CN105541559A - Method for producing aryl oxygenated compound from lignin in presence of perovskite oxide - Google Patents
Method for producing aryl oxygenated compound from lignin in presence of perovskite oxide Download PDFInfo
- Publication number
- CN105541559A CN105541559A CN201610043492.1A CN201610043492A CN105541559A CN 105541559 A CN105541559 A CN 105541559A CN 201610043492 A CN201610043492 A CN 201610043492A CN 105541559 A CN105541559 A CN 105541559A
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- China
- Prior art keywords
- perovskite oxide
- oxide catalyst
- xylogen
- aromatic base
- compound
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Links
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 34
- 229920005610 lignin Polymers 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title claims abstract 6
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000012263 liquid product Substances 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- -1 nitrate compound Chemical class 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 230000002779 inactivation Effects 0.000 claims 1
- 239000008187 granular material Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 229960001867 guaiacol Drugs 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 229910017771 LaFeO Inorganic materials 0.000 description 2
- 241000775848 Syringa oblata Species 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 1
- YIBXWXOYFGZLRU-UHFFFAOYSA-N syringic aldehyde Natural products CC12CCC(C3(CCC(=O)C(C)(C)C3CC=3)C)C=3C1(C)CCC2C1COC(C)(C)C(O)C(O)C1 YIBXWXOYFGZLRU-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
- C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/40—
-
- B01J35/60—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for producing an aryl oxygenated compound from lignin in the presence of perovskite oxide. The method for producing the aryl oxygenated compound from the lignin in the presence of the perovskite oxide comprises the steps that a perovskite oxide catalyst ABxB'1-xO3 is prepared, wherein the x is greater than or equal to 1 but is smaller than or equal to 1; the lignin and the perovskite oxide catalyst are fully mixed and then are tabletted, formed and smashed into granules, wherein the mass ratio of the lignin to the perovskite oxide catalyst is 0.1:1 to 3:1; the catalytic conversion reaction of the lignin is performed in a fixed bed reactor under inert atmosphere, and the obtained liquid is a product containing the aryl oxygenated compound, wherein the reaction temperature is 300-700 DEG C, the reaction time is 1-3 hours. The perovskite oxide catalyst prepared by means of the method can achieve catalytic conversion of the lignin at the relatively low temperature, the yield of the liquid product can be above 35%, and the selectivity of the aryl oxygenated compound can be above 80%.
Description
Technical field
The present invention relates to xylogen efficient catalytic to transform and recycling field, be specifically related to the method that perovskite oxide catalyst xylogen produces aromatic base oxygenatedchemicals.
Background technology
In global range, fossil energy is day by day exhausted, makes people in the urgent need to exploitation renewable energy source, to maintain the Sustainable development of environment and society.Xylogen, as being only second to cellulosic second largest biomass resource, gets more and more people's extensive concerning.The annual whole world can produce 1,500 hundred million tons of xylogen by plant-growth.China is large agricultural country, 5-6 hundred million tons of agricultural crop straws of annual generation are that China provides abundant Liginon Resource, but wherein only there is the raw material that 30% is used as paper industry, construction industry and handicraft, remaining is all burned or waste treatment, not only severe contamination is caused to physical environment, especially to the significant wastage of resource.Xylogen forms by hydroxyphenyl, guaiacyl and Syringa oblata Lindl. base three kinds of phenylpropyl alcohol alkane monomer polymerizations, and this constructional feature determines to utilize it to prepare chemical products with high added-value, especially aromatics.Therefore, utilize catalyst to transform xylogen and prepare aromatics, to China's economic construction and protection of natural resources and environment, all there is considerable meaning.
(the Chinese patent literature CN103739457B such as Sun Yong, 2015.07.01) invented under metal catalyst and alkali effect, in aqueous phase, catalysis bamboo lignin transforms, and the method for methyl catechol and Syringa oblata Lindl. alcohol is obtained through organic solvent extraction, this method operating procedure is simple, reaction conditions is gentle, but follow-up separation, purification process are comparatively complicated.Zhang Tao etc. (Chinese patent literature CN102476980A, 2012.05.30) invent under hydrothermal conditions, with non-zero valence tungsten be active ingredient, transition metal is the tungsten-based catalyst catalysis multiple xylogen raw material Hydrogenation of the second metal component is for C
6-C
9the method of phenolic compound, this method environmental friendliness, with low cost, but reaction process pressure is higher, and high to equipment requirements.Deng Haibo (Chinese patent literature CN102146025A, 2011.08.11) invented with ammoniacal liquor complexing lignin degradation products, and prepared the method for syringic aldehyde through bromination reaction and methoxyl group reaction, this method products therefrom productive rate can be good up to 50-60%, purity, but this process is complicated, and cost is higher.
The general structure of perovskite typed complex metal oxides is ABO
3, wherein, A is the metal ion of divalence that radius is larger or monovalence, and B position is the metal ion of tetravalence that radius is less or pentavalent, can conduction electron and O preferably
2-, therefore there is good catalytic performance.(the Chinese patent literature CN102850304A such as Ren Junli, 2013.01.02) invented the method preparing furfural with the Perovskite Catalytic xylan hydrolysis of load chromium, experiment finds that this kind of catalyst efficiency is high, and selectivity is good, easy reclaiming, reaction conditions is gentle.But take uhligite as catalyzer, Catalytic lignin selective oxidation is that the method for aromatics have not been reported.
Summary of the invention
The object of this invention is to provide the method that perovskite oxide catalyst xylogen produces aromatic base oxygenatedchemicals, this method is lower for solving xylogen utilising efficiency, discharges or burn the problem of contaminate environment.
The technical solution adopted for the present invention to solve the technical problems is: this perovskite oxide catalyst xylogen produces the method for aromatic base oxygenatedchemicals:
One, perovskite oxide catalyst AB
xb '
1-xo
3preparation, wherein 0≤x≤1:
(1) by A, B ' corresponding metal soluble salt is dissolved in deionized water, get a uniform mixture through stirring, in solution, two metal ion species volumetric molar concentrations are 0.2-0.8mol/L;
(2) in above-mentioned mixing solutions, add citric acid and EDTA, make A, the mol ratio of B ' two metal ion species total amount, citric acid, EDTA is 1:2:2-2:1:1, after abundant stirring, adding massfraction is 5-ammoniacal liquor of 10%, makes solution ph be 7-and 9, obtain solution Y;
(3) dissolve joining in the mixing solutions of ethanol, acetic acid, lactic acid containing B organic compound, fully stir the Z that gets a uniform mixture, the volume ratio of above-mentioned B organic compound, ethanol, acetic acid, lactic acid is 1:6:3:3-1:2:1:1;
(4) Y and Z solution is mixed, 30 and-make solution evaporation to colloidal mixture under stirring 20-after 50min, 70-95 DEG C of stirrings at 60 DEG C, drying and roasting acquisition perovskite oxide catalyst;
Two, the perovskite oxide catalyst mixed pressuring plate prepared of xylogen and step one:
Carry out compression molding after fully being mixed with perovskite oxide catalyst by xylogen and pulverize as particle, wherein the mass ratio of xylogen and perovskite oxide catalyst is 0.1:1-3:1;
Three, catalytic lignin conversion:
In fixed-bed reactor, under an inert atmosphere, temperature of reaction is 300-700 DEG C, reaction times 1-3hr, carries out catalytic lignin conversion reaction, obtains liquid for containing aromatic base oxygenatedchemicals product; Described reacted perovskite oxide catalyst recycles through oxidation regeneration.
AB described in such scheme
xb '
1-xo
3the metal soluble salt that middle A is corresponding is the one of Bi, La, Sr, Ca, Ba nitrate compound, the metal soluble salt of B ' correspondence is the one in Fe, Co, Ni and Mn nitrate compound, is the one in tetrabutyl titanate, zirconium-n-butylate containing B organic compound.
Perovskite oxide catalyst and xylogen compressing tablet after sufficiently mixing in such scheme, tableting pressure is 10-25MPa, the compressing tablet time is 5-30min, is broken for 50 by mixing flap-100mm particle.
The colloidal mixture that in such scheme, step one obtains is 100-dry after 12-24h for 150 DEG C, in air atmosphere, 600-1200 DEG C of roastings 4-12h, obtains perovskite oxide catalyst.
The aromatic base oxygenatedchemicals obtained in such scheme comprises phenol compound, guaiacol phenol compound, aromatic base diphenol compound, methoxyl group aromatic compounds.
The liquid product yield that in such scheme, xylogen selective catalytic oxidation obtains reaches more than 35%, and the selectivity of aromatic base oxygenatedchemicals reaches more than 80%.
In such scheme, perovskite oxide catalyst regeneration condition is: in air atmosphere, and temperature of reaction is 700-1000 DEG C, the reaction times is 10-and 60min.
The present invention has following beneficial effect:
1, the perovskite oxide catalyst that the present invention utilizes sol-gel processing to prepare has receives micro-dimension size, simultaneously loose porous, has larger specific surface area, has good electronics and O simultaneously
2-conductive performance, therefore to higher catalytic activity.
2, the present invention prepares the catalyzed conversion that perovskite oxide catalyst can realize xylogen under relatively lower temp, and liquid product yield can reach more than 35%, and the selectivity of aromatic base oxygenatedchemicals can reach more than 80%.
3, in reaction process of the present invention after catalyst surface coking, after oxidation regeneration, catalyzer can recycle, and catalyzer has good anti-sintering property, and this catalyzer has the longer life-span thus.
4, the present invention is by preparing aromatic base oxygenatedchemicals by catalytic lignin conversion, provides xylogen Efficient Conversion to utilize new way, improves economic benefit and the environmental benefit of xylogen.
Embodiment
The present invention is further illustrated below:
Embodiment 1:
Take 7.0140g ethylenediamine tetraacetic acid (EDTA), 6.9168g citric acid, be dissolved in 120mL deionized water, drip ammoniacal liquor until form colourless transparent solution; Add 4.7228gCa (NO
3)
26H
2o, after magnetic stirrer 5min, adds 1.6160gFe (NO
3)
39H
2o, stirs 5min and makes it to dissolve; Drip ammoniacal liquor to pH=8 obtained solution Y.Separately get a beaker, be 1:1:1:2 by the volume ratio of lactic acid, Glacial acetic acid, tetrabutyl zirconate and ethanol, be mixed into 30.70mL uniform solution, obtain solution Z.Solution Y is mixed with solution Z; Stir in heat-collecting magnetic stirring device, oil bath thermostatically heating to colloidal sol becomes sticky thick, and Heating temperature is 80 DEG C; Freeze-day with constant temperature in loft drier, temperature is 120 DEG C, and the time is 18hr; In 800 DEG C of roasting 6hr in retort furnace, after being cooled to room temperature, obtain CaZr
0.8fe
0.2o
3.
Take 2.5g xylogen and 2.5gCaZr
0.8fe
0.2o
3after abundant mixing, utilize powder compressing machine at 20MPa lower sheeting 10min, obtain flaky mixture, be crushed to 50-100mm particle.
Xylogen prepared by the present embodiment and CaZr
0.8fe
0.2o
3compound particles 3.0g, joins with temperature programming to 600 DEG C in differential fixed bed reactor, N
2flow is under the condition of 350mL/min, and reaction 2hr, obtain product liquid 0.58g, liquid product yield is 38.7%.Product liquid carries out gas-chromatography and mass spectrometry analysis, its primary product is aromatic base oxygenatedchemicals liquid, mainly comprise phenol compound (phenol, alkylphenol, aldehyde radical phenol), guaiacol phenol compound (methyl catechol, alkyl methyl catechol, ketone group methyl catechol), aromatic base diphenol compound and methoxyl group aromatic compounds, its overall selectivity is 82%.Post catalyst reaction is at 800 DEG C, and air flow quantity is 300mL/min, and the reaction times is 18min, and catalyzer can holomorphosis.
Embodiment 2:
Take 5.2611g ethylenediamine tetraacetic acid (EDTA), 5.1879g citric acid, be dissolved in 120mL deionized water, drip ammoniacal liquor until form colourless transparent solution; Add 6.4953gLa (NO
3)
26H
2o, after magnetic stirrer 5min, adds 4.4205gFe (NO
3)
39H
2o, stirs 5min and makes it to dissolve; Drip ammoniacal liquor to pH=9 obtained solution Y.Separately get a beaker, be 2:2:1:4 by the volume ratio of lactic acid, Glacial acetic acid, tetrabutyl titanate and ethanol, be mixed into 24.33mL uniform solution, obtain solution Z.Be blended in heat-collecting magnetic stirring device by solution Y and solution Z and be stirred to colloidal sol and become sticky thick, oil bath temperature is 80 DEG C; Put into thermostatic drying chamber in 120 DEG C of dry 12hr; In 700 DEG C of roasting 8hr in retort furnace; After being cooled to room temperature, obtain LaTi
0.5fe
0.5o
3.
Take 4g xylogen and 2gLaTi
0.5fe
0.5o
3after abundant mixing, utilize powder compressing machine to be 15MPa lower sheeting 15min at pressure, obtain flaky mixture, be crushed to 50-100mm particle.
Xylogen prepared by the present embodiment and LaTi
0.5fe
0.5o
3compound particles 3.0g, joins differential fixed bed reactor Program and is warming up to 500 DEG C, N
2flow is under the condition of 300mL/min, and reaction 2hr, obtain product liquid 0.82g, liquid product yield is 41%.Product liquid carries out gas-chromatography and mass spectrometry analysis, its primary product is aromatic base oxygenatedchemicals liquid, mainly comprise phenol compound (phenol, alkylphenol, aldehyde radical phenol), guaiacol phenol compound, aromatic base diphenol compound and methoxyl group aromatic compounds, its overall selectivity is 84.5%.Post catalyst reaction is at 800 DEG C, and air flow quantity is 300mL/min, and the reaction times is 45min, and catalyzer can holomorphosis.
Embodiment 3:
Take 5.8450g ethylenediamine tetraacetic acid (EDTA), 5.7640g citric acid, be dissolved in 120mL deionized water, drip ammoniacal liquor until form colourless transparent solution; Add 4.7228gCa (NO
3)
26H
2o, makes it to dissolve with magnetic stirrer 5min; Drip ammoniacal liquor to pH=7 obtained solution Y.Separately get a beaker, be 1:1:1:2 by the volume ratio of lactic acid, Glacial acetic acid, tetrabutyl zirconate and ethanol, be mixed into 38.35mL uniform solution, obtain solution B.Solution A is mixed with solution B; Stir in heat-collecting magnetic stirring device, oil bath thermostatically heating, Heating temperature is 80 DEG C, and heat-up time is 4hr, and colloidal sol becomes sticky thick; Freeze-day with constant temperature in loft drier, temperature is 120 DEG C, and the time is 12hr; In 900 DEG C of roasting 6hr in retort furnace, after being cooled to room temperature, obtain CaZrO
3.
Take 3g xylogen and 1gCaZrO
3after abundant mixing, utilize powder compressing machine at 20MPa lower sheeting 10min, obtain flaky mixture, be crushed to 50-100mm particle.
Xylogen prepared by the present embodiment and CaZrO
3compound particles 4.0g, joins with temperature programming to 600 DEG C in differential fixed bed reactor, N
2flow is under the condition of 300mL/min, and reaction 1hr, obtain product liquid 1.07g, liquid product yield is 35.5%.Product liquid carries out gas-chromatography and mass spectrometry analysis, its primary product is aromatic base oxygenatedchemicals liquid, mainly comprise phenol compound (phenol, alkylphenol), guaiacol phenol compound (methyl catechol, alkyl methyl catechol), aromatic base diphenol compound and methoxyl group aromatic compounds, its overall selectivity is 80.4%.Post catalyst reaction is at 800 DEG C, and air flow quantity is 500mL/min, and the reaction times is 30min, and catalyzer can holomorphosis.
Embodiment 4:
Take 8.7685g ethylenediamine tetraacetic acid (EDTA), 8.6465g citric acid, be dissolved in 120mL deionized water, drip ammoniacal liquor until form colourless transparent solution; Add 6.4953gLa (NO
3)
26H
2o, after magnetic stirrer 5min, adds 8.8410gFe (NO
3)
39H
2o, stirs 5min and makes it to dissolve; Drip ammoniacal liquor to pH=8.5 obtained solution Y.Solution Y is stirred in heat-collecting magnetic stirring device 80 DEG C to be heated to colloidal sol and to become sticky thick; Put into thermostatic drying chamber in 120 DEG C of dry 12hr; In 900 DEG C of roasting 6hr in retort furnace; After being cooled to room temperature, obtain LaFeO
3, pulverize with ball mill.
Take 3.0g xylogen and 3.0gCaFeO
3after abundant mixing, utilize powder compressing machine to be 30MPa lower sheeting 8min at pressure, obtain flaky mixture, be crushed to 50-100mm particle.
Xylogen prepared by the present embodiment and LaFeO
3compound particles 3.0g, joins differential fixed bed reactor Program and is warming up to 500 DEG C, N
2flow is under the condition of 300mL/min, and reaction 1.5hr, obtain product liquid 0.54g, liquid product yield is 36.0%.Product liquid is through GC-MS method, mainly comprise phenol compound (phenol, alkylphenol, ketone group phenol), guaiacol phenol compound (alkyl methyl catechol, aldehyde radical methyl catechol, ketone group methyl catechol), aromatic base diphenol compound and methoxyl group aromatic compounds, its overall selectivity is 83%.Post catalyst reaction is at 800 DEG C, and air flow quantity is 300mL/min, and the reaction times is 30min, and catalyzer can holomorphosis.
Claims (7)
1. perovskite oxide catalyst xylogen produces a method for aromatic base oxygenatedchemicals, it is characterized in that: this perovskite oxide catalyst xylogen produces the method for aromatic base oxygenatedchemicals:
One, perovskite oxide catalyst AB
xb '
1-xo
3preparation, wherein 0≤x≤1:
(1) by A, B ' corresponding metal soluble salt is dissolved in deionized water, get a uniform mixture through stirring, in solution, two metal ion species volumetric molar concentrations are 0.2-0.8mol/L;
(2) in above-mentioned mixing solutions, add citric acid and EDTA, make A, the mol ratio of B ' two metal ion species total amount, citric acid, EDTA is 1:2:2-2:1:1, after abundant stirring, adding massfraction is 5-ammoniacal liquor of 10%, makes solution ph be 7-and 9, obtain solution Y;
(3) dissolving joining in the mixing solutions of ethanol, acetic acid, lactic acid containing B organic compound, fully stirring the Z that gets a uniform mixture, the above-mentioned volume ratio containing B organic compound, ethanol, acetic acid, lactic acid is 1:6:3:3-1:2:1:1;
(4) Y and Z solution is mixed, 30 and-make solution evaporation to colloidal mixture under stirring 20-after 50min, 70-95 DEG C of stirrings at 60 DEG C, drying and roasting acquisition perovskite oxide catalyst;
Two, the perovskite oxide catalyst mixed pressuring plate prepared of xylogen and step (1):
Carry out compression molding after fully being mixed with perovskite oxide catalyst by xylogen and pulverize as particle, wherein the mass ratio of xylogen and perovskite oxide catalyst is 0.1:1-3:1;
Three, catalytic lignin conversion:
In fixed-bed reactor, under an inert atmosphere, temperature of reaction is 300-700 DEG C, reaction times 1-3hr, carries out catalytic lignin conversion reaction, obtains liquid for containing aromatic base oxygenatedchemicals product; Described reacted perovskite oxide catalyst recycles through oxidation regeneration.
2. perovskite oxide catalyst xylogen according to claim 1 produces the method for aromatic base oxygenatedchemicals, it is characterized in that: described AB
xb '
1-xo
3the metal soluble salt that middle A is corresponding is the one of Bi, La, Sr, Ca, Ba nitrate compound, the metal soluble salt of B ' correspondence is the one in Fe, Co, Ni and Mn nitrate compound, is the one in tetrabutyl titanate, zirconium-n-butylate containing B organic compound.
3. perovskite oxide catalyst xylogen according to claim 2 produces the method for aromatic base oxygenatedchemicals, it is characterized in that: described perovskite oxide catalyst and xylogen compressing tablet after sufficiently mixing, tableting pressure is 10-25MPa, the compressing tablet time is 5-30min, is broken for 50 by mixing flap-and 100mm particle.
4. perovskite oxide catalyst xylogen according to claim 3 produces the method for aromatic base oxygenatedchemicals, it is characterized in that: the colloidal mixture that described step one obtains is 100-after 150 DEG C of oven dry 12-24h, in air atmosphere, 600-1200 DEG C of roastings 4-12h, obtains perovskite oxide catalyst.
5. perovskite oxide catalyst xylogen according to claim 4 produces the method for aromatic base oxygenatedchemicals, it is characterized in that: the described aromatic base oxygenatedchemicals obtained comprises phenol compound, guaiacol phenol compound, aromatic base diphenol compound, methoxyl group aromatic compounds.
6. perovskite oxide catalyst xylogen according to claim 5 produces the method for aromatic base oxygenatedchemicals, it is characterized in that: the liquid product yield that described xylogen selective catalytic oxidation obtains reaches more than 35%, and the selectivity of aromatic base oxygenatedchemicals reaches more than 80%.
7. perovskite oxide catalyst xylogen according to claim 6 produces the method for aromatic base oxygenatedchemicals, it is characterized in that: the described perovskite oxide compound inactivation because of coking after the reaction, its regeneration condition is: in air atmosphere, 700-at 1000 DEG C be oxidized 10-60min.
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| CN107469818A (en) * | 2017-09-14 | 2017-12-15 | 利民化工股份有限公司 | CaZrO3The preparation method of carrier and by noble-metal-supported in supported catalyst and preparation method and application |
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