%.Online catalytic pyrolysis after product productive rate, and to change into the bio oil be the productive rate of raw material, sees Table 3.
Table 3. temperature of reaction is to the influence of online catalytic pyrolysis product productive rate.
| Embodiment | Temperature (℃) | Catalytic pyrolysis productive rate (%) | Transform back (%) | ||||
| Gas | Solid | Liquid | Gas | Solid (coking rate) | Liquid | ||
| 1 2 3 4 5 | 300 380 450 500 550 | 29.2 31.0 31.8 32.2 33.1 | 25.4 23.1 22.0 21.1 22.1 | 45.4 45.9 46.2 46.7 44.8 | 16.7 19.6 20.8 21.5 22.9 | 11.7 8.0 6.3 4.9 6.5 | 71.6 72.4 72.9 73.7 70.7 |
The fixed catalytic cracking temperature is 500 ℃, changes mass space velocity 0.5～7.0h
-1, other processing condition are consistent with embodiment 1～5.
The split product productive rate is consistent with embodiment 1～5 fast.
Online catalytic pyrolysis after product productive rate, and to change into the bio oil be the productive rate of raw material, sees Table 4.
Table 4. air speed is to the influence of online catalytic pyrolysis product productive rate
| Embodiment | Air speed (h -1) | Catalytic pyrolysis productive rate (%) | Transform back (%) | ||||
| Gas | Solid | Liquid | Gas | Solid (coking rate) | Liquid | ||
| 6 7 8 9 10 | 0.5 1 3 4 7 | 33.7 32.2 30.2 30.0 29.4 | 20.4 21.1 21.7 22.8 24.6 | 45.9 46.7 48.1 47.2 46.0 | 23.8 21.5 18.3 18.0 17.0 | 3.8 4.9 5.8 7.6 10.4 | 72.4 73.7 75.9 74.4 72.6 |
As seen, liquid yield of the present invention is apparently higher than non-online catalytic pyrolysis, and coking rate also is starkly lower than non-online catalytic pyrolysis.
Bio-oil under the highest condition of liquid yield in the foregoing description has been carried out hydrocarbon ultimate analysis, and calculated oxygen level by minusing, it the results are shown in Table 5.The bio-oil quality that obtains of the present invention can meet or exceed the quality of non-online crack refinement fully as can be seen from Table 5.
Elementary composition (the dehydration back) of table 5. bio-oil
| Reaction conditions | (wt.％) | ||
| C | H | O [a] | |
| Oil obtained by fast cracking (500 ℃) |
53.88 73.20 72.64 71.81 | 6.17 5.50 7.35 7.18 | 39.95 21.30 20.01 21.01 |
The content that [a] calculates by minusing to oxygen element.
Claims (10)
1. the method for an on-line catalytic pyrolysis fine purification of biomass, it comprises biomass material is carried out quick cracking, the product of gained directly carries out catalytic pyrolysis with the gasiform form, condensation obtains bio-oil again, it is characterized in that described quick split product after gas solid separation is removed solid particulate, carries out catalytic pyrolysis again.
2. the method for claim 1 is characterized in that described quick cracking carries out in normal pressure bubbling fluidized bed gasifier, its quick cracking temperature is 450～600 ℃, and gauge pressure pressure is 10～1000mmH
2O, the raw material residence time in fluidized-bed is 0.5～10s, and the splitting gas residence time is 0.1～4.0s.
3. method as claimed in claim 2 is characterized in that described quick cracking temperature is 470～530 ℃, and gauge pressure pressure is 30～100mmH
2O, the raw material residence time in fluidized-bed is 1.0～4.0s, and the splitting gas residence time is 0.5～2.0s.
4. the method for claim 1 is characterized in that described catalytic pyrolysis carries out in the atmospheric fixed bed reactor of downstriker, and the catalytic pyrolysis temperature is 300～550 ℃, and catalysis gauge pressure pressure is 10～100mmH
2O, mass space velocity are 0.5～7.0h
-1
5. method as claimed in claim 4 is characterized in that described catalytic pyrolysis temperature is 380～500 ℃, and catalysis gauge pressure pressure is 20～50mmH
2O, mass space velocity are 1～4h
-1
6. one kind is the custom-designed device of the enforcement described method of claim 1, it comprises hopper, feeder, quick cracking reactor, gas-solid separating device, catalytic cracking reaction device and the condensing works that connects successively, and the carrier gas steel cylinder that is connected with hopper and quick cracking reactor respectively.
7. device according to claim 6 is characterized in that described feeder is the adjustable feeding screw of rotating speed.
8. device according to claim 6 is characterized in that described quick cracking reactor is a normal pressure bubbling fluidized bed gasifier.
9. device according to claim 6 is characterized in that described gas-solid separating device is a cyclonic separator, and its below has the solid of reception ash bucket.
10. device according to claim 6 is characterized in that described catalytic cracking reaction device is the atmospheric fixed bed reactor of downstriker.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102051193A (en) * | 2011-01-10 | 2011-05-11 | 东南大学 | Method for preparing liquid fuel with low oxygen content by catalyzing and pyrolyzing biomass on line |
| CN102127462A (en) * | 2010-01-12 | 2011-07-20 | Ifp新能源公司 | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
| CN102277188A (en) * | 2011-07-25 | 2011-12-14 | 青岛福瑞斯生物能源科技开发有限公司 | Biomass thermal cracking liquefying fuel oil technology |
| CN102618312A (en) * | 2012-03-27 | 2012-08-01 | 清华大学 | New method for preparing fuel oil by co-pyrolysis of biomass and waste plastic |
| CN104357076A (en) * | 2014-11-10 | 2015-02-18 | 东南大学 | Double-stage catalytic reaction method for enhancing quality of biomass pyrolysis oil |
| CN107083252A (en) * | 2017-04-21 | 2017-08-22 | 东南大学 | A kind of chemical chain pyrolysis deoxidization technique that can reduce biomass pyrolysis oil oxygen content and system |
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| CN1240811C (en) * | 2002-03-29 | 2006-02-08 | 华东理工大学 | Process for hydrogenating oil obtained by fast cracking of bioplasm |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102127462A (en) * | 2010-01-12 | 2011-07-20 | Ifp新能源公司 | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
| CN102127462B (en) * | 2010-01-12 | 2015-05-13 | Ifp新能源公司 | Direct biomass hydroliquefaction process comprising two ebullated bed hydroconversion steps |
| CN102051193A (en) * | 2011-01-10 | 2011-05-11 | 东南大学 | Method for preparing liquid fuel with low oxygen content by catalyzing and pyrolyzing biomass on line |
| CN102277188A (en) * | 2011-07-25 | 2011-12-14 | 青岛福瑞斯生物能源科技开发有限公司 | Biomass thermal cracking liquefying fuel oil technology |
| CN102277188B (en) * | 2011-07-25 | 2014-06-18 | 青岛福瑞斯生物能源科技开发有限公司 | Biomass thermal cracking liquefying fuel oil technology |
| CN102618312A (en) * | 2012-03-27 | 2012-08-01 | 清华大学 | New method for preparing fuel oil by co-pyrolysis of biomass and waste plastic |
| CN102618312B (en) * | 2012-03-27 | 2014-12-24 | 清华大学 | New method for preparing fuel oil by co-pyrolysis of biomass and waste plastic |
| CN104357076A (en) * | 2014-11-10 | 2015-02-18 | 东南大学 | Double-stage catalytic reaction method for enhancing quality of biomass pyrolysis oil |
| CN104357076B (en) * | 2014-11-10 | 2016-04-27 | 东南大学 | A kind of two-stage catalytic reaction method improving biomass pyrolytic oil quality |
| CN107083252A (en) * | 2017-04-21 | 2017-08-22 | 东南大学 | A kind of chemical chain pyrolysis deoxidization technique that can reduce biomass pyrolysis oil oxygen content and system |
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