CN103084158A - Adsorption catalysis heat carrier for biomass pyrolysis - Google Patents
Adsorption catalysis heat carrier for biomass pyrolysis Download PDFInfo
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- CN103084158A CN103084158A CN2011103501234A CN201110350123A CN103084158A CN 103084158 A CN103084158 A CN 103084158A CN 2011103501234 A CN2011103501234 A CN 2011103501234A CN 201110350123 A CN201110350123 A CN 201110350123A CN 103084158 A CN103084158 A CN 103084158A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses an adsorption catalysis heat carrier for biomass pyrolysis or cracking, which is selected from active inorganic solid materials reacting with CO, CO2 and/or H2O, and is especially selected from alkali metal oxide, alkaline earth metal oxide, or their mixtures, such as CaO and/or MgO. The adsorption catalysis heat carrier is preferably renewable and/or reheatable through heat treatment after being used, and can be recycled. The catalysis heat carrier facilitates thermal cracking of biomass materials in pyrolysis process, especially facilitates fracture under heating of oxygen-containing organic functional groups, such as oxo-bridged bonds, in biomass, thus greatly reduces the oxygen content in final biomass oil, and improves various physical chemical properties of the biomass oil.
Description
Technical field
The present invention relates to a kind of adsoption catalysis heat carrier for pyrolysis or crack biomass material, more particularly, relate to a kind of in biomass pyrolysis process not only as promote catalyst that in pyrolysis, various reactions are carried out, but also as the heat carrier material that heat energy is provided to pyrolysis system and biological material with process gas, liquid and solid product, can also with pyrolysis gas in CO, CO
2And/or H
2O reacts and then reduces the multi-functional absorption catalytic thermal carrier of their concentration.
Background technology
Usually said living beings refer to terrestrial plant and water plant, for example timber, stalk, fallen leaves etc.Above-mentioned living beings can stably regenerate and output huge, its main component is hydrocarbon, therefore in fact strict, living beings are reproducible carbonaceous materials, its can be used as carry can material for the production of gaseous state, solid-state and liquid fuel.
Biomass pyrolytic or cracking are to be produced the step of the essential experience of above-mentioned fuel by living beings, in general, the pyrolysis of living beings is that living beings are mainly carried out the process of thermal decomposition in pyrolysis oven, and pyrolysis is the endothermic reaction, therefore need to provide heat-transfer material, in order to the pyrolysis pan feeding is carried out rapidly and effectively heating.Usually, hot carrier gas, be used as heat-transfer material as hydrogen or nitrogen, at this moment, hot carrier gas is preheated to high temperature before in being fed pyrolysis section or pyrolysis oven, to guarantee the operating temperature of pyrolysis, also heat is passed to the living beings pan feeding simultaneously.But, mainly contain the shortcoming of following three aspects: as the method for heat-transfer material with hot carrier gas: at first, be difficult to be applied in large-scale pyrolysis oven, because in the situation that a large amount of charging, the heat-transfer material of gaseous state is difficult to provide effective and uniform heating so that it reaches its operating temperature at short notice to pan feeding; Secondly, hot carrier gas need to be preheated to high temperature in advance, to reach or higher than operating temperature, but be not recycled or reclaim, so just greatly having improved running cost has wasted again mass energy, also has, the used heat carrier gas is sneaked in the gaseous state thermal decomposition product at last, need the very large cost of flower with it separation, and if do not carry out such separation, will greatly reduce grade and the calorific value of gaseous state thermal decomposition product.
In order to develop the heat-transfer material that more effectively is used for the pyrolysis living beings, people have done a lot of researchs to being used for the solid thermal carriers that biomass conversion is various products.For example, U.S. Patent application 2011/0067991 discloses a kind of pyrolytic process of living beings, wherein the living beings pan feeding mixes with the heat carrier that comprises at least a part of solid product Jiao, wherein Jiaozhuo of at least a portion biomass pyrolytic generation is that the solid thermal transfer medium is recycled in described pyrolytic process, on the other hand, Jiao's of remainder a part feeds in burning zone burns, so as for pyrolytic process provide heat.In this technique, the living beings pan feeding mixes with the heat carrier that comprises at least a part of solid product Jiao, living beings and burnt weight mixing ratio are 1: 1 to 1: 20, and use burnt high mixture ratio with living beings can promote the formation of synthesis gas and low-molecular-weight organic matter, reduced again the ratio of liquid product in the thermal decomposition product simultaneously.
Yet in above-mentioned technique, hot Jiaozhuo is heat carrier when burning zone is got back to pyrolysis section, its temperature is 1000 ℃ of left and right, more much higher than the pyrolysis temperature that is defined as 300 ℃ to 600 ℃, this may have a negative impact to operability and the adaptability of pyrolysis section or pyrolysis oven, thereby causes blockage problem because finely-ground coke will soften under such high temperature.When described Jiao was transported in pyrolysis section or pyrolysis oven, finely-ground coke usually can soften and be bonded on the surface at equipment connection place, and result causes blockage problem, and this is extremely dangerous to operation.
On the other hand, as some patent documentations are reported, if above-mentioned technique in the situation that implement as heat carrier with quartz sand, pottery, diamond dust, carbide or other exotic material, can obtain some improvements.For example, used quartz sand as heat carrier in CN101880552; Used Ceramic Balls as heat carrier in CN101220285; Used emergy as heat carrier in US4186079, and with the carbonaceous material pan feeding premixed that will carry out pyrolysis, and above-mentioned heat carrier is all the solid heat transfer medium of relative inertness, does not show in use any catalytic activity feature.
US7901568 disclose a kind of solid-state or high sticking carbon back is carried can material, for example biomass conversion is the method for liquid state and gaseous reaction products, in the method, requiring carbon back to carry can first fully contact with the pellet type catalyst material by material, and wherein said pellet type catalyst material is selected from: oxide, hydroxide and the carbonate of cationic clay, anionic clay, natural clay, hydration talcum or analog, stratified material, ore, mineral, alkali and alkaline earth metal ions or their mixture.in the method, described pellet type catalyst material mainly is used as pyrolysis catalysts, but under some specific occasion, it also is used as heat carrier and heat-carrying is brought in pyrolysis system or heat is passed to that the carbon back for the treatment of pyrolysis carries can material, even but in the situation that this catalyst material is used as heat carrier, it is also that carbonaceous material-be carbon back for usually said wide scope carries can material, but not specifically only for biological material, the function of described catalyst material is mainly also to descend in the condition that keeps equal or similar thermal decomposition speed or heat conversion to hanging down the pyrolysis temperature simultaneously.
The disclosure of above-mentioned mentioned all patent documentations is introduced with for referencial use in full at this.
But the chemical composition of the chemical composition of living beings and the bio-oil that is obtained by biomass pyrolytic or cracking is with other carbonaceous material, for example coal, heavy oil or compared by the liquid fuel that their pyrolysis or cracking obtain, tool is very different, wherein maximumly be not both: the oxygen content of living beings and bio-oil is very high, for example the oxygen content of living beings can surpass 55 % by weight usually, more than the oxygen content of bio-oil also can reach 30 % by weight; And the oxygen content of other carbonaceous material is no more than 30 % by weight usually, and the oxygen content of the liquid fuel that its pyrolysis or cracking obtain is within the 10-20 % by weight.
Physics, the chemical property of the greatly deteriorated bio-oil as liquid fuel of the higher meeting of oxygen content in bio-oil, and reduce its grade and calorific value, thereby greatly limited its range of application, brought difficulty also for simultaneously its post processing, for example compare with other liquid fuel, its viscosity is high, volatility is little, calorific value is low, and corrosivity is large, heat endurance is very poor, be easy to the hardening that bonds after touching air, cause to store and the transportation difficulty.The oxygen content that how to reduce formed bio-oil in pyrolytic process is a very challenging technical barrier, and the solution of Patents or bibliographical information this respect is not yet arranged so far.
In fact, the pyrolysis that comprises the carbonaceous material of living beings is considered to a kind of complexity, comprehensively thermal balance process and kinetics process usually.In the carbonaceous material pyrolysis therebetween, pyrolysis not only discharges volatile matter, and volatile matter also cracking and/or second pyrolysis can occur simultaneously, and coking even occurs, and is attended by hydrogen and oxygen transfer.if heat carrier not only can provide rapidly and more effective heat shifts, so that in the extremely short time, as greatly improving the temperature of the carbonaceous material for the treatment of pyrolysis in the several seconds, but also show catalytic activity feature and hydrogen and/or oxygen forwarding function, particularly make the oxygen that carries in the organic carbon hydrogen compound deviate to form inorganic compound gas and remove from oil, such catalytic thermal carrier will be particularly suitable for pyrolysis or crack biomass material, because it will help to remove the oxygen composition in bio-oil in pyrolytic process, help to improve the productive rate of bio-oil, with the quality of improving bio-oil, for example obtain lighter and more valuable bio-oil.
Yet regrettably up to the present, although attempt through a lot, still do not find to possess the catalytic thermal carrier that the oxygen realized that is used for the pyrolysis living beings shifts or oxygen is removed of above-mentioned functions.Therefore, still need to develop the multi-functional catalytic activity heat carrier for Biomass Characteristics that possesses above-mentioned each function, such heat carrier can realize that Rapid Thermal shifts and biomass pyrolytic is shown catalytic performance, can also remove the oxygen composition in bio-oil.
Summary of the invention
The invention provides and a kind ofly not only improved hot transfer efficiency but also biomass pyrolytic or cracking are shown catalytic activity, also have that organic oxygen in the bio-oil that pyrolysis or cracking are formed is transformed into inorganic oxygen and the adsoption catalysis heat carrier of the ability of deviating from from bio-oil.
The adsoption catalysis heat carrier that the present invention is used for pyrolysis or crack biomass material can be selected from: with CO, CO
2And/or H
2The active inorganic solid state material that O reacts, particularly: alkali metal oxide, alkaline earth oxide or their mixture, and preferably: CaO and/or MgO.
Above-mentioned adsoption catalysis heat carrier after use or adsorb saturated after, renewable and/or hot again through heat treatment, and be reused, it can use separately, also can with other solid state heat carrier material or other pyrolysis or catalyst for cracking material compound use, but wherein other solid state heat carrier material inertia or active inorganic mineral material, for example quartz sand, ceramic sand, ore tailings or their mixture etc.; But and the catalyst cationic clay of other pyrolysis or crack biomass, anionic clay, natural clay, stratified material, hydration talcum or analog, ore or its discarded object, mineral or its mine tailing, industrial solid castoff or their mixture etc.
Above-mentioned adsoption catalysis heat carrier is Powdered, graininess or other any solid forms.But preferably have the graininess that specified particle diameter distributes, for example particle size range is at 10～1000 microns, preferably the particle between 10～200 microns.Simultaneously in order to increase heat transfer, contact and/or catalytic reaction area, preferably described adsoption catalysis heat carrier is porous, more preferably, make it have certain mechanical strength for the stability that keeps adsoption catalysis heat carrier grain shape, above-mentioned adsoption catalysis heat carrier particle can experience sintering to a certain degree under the condition that keeps its characterization of adsorption and catalysis characteristics.
Description of drawings
Fig. 1 is the flow chart of a technical scheme of the biomass pyrolysis system of use adsoption catalysis heat carrier of the present invention.
The specific embodiment
For operation principle and the applicability that adsoption catalysis heat carrier of the present invention is described, describe an exemplary embodiment of the present invention in detail below with reference to accompanying drawing, with clear advantage and the characteristic of understanding adsoption catalysis heat carrier in the biomass pyrolysis system that uses adsoption catalysis heat carrier of the present invention.
Biomass fast pyrogenation or cracking usually need very fast programming rate, for example 10
2-10
4K/ second, and the extremely short time of staying, for example 0.2-3 second, and moderate pyrolysis temperature, for example 350-550 ℃.The rapid thermal decomposition in weary oxygen environment of organic polymer in only just making living beings under such condition is short chain molecule, the growing amount of solid state heat hydrolysis products-Jiao and gaseous state thermal decomposition product-pyrolysis gas is dropped to minimum, and make the productive rate of liquid heat hydrolysis products-bio-oil reach maximum.At above-mentioned fast pyrogenation, even dodge the solution process, the secondary response of product can be reduced to minimum, many functional groups in living beings or pyrolysis produce valuable in the middle of the phase product kept.Fast pyrogenation although it is so or sudden strain of a muscle solution can obtain higher bio oil productive rate, but are being the process of bio-oil from biomass conversion, and the content of oxygen element is not special large.Discussed too high oxygen content is brought in bio-oil series of problems front, just no longer describe in detail at this, but the oxygen content that reduces in bio-oil is grade and the calorific value that promotes bio-oil, an important ring of widening its range of application.
A large amount of studies confirm that: the oxygen element in bio-oil exists with the form of multiple organo-functional group, for example the form with bridging oxygen key, carbonyl and hydroxyl exists, the physical form of concrete manifestation is: acid, phenol, aldehyde, alcohol, ketone, ether, quinine, furans etc.Under suitable pyrolysis or cracking temperature, thermal cracking or thermal decomposition can occur in above-mentioned oxygen functional group, and to discharge CO, CO
2And/or H
2The form of O is removed oxygen wherein, produces simultaneously the very high free radical of a large amount of activity.In fact, in above-mentioned oxygen-containing functional group, the most weak and the easiest cracking of bridging oxygen key and being removed is said usually, and the order of the heat endurance of above-mentioned organic oxygen functional group is successively :-OH＞=C=O＞-COOH＞-OCH
3, wherein the heat endurance of bridging oxygen key and/or carboxyl is the poorest, and the bridging oxygen key just begins cracking at about 250 ℃ and forms CO, CO
2Or H
2O, carboxyl begin cracking and form CO under about 200 ℃
2And H
2O, and carbonyl just can be decomposed to form CO under about 400 ℃.
Therefore, theoretically, in the bio-oil that produces in pyrolytic process, at least a portion of contained oxygen element is can be with CO, CO during pyrolysis
2And/or H
2The form of O is removed, but regrettably: the bio-oil that produces during pyrolysis is gaseous state, and mixes with pyrolysis gas, and the main component of pyrolysis gas is CO, H
2, CO
2, H
2O and/or CH
4Be balanced reaction in the cracking of above-mentioned organic oxygen functional group, be subjected in the situation of thermodynamics of reactions and/or kinetics restriction the CO of high concentration, CO
2, and H
2The existence of O has almost limited the cracking reaction of this organic oxygen functional group, and this is also why to be the process of bio-oil from biomass conversion, and the content of oxygen element is not special large reason.
Therefore, in the prior art, bio-oil often by the condensation realization with separating of pyrolysis gas after liquefy oil, carry out again modification, to reduce oxygen content wherein, improve its grade and calorific value and other physics and chemistry performance, wherein the most frequently used method of modifying is catalytic pyrolysis, for example hydrogenation catalyst thermal cracking or catalytic hydroprocessing thermal cracking, with the mode of the post processing catalytic pyrolysis by bio-oil, with the part of oxygen in bio-oil with CO, CO
2And/or H
2The form of O is removed.But the post processing mode of this catalytic pyrolysis has increased complexity and the production cost of operation, above-mentioned thermal cracking effect simultaneously can make bio-oil generate lighter organic component and heavier organic component, part biological matter oil also may polymerization form Jiao, and coking rate can be up to the 8-25 % by weight sometimes.
If can on-the-spot remove CO, CO in pyrolysis gas in pyrolytic process
2And/or H
2O makes CO, CO in gaseous state bio-oil and pyrolysis gas mixture
2And/or H
2The concentration decrease of O, in bio-oil, the restriction of the thermodynamics of reactions of oxygen-containing functional group cracking reaction and/or kinetics will be broken, and reaction will be towards generating CO, CO
2And/or H
2The direction of O tilts, oxygen content in the gaseous state bio-oil is obviously reduced, even the bio-oil that obtains needs further modification of later stage, also can reduce thermodynamics of reactions and/or the kinetics restriction of later stage modification, and load and the cost of corresponding minimizing processing.
If during biomass pyrolytic, have a kind of material can play the effect of heat carrier, can play again the catalyst action that promotes pyrolysis or each reaction of crack biomass, also can play the scene or moment CO absorption, CO
2And/or H
2The effect of the adsorbent of O, above-mentioned purpose just can realize, and due to the CO in pyrolysis gas
2And/or H
2O greatly reduces as the content of fuel gas impurity, and the grade of pyrolysis gas and calorific value also can improve greatly, and this is to oxygen content in the reduction bio-oil or the quality that improves pyrolysis gas all is of great benefit to.
Adsoption catalysis heat carrier of the present invention be exactly can play above-mentioned each effect, and specially for the multifunctional material of biomass composition characteristic, it is selected from: can with CO, CO
2And/or H
2The active inorganic solid state material that O reacts, particularly: alkali metal oxide, alkaline earth oxide or their mixture, and preferably: CaO and/or MgO.
As shown in Figure 1, in described biomass pyrolysis system, the adsoption catalysis heat carrier is brought heat in pyrolysis oven 20, with process gas, liquid and using pyrolysis product from reheater 50 as heat-transfer material; The liquid yield that the catalysis characteristics of adsoption catalysis heat carrier makes the productivity ratio of liquid heat hydrolysis products under the same operation condition use the heat carrier that does not have catalysis characteristics of relative inertness to obtain is high, and the characterization of adsorption of adsoption catalysis heat carrier make under same operation condition liquid heat hydrolysis products contain the oxygen rate than the product liquid that uses the heat carrier that do not have characterization of adsorption and obtain to contain the oxygen rate low.
In this exemplary embodiment, have the solid-state biomass material pan feeding of specified particle diameter distribution (PSD) and injected rapidly pyrolysis oven 20 through pipeline 11 and pipeline 63 respectively by hot again adsoption catalysis heat carrier, described pyrolysis oven 20 for example comprises hot adsoption catalysis heat carrier horizontal moving bed of fluidisation, thereby and the adsoption catalysis heat carrier is catalytic activity to all kinds of reactions that occur in pyrolytic process improves pyrolysis or cracking reaction process.Preferably, the solid particle in described pyrolysis oven 20 is fluidized by means of mechanical device.The fluidisation of the solid particle above fluid bed is by means of with extra fluidizing gas, for example realize from the water vapour of pipeline 22, in order to realize abundant mixing and the close contact of biological material and hot adsoption catalysis heat carrier in the short time at the utmost point.
In pyrolysis oven 20, being transferred in biological material except heat from the adsoption catalysis heat carrier, under the existence of water vapour, between biological material and hot adsoption catalysis heat carrier, following a plurality of reaction can occur: the cracking of the thermal decomposition of biological material and the release of volatile matter, volatile matter and/or second pyrolysis, coking, Jiao-steam reformation, Jiao-CO 2 reformation, and weak water gas reaction etc.The extent of reaction of above-mentioned reaction depends on the operating condition of biomass composition characteristic and pyrolysis, for example maximum temperature of biomass composition, the time of staying and pyrolysis etc.
Wherein, living beings can be thermal decomposited and be volatile matter and/or fixed carbon and water, and have the adsoption catalysis heat carrier of catalytic activity also to can be used as CO, CO that adsorbent and biological material pyrolysis discharge
2And/or H
2The O reaction, for example:
C
xH
yO
z(living beings) → CO+H
2+ CH
4+ CO
2+ H
2O (1)
C
xH
yO
z→CO
2+H
2+CH
4+H
2O (2)
During this time, the adsoption catalysis heat carrier (is used M
xO
yExpression, wherein M represents metal, for example alkali metal or alkaline-earth metal) except showing the pyrolysis catalytic activity, for example following adsorption reaction also occurs:
M
xO
y+CO
2→M
a(CO
3)
b (3)
M
xO
y+H
2O→M
c(OH)
d (4)
M
xO
y+CO+H
2O→M
a(CO
3)
b+H
2 (5)
Above-mentioned adsorption reaction will cause CO, CO in the mixture of gaseous state bio-oil that pyrolysis produces and pyrolysis gas
2And H
2Content or the concentration of O significantly descend, and then the oxygen organo-functional group that contains that is conducive in the gaseous state bio-oil is cracked into CO, CO
2And H
2O and removing from bio-oil also is conducive to that in the gaseous state bio-oil, oxygen containing long-chain heavy oil component is cracked into oxygen-free short chain light oil constituents simultaneously, and then improves grade and the physical and chemical performance of the bio-oil that obtains.Test simultaneously also confirms: adsorb the adsoption catalysis heat carrier after saturated, for example M
a(CO
3)
bAnd M
c(OH)
dStill each reaction of pyrolytic process is catalytic activity.
Jiao's (solid product) that biomass pyrolytic produces can with CO 2 reformation, it relates to and burntly forms carbon monoxide with carbon dioxide reaction, and water vapour also can be reformed with Jiao, it relates to the Jiao Yushui reaction and generates carbon monoxide and hydrogen.
C+CO
2→CO (6)
H
2O+C→CO+H
2 (7)
Two reactions of other that also can relate in this process are water gas reaction and methanation reaction, and it is as follows:
CO+H
2O←→CO
2+H
2 (8)
CO+H
2←→CH
4+H
2O (9)
CO+H
2←→CH
4+CO
2 (10)
Under the catalytic action of adsoption catalysis heat carrier, other reaction of living beings and water vapour and carbon dioxide also can occur in described pyrolysis oven 20, for example:
C
xH
yO
z+CO
2→CO+H
2 (11)
CO
2+H
2←→CH
4+H
2O (12)
In pyrolytic process, biological material contacts and mixes with adsoption catalysis heat carrier hot or heat again, and the temperature of described adsoption catalysis heat carrier is preferably 600～1000 ℃, more preferably 800～1000 ℃; The weight mixing ratio of adsoption catalysis heat carrier and biological material pan feeding preferably is about 200/1～1/20, be more preferably 40/1～1/10, the accurate weight mixing ratio of concrete operating adsoption catalysis heat carrier solid particle and biological material pan feeding should be mainly according to the thermal balance Location of requirement of pyrolysis system.
The gas-phase product that comprises gaseous state bio-oil and pyrolysis gas moves to from pyrolysis oven 20 in condenser 30 by pipeline 31, and the shock chilling medium Quench that gas-phase product preferably is introduced into is not to substantially occuring below the temperature of second pyrolysis, then by pipeline 32 from comprising H
2, CH
4, CO and CO
2Pyrolysis gas in separate and biomass collection oily.Pyrolysis gas after above-mentioned separating biomass oil can be passed in the filter (not shown) that contains carbon dioxide absorber by pipeline 33 and further be purified, in order to be translated into the gaseous fuel that can be used as high heating value more, mainly comprise H
2, CH
4Purer pyrolysis gas with CO.Biological material is converted into Jiao or solid product through dehydration with after removing volatile matter in pyrolysis oven 20, be moved to subsequently in solid-solid separation system 40, this system 40 comprises at least one solid-solid separator, described separator can be utilize the particle diameter of particle poor, density contrast or magnetic difference and the separator of any type of working or playing a role, preferably, should solid-solid separator be sieve, in order to by pipeline 42, Jiao or solid product are separated from saturated and cooling useless adsoption catalysis heat carrier.If the saturated cooling useless adsoption catalysis heat carrier of sub-fraction is arranged fails to realize and effectively the separating of using pyrolysis product, also can be inevitably, undesirably be discharged from by pipeline 42 together with the using pyrolysis product, therefore will cause a part of adsoption catalysis heat carrier of loss in pyrolysis system.If such situation occurs, the fresh adsoption catalysis heat carrier of same amount need to be added in pyrolysis system.Useless adsoption catalysis heat carrier enters heat and regeneration again in adsoption catalysis heat carrier reheater 50 by pipeline 51.A certain proportion of can't entering in adsoption catalysis heat carrier reheater 50 with useless adsoption catalysis heat carrier with the finely-ground coke that useless adsoption catalysis heat carrier realization effectively separates also arranged certainly, these finely-ground cokes can be in adsoption catalysis heat carrier reheater 50 burn with the hot-air that passes into, in order to the heat of heat and required part or all of regeneration is provided to useless adsoption catalysis heat carrier again.
By described solid-saturated cooling useless adsoption catalysis heat carrier that solid separation system 40 separates enters in described reheater 50 by pipeline 51, this reheater 50 can be selected from moving-burden bed reactor, fluidized-bed reactor or riser reactor, preferably, can select riser reactor, wherein saturated and cooling useless adsoption catalysis heat carrier is promoted near the top of reheater 50 by the high pressure that is blown into via pipeline 52 from reheater 50 bottoms and high-temperature hot air.In being raised the process of moving up, the heat that in the heat that above-mentioned saturated and cooling useless adsoption catalysis heat carrier is brought into by high-temperature hot air and the finely-ground coke of bringing into and above-mentioned hot-air, the combustion reaction of oxygen generation is emitted and heating, and following desorb reaction occurs, thereby be converted into fresh, regeneration and hot adsoption catalysis heat carrier again.
M
a(CO
3)
b→M
xO
y+CO
2 (13)
M
c(OH)
d→M
xO
y+H
2O (14)
Usually, above-mentioned desorb reaction occurs under 500 ℃-1200 ℃, and for example calcium carbonate decomposes under 825 ℃; Magnesium carbonate decomposes under 540 ℃; Calcium hydroxide decomposes under 580 ℃; And magnesium hydroxide decomposes under 490 ℃, and they become metal oxide after decomposing, and discharge CO
2And H
2O。Therefore, the operating temperature of reheater 50 will be higher than the decomposition temperature of above-mentioned useless adsoption catalysis heat carrier, in order to guarantee desorb or decompose fully and completely.
Fresh, regeneration and again heat the adsoption catalysis heat carrier with entering in cyclone cluster 60 by pipeline 61, to realize the adsoption catalysis heat carrier of heat and separating of waste gas, waste gas that is to say again, burning gases are moved out of in cyclone cluster 60 through pipeline 62, in order to be for further processing and/or reclaim heat.The operating temperature of described adsoption catalysis heat carrier reheater 50 generally is about 550～1000 ℃, compares usually high with the operating temperature of pyrolysis.
From in described reheater 50 fresh, regeneration and again heat high temperature adsorption catalytic thermal carrier and biological material pan feeding be recycled in described pyrolysis oven 20 by pipeline 63 and pipeline 11 respectively, heat then occurs in described pyrolysis oven 20 again to be shifted, catalysis is carried out in all kinds of reactions that pyrolysis occurs therebetween, and CO, the CO of absorption pyrolysis generation
2And H
2O, thus realize next circulation.
Fresh adsoption catalysis heat carrier can join pyrolysis system from arbitrary suitable position, for example, it can be introduced directly in pyrolysis oven 20 or pyrolysis oven 20 pipeline 63 before, also can directly join in reheater 50, or add as the mixture of biological material pan feeding and fresh adsoption catalysis heat carrier.
In another embodiment of the present invention, the adsoption catalysis heat carrier can mix with heat carrier material and/or the pyrolysis catalysts component of relative inertness, randomly, can carry out spray-drying and it is a granulated into particle the above-mentioned mixture that obtains or adsoption catalysis heat carrier powder.Specifically; pulverize and/or grind adsoption catalysis heat carrier material or said mixture; obtain particle diameter and be preferably 5～50 microns, the fine powder of 10～30 microns more preferably; then the fine powder that obtains and inorganic cement and optional clay are mixed; obtain uniform mixture paste; then the above-mentioned uniform mixture paste of spray-drying, thus form adsoption catalysis heat carrier particle or contain the compound particles of adsoption catalysis heat carrier component.
Need to prove: above-mentioned adsoption catalysis heat carrier is Powdered, graininess or other any solid forms.But preferably have the graininess that specified particle diameter distributes, for example particle size range is at 10～1000 microns, preferably the particle between 10～200 microns.In order to increase heat transfer, contact and/or catalytic reaction area, preferably described adsoption catalysis heat carrier is porous, is more preferably the porous particle of sintering simultaneously.
Optional or preferably, a blender can be set, as descending blender, cyclone mixer in pyrolysis reactor 20, or a mixed zone.Such equipment can make heat from adsoption catalysis heat carrier particle fast transfer in the biological material pan feeding.In above-mentioned blender or mixed zone, mixing and heat shift and generally will occur within the time of 0.1 second.The rate of heat addition to the biological material pan feeding can meet or exceed 1000 ℃/second.When the biological material pan feeding was solid, particle size generally should be less than 6 millimeters, for example the 1-3 millimeter; When the biological material pan feeding was atomized liquid, particle size generally should be less than 1 millimeter, for example 100 microns-1 millimeter.Above-mentioned blender or mixed zone preferably provide close contact and fully mix to adsoption catalysis heat carrier and biological material pan feeding.
Advantage and the feature of adsoption catalysis heat carrier of the present invention are as described below:
1) with use traditional inert inorganic heat carrier, as the sand facies ratio, condensable thermal decomposition product, be that the productive rate of product liquid-bio-oil improves 3～5 % by weight;
2) because adsoption catalysis heat carrier of the present invention possesses high density and high heat-carrying capacity, cause the inlet amount of the biological material pan feeding for the treatment of pyrolysis to improve approximately 10%;
3) compare adsorbable CO, the CO that forms in a large number of adsoption catalysis heat carrier of the present invention in pyrolytic process with traditional heat carrier
2And/or H
2O, thus just can on-the-spot they be removed from pyrolysis gas in pyrolytic process, make CO, CO in gaseous state bio-oil and pyrolysis gas mixture
2And/or H
2The concentration decrease of O, in bio-oil, therefore the restriction of the thermodynamics of reactions of oxygen-containing functional group cracking reaction and/or kinetics will be broken, and reaction will be towards generating CO, CO
2And/or H
2The direction of O tilts, and makes like this oxygen content in the gaseous state bio-oil obviously reduce, thereby obviously improves grade and the quality of bio-oil;
4) adsoption catalysis heat carrier of the present invention is owing to having adsorbed the CO, the CO that form in a large number in pyrolytic process
2And/or H
2O makes the CO in pyrolysis gas
2And/or H
2O greatly reduces as the content of fuel gas impurity, and the grade of pyrolysis gas and calorific value will improve greatly.
5) because adsoption catalysis heat carrier of the present invention is catalytic activity to all kinds of reactions that occur in biological material pan feeding pyrolytic process, particularly hydrogenation reaction and/or the cracking reaction of the volatile matter that discharges in pyrolytic process are catalytic activity, therefore use the molecular structure of the liquid phase thermal decomposition product that adsoption catalysis heat carrier of the present invention obtains obviously to be different to use the molecular structure of the liquid phase thermal decomposition product that traditional inorganic heat carrier obtains, will for example cause like this that liquid phase thermal decomposition product-bio-oil of the present invention is lighter, viscosity is lower, grade is higher, better quality.
In sum, adsoption catalysis heat carrier of the present invention is given and is used the biomass pyrolysis system of adsoption catalysis heat carrier of the present invention to bring a series of benefits, it has not only improved productive rate and the quality of some particular thermal hydrolysis products, and has improved working condition and the production efficiency of thermal decomposition product.
Embodiment
Following embodiment is only as illustration purpose, and do not mean that the present invention is carried out any type of restriction.Except as otherwise noted, otherwise following percentage all represent with weight.
Embodiment 1
Particle size range is about the fresh calcium oxide particle of 50～200 μ m as adsoption catalysis heat carrier of the present invention.Its specific area is about 300～450m
2/ g.
The useless hardwood sawdust that above-mentioned adsoption catalysis heat carrier particle and particle diameter is about 600 μ m-1mm mixes, shown in an element table 1 composed as follows of useless hardwood sawdust.The weight mixing ratio of described adsoption catalysis heat carrier particle and sawdust is about 4: 1.
Table 1
| C | H | O | N | S | Ash content |
| 46-51％ | 7.1-8.7％ | 44-47％ | 0.2-0.5％ | 0.3％ | 1％ |
In above-mentioned material infeed pyrolysis system as shown in Figure 1, wherein pyrolysis oven is the fluidized bed type pyrolysis oven, the pyrolysis operations temperature is 500 ℃, operating pressure is normal pressure, simultaneously, the hot water and steam that temperature is about 550 ℃ sprays in described pyrolysis oven, and the adsoption catalysis heat carrier that is about 900 ℃ from the temperature of adsoption catalysis heat carrier reheater is introduced in pyrolysis oven, and fully mix with useless hardwood sawdust and the hot water and steam that sprays into, cause useless hardwood sawdust generation pyrolysis.Thermal decomposition product comprises gas-phase product and solid product, and wherein gas-phase product is moved in condenser subsequently, and the gaseous state bio-oil is converted into liquid biological matter oil through condensation in condenser, and realizes separating with the gaseous state thermal decomposition product.Sawdust pan feeding time of staying in pyrolysis oven is about 15～20 minutes, and gas-phase product is less than approximately 1 second in the time of staying in pyrolysis oven after generation.
Shown in the chemical composition or an element table 2 composed as follows and table 3 of the formed pyrolysis gas of above-mentioned pyrolysis oven and condensed liquid product-bio-oil.
Table 2
| CO | H 2 | CO 2 | CH 4 | H 2O |
| 28-31％ | 38-41％ | 18-21％ | 7-8％ | 6％ |
Table 3
| C | H | O | N | S |
| 63-66％ | 7-8％ | 27-30％ | 0.1-0.2％ | 0.1-0.2％ |
The productive rate of various thermal decomposition products (weight) is as shown in following table 4.
Table 4
| Bio-oil | Semicoke | Gas |
| 62.70％ | 18.92％ | 18.38％ |
The comparative example 1
Except the adsoption catalysis heat carrier particle of the present invention in embodiment 1 is replaced to silica sand, repeat the experimental procedure described in embodiment 1, in the particle diameter of silica sand and embodiment 1, the particle diameter of adsoption catalysis heat carrier used is identical.
Shown in the chemical composition or an element table 5 composed as follows and table 6 of the formed pyrolysis gas of above-mentioned pyrolysis oven and condensed liquid product-bio-oil.
Table 5
| CO | H 2 | CO 2 | CH 4 | H 2O |
| 26-29％ | 34-37％ | 24-27％ | 6-7％ | 7％ |
Table 6
| C | H | O | N | S |
| 57-60％ | 6-7％ | 34-37％ | 0.1-0.2％ | 0.1-0.2％ |
The productive rate of various thermal decomposition products (weight) is as shown in table 7.
Table 7
| Bio-oil | Semicoke | Gas |
| 54.34％ | 25.99％ | 19.67％ |
Data by comparison sheet 2-table 7 are as can be known: compare with conventional inert solid heat carrier-silica, use adsoption catalysis heat carrier of the present invention can make the productive rate of bio-oil be increased to 62.70% by 54.34%; CO in pyrolysis gas
2Content is reduced to 18-21% by 24-27%; Oxygen content in bio-oil is reduced to 27-30% by 34-37%.The grade of bio-oil and physical and chemical performance have obtained remarkable improvement, simultaneously the CO in pyrolysis gas
2Impurity has obtained obvious minimizing.
Embodiment 2
Particle size range is about the fresh magnesium oxide particle of 50～150 μ m as adsoption catalysis heat carrier of the present invention.Its specific area is about 350～500m
2/ g.
The lignin that above-mentioned adsoption catalysis heat carrier particle and particle diameter is about 150 μ m-300 μ m mixes, shown in the element of a lignin table 8 composed as follows.The weight mixing ratio of described adsoption catalysis heat carrier particle and lignin is about 6: 1.
Table 8
| C | H | O | N | S | Ash content |
| 58.2％ | 6.1％ | 35.4％ | 0.27％ | 0.03％ | 0％ |
In above-mentioned material infeed pyrolysis system as shown in Figure 1, wherein pyrolysis oven is the fluidized bed type pyrolysis oven, the pyrolysis operations temperature is 450 ℃, operating pressure is normal pressure, simultaneously, the hot water and steam that temperature is about 500 ℃ sprays in described pyrolysis oven, and the adsoption catalysis heat carrier that is about 600 ℃ from the temperature of adsoption catalysis heat carrier reheater is introduced in pyrolysis oven, and fully mix with lignin and the hot water and steam that sprays into, cause lignin generation pyrolysis.Thermal decomposition product comprises gas-phase product and solid product, and wherein gas-phase product is moved in condenser subsequently, and the gaseous state bio-oil is converted into liquid biological matter oil through condensation in condenser, and realizes separating with the gaseous state thermal decomposition product.Lignin pan feeding time of staying in pyrolysis oven is about 5～10 seconds, and gas-phase product is less than approximately 1.5 seconds in the time of staying in pyrolysis oven after generation.
Shown in the chemical composition or an element table 9 composed as follows and table 10 of the formed pyrolysis gas of above-mentioned pyrolysis oven and condensed liquid product-bio-oil.
Table 9
| CO | H 2 | CO 2 | CH 4 | H 2O |
| 31.1％ | 35.6％ | 19.4％ | 7.6％ | 6.3％ |
Table 10
| C | H | O | N | S |
| 70％ | 7.9％ | 22％ | 0.1％ | 0％ |
The productive rate of various thermal decomposition products (weight) is as shown in following table 11.
Table 11
| Bio-oil | Semicoke | Gas |
| 55.7％ | 33.9％ | 10.4％ |
The comparative example 2
Except the adsoption catalysis heat carrier particle of the present invention in embodiment 2 is replaced to zircon sand, repeat the experimental procedure described in embodiment 2, in the particle diameter of zircon sand and embodiment 2, the particle diameter of adsoption catalysis heat carrier used is identical.
Shown in the chemical composition or an element table 12 composed as follows and table 13 of the formed pyrolysis gas of above-mentioned pyrolysis oven and condensed liquid product-bio-oil.
Table 12
| CO | H 2 | CO 2 | CH 4 | H 2O |
| 29.8％ | 32.6％ | 23.8％ | 6.2％ | 7.6％ |
Table 13
| C | H | O | N | S |
| 66％ | 6.9％ | 27.0％ | 0.1％ | 0％ |
The productive rate of various thermal decomposition products (weight) is as shown in table 14.
Table 14
| Bio-oil | Semicoke | Gas |
| 50.12％ | 38.10％ | 11.78％ |
Data by comparison sheet 9-table 14 are as can be known: compare with conventional inert solid heat carrier-zircon sand, use adsoption catalysis heat carrier of the present invention can make the productive rate of bio-oil be increased to 55.7% by 50.12%; CO in pyrolysis gas
2Content is reduced to 19.4% by 23.8%; Oxygen content in bio-oil is reduced to 22% by 27%.The grade of bio-oil and physical and chemical performance have obtained remarkable improvement, simultaneously the CO in pyrolysis gas
2Impurity has obtained obvious minimizing.
Term used in this manual and form of presentation, only as descriptive and non-limiting term and form of presentation, when using these terms and form of presentation, the feature that will represent and describe unintentionally or any equivalent exclusion of its part.
Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize that in the situation that do not break away from principle of the present invention and spirit can be carried out any accommodation and improvement to these embodiments, protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (10)
1. an adsoption catalysis heat carrier that is used for pyrolysis or crack biomass, is characterized in that described adsoption catalysis heat carrier is selected from: with CO, CO
2And/or H
2The active inorganic solid state material that O reacts.
2. adsoption catalysis heat carrier according to claim 1, it further is selected from: alkali metal oxide, alkaline earth oxide or their mixture.
3. adsoption catalysis heat carrier according to claim 2, it further is selected from: CaO and/or MgO.
4. adsoption catalysis heat carrier according to claim 1, wherein said adsoption catalysis heat carrier is using and/or again heat renewable by heat treatment, and is reused.
5. adsoption catalysis heat carrier according to claim 1, the catalyst of wherein said adsoption catalysis heat carrier and any pyrolysis or crack biomass or any solid state heat carrier compound use.
6. adsoption catalysis heat carrier according to claim 5, the catalyst of wherein said pyrolysis or crack biomass is selected from: cationic clay, anionic clay, natural clay, stratified material, hydration talcum or analog, ore or its discarded object, mineral or its mine tailing, industrial solid castoff or their mixture.
7. adsoption catalysis heat carrier according to claim 5, wherein said solid state heat carrier is selected from: inertia or active inorganic mineral material.
8. catalytic thermal carrier according to claim 7, wherein said inertia or active inorganic mineral material are quartz sand, ceramic sand, ore tailings or their mixture.
9. according to claim 1-8 one of any described adsoption catalysis heat carriers, wherein said adsoption catalysis heat carrier are porous sintered or sintered particles not.
10. according to claim 1-8 one of any described adsoption catalysis heat carriers, the particle size range of wherein said adsoption catalysis heat carrier is 10～1000 microns.
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| CN113617360A (en) * | 2021-08-02 | 2021-11-09 | 山东理工大学 | Preparation method of catalytic heat carrier and application of catalytic heat carrier in self-heating pyrolysis liquefaction |
| CN115228385A (en) * | 2021-04-23 | 2022-10-25 | 国家能源集团宁夏煤业有限责任公司 | Fixed bed catalyst filling method and corresponding reaction testing method |
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| CN113617360A (en) * | 2021-08-02 | 2021-11-09 | 山东理工大学 | Preparation method of catalytic heat carrier and application of catalytic heat carrier in self-heating pyrolysis liquefaction |
| CN113617360B (en) * | 2021-08-02 | 2023-09-26 | 山东理工大学 | Preparation method of catalytic heat carrier and application of catalytic heat carrier in self-heating pyrolysis liquefaction |
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