CN101486695B - Solid acid catalysis and supercritical extraction coupled furfural preparation method and apparatus - Google Patents
Solid acid catalysis and supercritical extraction coupled furfural preparation method and apparatus Download PDFInfo
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- CN101486695B CN101486695B CN2009100780356A CN200910078035A CN101486695B CN 101486695 B CN101486695 B CN 101486695B CN 2009100780356 A CN2009100780356 A CN 2009100780356A CN 200910078035 A CN200910078035 A CN 200910078035A CN 101486695 B CN101486695 B CN 101486695B
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000011973 solid acid Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000007171 acid catalysis Methods 0.000 title claims abstract description 18
- 238000000194 supercritical-fluid extraction Methods 0.000 title claims abstract description 15
- 238000000605 extraction Methods 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012530 fluid Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- 230000007797 corrosion Effects 0.000 claims abstract description 7
- 238000005260 corrosion Methods 0.000 claims abstract description 7
- 238000004939 coking Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 230000002779 inactivation Effects 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims abstract description 5
- 239000003930 superacid Substances 0.000 claims abstract description 4
- 239000000945 filler Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229960003487 xylose Drugs 0.000 claims description 32
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 claims description 28
- 238000012856 packing Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 12
- 208000036822 Small cell carcinoma of the ovary Diseases 0.000 claims description 11
- 201000005292 ovarian small cell carcinoma Diseases 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000006210 cyclodehydration reaction Methods 0.000 claims description 8
- 230000002411 adverse Effects 0.000 claims description 7
- 230000007812 deficiency Effects 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 230000004087 circulation Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000001934 delay Effects 0.000 claims description 4
- 239000012013 faujasite Substances 0.000 claims description 4
- 231100000252 nontoxic Toxicity 0.000 claims description 4
- 230000003000 nontoxic effect Effects 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000009992 mercerising Methods 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000012071 phase Substances 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 2
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 150000002972 pentoses Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 238000001311 chemical methods and process Methods 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- -1 hydrogenation Chemical compound 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Furan Compounds (AREA)
Abstract
The present invention discloses a solid-acid catalysis and supercritical extraction coupling preparation method of furfural and a device thereof, pertaining to the technical field of the preparation of biobased chemicals. The method adopts solid acid as a catalyst, such as superacid or molecular sieve, and uses supercritical CO2 (SCCO2) for on-line extraction and separation of products. In the whole preparation process of the furfural, raw material aqueous phase and supercritical fluid phase successively enter a tower for realizing the countercurrent contact multiple-extraction which is carried out in a catalysis filling extracting tower. In the whole process, the solid acid is easily separated from the product, can be recycled and has little corrosion to equipment. Discharge amount of the three wastes is small and operation is convenient and safe. Furthermore, the SCCO2 has low cost, no toxicity, good diffusivity performance and easily controllable solubility, and such a defect as mass transmission efficiency reduction in a heterogeneous catalytic reaction after the use of the solid acid can be overcome when the SCCO2 is used for on-line extraction of the furfural, so as to immediately remove coking precursors from a catalyst pore passage, thereby deferring the inactivation of the catalyst, realizing green and clean production technology and wide application prospect.
Description
Technical field
The invention belongs to the preparing technical field of bio-based chemical, particularly by a kind of solid acid catalysis of wood sugar catalytic dehydration cyclisation and supercritical extraction coupled furfural preparation and device.
Background technology
Fossil resource reserves such as oil are limited, non-renewable, and crude oil price rises violently in recent years, increasing environmental pollution makes people be badly in need of seeking new alternate resources.That biomass have is renewable, do not produce clean greenhouse gas emission, use advantages such as pollution-free, therefore be with biomass the alternative materials of fossil resource prepare chemical, macromolecular material and bioenergy fuel be prepared into the research focus.The preparation of bioenergy fuel is general makes the hardware and software platform compound with biomass material earlier, and then produces other numerous chemical by these hardware and software platform compounds, and furfural promptly is a kind of so crucial biomass hardware and software platform compound.
Furfural formal name used at school furaldehyde is important heterogeneous ring compound and organic chemical industry's intermediate.Its chemical property is active, can be by numerous derivatives such as prepared in reaction furfuryl alcohol, furans, tetrahydrofuran (THF), cis-butenedioic anhydride, furancarboxylic acid such as hydrogenation, oxidation and condensations.Furfural and derivative thereof are widely used in industries such as petroleum industry, chemical industry, medicine, food and synthetic rubber, synthetic resins.
The main raw material of producing furfural is the corn cob that contains piperylene (hemicellulose), maize straw, bagasse, wheat straw, rice husk, Pericarppium arachidis hypogaeae, cotton seed hulls etc.These are biomass waste mostly, so the production of furfural helps the total composition utilization of biomass.Furfural is through pentosan hydralysis system pentose and two steps of pentose cyclodehydration
Poly-pentose pentose furfural
Make.Independently carrying out the two-step approach of two steps Mierocrystalline cellulose and the hemicellulose in can separate raw materials separately and be used respectively in two reactors, is the inexorable trend of future development.
To obtain pentose technology very ripe for the first step pentosan hydralysis in the two-step approach, and research emphasis is in second step, i.e. pentose cyclodehydration system furfural, and the pentose here mainly is a wood sugar, below promptly is raw material with the wood sugar.The reaction of wood sugar cyclodehydration is an acid catalyzed reaction, shortcomings such as at present the industrial liquid strong acid such as sulfuric acid, hydrochloric acid that generally use are made catalyzer, and there is disposable consumption in these catalyzer, consumption is big and the use that can not repeat to regenerate, equipment corrosion and seriously polluted and postprocessing working procedures be many.In the furfural production process, in order to improve yield, suppress the furfural generation side reaction of generation, adopt operations such as stripping, solvent extraction that the furfural that generates is in time shifted out from system usually.But the vaporizing extract process steam consumption is big, the energy consumption height, and thermolysis also can take place in furfural under the high temperature; The solvent extraction rule needs toxic in a large number, volatile organic solvent circulations such as toluene, and environment is polluted.
China is the largest production state and the export State of furfural and converted products thereof at present.But conventional production methods makes China's furfural industry cause severe contamination to environment, and 1 ton of furfural of every production just produces about 20 tons of acid-bearing wastewater.Therefore, the theory of cleaner production is introduced in the production technique of furfural, employing can be used in the friendly catalyzer of novel environmental of wood sugar cyclodehydration, the online extraction process of furfural of development environmental protection, by modern Green Chemical Technology contaminated solution problem from the source, most important to the sound development of this representative biomass chemical industry of furfural.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of solid acid catalysis and supercritical extraction coupled furfural preparation and device at the deficiency of traditional technology.It is characterized in that described solid acid catalysis and supercritical extraction coupled furfural preparation are to be catalyzer with solid acids such as super acids or molecular sieves, adopt supercritical co (SCCO
2. ') the on-line extraction separated product, whole furfural preparation process is carried out in the catalytic filler extraction tower, in whole process solid acid easily and product separation, can regeneration, equipment corrosion is little, three waste discharge is few, easy and safe to operate, and SCCO
2Cheap, nontoxic, diffusion is good, the solubility property easy-regulating, SCCO
2The on-line extraction furfural can also overcome and uses the deficiency that mass-transfer efficiency descends in the heterogeneous catalytic reaction behind the solid acid, removes the coking presoma that produces in the catalyzer duct immediately, thereby delays the inactivation of catalyzer.
Concrete steps are as follows:
1) solid acid catalyst places the filler extraction reaction tower as filler after the filler type that changes into is handled;
2) carbonic acid gas CO
2After being cooled to liquid phase, water cooler is stored in liquid CO
2In the storage tank;
3) liquid CO
2Become supercutical fluid after compressed, the preheater preheating, enter from the bottom to top in the filler extraction reaction tower with the flow of 30ml/min;
4) the wood sugar aqueous feed solution is from top to bottom squeezed in the filler extraction reaction tower by the high-pressure material pump after the preheater preheating again;
5) in packed extraction tower, the cyclodehydration reaction takes place and generates the fluid reactant furfural in wood sugar under the effect of described packing type catalyst;
6) the fluid reactant furfural carries out the adverse current Continuous Contact with the supercutical fluid that advances tower, and furfural is dissolved in supercritical CO
2Derive from filler extraction reaction tower top in the fluid and thereupon, enter in the knockout tower;
7) in knockout tower, regulate supercritical CO
2Pressure makes it to become normal pressure CO
2Gas, circulation is cooled to CO
2Liquid enters liquid CO
2Storage tank is because CO
2Loss, and in time replenish; Be dissolved in supercritical CO
2In furfural enter the product jar after in knockout tower, separating out separation.
Described in knockout tower supercritical CO
2Pressure should keep CO in the tower
2Pressure is 7～9MPa.
The mass percent concentration of the described feeding wood sugar aqueous solution is 3～100%.
Described catalyzer is that filler changes into the SO that type is handled
4 2-/ TiO
2, SO
4 2-/ ZrO
2, faujasite molecular sieve or mercerising molecular sieve.
Described wood sugar aqueous feed solution is 160～200 ℃ through the preheating temperature of preheater preheating, the insulation of tower external jacket.
The device of described solid acid catalysis and supercritical extraction coupled preparation furfural is characterized in that, CO
2Input tube 9, water cooler 1, liquid CO
2Storage tank 2, CO
2Compression pump 3 and CO
2Be connected filler extraction reaction tower 5 bottoms after preheater 4 series connection, wood sugar aqueous solution preheater 8 is connected with high-pressure material pump 6, high-pressure material pump 6 is connected to filler extraction reaction tower 5 tops, filler extraction reaction tower 5 top delivery ports are connected to knockout tower 7 middle parts, knockout tower 7 bottoms output furfural, the CO on knockout tower 7 tops
2Delivery line 10 and CO
2Input tube 9 connects.
The present invention compared with prior art has the following advantages and beneficial effect:
1. replacing traditional liquid acid with solid acid is catalyzer, product and catalyzer separate easily, and recyclable repeated use, environmental pollution and equipment corrosion greatly reduce.
2. compare with conventional organic solvents, to be that extraction solvent has nontoxic, do not burn free of contamination advantage with supercritical co.In addition, can realize separating of solvent and solute by decompression, technology is simple, easy to operate, the process adjustment is flexible.
3. supercutical fluid on-line extraction furfural can also be removed the coking presoma that produces in the catalyzer duct immediately, thereby delays the inactivation of catalyzer, alleviated well in the solid acid catalysis reaction the weak slightly and catalyzer of mass transfer effect may coking and deactivation etc. deficiency.
4. the used filler extraction reaction tower of the present invention can realize that the raw material water goes into tower mutually continuously with supercutical fluid, and the two phase countercurrent flow MULTI CONTACT is reacted and extracted, thereby efficient improves greatly.New device has overcome most SCCO
2The limited deficiency of intermittent type single-stage extraction throughput of extraction process has clear superiority.
5. the present invention makes packing type with solid acid catalyst and plays the difunctional of catalyzer and filler, takes into account reaction effect and mass transfer effect, has overcome the deficiency of traditional catalyst packing or binding method, thereby significantly improves the efficient of reaction, extraction technology.
The present invention is incorporated into solid acid catalysis and these two important green methods of supercritical carbon dioxide extraction in the process of wood sugar cyclodehydration system furfural simultaneously in a word, and the contact carrying out of design new catalytic packed extraction tower continuous countercurrent catalytic process and extraction process, the solid acid catalyst filler is changed into type, play the difunctional of catalyzer and filler, realized the greenization and the high efficiency continuously of whole process.
Description of drawings
Fig. 1 is the device and the process flow diagram of solid acid catalysis and supercritical extraction coupled preparation furfural.
Embodiment
The invention provides a kind of solid acid catalysis and supercritical extraction coupled furfural preparation and device.Described solid acid catalysis and supercritical extraction coupled furfural preparation are to be catalyzer with solid acids such as super acids or molecular sieves, adopt supercritical co (SCCO
2) the on-line extraction separated product, whole furfural preparation process is carried out in the catalytic filler extraction tower, in whole process solid acid easily and product separation, can regeneration, equipment corrosion is little, three waste discharge is few, easy and safe to operate, and SCCO
2Cheap, nontoxic, diffusion is good, the solubility property easy-regulating, SCCO
2The on-line extraction furfural can also overcome and uses the deficiency that mass-transfer efficiency descends in the heterogeneous catalytic reaction behind the solid acid, removes the coking presoma that produces in the catalyzer duct immediately, thereby delays the inactivation of catalyzer.Below in conjunction with drawings and Examples the present invention is illustrated.
Figure 1 shows that the device and the process flow diagram of solid acid catalysis and supercritical extraction coupled preparation furfural.Shown in the figure, concrete technical process is: the solid acid catalyst filler type that changes into is handled the back and is placed filler extraction reaction tower 5 as filler, by CO
2The CO of input tube 9 inputs
2, after water cooler 1 is cooled to liquid phase, be stored in liquid CO
2In the storage tank 2, liquid CO
2Through CO
2Compression pump 3 compressions, CO
2Become supercritical CO after preheater 4 preheatings
2Fluid enters filler extraction reaction tower 5 from the bottom to top, and the wood sugar aqueous feed solution again by the flow of high-pressure material pump 6 with 30ml/min, is from top to bottom squeezed in the filler extraction reaction tower 5 after 8 preheatings of wood sugar aqueous solution preheater.In packed extraction tower, the cyclodehydration reaction takes place and generates the fluid reactant furfural in wood sugar under the effect of packing type catalyst.Fluid reactant furfural and the supercritical CO that advances tower
2Fluid carries out the adverse current Continuous Contact, and furfural is dissolved in supercritical CO
2In the fluid, and derive from filler extraction reaction tower 5 tops thereupon, enter in the knockout tower 7.In knockout tower 7, regulate supercritical CO
2Pressure makes it to become normal pressure CO
2Gas, circulation is cooled to CO
2Liquid returns from filler extraction reaction tower 5 bottoms and enters liquid CO
2Storage tank 2.Be dissolved in supercritical CO
2In furfural in knockout tower 7, separate out and separate the back and enter the product jar from knockout tower 7 bottoms.Because CO
2Loss, need in time to replenish.
Common SCCO
2Based on the intermittent type of single-stage extraction, throughput is limited mostly for extraction process, and packed extraction tower can be realized operation continuously and two-phase multi-stage extraction, thereby has clear superiority.Similar with the relative more catalytic distillation of research, tower reaction, extraction normally is fixed in catalyzer packing or binding in the packing tower, hydrodynamic performance and mass-transfer performance to tower have a negative impact, and reactant can not in time separate with product, and make and the loading and unloading complexity.Thereby the present invention makes packing type with solid acid catalyst makes it have catalyzer and the difunctional efficient that significantly improves reaction, extraction technology of filler.The solid acid catalyst that the present invention selects for use comprises solid super-strong acid and zeolite molecular sieve, can obtain Al by alumilite process for solid super-strong acid
2O
3-Al packing type carrier, and then introduce corresponding active ingredient with pickling process and obtain the packing type solid super-strong acid; The filler of the molecular sieve type that changes into then generates molecular screen membrane by methods such as in-situ crystallizations on the packing type carrier.The solid acid that filler changes into type promptly can be used as unique packing component, thus the novel appts of the catalyzed reaction of designing and multi-stage solvent extraction isolation integral, and the present invention is referred to as the new catalytic packed extraction tower.The raw material water can be gone into tower mutually continuously with supercutical fluid in this equipment, the extraction of two phase countercurrent flow MULTI CONTACT, thereby efficient improves greatly.
Therefore, the present invention is by improving in multi-faceted greenization such as catalyzer, extraction solvent, operating method, conversion unit, proposition is the packing type solid acid catalysis of reactor, the wood sugar system furfural green technology of supercritical carbon dioxide extraction coupling technique with the new catalytic packed extraction tower, has important application prospects and realistic price.
Except wood sugar system furfural, the green technology that the present invention proposes also has good use for reference of planning to other relevant chemical processes.Further specify main points of the present invention below by embodiment.
Embodiment 1
In new packing extractive reaction tower shown in Figure 1, react.The tower internal diameter is 50mm, tower height 900mm.CO
2Compressed pump 3 and preheater 4 enter reaction tower from storage tank, adjust CO
2Flow keeps CO in the tower
2Pressure is 7.8MPa, and the feeding mass percent concentration is 20% the wood sugar aqueous solution, and flow is 30ml/min.Catalyzer is that filler changes into the SO that type is handled
4 2-/ TiO
2, tower inner catalyst total mass is 1800g.CO in the tower
2On catalyzer, carry out the adverse current Continuous Contact with xylose solution.The wood sugar aqueous solution that preheating feeds, making it temperature is 170 ℃, the insulation of tower external jacket makes the interior temperature of tower above 160 ℃.Transformation efficiency is 92%, and selectivity is 80%, and yield is 73.6%.
In new packing extractive reaction tower shown in Figure 1, react.The tower internal diameter is 50mm, tower height 900mm.CO
2Compressed pump 3 and preheater 4 enter reaction tower from storage tank, adjust CO
2Flow keeps CO in the tower
2Pressure is 7.2MPa, and the feeding mass percent concentration is 5% the wood sugar aqueous solution, and flow is 30ml/min.Catalyzer is that filler changes into the SO that type is handled
4 2-/ ZrO
2, tower inner catalyst total mass is 1800g., CO in the tower
2On catalyzer, carry out the adverse current Continuous Contact with xylose solution.The wood sugar aqueous solution that preheating feeds, making it temperature is 180 ℃, the insulation of tower external jacket makes the interior temperature of tower above 170 ℃.Transformation efficiency is 89%, and selectivity is 79%, and yield is 70.3%.
Embodiment 3
In new packing extractive reaction tower shown in Figure 1, react.The tower internal diameter is 50mm, tower height 900mm.CO
2Compressed pump 3 and preheater 4 enter reaction tower from storage tank, adjust CO
2Flow keeps CO in the tower
2Pressure is 8.0MPa, and the feeding mass percent concentration is 10% the wood sugar aqueous solution, and flow is 30ml/min.Catalyzer is that filler changes into the faujasite molecular sieve that type is handled, and tower inner catalyst total mass is 1800g.CO in the tower
2On catalyzer, carry out the adverse current Continuous Contact with xylose solution.The wood sugar aqueous solution that preheating feeds, making it temperature is 200 ℃, the insulation of tower external jacket makes the interior temperature of tower above 190 ℃.Transformation efficiency is 94%, and selectivity is 81%, and yield is 76%.
Embodiment 4
In new packing extractive reaction tower shown in Figure 1, react.The tower internal diameter is 50mm, tower height 900mm.CO
2Compressed pump 3 and preheater 4 enter reaction tower from storage tank, adjust CO
2Flow keeps CO in the tower
2Pressure is 7.0MPa, and the feeding mass percent concentration is 30% the wood sugar aqueous solution, and flow is 30ml/min.Catalyzer is that filler changes into the mordenite molecular sieve that type is handled, and tower inner catalyst total mass is 1800g.CO in the tower
2On catalyzer, carry out the adverse current Continuous Contact with xylose solution.The wood sugar aqueous solution that preheating feeds, making it temperature is 191 ℃, the insulation of tower external jacket makes the interior temperature of tower above 180 ℃.Transformation efficiency is 88%, and selectivity is 76%, and yield is 70%.
The foregoing description shows, changes into the solid super-strong acid (SO of type with filler
4 2-/ TiO
2And SO
4 2-/ ZrO
2), zeolite molecular sieve (faujasite molecular sieve and mercerising molecular sieve) is catalyzer and extraction stuffing, with the supercritical co is extraction solvent, carry out wood sugar catalysis system furfural in new packing extractive reaction tower, have good experimental result, yield can reach more than 70%.Because novel process environmental pollution and equipment corrosion are few, can serialization production, solve current furfural and produced ubiquitous problem of environmental pollution, have huge economic benefit, meet the general requirement of contemporary sustainable society development.
Claims (3)
1. a solid acid catalysis and supercritical extraction coupled furfural preparation, described solid acid catalysis and supercritical extraction coupled furfural preparation are to be catalyzer with super acids or molecular sieve solid acid, adopt supercritical co SCCO
2The on-line extraction separated product, whole furfural preparation process is carried out in the catalytic filler extraction tower, in whole process solid acid easily and product separation, can regeneration, equipment corrosion is little, three waste discharge is few, easy and safe to operate, and SCCO
2Cheap, nontoxic, diffusion is good, the solubility property easy-regulating, SCCO
2The on-line extraction furfural can also overcome and uses the deficiency that mass-transfer efficiency descends in the heterogeneous catalytic reaction behind the solid acid, removes the coking presoma that produces in the catalyzer duct immediately, thereby delays the inactivation of catalyzer; It is characterized in that concrete steps are as follows:
1) solid acid catalyst places the filler extraction reaction tower as filler after the filler type that changes into is handled;
2) carbonic acid gas is stored in liquid CO after water cooler is cooled to liquid phase
2In the storage tank;
3) liquid CO
2Become supercutical fluid after compressed, the preheater preheating, adjust CO
2Flow keeps CO in the reaction tower
2Pressure is 7～9MPa, enters from the bottom to top in the filler extraction reaction tower;
4) the feeding mass percent concentration is 3～30% the wood sugar aqueous solution, through 160～200 ℃ of preheatings of preheater, by the insulation of tower external jacket, by the flow of high-pressure material pump with 30ml/min, from top to bottom squeezes in the filler extraction reaction tower again;
5) in packed extraction tower, the cyclodehydration reaction takes place and generates the fluid reactant furfural in wood sugar under the effect of packing type catalyst;
6) the fluid reactant furfural carries out the adverse current Continuous Contact with the supercutical fluid that advances tower, and furfural is dissolved in supercritical CO
2Derive from filler extraction reaction tower top in the fluid and thereupon, enter in the knockout tower,
7) in knockout tower, regulate supercritical CO
2Pressure makes it to become normal pressure CO
2Gas, circulation is cooled to CO
2Liquid enters liquid CO
2Storage tank is because CO
2Loss, and in time replenish; Be dissolved in supercritical CO
2In furfural enter the product jar after in knockout tower, separating out separation.
2. according to described solid acid catalysis of claim 1 and supercritical extraction coupled furfural preparation, it is characterized in that described catalyzer is that filler changes into the SO that type is handled
4 2-/ TiO
2, SO
4 2-/ ZrO
2, faujasite molecular sieve or mercerising molecular sieve.
3. the device of a solid acid catalysis and supercritical extraction coupled preparation furfural is characterized in that CO
2Input tube (9), water cooler (1), liquid CO
2Storage tank (2), CO
2Compression pump (3) and CO
2Be connected filler extraction reaction tower (5) bottom after preheater (4) series connection, wood sugar aqueous solution preheater (8) is connected with high-pressure material pump (6), high-pressure material pump (6) is connected to filler extraction reaction tower (5) top, filler extraction reaction tower (5) top delivery port is connected to knockout tower (7) middle part, knockout tower (7) bottom output furfural, the CO on knockout tower (7) top
2Delivery line (10) and CO
2Input tube (9) connects.
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| CN103270028B (en) | 2010-12-21 | 2015-11-25 | 纳幕尔杜邦公司 | By the side chain in stillage or syrup not fermentable sugars prepare the method for furfural |
| US9181210B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Processes for making furfurals |
| WO2013102027A1 (en) | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| CA2859898A1 (en) * | 2011-12-28 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Process for the production of furfural |
| BR112014015988A8 (en) | 2011-12-28 | 2017-07-04 | Du Pont | process |
| CN103396385A (en) * | 2013-08-09 | 2013-11-20 | 黄馨莹 | Method for extracting furfural from longan pericarps |
| TWI586431B (en) * | 2016-05-26 | 2017-06-11 | 國立中山大學 | Homogenous supercritical fluid reaction method and apparatus thereof |
| CN107445926A (en) * | 2016-05-31 | 2017-12-08 | 中国科学院大连化学物理研究所 | A kind of method that biphase gas and liquid flow xylose dehydration prepares furfural |
| CN107445927A (en) * | 2016-05-31 | 2017-12-08 | 中国科学院大连化学物理研究所 | The technique that a kind of xylose dehydration prepares furfural |
| CN106045949B (en) * | 2016-06-24 | 2018-11-20 | 华东交通大学 | One kind is in supercritical CO2The method of middle catalytic degradation oil tea shell preparation product containing furfural |
| CN105944627A (en) * | 2016-07-06 | 2016-09-21 | 北京神雾环境能源科技集团股份有限公司 | Device for preparing ethylene from acetylene through selective hydrogenation |
| CN108383810A (en) * | 2017-02-03 | 2018-08-10 | 中国科学院大连化学物理研究所 | A kind of technique of xylose continuous production furfural |
| CN110642813B (en) * | 2019-09-09 | 2023-04-28 | 山东省化工研究院 | Preparation process of furfural |
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| CN1228427A (en) * | 1999-02-05 | 1999-09-15 | 孙传经 | Method for extracting and separating natural vitamin E from soybeam deodorized material by supercritical CO2 |
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| CN1228427A (en) * | 1999-02-05 | 1999-09-15 | 孙传经 | Method for extracting and separating natural vitamin E from soybeam deodorized material by supercritical CO2 |
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| Claude Moreau, et al.Selective preparation of furfural from xylose over microporous solid acid catalysts.《Industrial Crops and Products》.1998,第7卷95-99. * |
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