CN102851054B - C2-C9 chemical product produced from biomass, its preparation method and application - Google Patents
C2-C9 chemical product produced from biomass, its preparation method and application Download PDFInfo
- Publication number
- CN102851054B CN102851054B CN201210355747.XA CN201210355747A CN102851054B CN 102851054 B CN102851054 B CN 102851054B CN 201210355747 A CN201210355747 A CN 201210355747A CN 102851054 B CN102851054 B CN 102851054B
- Authority
- CN
- China
- Prior art keywords
- distillation
- biomass
- rice husk
- bio oil
- residual jiao
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for production of a C2-C9 chemical product from biomass. The method comprises the steps of: (1) subjecting the biomass to flash pyrolysis so as to obtain bio-oil; (2) conducting atmospheric distillation on the bio-oil obtained in step (1) so as to isolate a light component distillate liquid and heavy component distillation residual coke, with the main ingredient of the distillate liquid being a C2-C9 compound; and (3) adding the distillation residual coke obtained in step (2) into the biomass in step (1) in proportion and conducting mixing, and repeating the processes of step (1) and step (2). In the invention, only rice husk biomass is taken as a raw material, the needed major equipment is an ordinary pyrolysis reactor and a distillation kettle, and the operating conditions are simple. Compared with the prior art, the bio-oil has no need for any pretreatment process, high pressure or high vacuum operation, and any additional reagent. Thus, the method has obvious economic advantages and is convenient for industrial promotion.
Description
Technical field
The invention belongs to derived energy chemical technical field, relate to a kind of C that utilizes biomass to produce
2-C
9chemicals and its preparation method and application.
Background technology
Consumption along with fossil oil in world wide, each state all utilizes reproducible clean energy at active development, wherein biomass energy is compared the renewable energy source forms such as sun power, wind energy and is had advantages of easily and obtain, easily store and easily transportation, therefore towards research other renewable energy source relative to base application of biomass energy maturation relatively.China is large agricultural country, and the agricultural wastes quantity discharged consisting of rice husk, stalk etc. is every year huge, and these waste current overall contexts utilize degree lower, and this is actually the huge waste of biomass resource.
Biomass fast pyrogenation be a kind of under the inert atmosphere of 400 ~ 600 ℃ rapidly lysed biomass polymer form the technique of small-molecule substance, the residence time of biomass in reactor short (1 ~ 2s), the volatile small molecule material leaving from reactor is divided into bio oil (also claiming pyrolysis oil) and condensible gas two portions not after rapid condensation.The main purpose of biomass fast pyrogenation is to produce high-quality bio oil, by-product not condensible gas (main component is CO
2, CO, H
2, CH
4deng) and charcoal.Condensible gas and charcoal can not provide pyrolysis reactor required heat by burning, so can reach 100% in the utilization ratio of pyrolytic process Raw, are a kind of cleaning procedures of no waste discharge.In brief, fast pyrogenation process required time is short, be easy to promote, technique is simple, with low cost, and solid waste changed into the bio oil of economic worth, has the double benefit of economy and environment two aspects.
Bio oil is the main end product of biomass fast pyrogenation technique, and its character is variant with the difference of raw material and pyrolytic process condition.The significant parameter that characterizes its quality has calorific value, flash-point, density, viscosity, water ratio, pH, ultimate analysis and substance classes.Bio oil can directly be used on static combustion device as fuel, is used for producing heat and generating power; Also can be through upgrading and further production traffic fuel, bulk chemical and fine chemicals after refining.
With bio oil petroleum replacing, be that raw material production chemical has attracted the sight of many researchers in world wide, but some unfavorable character of current bio oil have seriously restricted the development and application of its technological process.Different from oil, biological oil composition complexity and oxygen level are high, comprise the hundreds of kind organism such as carboxylic acid, aldehyde ketone, phenol, alcohol, ester, anhydrosugar, and water (massfraction accounts for 25-35%) and xylogen oligomer.Bio oil has the feature of poor heat stability, under the long-term storage or heating condition of bio oil, complex chemical reaction (as esterification, polycondensation, polyreaction) occurs so many material each other changes the bulk property of bio oil, be embodied in and be separated, this process is commonly called as " aging ".
The process that the bio oil of take is raw material production chemical can be divided into two large classes: a kind of is that some composition of bio oil integral body or bio oil is carried out to the directed conversion of catalysis, as is converted into the hydro carbons that character is more stable; Another kind is to having there is the separation and extraction of material in bio oil.For these two class methods, the unstable of bio oil is all very large obstacle.In the first kind (directed conversion) technique, due to thermo-sensitivity and the high viscosity of bio oil, the carbon distribution that bio oil " aging " forms is easily deposited on catalyst surface and makes catalyst deactivation.
For separation and extraction chemical from bio oil, traditional petrochemical complex unit operation, as isolation technique such as air distillation, underpressure distillation, there is easy and simple to handle, technical maturity, with low cost, but residual Jiao of unmanageable distillation that bio oil produces when being heated has not only reduced separation efficiency, and has increased waste discharge amount.Conventionally investigator is devoted to avoid biological oil deterioration and residual Jiao's of distillation generation.The people such as Wang adopt " molecular distillation " technology operating under high vacuum, bio oil is divided into lightweight, middle matter and heavy ends three parts under 60Pa, 70-130 ℃ condition, wherein light component is mainly containing volatile small molecule acids, ketone, phenols and furans and water, in still-process, there is not coking phenomenon (Separation of Bio-oil by Molecular Distillation.Fuel Processing Technology2009,90,738-745); But the disposal of the heavy component of its gained (asphalt cement shape material) remains a difficult problem, and ultrahigh vacuum(HHV) operation has significantly increased facility investment and running cost.The people such as Deng add high boiling alcoholic solvent (glycerol) dilution bio oil in air distillation process, in still-process, there is not coking phenomenon (Green Solvent for Flash Pyrolysis Oil Separation.Energy & Fuels 2009 yet, 23,3337-3338); But alcohols material reacts and loses (each still-process loss glycerol 12 ~ 16%) with a large amount of aldoketoneses that exist and acid in bio oil, and running cost is increased; And after still-process finishes, the heavy constituent in bio oil (can not distill material) need to be passed through the technique by-product xylogen oligomers such as aqueous precipitation, filtration, washing, produces a large amount of waste water in this process, has increased pollution processing pressure.
Summary of the invention
The deficiency existing for prior art, the object of this invention is to provide a kind of with low cost, environmental friendliness, can steady running the biomass of utilizing produce C
2-C
9the method of Chemicals.
Another object of the present invention is to provide C prepared by aforesaid method
2-C
9chemicals.
An also object of the present invention is to provide the application of aforesaid method in preparing bioenergy.
In order to realize object of the present invention, the invention provides a kind of biomass of utilizing and produce C
2-C
9the method of Chemicals, it comprises the following steps:
(1) biomass fast pyrogenation is made to bio oil;
(2) bio oil step (1) being obtained is carried out air distillation, isolates light component distillate and heavy constituent and distills residual Jiao, and the main component of described distillate is C
2-C
9compound;
(3) in proportion residual Jiao of distillation of step (2) gained is added in step (1) biomass and mixed, the process of repeating step (1) and (2).As required, this step can repeatedly loop.
Wherein, the described biomass of step (1) are agriculture and forestry organic waste material, are preferably dry rice husk; The particle diameter of described dry rice husk is not more than 300 μ m(standard sieve 60 orders), its moisture content is less than 5wt.%; Preferred, the particle diameter of described dry rice husk is for being not more than 88 μ m(180 orders).
Described in step (1), fast pyrogenation is to react under atmosphere of inert gases; Preferably, be in pyrolysis reactor, to pass into rare gas element, described rare gas element is preferably Ar or N
2; The temperature of described fast pyrogenation is 400 ~ 600 ℃, is preferably 450 ℃; Temperature rise rate>=300 of pyrolysis feed ℃/s.
Bio oil described in step (1) is that the volatile matter in pyrolytic process produces through condensation, and described condensing temperature is-20 ~ 30 ℃, is preferably-10 ℃.
Wherein, the described air distillation of step (2) is intermittent type air distillation, and its actual conditions is preferably: pressure is 0.1MPa, and temperature is 20 ~ 240 ℃.
Still-process gained distillate is 50 ~ 55wt.% with respect to the productive rate of bio oil, and its organic constituent content is 30wt.%, and remainder is water.In distillate, main organic substance is C
2-C
9organic carboxyl acid class, aldehydes, ketone, ester class, alcohols, phenolic compound.Wherein, acetic acid, propionic acid, the pyruvic alcohol separation efficiency in still-process is all more than 85%.
Residual Jiao of described distillation remains in the material in still kettle after bio oil air distillation end of processing, brown solid darkly under room temperature.The productive rate that distills residual Jiao in air distillation process is 45 ~ 50wt.%.
Wherein, residual Jiao of the described distillation of step (3) also comprised distilling residual Jiao's pulverizing and milled processed before mixing with biomass, and its particle diameter is preferably and is not more than 300 μ m(60 orders).
Residual Jiao of described distillation accounts for total raw material mass ratio and is preferably 10 ~ 35%; Described total raw material is the summation of residual Jiao of distillation and rice husk; Preferred, the mass ratio of residual Jiao of described distillation and rice husk is 1:4.
Described method also further comprises the separation of distillate, is preferably rectifying.
The C that the present invention also provides aforesaid method to prepare
2-C
9chemicals, described C
2-C
9chemicals are organic carboxyl acid class, aldehydes, ketone, ester class, alcohols and phenolic compound.
Preferably, described C
2-C
9organic carboxyl acid comprise acetic acid, propionic acid, butanic acid etc.;
C
2-C
9aldehydes comprise furtural, 5 methyl furfural etc.;
C
2-C
9ketone comprise pyruvic alcohol, 2,3-dimethyl diketone, 2-butanone, 2,3-diacetylmethane, 3-amylene-2-ketone, 1-hydroxy-2-butanone, diacetone peroxide, 2-methyl-2-cyclopentene-1-one, 2-furyl methyl ketone, 3-methyl-2-cyclopentene-1-one, 3-methyl isophthalic acid, 2-cyclopentanedione, 1-acetoxyl group-2-butanone etc.;
C
2-C
9ester class comprise Pyruvic Acid Ethyl ester etc.;
C
2-C
9alcohols comprise furfuralcohol etc.;
C
2-C
9phenols comprise phenol, ortho-methyl phenol, p-methyl phenol, methyl catechol, p-ethyl phenol, 4-methyl guaiacol and 4,4-ethyl guaiacol etc.
The present invention also further provides the application of aforesaid method in preparing bioenergy.
Beneficial effect of the present invention:
Method of the present invention is the direct air distillation of bio oil and the coupling of two chemical processes of copyrolysis fast, and concrete technological process is shown in Fig. 1.This technique only be take rice husk biomass as raw material, the major equipment needing is common pyrolysis reactor and still kettle (this experiment adopts the simple and easy water distilling apparatus that round-bottomed flask and prolong are barricaded as to replace still kettle), simple operating conditions, compared with prior art, bio oil, without any pre-treating technology, operates without high pressure or high vacuum, and without any additional reagent, economic advantages are obvious, are convenient to industry and promote.
The present invention is the product of typical " reverse thinking ", and the development of the existing isolation technique of bio oil all take that to avoid the coking of bio oil be principle, yet, the in the situation that of bio oil noncoking, along with light component in bio oil is separated, remaining bio oil presents sticky pitch shape, is difficult to dispose.In present method, heavy constituent in bio oil obtains thoroughly aging in straight run distillation process, under room temperature, be solid, than sticky bituminous substances good utilisation more, can utilize the thermochemical techniques such as fast pyrogenation to carry out resource utilization, avoid the generation of waste, meet the cleaner production theory of " zero refuse ", so present method has had good environmental benefit.
Copyrolysis experiment showed, with the independent pyrolysis of rice husk biomass and compares fast, in rice husk, adds residual Jiao of appropriate distillation, and prepared bio oil not only productive rate is higher, and quality is better, and the stable components of bio oil.So the prepared bio oil of this copyrolysis process can substitute rice husk bio oil completely.The rice husk consumption of 20-35% has been saved in the utilization of distilling residual Jiao, has improved industrial production efficiency.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2-1,2-2 and 2-3 are followed successively by the GC-MS total ion current figure of distillate a, distillate b, distillate c.
Fig. 3 is the GC spectrogram of distillate and protista oil.
Fig. 4 is the GC-MS total ion current figure of protista oil.
Fig. 5 is rice husk (125 ~ 300 μ m) fast pyrogenation and distills residual Jiao (≤300 μ m) and the quick productive rate data of gas-liquid-solid three-phase product in copyrolysis process of rice husk (125 ~ 300 μ m).
Fig. 6 is rice husk (≤88 μ m) fast pyrogenation and distills residual Jiao (≤300 μ m) and the quick productive rate data of gas-liquid-solid three-phase product in copyrolysis process of rice husk (≤88 μ m).
The proportioning raw materials that Fig. 7-1,7-2 and 7-3 are corresponding is respectively 100/0,80/20 and 65/35(rice husk/distill residual Jiao, w/w) time, distill the fast GC-MS total ion current figure of copyrolysis gained bio oil of residual Jiao (≤300 μ m) and rice husk (≤88 μ m), wherein the 100/0 fast pyrogenation process that represents rice husk (≤88 μ m).
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The test of the liquid aqueous rate described in the present embodiment adopts ASTM D 1744-92 standard method, and instrument is ZKF-1 type karl Fischer moisture content tester, and solvent is chloroform and methyl alcohol mixed liquor (chloroform: methyl alcohol=3:1, v/v).
The rice husk bio oil adopting in the present embodiment (being designated as protista oil) is bought from Anhui Yineng Biologic energy Co., Ltd. (lot identification mark 110615-1).The water ratio of this bio oil is 30.3wt.% after measured, and pH is 3.1, and density is 1.175g/cm
3.
Get the above-mentioned bio oil of 577g, add in 1000mL round-bottomed flask, in oil bath heating, magnetic agitation situation, slowly by 20 ℃, be heated to 240 ℃, volatile matter produces distillate after the prolong that the mobile tap water of 20 ℃ is cooling medium and (is designated as distillate a) through take.Extend in time, in round-bottomed flask, the volume of bio oil reduces gradually, and further sticky.Slowly be warming up to 240 ℃, and keep this temperature until produce without distillate, stop heating, still-process finishes.Take out round-bottomed flask, be cooled to after room temperature, in flask, resistates brown solid darkly, is residual Jiao of distillation.In heat-processed, should regulate temperature rise rate, make it should not be too fast, with 1-2 per second, drip distillate and be advisable.This still-process 6h approximately consuming time, collects distillate a299.21g, and its productive rate is 51.86wt.%.Water ratio in distillate a is 71.6wt.% after measured.
First main organism in distillate a carries out qualitative analysis with GC-MS, adopts HP-5MS capillary column (30m * 0.25mm i.d. * 0.25 μ m), high-purity He(99.999%) as carrier gas, flow velocity is 1mL/min.Column temperature program is 40 ℃ and retains 5min, rises to 180 ℃, then rise to 250 ℃ with 10 ℃/min with 4 ℃/min.Sample size is 1 μ L, and splitting ratio is 20:1.
The GC-MS total ion current figure of distillate a is shown in Fig. 2-1.The essential substance identifying is listed in table 1.
Essential substance in table 1 bio oil distillate
*standard atmosphere is depressed
By Fig. 2-1 and table 1, can be found out, the organism in distillate a is mainly C
2-C
9organic acid, aldehyde, ketone, alcohol, ester, aldehydes matter, their boiling spread is 80-248 ℃.
Next with GC-FID, 10 kinds of compounds such as a large amount of acetic acid existing, pyruvic alcohol, phenol in distillate a and protista oil are done to quantitative assay, adopt OV-1701 capillary column (30m * 0.32mm i.d. * 1.00 μ m), column temperature program is 40 ℃ and retains 12min, with 4 ℃/min, rise to 180 ℃, then rise to 250 ℃ with 10 ℃/min.Qualitative to chromatographic peak with the appearance time of standard substance, the 1-bromobenzene of usining is quantitative as internal standard substance.
Fig. 3 is shown in by GC collection of illustrative plates.Every kind of material concentration in distillate a and protista oil, and their separation efficiencies in still-process are listed in table 2.
The separation efficiency of essential substance in table 2 distillate a
* Y is distillate a productive rate, is 51.86% herein.
*propionic acid and butanic acid polarity are stronger, and in nonpolar HP-5MS chromatographic column, response value is lower, therefore GC-MS
In result, do not show; And have fine response in the OV-1701 of middle polarity chromatographic column.
In this air distillation operation, the separation efficiency of the acetic acid in bio oil (118 ℃ of boiling points), propionic acid (141 ℃ of boiling points) and furtural (boiling point 161-162 ℃) is all higher than 85%; The separation efficiency of pyruvic alcohol (boiling point 145-146 ℃), butanic acid (164 ℃ of boiling points) and furfuralcohol (boiling point 170-171 ℃) is between 54-62%; By contrast, the separation efficiency of aldehydes matter is relatively low, and this boiling point with them is relatively high relevant, and the boiling point of phenol, methyl catechol, ortho-methyl phenol and p-methyl phenol is respectively 182,205,191 and 202.3 ℃.
Compound in bio oil is nearly hundreds of, and boiling point distribution is not from tens to hundreds of degree Celsius etc.In conjunction with Fig. 4, can find out some high boiling substances in bio oil, as pyrocatechol (25.48min, 245.5 ℃ of boiling points), 2-methoxyl group-4-methylphenol (25.56min, 220 ℃ of boiling points), coumaran (26.45min, 188 ℃ of boiling points), 4-methyl pyrocatechol (28.77min, 251 ℃ of boiling points), Levoglucosan (35.69min, 383.8 ℃), 2-methoxyl group-4-hydroxyl phenylacrolein (41.92min, 360 ℃) etc. almost can not be distilled.The solid that in they and bio oil, other material changes chocolate into by complicated polymerization, polycondensation distills residual Jiao.
Ultimate analysis and the proximate analysis of distilling residual Jiao and rice husk the results are shown in Table 3.
Table 3 rice husk and residual Jiao's of distillation ultimate analysis and proximate analysis
Ultimate analysis shows, the carbon content of distilling residual Jiao is 66.10wt.%, be higher than the carbon content of rice husk 38.26wt.%; The oxygen level of distilling residual Jiao only has half of rice husk.The proximate analysis of the two shows, rice husk and residual Jiao's of distillation volatile content is respectively 67.91wt.% and 61.03wt.%.Can find out, the volatile matter of the two, in same level, therefore can utilize this kind of thermochemical techniques of fast pyrogenation, makes to distill residual burnt devolatilization (devolatilization) reaction that occurs under suitable condition, be converted into not condensible gas and bio oil, turn waste into wealth.
Embodiment 2
The fast pyrogenation of rice husk (125 ~ 300 μ m) carries out on laboratory scale pyrolysis reactor.This pyrolysis reactor is katabatic drainage free fall type fixed-bed reactor (Total recovery of nitrogen and phosphorus from three wetland plants by fast pyrolysis technology.Bioresource Technology 2011,102,3471-3479; Selectively improving the bio-oil quality by catalytic fast pyrolysis of heavy metals polluted biomass:Take copper (Cu) as an example.Environmental Science & Technology 2012,46,7849-7856).First, after rice husk being pulverized, being ground, get 125 μ m≤particle diameter≤300 μ m(60-120 orders) rice husk particle, be dried to constant weight in 105 ℃, now the moisture content of rice husk is 3.01wt.%.Take 5.000 ± 0.002g rice husk particle as pyrolysis feed.Pyrolysis zone is heated to after 450 ℃, with the flow velocity of 0.4L/min, passes into rare gas element N
2to pyrolysis reactor, keep 20min with thorough excluding air.Subsequently at the N of 0.16L/min
2under atmosphere, rice husk raw material enters pyrolysis zone with the form of freely falling body, and it is heated to rapidly 450 ℃ (temperature rise rate>=300 ℃/s) in decline process, and the pyrolysis steam that pyrolysis zone produces is through N
2carrying by temperature is the ethanol bath condenser of-10 ℃, produces bio oil in condenser.The charcoal producing in pyrolytic process is retained in pyrolysis zone.Raw material, all by after pyrolysis, makes reactor at the N of 0.16L/min
2in atmosphere, be cooled to room temperature, the bio oil in collection condenser and the charcoal in pyrolysis zone, weigh their quality to calculate respectively its productive rate, and the productive rate of condensible gas does not subtract calculating by difference.The productive rate data of gas-liquid-solid three-phase product are shown in Fig. 5.
The quick copyrolysis that distills residual Jiao (≤300 μ m) and rice husk (125 ~ 300 μ m) also carries out on this pyrolysis reactor.First, residual Jiao of the distillation obtaining in embodiment 1 (moisture content 1.11wt.%, as received basis) is pulverized, is ground to particle diameter≤300 μ m(standard sieve 60 orders) particle.After rice husk is pulverized, ground, get 125 μ m≤particle diameter≤300 μ m(60-120 orders) rice husk particle, be dried to constant weight in 105 ℃, now the moisture content of rice husk is 3.01wt.%.Take according to a certain percentage residual Jiao of distillation and rice husk particle, making total mass is 5.000 ± 0.002g, and the two is mixed, and is pyrolysis feed.In rice husk/distill residual Jiao's mass ratio, two kinds of ratio from 70/30 to 90/10 variations that raw material mixes.Rice husk is consistent with rice husk fast pyrogenation process with the parameter of the quick copyrolysis process of residual Jiao of distillation, the N that 450 ℃ of pyrolysis temperatures, carrier gas are 0.16L/min
2, condensing temperature-10 ℃.After raw material is all by pyrolysis, make reactor at the N of 0.16L/min
2in atmosphere, be cooled to room temperature, the bio oil in collection condenser and the charcoal in pyrolysis zone, weigh their quality to calculate respectively its productive rate, and the productive rate of condensible gas does not subtract calculating by difference.The productive rate data of gas-liquid-solid three-phase product are also shown in Fig. 5.
As shown in Figure 5, during with the independent pyrolysis of 60-120 object rice husk, bio oil productive rate (44.83wt.%) is compared, to distill residual Jiao and mix rear copyrolysis with rice husk, the productive rate of the bio oil producing only 44.33-46.12wt.% among a small circle in fluctuation, within the specific limits, the productive rate of bio oil changes with the ratio of raw material hardly in this explanation.When especially distilling residual burnt content being 15wt.% in raw material, the productive rate of bio oil is 46.12wt.%, slightly higher than the bio oil productive rate under other ratio, thus 85/15(rice husk/distill residual Jiao, w/w) be a preferred proportion of quick copyrolysis.
Along with distilling the increase of residual burnt content in raw material, the productive rate of charcoal presents the trend of rising on the whole, and this can explain with rice husk and residual Jiao's of distillation fixed carbon content.According to table 3, the fixed carbon content of rice husk is 19.63wt.%, and the fixed carbon content (38.47wt.%) that distills residual Jiao is almost the twice of rice husk, thereby distills residual Jiao and easily than fixed carbon, produce more charcoal.Burning by charcoal can provide pyrolytic reaction and the required heat of still-process, therefore, compares with the independent pyrolysis of rice husk, and in copyrolysis process, the increase of charcoal productive rate is also useful for energy recovery and the circulation of system.
Embodiment 3
What the present embodiment was described is the fast pyrogenation process of rice husk (≤88 μ m) and rice husk (≤88 μ m) and residual Jiao's of distillation (≤300 μ m) quick copyrolysis process.
The fast pyrogenation process raw material used of rice husk (≤88 μ m) is dry rice husk particle, its preparation process is as follows: rice husk is ground to particle diameter≤88 μ m(180 order) after, be dried to constant weight in 105 ℃, now rice husk powder moisture content is 3.01wt.%.
The residual coke powder of the distillation obtaining in embodiment 1 is broken, grind, be sized to particle diameter≤300 μ m(60 order); Take according to a certain percentage distillation residual Jiao (≤300 μ m) and dry rice husk particle (≤88 μ m), making total mass is 5.000 ± 0.002g, the two is mixed, as the raw material of quick copyrolysis process.In rice husk/distill residual Jiao's mass ratio, two kinds of ratio from 65/35 to 85/15 variations that raw material mixes.
It is identical that (being total to) pyrolytic process is described with embodiment 2, and pyrolysis temperature is 450 ℃, and condensing temperature is-10 ℃, the N that carrier gas is 0.16L/min
2, the productive rate data of gained gas-liquid-solid three-phase product are shown in Fig. 6.
According to Fig. 6, three-phase productive rate during the independent pyrolysis of particle diameter≤180 object rice husk is respectively: bio oil, 46.19wt.%; Condensible gas not, 17.43wt.%; Charcoal, 36.38wt.%.When distilling residual burnt content changing between 15-35% in raw material, the productive rate of copyrolysis gained bio oil all 44.98-47.23wt.% among a small circle in change, productive rate of this explanation bio oil changes with the ratio of raw material hardly.When the content that distills residual Jiao in raw material is 20wt.%, the productive rate of bio oil is 47.23wt.%, is maximum value in all proportions.Therefore 80/20(rice husk/distill residual Jiao, w/w) is a preferred proportion of quick copyrolysis.
With the increase of distilling residual burnt content in raw material, the copyrolysis gained not productive rate of condensible gas reduces (when distilling residual burnt content being 35% in raw material gradually, productive rate reaches minimum value 13.53wt.%), the productive rate of charcoal increases while being 35% (in raw material, distill residual burnt content, productive rate reaches maximum value 41.21wt.%) gradually.
Copyrolysis gained bio oil is carried out to ultimate analysis, the results are shown in table 4.
Table 4 is the ultimate analysis * of (being total to) pyrolysis gained bio oil fast
*c, H, N content is measured on Vario EL cube elemental analyser, and O content calculates by minusing.
Ultimate analysis shows, when distilling residual burnt content being 15-35wt.% in raw material, the carbon content of gained bio oil changes between 30.11-34.13wt.%, and oxygen level changes between 56.82-60.58wt.%.During with the independent pyrolysis of rice husk, gained bio oil is compared, and except 15wt.%, the carbon content of the bio oil of the proportioning raw materials gained of all the other ratios is higher, and oxygen level is lower, i.e. better quality.
While being 0,20% and 35% with GC-MS to distilling residual burnt content in raw material, the organic composition of prepared bio oil is identified, the results are shown in table 5, GC-MS total ion current figure is shown in respectively Fig. 7-1, Fig. 7-2, Fig. 7-3.
Essential substance in quick (being total to) pyrolysis gained bio oil of table 5
*x/y represents rice husk and the mass ratio that distills residual Jiao in pyrolysis feed, and 100/0 represents that pyrolysis feed is all rice husk.
By 5 figure and Fig. 7-1, Fig. 7-2, Fig. 7-3 can be found out, add the residual defocused copyrolysis of a small amount of distillation in rice husk, basic identical when main organism and the independent pyrolysis of rice husk in prepared bio oil, the content of these organism in bio oil difference slightly just.The new organic compound that does not occur high density in the bio oil of copyrolysis gained, this explanation is measurable and controlled by the process of this copyrolysis explained hereafter bio oil.
The present embodiment is that in pyrolysis feed, the particle diameter of rice husk is different from the key distinction of embodiment 2.In fast pyrogenation process, the devolatilization time of grain diameter influence's biomass of powder, the contraction process of particle, and then affect heat transfer parameter and the mass transfer processes such as nusselt number and Biot number, finally the productive rate of pyrolysis product is exerted an influence.This example and embodiment 2 the results are shown in table 6.
The copyrolysis result comparison of the different rice husk particle diameters of table 6
Can find out, in rice husk and residual Jiao's of distillation quick copyrolysis process, the particle diameter that suitably reduces rice husk biomass not only contributes to improve the productive rate of bio oil, and can allow to add and more distill residual Jiao in rice husk, thereby improves distilling residual Jiao's processing power.
Embodiment 4
According to the description of embodiment 3, in pyrolysis temperature, be 450 ℃, condensing temperature is-10 ℃, the N that carrier gas is 0.16L/min
2atmosphere, and take the rice husk particle that 4.000 ± 0.002g is dry (≤88 μ m) and 1.000 ± 0.002g distills residual Jiao, the two is mixed, as pyrolysis feed, carry out copyrolysis experiment.Now in raw material, rice husk is 80/20 with residual Jiao's of distillation mass ratio, is the determined preferred proportion of embodiment 3.Repeat this copyrolysis process 4 times, by the bio oil centralized collection obtaining at every turn.Get this copyrolysis gained bio oil 5.26g, be placed in 10mL round-bottomed flask, connect microscale distillation head, in oil bath heating, magnetic agitation situation, be slowly heated to 240 ℃, and keep this temperature, until stop heating while producing without distillate.In heat-processed, the generation speed of distillate is that 1-2 per second drips.This still-process 2h approximately consuming time, collects distillate 2.81g, and its productive rate is 53.42wt.%.This distillate is designated as distillate b, and its GC-MS total ion current figure is shown in Fig. 2-2, and contained main organism is listed in table 1.
Residual Jiao of distillation (being designated as the residual burnt b of distillation) who remains in round-bottomed flask is taken out, pulverize, grind, be sized to particle diameter≤300 μ m(60 order).Take the residual burnt b of 1.09g distillation, after mixing with the dry rice husk particle (≤88 μ m) of 4.36g, as raw material, carry out copyrolysis experiment.Now in raw material, rice husk is also 80/20 with residual Jiao's of distillation mass ratio, is the determined preferred proportion of embodiment 3.Pyrolysis temperature is 450 ℃, and condensing temperature is-10 ℃, the N that carrier gas is 0.16L/min
2atmosphere, takes the bio oil 1.23g collecting, and is placed in 5mL round-bottomed flask, connects microscale distillation head, in oil bath heating, magnetic agitation situation, is slowly heated to 240 ℃, and keeps this temperature, until stop heating while producing without distillate.In heat-processed, the generation speed of distillate is that 1-2 per second drips.This still-process 1h approximately consuming time, collects distillate 0.68g, and its productive rate is 54.99wt.%.This distillate is designated as distillate c, and its GC-MS total ion current figure is shown in Fig. 2-3, and contained main organism is listed in table 1.
The object of the present embodiment is the ingredient stability of distillate when investigating this technique and moving continuously.By GC-MS technology, the main organism in distillate b in distillate a, the present embodiment in embodiment 1 and distillate c is identified, result shows, the main organic material composition in three distillates is consistent, is C
2-C
9series lightweight organism, illustrates the stay in grade of the end product---distillate---of this circulation technology, and this technique can continuously, stably be produced these materials.
Claims (10)
1. one kind is utilized biomass to produce C
2-C
9the method of Chemicals, it comprises the following steps:
(1) biomass fast pyrogenation is made to bio oil;
(2) bio oil step (1) being obtained is carried out air distillation, isolates light component distillate and heavy constituent and distills residual Jiao, and the main component of described distillate is C
2-C
9compound;
(3) in proportion residual Jiao of distillation of step (2) gained is added in step (1) biomass and mixed, the process of repeating step (1) and (2).
2. method according to claim 1, is characterized in that, the described biomass of step (1) are dry rice husk, and its particle diameter is not more than 300 μ m, and its moisture content is less than 5wt.%.
3. method according to claim 2, is characterized in that, the particle diameter of described dry rice husk is for being not more than 88 μ m.
4. method according to claim 1, is characterized in that, the temperature of the described fast pyrogenation of step (1) is 400 ~ 600 ℃.
5. method according to claim 1, is characterized in that, the described air distillation of step (2) is intermittent type air distillation, and distillation temperature is 20 ℃ to 240 ℃.
6. method according to claim 1, is characterized in that, residual Jiao of the described distillation of step (3) also comprised that before mixing with biomass residual Jiao's of described distillation particle diameter is not more than 300 μ m to distilling residual Jiao's pulverizing and milled processed.
7. method according to claim 1, is characterized in that, it is 10 ~ 35% that residual Jiao of the described distillation of step (3) accounts for total raw material mass ratio.
8. method according to claim 7, is characterized in that, the mass ratio of residual Jiao of described distillation and rice husk is 1:4.
9. the C that described in claim 1 ~ 8 any one prepared by method
2-C
9chemicals, is characterized in that, described C
2-C
9chemicals are organic carboxyl acid class, aldehydes, ketone, ester class, alcohols and phenolic compound.
10. the application of method in preparing bioenergy described in claim 1 ~ 8 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210355747.XA CN102851054B (en) | 2012-09-21 | 2012-09-21 | C2-C9 chemical product produced from biomass, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210355747.XA CN102851054B (en) | 2012-09-21 | 2012-09-21 | C2-C9 chemical product produced from biomass, its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102851054A CN102851054A (en) | 2013-01-02 |
| CN102851054B true CN102851054B (en) | 2014-11-05 |
Family
ID=47398040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210355747.XA Expired - Fee Related CN102851054B (en) | 2012-09-21 | 2012-09-21 | C2-C9 chemical product produced from biomass, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102851054B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756700B (en) * | 2014-01-27 | 2015-08-19 | 华东理工大学 | A kind of method improving pyrolysis of coal semi coking tar quality |
| CN112322384A (en) * | 2020-09-22 | 2021-02-05 | 天津大学 | Multistage reduced pressure distillation separation device and method for photovoltaic biological oil |
| CN116420830A (en) * | 2023-04-19 | 2023-07-14 | 江西金糠新材料科技有限公司 | Method and system for preparing food-grade rice hull vinegar, rice hull vinegar beverage and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709224A (en) * | 2009-11-06 | 2010-05-19 | 中国科学技术大学 | Biomass spiral pyrolysis device and pyrolysis process |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
| WO2011096912A1 (en) * | 2010-02-08 | 2011-08-11 | Kior Inc. | Two-step process for producing high yields of oil from biomass |
-
2012
- 2012-09-21 CN CN201210355747.XA patent/CN102851054B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101709224A (en) * | 2009-11-06 | 2010-05-19 | 中国科学技术大学 | Biomass spiral pyrolysis device and pyrolysis process |
| WO2011096912A1 (en) * | 2010-02-08 | 2011-08-11 | Kior Inc. | Two-step process for producing high yields of oil from biomass |
| CN101824330A (en) * | 2010-04-30 | 2010-09-08 | 中国科学技术大学 | Catalytic thermal cracking method for lignin |
Non-Patent Citations (4)
| Title |
|---|
| "Separation characteristics of biomass pyrolysis oil in molecular distillation";Zuogang Guo;《Separation and Purification Technology》;20101201;第76卷(第1期);第52-57页 * |
| "Separation of Bio-oil by Molecular Distillation";Shurong Wang;《Fuel Processing Technology》;20090531;第738-745页 * |
| Shurong Wang."Separation of Bio-oil by Molecular Distillation".《Fuel Processing Technology》.2009, * |
| Zuogang Guo."Separation characteristics of biomass pyrolysis oil in molecular distillation".《Separation and Purification Technology》.2010,第76卷(第1期),52-57. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102851054A (en) | 2013-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tahir et al. | Demonstrating the suitability of canola residue biomass to biofuel conversion via pyrolysis through reaction kinetics, thermodynamics and evolved gas analyses | |
| Yanik et al. | Fast pyrolysis of agricultural wastes: Characterization of pyrolysis products | |
| Erdogdu et al. | Pyrolysis of goat manure to produce bio-oil | |
| Muradov et al. | Pyrolysis of fast-growing aquatic biomass–Lemna minor (duckweed): Characterization of pyrolysis products | |
| Tao et al. | Multi-step separation of different chemical groups from the heavy fraction in biomass fast pyrolysis oil | |
| Părpăriţă et al. | Pyrolysis behaviors of various biomasses | |
| Demiral et al. | Pyrolysis of grape bagasse: effect of pyrolysis conditions on the product yields and characterization of the liquid product | |
| Ortega et al. | Physical and chemical characteristics of aging pyrolysis oils produced from hardwood and softwood feedstocks | |
| Tran et al. | Fast pyrolysis of pitch pine biomass in a bubbling fluidized-bed reactor for bio-oil production | |
| Naqvi et al. | Catalytic pyrolysis of paddy husk in a drop type pyrolyzer for bio-oil production: The role of temperature and catalyst | |
| Kim et al. | Influence of reaction conditions on bio-oil production from pyrolysis of construction waste wood | |
| Konur | Characterization and properties of biooils: A review of the research | |
| Ly et al. | Catalytic pyrolysis of spent coffee waste for upgrading sustainable bio-oil in a bubbling fluidized-bed reactor: experimental and techno-economic analysis | |
| Wang et al. | Studies on thermal decomposition behaviors of demineralized low-lipid microalgae by TG-FTIR | |
| Papari et al. | Study of selective condensation for woody biomass pyrolysis oil vapours | |
| Rijo et al. | Catalyzed pyrolysis of coffee and tea wastes | |
| Danje | Fast pyrolysis of corn residues for energy production. | |
| Ji et al. | The pyrolysis of lipid-extracted residue of Tribonema minus in a fixed-bed reactor | |
| Ly et al. | Effects of torrefaction on product distribution and quality of bio-oil from food waste pyrolysis in N2 and CO2 | |
| Zhuang et al. | Microwave-assisted hydrothermal liquefaction for biomass valorization: Insights into the fuel properties of biocrude and its liquefaction mechanism | |
| Ateş et al. | Comparison of non-catalytic and catalytic fast pyrolysis of pomegranate and grape marcs under vacuum and inert atmospheres | |
| CN102851054B (en) | C2-C9 chemical product produced from biomass, its preparation method and application | |
| CN104031671B (en) | A kind of biomass pyrolytic prepares the method for bio oil | |
| Qin et al. | Effect of temperature on the physicochemical characteristics of pine nut shell pyrolysis products in a screw reactor | |
| Xu et al. | Investigation of the combination of fractional condensation and water extraction for improving the storage stability of pyrolysis bio-oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141105 Termination date: 20200921 |