CN104230615B - The method of biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone - Google Patents
The method of biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone Download PDFInfo
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- CN104230615B CN104230615B CN201410420358.XA CN201410420358A CN104230615B CN 104230615 B CN104230615 B CN 104230615B CN 201410420358 A CN201410420358 A CN 201410420358A CN 104230615 B CN104230615 B CN 104230615B
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Abstract
The present invention is the method from biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone, comprises the following steps: (1) raw material is biomass derivatives γ-valerolactone, is produced by the hydrogenation reaction of levulinic acid; (2) in zeolite molecular sieve, one or more transition metal are introduced, temperature of reaction 350 ~ 550 DEG C, with fixed bed or thermopnore for reactor, the catalyzer of preparation feedback; (3) under inertia or reducing atmosphere, reaction pressure is 0 – 10MPa, and raw material γ-valerolactone and catalyst exposure are reacted; (4) after pyrolysis gas condensation, collect the product liquid in condensation receptor, namely obtain aromatic hydrocarbons and the cyclopentenone product of benzene, toluene and dimethylbenzene; Advantage: adopt reproducible biomass derivatives γ-valerolactone to be raw material, reaction conditions is gentleer, catalyst preparing is simple, easy recycling use.
Description
Technical field
The present invention relates to a kind of method of biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone.
Background technology
Take biomass as raw material, development fuel alcohol, biofuel, biological Hydrogen Energy etc. biomass energy and bio-based chemical, will for solving foreseeable future source of energy crisis and crisis of resource, and safeguarding national security provides strong technical support with Economic development.Biomass uniquely can substitute the renewable resources that fossil resource conversion obtains liquid fuel and chemical, and in recent years, catalyzed conversion biomass-making receives people for the research of various platform chemicals and pays close attention to more and more widely.It is the same with levulinic acid (LA),
γ-valerolactone (GVL) is also considered to a kind of novel biomass based platform compound with widespread use potential, to its efficient catalytic transform and efficiency utilization significant.Levulinic acid can obtain from the acidic hydrolysis of lignocellulose biomass; And GVL can be obtained by hydrogenation of levulinic acid.
At present mainly aromatization of low carbon hydrocarbon is concentrated on to the research of industrial production aromatic hydrocarbons.Patent CN103664475A discloses a kind of method of aromatization of low carbon hydrocarbon, mainly solves the problem of the low-carbon (LC) aromatization poor catalyst stability existed in prior art.Be 400 ~ 700 DEG C by adopting in temperature of reaction, reversed stress is 0 ~ 2.0MPa, and air speed is 0.01 ~ 10 hour
-1condition under, make lower carbon number hydrocarbons raw material and catalyst exposure, reaction generates containing the aromatic product of benzene, toluene and dimethylbenzene.Good aromatization activity and stability can be obtained by the method.
Summary of the invention
What the present invention proposed is a kind of method of biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone, its object is to for deficiency of the prior art, catalyzer will be made to prepare aromatic hydrocarbons afterwards through simple modification, higher aromatic hydrocarbons and cyclopentenone productive rate can be reached.Reaction conditions is gentleer, and catalyst preparing is simple, easy recycling use.
Technical solution of the present invention: from the method for biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone, comprise the following steps:
(1) raw material is biomass derivatives γ-valerolactone, is produced by the hydrogenation reaction of levulinic acid;
(2) in zeolite molecular sieve, one or more transition metal are introduced, temperature of reaction 350 ~ 550 DEG C, with fixed bed or thermopnore for reactor, the catalyzer of preparation feedback;
(3) under inertia or reducing atmosphere, reaction pressure is 0-10MPa, and raw material γ-valerolactone and catalyst exposure are reacted;
(4) after pyrolysis gas condensation, collect the product liquid in condensation receptor, namely obtain aromatic hydrocarbons and the cyclopentenone product of benzene, toluene and dimethylbenzene;
(5) product is analyzed by GC and GC-MS.
Advantage of the present invention: compared with prior art, the present invention mainly adopts transition metal to carry out modification to ZSM-5.The Br nsted acid that metal ion replaces after being introduced into catalyzer on molecular sieve generates the metal ion with Lewis acid feature, can suppress partially polymerized reaction, delay carbon deposition rate, and improve the dehydrogenation of catalyzer.At optimum conditions, GVL product liquid aromatic hydrocarbons at 500 DEG C has 99.01%.M/ZSM-5(is as Zn) than HZSM-5(Si/Al=25) more effective to pyrolysis, show that the selectivity of Zn species to aromatic product of high dispersing has important promoter action.
Embodiment
From the method for biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone, comprise the following steps:
(1) raw material is biomass derivatives γ-valerolactone, is produced by the hydrogenation reaction of levulinic acid;
(2) in zeolite molecular sieve, one or more transition metal are introduced, temperature of reaction 350 ~ 550 DEG C, with fixed bed or thermopnore for reactor, the catalyzer of preparation feedback;
(3) under inertia or reducing atmosphere, reaction pressure is 0-10MPa, and raw material γ-valerolactone and catalyst exposure are reacted;
(4) after pyrolysis gas condensation, collect the product liquid in condensation receptor, namely obtain aromatic hydrocarbons and the cyclopentenone product of benzene, toluene and dimethylbenzene.
Described zeolite molecular sieve is micropore containing silicon, aluminium, phosphorus structure or mesopore molecular sieve, comprises ZSM-5, ZSM-11, Beta zeolite, y-type zeolite, mordenite, MCM-22, SAPO-34.
A kind of metal of described introducing, comprises Zn, Ga, Fe, Mo.
The mass ratio of the sial of the described zeolite molecular sieve containing sial is 0-100.
Described inert atmosphere is N
2, CO
2, the one in He, Ar, reducing atmosphere is H
2with the one in CO.
Specific experiment method and apparatus involved in following embodiment if no special instructions, is ordinary method or implements according to the condition of manufacturer's specification sheets suggestion.Involved reagent is commercially available.
Embodiment 1
The thermolysis of GVL aromizing: GVL is carried out in the tubular reactor be made up of silica glass, and experimental result is as shown in table 1.
The reaction result of table 1GVL under various catalyzer
Reaction conditions: temperature of reaction, 500 DEG C; Catalyzer, 0.5g; GVL, 2.5g(flow velocity is 2.4ml/h) and N
2, 30ml/min; Reaction times: 60min.
Carbon yield %
As can be seen from Table 1, Zn/ZSM-5 can obtain 99.53% aromatic hydrocarbon yield, and HZSM-5 can obtain the cyclopentenone yield of 10.83%.
Embodiment 2
GVL aromatization method is with embodiment 1, and difference is: select 1.3%Zn/ZSM-5 to be as catalyzer, and the impact on reaction yield under investigation different catalysts consumption, experimental result is as shown in table 2.
Table 2 catalyst levels is on the impact of GVL catalyzed conversion product
Reaction conditions: temperature of reaction, 500 DEG C; Catalyzer 1.3%Zn/ZSM-5; GVL, 4.6g(flow velocity is 2.4ml/h); N
2, 30ml/min; Reaction times: 100min.
Carbon yield %.
As shown in Table 2, when catalyzer usage quantity increases gradually, the transformation efficiency of product increases, and the yield of aromatic hydrocarbons increases, and the yield of cyclopentenone first reduces rear increase, and the per-cent of product liquid first increases rear minimizing, and gas per-cent reduces gradually.
Embodiment 3
GVL aromatization method is with embodiment 1, and difference is: select 1.3%Zn/ZSM-5 to be as catalyzer, investigate the yield of this product at the product of different temperature.Experimental result is as shown in table 3.
Table 3GVL catalyzed conversion at different temperatures
Reaction conditions: catalyzer 1.3%Zn/ZSM-5,0.5g; GVL, 2.5g(flow velocity is 2.4ml/h) and N
2, 30ml/min; Reaction times: 60min.
Carbon yield %.
As shown in Table 3, usually, at 450 DEG C, the yield of GVL transformation efficiency and aromatic hydrocarbon is lower, and the yield of aromatic hydrocarbon increases at relatively high temperatures.Usually, at 500 DEG C, the aromatic product of the highest yield is obtained.But at 550 DEG C, the yield of aromatic hydrocarbon starts to decline, because aromatic hydrocarbon at these temperatures also can carry out thermolysis, causes more gaseous product.The yield of Benzene and Toluene increases gradually, and the yield of ethylbenzene, p-Xylol first increases then to decline, and cyclopentenone yield first reduces and increases.Predominant gas product is CO and CO
2.
Embodiment 4
GVL aromatization method is with embodiment 1, and difference is: select 1.3%Zn/ZSM-5 to be as catalyzer, and GVL sends into heating zone by an automatic sampler and uses the nitrogen purging of different in flow rate.Investigate the products distribution rule under different nitrogen flow rate condition.Experimental result is as shown in table 4.
Table 4 nitrogen flow rate is on the impact of GVL catalyzed conversion
Reaction conditions: temperature of reaction, 500 DEG C; Catalyzer 1.3%Zn/ZSM-5,0.5g; GVL, 2.5g(flow velocity is 2.4ml/h); Reaction times: 60min.
Carbon yield %.
As shown in Table 4, under the minimum flow velocity (30ml/min) of nitrogen, liquid yield is 7.36%, and primary product is benzene.Under the flow velocity (50ml/min) of nitrogen, the highest 18.49%. of being of liquid yield increases along with nitrogen flow rate, and the yield of cyclopentenone product also increases gradually, and the yield of aromatic product then reduces gradually.
Embodiment 5
GVL aromatization method is with embodiment 1, and difference is: select 1.3%Zn/ZSM-5 to be as catalyzer, and investigate the impact of reaction times on reaction, experimental result is as shown in table 5.
The catalyzed conversion of table 5GVL differential responses time
As shown in Table 5, along with the increase in reaction times, product yield and aromatics yield first increase rear minimizing, and liquid percentage increases gradually, and gas per-cent now increases rear minimizing.In product, the per-cent of aromatic hydrocarbon first increases rear minimizing, and the per-cent of cyclopentenone first reduces rear increase.The highest aromatic hydrocarbon yield 99.01% and peak rate of conversion 99.66% is reached in 60min reaction.
Claims (2)
1., from the method for biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone, it is characterized in that, the method comprises the following steps:
(1) raw material is biomass derivatives γ-valerolactone, is produced by the hydrogenation reaction of levulinic acid;
(2) in zeolite molecular sieve, one or more transition metal are introduced, temperature of reaction 350 ~ 550 DEG C, with fixed bed or thermopnore for reactor, catalyzer 1.3%Zn/ZSM-5,2.6%ZnZSM-5 of preparation feedback;
(3) under inertia or reducing atmosphere, reaction pressure is 0-10MPa, and raw material γ-valerolactone and catalyst exposure are reacted;
(4) after pyrolysis gas condensation, collect the product liquid in condensation receptor, namely obtain aromatic hydrocarbons and the cyclopentenone product of benzene, toluene and dimethylbenzene.
2. the method from biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone according to claim 1, it is characterized in that, described inert atmosphere is N
2, CO
2, a kind of in He, Ar, reducing atmosphere is H
2with a kind of in CO.
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| CN106256811B (en) * | 2015-06-19 | 2019-01-25 | 中国石油化工股份有限公司 | The composition that the method and this method for synthesizing aromatic hydrocarbons obtain |
| CN106316768B (en) * | 2015-06-19 | 2019-05-14 | 中国石油化工股份有限公司 | The highly selective method for preparing dimethylbenzene |
| CN106316767B (en) * | 2015-06-19 | 2019-06-11 | 中国石油化工股份有限公司 | Lactone compound aromatization method |
| CN106316763B (en) * | 2015-06-19 | 2019-02-19 | 中国石油化工股份有限公司 | The method of lactone compound aromatisation production aromatic hydrocarbons |
| CN106316743B (en) * | 2015-06-19 | 2019-05-14 | 中国石油化工股份有限公司 | The method of lactone compound production aromatic hydrocarbons |
| CN106256809B (en) * | 2015-06-19 | 2019-04-12 | 中国石油化工股份有限公司 | The composition that the method and this method of biomass production aromatic hydrocarbons obtain |
| CN106256808B (en) * | 2015-06-19 | 2019-07-09 | 中国石油化工股份有限公司 | The method of lactone compound aromatisation |
| ES2880326T3 (en) * | 2015-06-19 | 2021-11-24 | China Petroleum & Chem Corp | Methods for making aromatic hydrocarbon, paraxylene, and terephthalic acid |
| CN106336339B (en) * | 2015-07-17 | 2019-03-08 | 中国石油化工股份有限公司 | A method of producing aromatic hydrocarbons |
| CN105032475B (en) * | 2015-09-09 | 2017-09-15 | 山东省科学院能源研究所 | For the molecular sieve catalyst of modified ZSM-5 5 of biomass pyrolytic light aromatics and application |
| CN107586238B (en) * | 2016-07-08 | 2020-03-27 | 中国石油化工股份有限公司 | Method for aromatizing lactone compounds |
| CN107586243B (en) * | 2016-07-08 | 2020-03-27 | 中国石油化工股份有限公司 | Process for producing aromatic hydrocarbon |
| CN107586241B (en) * | 2016-07-08 | 2020-04-17 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon from lactone compound |
| CN107586244B (en) * | 2016-07-08 | 2020-03-27 | 中国石油化工股份有限公司 | Process for producing aromatic hydrocarbon |
| CN107721790B (en) * | 2016-08-10 | 2020-04-17 | 中国石油化工股份有限公司 | Process for producing aromatic hydrocarbon |
| CN107721792B (en) * | 2016-08-10 | 2020-04-17 | 中国石油化工股份有限公司 | Process for producing aromatic hydrocarbon |
| CN107721789B (en) * | 2016-08-10 | 2021-05-11 | 中国石油化工股份有限公司 | Method for aromatizing lactone compounds |
| CN107083254B (en) * | 2017-06-27 | 2018-11-06 | 东莞理工学院 | A method of utilizing gamma-valerolactone liquid fuel was prepared |
| CN110882716B (en) * | 2019-10-16 | 2022-06-17 | 天津大学 | Preparation method for converting biomass derived furfural into gamma-valerolactone by solid acid catalyst one-pot multi-step catalysis |
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