CN108774538A - A kind of method of active carbon deposit component in acquisition catalytic pyrolysis of biomass - Google Patents
A kind of method of active carbon deposit component in acquisition catalytic pyrolysis of biomass Download PDFInfo
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- CN108774538A CN108774538A CN201810420257.0A CN201810420257A CN108774538A CN 108774538 A CN108774538 A CN 108774538A CN 201810420257 A CN201810420257 A CN 201810420257A CN 108774538 A CN108774538 A CN 108774538A
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- catalyst
- active carbon
- catalytic pyrolysis
- carbon deposit
- biomass
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 a kind of methods of active carbon deposit component in acquisition catalytic pyrolysis of biomass, include the following steps：Every time before experiment, used catalyst is put into catalytic pyrolysis reaction device under oxygen atmosphere and is calcined；Catalyst and material are ready to after being put into catalytic pyrolysis reaction device, biomass catalyzing agent pyrolytic reaction is carried out；It according to time induction period obtained by previous step, determines and stops reaction time point, stop feeding and cooling down rapidly, take out catalyst；The catalyst sample after reaction is weighed, is fitted into special container, qualitative analysis is carried out to active carbon deposit component therein.The acquisition methods of the present invention are simple for process, by controlling the chilling period of catalyst, effectively obtain the active carbon deposit component in Biomass catalysis pyrolysis, and understand catalytic pyrolysis of biomass reaction mechanism to a certain extent.
Description
Technical field
The present invention relates to biomass thermal chemical conversion technical fields, more particularly in a kind of acquisition catalytic pyrolysis of biomass
The method of active carbon deposit component.
Background technology
In catalytic pyrolysis of biomass, the small molecule carbon deposit of catalytic inner, which has the generation of target product, can not be ignored
It influences.It is reacted early period in catalysis, a large amount of activity carbon deposits make catalyst framework be changed into an organic active system, then active
Carbon deposit occurs chemical reaction with biomass material and generates the target products such as alkene and aromatic hydrocarbon.Oxygen-containing big point of some biomass pyrolytics
Son cannot enter catalyst duct, and polymerization in catalyst surface so that form macromolecular carbon deposit on a catalyst；Some biomass
Be pyrolyzed active small molecular also can occur polymerisation formation carbon deposit to block duct in catalyst surface.Therefore, how is research
It is very great to obtain active carbon deposit component meaning in catalytic pyrolysis of biomass.
In-situ techniques are more universal in the method for active carbon deposit component in current acquisition catalytic pyrolysis of biomass, but former
Position spectrogram information amount is larger, it is difficult to obtain accurate information.Therefore the present invention interrupts reaction within accurate induction period, controls urgency
The time of quickly cooling but takes out the extraction that catalyst carries out active carbon deposit, obtains accurately active carbon deposit component, understands catalysis
Real-time intermediate material inside agent, understands catalytic pyrolysis of biomass reaction mechanism to a certain extent.
Invention content
The present invention be directed to currently in order to obtain active carbon deposit component on-line testing information in catalytic pyrolysis of biomass it is complicated and
The problems such as On-line testing is difficult is studied and has invented a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass.
For above-mentioned technical purpose, the present invention will take the following technical solution：
The method of active carbon deposit component, includes the following steps in a kind of acquisition catalytic pyrolysis of biomass：
1) used catalyst is put into catalytic pyrolysis reaction device under oxygen atmosphere and is calcined before experiment every time；
2) catalyst and material are ready to after being put into catalytic pyrolysis reaction device, are carried out at a temperature of setting at one
20min biomass catalyzing agent pyrolytic reactions；
3) it according to time induction period obtained by previous step, determines and stops reaction time point, stop feeding and cooling down rapidly, take out
Catalyst；
4) catalyst sample after 50mg reactions is weighed, is fitted into special container, the HF aqueous solutions of 10mL is added, oscillation is shaken
1h is stood after even, after molecular sieve catalyst is completely dissolved, 2mL dichloromethane is added into solution, oscillation is poured into point after shaking up
Stratification in liquid funnel separates lower layer's oily liquids, and qualitative analysis is carried out to active carbon deposit component therein.
Further, oxygen atmosphere used in catalyst calcination is 100mL/min, calcination time 1h in the step 1).
Further, catalyst selects HZSM-5 catalyst or HY catalyst in the step 1).
Further, the yield of hydro carbons first increases to certain with the reaction time in catalytic pyrolysis of biomass in the step 2)
One maximum value, is then gradually reduced.
Further, catalysis pyrolysis temperature chooses 500 DEG C, 550 DEG C, 600 DEG C and 650 DEG C in the step 2).
Further, in the step 3), active carbon deposit is mainly formed in induction period, chooses end time induction period point and stops
Only catalytic pyrolysis reaction, and by conversion zone rapid cooling.
Further, the material of the container equipped with catalyst is polytetrafluoroethylene (PTFE) in the step 4).
Further, HF concentration of aqueous solution is 40% in the step 4).
Further, qualitative point is carried out using GC/MS and HPLC to the active carbon deposit component obtained out in the step 4)
Analysis.
According to above-mentioned technical solution, compared with the existing technology, the present invention has following advantageous effect：Compared to original position
Test mode, acquisition methods of the invention are simple for process, and information content is simple, are easy therefrom to obtain accurate information；It is urged by control
The chilling period of agent, it is ensured that secondary response does not occur, effectively obtains the active carbon deposit component in Biomass catalysis pyrolysis,
And catalytic pyrolysis of biomass reaction mechanism is understood to a certain extent.
Description of the drawings
Fig. 1 is the flow chart of the acquisition methods of active carbon deposit component in catalytic pyrolysis of biomass；
Fig. 2 form biomass pyrolysis modelling object furans catalyzed conversion olefins yield on HZSM-5 catalyst changes with time
Relationship；
Fig. 3 form biomass pyrolysis modelling object furans catalyzed conversion olefins yield on HY catalyst changes with time pass
System；
Fig. 4 be at 500 DEG C of reaction temperature biomass pyrolytic modelling object furans on HZSM-5 catalyst two in catalyzed conversion
The GC/MS spectrograms of chloromethane alkane extract；
Fig. 5 be at 650 DEG C of reaction temperature biomass pyrolytic modelling object furans on HZSM-5 catalyst two in catalyzed conversion
The GC/MS spectrograms of chloromethane alkane extract.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes.
The technique for obtaining active carbon deposit component in catalytic pyrolysis of biomass of embodiment as shown in Figure 1, including it is as follows
Step：
S10, used catalyst is put into catalytic pyrolysis reaction device under oxygen atmosphere and is calcined.
Wherein, oxygen atmosphere used in catalyst calcination is 100mL/min, and calcination time is two hours.
Catalyst selects HZSM-5 catalyst and HY catalyst.
S20, catalyst and material are ready to after being put into catalytic pyrolysis reaction device, are carried out at a temperature of setting at one
20min biomass catalyzing agent pyrolytic reactions.
Wherein, the yield of hydro carbons first increases to a certain maximum value with the reaction time in catalytic pyrolysis of biomass, then by
It is decrescence small.
It is catalyzed pyrolysis temperature and chooses 500 DEG C, 550 DEG C, 600 DEG C and 650 DEG C.
S30, according to time induction period obtained by previous step, determine and stop reaction time point, stop feeding and simultaneously cools down rapidly, take
Go out catalyst.
Wherein, active carbon deposit is mainly formed in induction period, chooses end time induction period point and stops catalytic pyrolysis reaction, and
By conversion zone rapid cooling.
S40, the catalyst sample after 50mg reactions is weighed, is fitted into special container, the HF aqueous solutions of 10mL are added, vibrates
1h is stood after shaking up；After molecular sieve catalyst is completely dissolved, 2mL dichloromethane is added into solution, oscillation is poured into after shaking up
Stratification in separatory funnel separates lower layer's oily liquids, carries out qualitative analysis.
Wherein, the material that the container of catalyst is housed is polytetrafluoroethylene (PTFE).
HF concentration of aqueous solution is 40%.
The active carbon deposit component of extraction gained carries out qualitative analysis using GC/MS and HPLC.
It is specific implementation mode below：
Embodiment 1
Catalyst is HZSM-5, SiO2/Al2O3=30, for particle diameter distribution between 50~200 mesh, pyrolysis modelling object is furan
It mutters.
Used catalyst HZSM-5 is put into reactor two hours of calcining under the oxygen atmosphere of 100mL/min, is waited for
After calcining, reactant furans is added into reactor, sets pyrolysis time as 20min, then respectively by material and catalysis
Agent is reacted at a temperature of 500 DEG C, and the gained olefins yield relationship that changes with time is as shown in Figure 2.After completion of the reaction, it sets
Pyrolysis temperature is 500 DEG C, and reaction is interrupted when the reaction time is 2min, stops feeding and cooling down rapidly, then takes out catalysis
Agent is spare.
The catalyst sample after 50mg reactions is weighed, is fitted into politef container, 10mL is then added into container
The HF aqueous solutions of concentration 40%, oscillation stand 1h after shaking up, after HZSM-5 catalyst is completely dissolved, are added into solution
2mL dichloromethane, oscillation pour into stratification in separatory funnel after shaking up, and are to obtain out in the lower layer's oily liquids separated
Active carbon deposit carries out GC/MS chromatography to the oily liquids containing active carbon deposit of taking-up, and the results are shown in Figure 4.
Embodiment 2
Step is substantially the same manner as Example 1, the difference is that pyrolysis temperature is 550 DEG C, interrupting reaction time point is
2min, the gained olefins yield relationship that changes with time are as shown in Figure 2.
Embodiment 3
Step is substantially the same manner as Example 1, the difference is that pyrolysis temperature is 600 DEG C, interrupting reaction time point is
3min, the gained olefins yield relationship that changes with time are as shown in Figure 2.
Embodiment 4
Step is substantially the same manner as Example 1, the difference is that pyrolysis temperature is 650 DEG C, interrupting reaction time point is
6min, gained olefins yield change with time relationship as shown in Fig. 2, to extraction gained the oily liquids containing active carbon deposit into
Row GC/MS chromatography, the results are shown in Figure 5.
Embodiment 5
Step is substantially the same manner as Example 1, the difference is that catalyst is HY catalyst, SiO2/Al2O3=5, gained
The olefins yield relationship that changes with time is as shown in Figure 3.
Embodiment 6
Step is substantially the same manner as Example 2, the difference is that catalyst is HY catalyst, SiO2/Al2O3=5, gained
The olefins yield relationship that changes with time is as shown in Figure 3.
Embodiment 7
Step is substantially the same manner as Example 3, the difference is that catalyst is HY catalyst, SiO2/Al2O3=5, gained
The olefins yield relationship that changes with time is as shown in Figure 3.
Embodiment 8
Step is substantially the same manner as Example 4, the difference is that catalyst is HY catalyst, SiO2/Al2O3=5, gained
The olefins yield relationship that changes with time is as shown in Figure 3.
The corresponding chemical substance of each characteristic peak see the table below 1 in Fig. 4 and Fig. 5.
Table 1
Although the present invention has been described by way of example and in terms of the preferred embodiments, embodiment is not for the purpose of limiting the invention.Not
It is detached from the spirit and scope of the present invention, any equivalent change or retouch done also belongs to the protection domain of the present invention.Cause
This protection scope of the present invention should be using the content that claims hereof is defined as standard.
Claims (9)
1. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass, which is characterized in that include the following steps：
1) used catalyst is put into catalytic pyrolysis reaction device under oxygen atmosphere and is calcined before experiment every time；
2) catalyst and material are ready to after being put into catalytic pyrolysis reaction device, 20min lifes is carried out at a temperature of setting at one
Material catalyst pyrolytic reaction；
3) it according to time induction period obtained by previous step, determines and stops reaction time point, stop feeding and cooling down rapidly, take out catalysis
Agent；
4) catalyst sample after 50mg reactions is weighed, is fitted into special container, the HF aqueous solutions of 10mL are added, after oscillation shakes up
1h is stood, after molecular sieve catalyst is completely dissolved, 2mL dichloromethane is added into solution, liquid separation leakage is poured into oscillation after shaking up
Stratification in bucket separates lower layer's oily liquids, and qualitative analysis is carried out to active carbon deposit component therein.
2. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass according to claim 1, feature exist
In：Oxygen atmosphere used in catalyst calcination is 100mL/min, calcination time 1h in the step 1).
3. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass according to claim 1, feature exist
In：Catalyst is HZSM-5 catalyst or HY catalyst in the step 1).
4. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass according to claim 1, feature exist
In：The yield of hydro carbons first increases to a certain maximum value with the reaction time in catalytic pyrolysis of biomass in the step 2), then
It is gradually reduced.
5. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass according to claim 1, feature exist
In：Catalysis pyrolysis temperature chooses 500 DEG C, 550 DEG C, 600 DEG C and 650 DEG C in the step 2).
6. the method for active carbon deposit component, feature exist in a kind of extraction catalytic pyrolysis of biomass according to claim 1
In：Active carbon deposit is mainly formed in induction period in the step 3), chooses end time induction period point and stops catalytic pyrolysis reaction,
And by conversion zone rapid cooling.
7. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass according to claim 1, feature exist
In：The material of the special container equipped with catalyst is polytetrafluoroethylene (PTFE) in the step 4).
8. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass according to claim 1, feature exist
In：HF concentration of aqueous solution is 40% in the step 4).
9. a kind of method obtaining active carbon deposit component in catalytic pyrolysis of biomass according to claim 1, feature exist
In：Qualitative analysis is carried out using GC/MS and HPLC to the active carbon deposit component obtained out in the step 4).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218292A (en) * | 2020-01-15 | 2020-06-02 | 江苏大学 | Device and method for rapidly cooling system by using residual heat of biomass catalytic pyrolysis reactor |
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| US20090165378A1 (en) * | 2007-08-01 | 2009-07-02 | Agblevor Foster A | Fractional catalytic pyrolysis of biomass |
| CN102653691A (en) * | 2012-02-29 | 2012-09-05 | 东南大学 | Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil |
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2018
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| US20090165378A1 (en) * | 2007-08-01 | 2009-07-02 | Agblevor Foster A | Fractional catalytic pyrolysis of biomass |
| CN102653691A (en) * | 2012-02-29 | 2012-09-05 | 东南大学 | Device and method for preparing oxygen-containing liquid fuel by catalytically converting biological oil |
| CN104785287A (en) * | 2015-03-18 | 2015-07-22 | 东南大学 | Modification method for improving stability of catalyst in catalytic pyrolysis of biomass |
| CN107469802A (en) * | 2017-06-15 | 2017-12-15 | 江苏大学 | It is a kind of to be used to produce catalyst of rich aromatic hydrocarbons bio-fuel-oil and preparation method thereof |
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| CN111218292A (en) * | 2020-01-15 | 2020-06-02 | 江苏大学 | Device and method for rapidly cooling system by using residual heat of biomass catalytic pyrolysis reactor |
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