CN103342688A - Method for preparing furfural by one-step selective catalytic cracking - Google Patents
Method for preparing furfural by one-step selective catalytic cracking Download PDFInfo
- Publication number
- CN103342688A CN103342688A CN2013102901243A CN201310290124A CN103342688A CN 103342688 A CN103342688 A CN 103342688A CN 2013102901243 A CN2013102901243 A CN 2013102901243A CN 201310290124 A CN201310290124 A CN 201310290124A CN 103342688 A CN103342688 A CN 103342688A
- Authority
- CN
- China
- Prior art keywords
- furfural
- bagasse
- liquid
- catalyzer
- phase product
- 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.)
- Granted
Links
Images
Landscapes
- Furan Compounds (AREA)
Abstract
The invention provides a method for preparing furfural by one-step selective catalytic cracking. The method comprises the following steps of: reacting at 500 DEG C-550 DEG C in a nitrogen gas atmosphere by using bagasse as the material, using an HZSM-5 molecular sieve with ZnCl2 loading capacity of 10wt%-30wt% as the catalyst; and collecting the reaction product after cooling the reaction product by icy-water bath to obtain a liquid-phase production containing furfural. The method for preparing the furfural by one-step selective catalytic cracking has the beneficial effects that firstly, a B acid system is not adopted for hydrolyzing, so that the device corrosion is greatly lowered, the device investment is reduced and the operation is simpler; secondly, compared with documentary data, high furfural yield is obtained and the material utilization rate is higher; and thirdly, in addition to the main product furfural, various chemical base materials or by-products with a high additional value are obtained, so that the method disclosed by the invention has a better market application value.
Description
(1) technical field
The present invention relates to the method that a kind of single stage method selectivity catalytic pyrolysis prepares furfural.
(2) background technology
Furfural has purposes widely as the important chemical intermediate: 1. be to produce the furfuryl alcohol raw material, furfuryl alcohol is the main production raw material of furane resin; 2. be the raw material of the multiple medicine of preparation and Industrial products; 3. can prepare suceinic aldehyde, the latter is for producing the atropinic raw material of medicine; 4. as solvent; 5. can replace formaldehyde and phenol condensation, make resol etc.Biomass are the energy as an alternative, along with the minimizing day by day of fossil energy, will bring into play unrivaled effect.The main composition of biomass is Mierocrystalline cellulose, hemicellulose and xylogen.Because furfural is a kind of hardware and software platform compound of biomass, therefore can obtain by Mierocrystalline cellulose and hemicellulose dehydration reaction.The main method of industrial preparation furfural is biomass and dilute sulphuric acid altogether behind the thermal hydrolysis, gets through stripping, condensation, distillation, vacuum refining again.
But the aforesaid method the first step is hot altogether with acid, can increase the corrodibility of equipment like this, has improved facility investment.At present the furfural price is still higher, and this is by higher production cost and less industrial scale decision.Known, the quick cracking of biomass can obtain containing the liquid-phase product of furans etc., but contained system is very complicated in this liquid phase (nearly hundreds of material), and the content of furfural very low (＜5%).How biomass resource effectively is converted into the key that the single liquid-phase product of content becomes research.
(3) summary of the invention
The object of the invention provides a kind of method of utilizing biomass to prepare furfural, and this method is simple to operate, and facility investment is little, does not see relevant report up to now.
The technical solution used in the present invention is:
A kind of single stage method selectivity catalytic pyrolysis prepares the method for furfural, and described method is to be raw material with bagasse, with ZnCl
2Charge capacity 10～30wt%(is in the Zn quality) the HZSM-5 molecular sieve be catalyzer, in nitrogen atmosphere, under 500～550 ℃, react, reaction product is collected by ice-water bath cooling back, obtains containing the liquid-phase product of furfural.Described bagasse is that sugar refinery is that raw material presses the last bagasse in sugar back with the sugarcane.
The present invention adopts the one-step catalytic cracking directly to obtain being rich in the liquid product of furfural, improved the selectivity of furfural greatly, and method is simple to operate, and is lower to the requirement of equipment.In addition, the present invention can also obtain the chemicals of other several basic raw material for chemical industry or high added value; The heavy constituent of liquid phase can be used as oil fuel; Solid is coke, can be used as the substitute of coal.
Preferably, described bagasse is 1:0.1～10 with the ratio of catalyst quality.
Preferably, described method is as follows:
(1) bagasse is made 100～200 purpose powder at 80～110 ℃ of down dry 10～12h;
(2) be that the ratio of 1:0.5～8 takes by weighing bagasse and catalyzer according to the ratio of bagasse and catalyst quality, mix;
(3) step (2) gained mixture is packed into the silica tube middle part, silica tube one end connects nitrogen inlet, and the other end connects condensing works, and condensing works is provided with waste gas outlet and liquid-phase product outlet, is built into packed bed reactor;
(4) feed nitrogen replacement and go out air in the reactor, continue to feed nitrogen, be warming up to 500～550 ℃ rapidly with the temperature rise rate of 50～80 ℃/min, and stop 5～10min;
(5) reaction is closed nitrogen after finishing, and reactor naturally cools to room temperature, collects the liquid-phase product (the liquid-phase product yield generally is fixed as about 50%) that obtains containing furfural in the liquid-phase product exit.
Preferably, described catalyzer prepares as follows: the ZnCl that takes by weighing in proportion
2With the HZSM-5 molecular sieve, be dissolved in 15～20ml deionized water, stir 5～10min, treat ZnCl
2Fully after the dissolving, airtight leave standstill 12～24h after, place the down dry 4～6h of 80～90 ℃ of air dry ovens, again in 100～110 ℃ of down dry 10～12h, obtain the ZnCl of charge capacity 10～30wt%
2/ HZSM-5 catalyzer.
Beneficial effect of the present invention is mainly reflected in: (1) the present invention does not adopt the B acid system to be hydrolyzed, and has greatly reduced equipment corrosion, has reduced facility investment, operates simpler; (2) the present invention is than data in literature, furfural content height in the liquid-phase product, and utilization ratio of raw materials is also higher; (3) the present invention is except the primary product furfural, and other has the by product of multiple chemical industry basic raw material or high added value, makes method of the present invention have better market using value.
(4) description of drawings
Fig. 1 is apparatus of the present invention sketch.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Preparation of Catalyst:
(1) takes by weighing 0.4g ZnCl
2With 1g HZSM-5 molecular sieve, be dissolved in the 20ml deionized water;
(2) the described sample of step (1) is stirred 10min, treat ZnCl
2After dissolving fully, the airtight 24h that leaves standstill;
(3) the described sample of step (2) is placed 80 ℃ of following dry 6h of air dry oven, again in 110 ℃ of following dry 12h, namely get ZnCl afterwards
2/ HZSM-5 catalyzer, standby.
The preparation of furfural:
(1) with bagasse dry 12h under 100～110 ℃; The biomass material that the present invention chooses is that the last bagasse in sugar back is pressed in sugar refinery, Quanzhou, Fujian.
(2) on crusher with the bagasse fragmentation into about 150 purpose powder;
(3) take by weighing catalyzer and bagasse according to part by weight, then the two is mixed;
(4) mixture is packed into the silica tube middle part that internal diameter is 20mm, puts up packed bed reactor, as shown in Figure 1;
(5) before the experiment beginning, logical nitrogen carries out air tight test, and nitrogen flow is 40ml/min, and logical nitrogen 3～5min is continued in the good back of resistance to air loss, discharges the air of reaction tubes inside;
(6) temperature rise rate with 50～80 ℃/min is warming up to 500～550 ℃ rapidly with reaction tubes, and stops 5～10min, and liquid-phase product is collected by ice-water bath cooling back, through its composition of gas-chromatography off-line analysis;
(7) after experiment finishes, lower the temperature, close nitrogen, and carry out follow-up calculation of correlation.
Embodiment 1:
Take by weighing 6g catalyzer and 3g bagasse, be packed into reaction tubes after, at first logical nitrogen carries out air tight test.After resistance to air loss is good, wait about 3min, to carry out quick cracking experiment under the temperature rise rate of 50 ℃/min, reacting whole temperature is 500 ℃ again, and stops 5min down at 500 ℃.Close nitrogen then, reaction tubes naturally cools to room temperature.Obtain the about 1.5g of liquid-phase product by ice-water bath cooling collection, through its composition of gas chromatographic analysis, wherein furfural content is 15.9wt%.
Embodiment 2:
Take by weighing 5g catalyzer and 5g bagasse, be packed into reaction tubes after, at first logical nitrogen carries out air tight test.After resistance to air loss is good, wait about 3min, to carry out quick cracking experiment under the temperature rise rate of 50 ℃/min, reacting whole temperature is 500 ℃ again, and stops 5min down at 500 ℃.Close nitrogen then, reaction tubes naturally cools to room temperature.Obtain the about 2.5g of liquid-phase product by ice-water bath cooling collection, through its composition of gas chromatographic analysis, wherein furfural content is 27.5wt%.
Embodiment 3:
Take by weighing 1g catalyzer and 3g bagasse, be packed into reaction tubes after, at first logical nitrogen carries out air tight test.After resistance to air loss is good, wait about 3min, to carry out quick cracking experiment under the temperature rise rate of 50 ℃/min, reacting whole temperature is 500 ℃ again, and stops 5min down at 500 ℃.Close nitrogen then, reaction tubes naturally cools to room temperature.Obtain the about 1.5g of liquid-phase product by ice-water bath cooling collection, through its composition of gas chromatographic analysis, wherein furfural content is 27.5wt%.
Embodiment 4:
Take by weighing 1g catalyzer and 4g bagasse, be packed into reaction tubes after, at first logical nitrogen carries out air tight test.After resistance to air loss is good, wait about 3min, to carry out quick cracking experiment under the temperature rise rate of 50 ℃/min, reacting whole temperature is 500 ℃ again, and stops 5min down at 500 ℃.Close nitrogen then, reaction tubes naturally cools to room temperature.Obtain the about 2.0g of liquid-phase product by ice-water bath cooling collection, through its composition of gas chromatographic analysis, wherein furfural content is 24.5wt%.
Embodiment 5:
Take by weighing 1g catalyzer and 5g bagasse, be packed into reaction tubes after, at first logical nitrogen carries out air tight test.After resistance to air loss is good, wait about 3min, to carry out quick cracking experiment under the temperature rise rate of 50 ℃/min, reacting whole temperature is 500 ℃ again, and stops 5min down at 500 ℃.Close nitrogen then, reaction tubes naturally cools to room temperature.Obtain the about 2.5g of liquid-phase product by ice-water bath cooling collection, through its composition of gas chromatographic analysis, wherein furfural content is 29.2wt%.
Embodiment 6:
Take by weighing 1g catalyzer and 6g bagasse, be packed into reaction tubes after, at first logical nitrogen carries out air tight test.After resistance to air loss is good, wait about 3min, to carry out quick cracking experiment under the temperature rise rate of 50 ℃/min, reacting whole temperature is 500 ℃ again, and stops 5min down at 500 ℃.Close nitrogen then, reaction tubes naturally cools to room temperature.Obtain the about 3.0g of liquid-phase product by ice-water bath cooling collection, through its composition of gas chromatographic analysis, wherein furfural content is 22.2wt%.
Embodiment 7:
Take by weighing 1g catalyzer and 7g bagasse, be packed into reaction tubes after, at first logical nitrogen carries out air tight test.After resistance to air loss is good, wait about 3min, to carry out quick cracking experiment under the temperature rise rate of 50 ℃/min, reacting whole temperature is 500 ℃ again, and stops 5min down at 500 ℃.Close nitrogen then, reaction tubes naturally cools to room temperature.Obtain the about 3.5g of liquid-phase product by ice-water bath cooling collection, through its composition of gas chromatographic analysis, wherein furfural content is 20.4wt%.
Claims (4)
1. a single stage method selectivity catalytic pyrolysis prepares the method for furfural, it is characterized in that described method is is raw material with bagasse, with ZnCl
2The HZSM-5 molecular sieve of charge capacity 10～30wt% is catalyzer, in nitrogen atmosphere, reacts under 500～550 ℃, and reaction product is collected by ice-water bath cooling back, obtains containing the liquid-phase product of furfural.
2. the method for claim 1 is characterized in that described bagasse and the ratio of catalyst quality are 1:0.1～10.
3. the method for claim 1 is characterized in that described method is as follows:
(1) bagasse is made 100～200 purpose powder at 80～110 ℃ of down dry 10～12h;
(2) be that the ratio of 1:0.5～8 takes by weighing bagasse and catalyzer according to the ratio of bagasse and catalyst quality, mix;
(3) step (2) gained mixture is packed into the silica tube middle part, silica tube one end connects nitrogen inlet, and the other end connects condensing works, and condensing works is provided with waste gas outlet and liquid-phase product outlet, is built into packed bed reactor;
(4) feed nitrogen replacement and go out air in the reactor, continue to feed nitrogen, be warming up to 500～550 ℃ rapidly with the temperature rise rate of 50～80 ℃/min, and stop 5～10min;
(5) reaction is closed nitrogen after finishing, and reactor naturally cools to room temperature, collects the liquid-phase product that obtains containing furfural in the liquid-phase product exit.
4. as the described method of one of claim 1～3, it is characterized in that described catalyzer prepares as follows: the ZnCl that takes by weighing in proportion
2With the HZSM-5 molecular sieve, be dissolved in 15～20ml deionized water, stir 5～10min, treat ZnCl
2Fully after the dissolving, airtight leave standstill 12～24h after, place the down dry 4～6h of 80～90 ℃ of air dry ovens, again in 100～110 ℃ of down dry 10～12h, obtain the ZnCl of charge capacity 10～30wt%
2/ HZSM-5 catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310290124.3A CN103342688B (en) | 2013-07-10 | 2013-07-10 | Method for preparing furfural by one-step selective catalytic cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310290124.3A CN103342688B (en) | 2013-07-10 | 2013-07-10 | Method for preparing furfural by one-step selective catalytic cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103342688A true CN103342688A (en) | 2013-10-09 |
| CN103342688B CN103342688B (en) | 2015-06-03 |
Family
ID=49277526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310290124.3A Active CN103342688B (en) | 2013-07-10 | 2013-07-10 | Method for preparing furfural by one-step selective catalytic cracking |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103342688B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906671A (en) * | 2016-04-27 | 2016-08-31 | 浙江工业大学 | Method for preparing high-additional-value chemicals by different pH acid-alkali pretreatment of biomass and one-step cracking |
| CN115108883A (en) * | 2021-03-17 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of benzyl chloride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352689A (en) * | 2007-07-25 | 2009-01-28 | 中国科学院大连化学物理研究所 | Modification method of molecular sieve catalyst for hexene aromatization reaction |
| CN101717383A (en) * | 2009-11-20 | 2010-06-02 | 中国科学技术大学 | Method for preparing furfural and special reaction equipment thereof |
| CN101948452A (en) * | 2010-08-13 | 2011-01-19 | 中国科学院山西煤炭化学研究所 | Method for producing hydroxymethylfurfural by cellulose-containing biomass |
| CN102575301A (en) * | 2010-01-27 | 2012-07-11 | 科学与工业研究委员会 | A one pot and single step hydrolytic process for the conversion of lignocellulose into value added chemicals |
-
2013
- 2013-07-10 CN CN201310290124.3A patent/CN103342688B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101352689A (en) * | 2007-07-25 | 2009-01-28 | 中国科学院大连化学物理研究所 | Modification method of molecular sieve catalyst for hexene aromatization reaction |
| CN101717383A (en) * | 2009-11-20 | 2010-06-02 | 中国科学技术大学 | Method for preparing furfural and special reaction equipment thereof |
| CN102575301A (en) * | 2010-01-27 | 2012-07-11 | 科学与工业研究委员会 | A one pot and single step hydrolytic process for the conversion of lignocellulose into value added chemicals |
| CN101948452A (en) * | 2010-08-13 | 2011-01-19 | 中国科学院山西煤炭化学研究所 | Method for producing hydroxymethylfurfural by cellulose-containing biomass |
Non-Patent Citations (1)
| Title |
|---|
| WEI-LIANG FANCHIANG ET. AL.: "Catalytic fast pyrolysis of furfural over H-ZSM-5 and Zn/H-ZSM-5 catalysts", 《APPLIED CATALYSIS A: GENERAL》, vol. 419420, 25 January 2012 (2012-01-25), pages 102 - 110 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906671A (en) * | 2016-04-27 | 2016-08-31 | 浙江工业大学 | Method for preparing high-additional-value chemicals by different pH acid-alkali pretreatment of biomass and one-step cracking |
| CN115108883A (en) * | 2021-03-17 | 2022-09-27 | 山东泰和水处理科技股份有限公司 | Preparation method of benzyl chloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103342688B (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Efficient production of furfural from xylose and wheat straw by bifunctional chromium phosphate catalyst in biphasic systems | |
| Yang et al. | The optimization of formic acid hydrolysis of xylose in furfural production | |
| Aho et al. | Catalytic pyrolysis of biomass in a fluidized bed reactor: influence of the acidity of H-beta zeolite | |
| Liu et al. | Hydrothermal liquefaction of cypress: effects of reaction conditions on 5-lump distribution and composition | |
| Vásquez et al. | Gas-phase catalytic transfer hydrogenation of methyl levulinate with ethanol over ZrO2 | |
| CN103447060B (en) | Catalyst and treatment method for upgrading tar by using catalyst | |
| Huang et al. | Homogeneous Catalytic Hydrogenation of Bio‐Oil and Related Model Aldehydes with RuCl2 (PPh3) 3 | |
| Hu et al. | Investigation of deactivation mechanisms of a solid acid catalyst during esterification of the bio-oils from mallee biomass | |
| CN101579637B (en) | Method for preparing molecular sieve solid acid catalyst used for preparing ethylene by ethanol dehydration | |
| Shao et al. | Evolution of coke in the catalytic conversion of biomass-derivates by combined in-situ DRIFTS and ex-situ approach: Effect of functional structure | |
| Feng et al. | Synchronous conversion of lignocellulosic polysaccharides to levulinic acid with synergic bifunctional catalysts in a biphasic cosolvent system | |
| Wang et al. | Role of pretreatment with acid and base on the distribution of the products obtained via lignocellulosic biomass pyrolysis | |
| David et al. | The use of p-sulfonic acid calix [4] arene as organocatalyst for pretreatment of sugarcane bagasse increased the production of levoglucosan | |
| Zhao et al. | Intensified levulinic acid/ester production from cassava by one-pot cascade prehydrolysis and delignification | |
| Huang et al. | Two-step conversion of cellulose to levoglucosenone using updraft fixed bed pyrolyzer and catalytic reformer | |
| Tian et al. | Sulfated attapulgite for catalyzing the conversion of furfuryl alcohol to ethyl levulinate: Impacts of sulfonation on structural transformation and evolution of acidic sites on the catalyst | |
| Cueto et al. | Aldol condensation of biomass-derived levulinic acid and furfural over acid zeolites | |
| CN105348228B (en) | Method and device for industrially and continuously producing tetrahydrofurfuryl alcohol diethyl ether | |
| Luo et al. | Two-step hydrothermal conversion of Pubescens to obtain furans and phenol compounds separately | |
| CN104138753B (en) | A kind of tinbase montmorillonite catalyst is the application of furfural with preparation method and catalysis xylose thereof | |
| CN106631720A (en) | Method for directly synthesizing polyoxymethylene dimethyl ether by taking dilute formaldehyde and methylal as raw materials | |
| Saragai et al. | Catalytic deep eutectic solvent for levoglucosenone production by pyrolysis of cellulose | |
| CN105503784B (en) | A kind of method and device for industrializing ultrasonic response production tetrahydrofurfuryl alcohol ether | |
| CN103342688B (en) | Method for preparing furfural by one-step selective catalytic cracking | |
| CN102260229A (en) | Method for preparing 5-hydroxymethylfurfural and 5-alkoxymethylfurfural |
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 |