CN102372607A - Method for preparing single benzene ring phenolic compound from alkali lignin - Google Patents
Method for preparing single benzene ring phenolic compound from alkali lignin Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920005610 lignin Polymers 0.000 title claims abstract description 19
- 239000003513 alkali Substances 0.000 title claims abstract description 17
- -1 benzene ring phenolic compound Chemical class 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002585 base Substances 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 150000002989 phenols Chemical class 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000008346 aqueous phase Substances 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 235000015320 potassium carbonate Nutrition 0.000 claims description 8
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 235000012255 calcium oxide Nutrition 0.000 claims description 5
- 229960001867 guaiacol Drugs 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 claims 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 2
- 235000011181 potassium carbonates Nutrition 0.000 claims 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 229930003836 cresol Natural products 0.000 claims 1
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- 241000775848 Syringa oblata Species 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000001896 cresols Chemical class 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- LZFOPEXOUVTGJS-UHFFFAOYSA-N cis-sinapyl alcohol Natural products COC1=CC(C=CCO)=CC(OC)=C1O LZFOPEXOUVTGJS-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920005611 kraft lignin Polymers 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种催化转化碱木质素制备单苯环酚类化合物的方法。在反应温度为90℃-180℃、氢气压力为1.0MPa-10.0MPa的条件下，在金属纳米粒子催化剂的作用下，于水相中，加氢降解碱木质素制备单苯环酚类化合物。反应中加入有碱类化合物。所述的金属纳米粒子催化剂可以为Fe、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag或Au中的一种或多种的任意比。该方法反应条件温和，能耗低，成本低，操作安全性高，产物易分离。A method for catalytically converting alkali lignin to prepare monobenzene ring phenolic compounds. Under the conditions of a reaction temperature of 90 DEG C. to 180 DEG C. and a hydrogen pressure of 1.0 MPa to 10.0 MPa, under the action of a metal nanoparticle catalyst, hydrogenation degrades alkali lignin in an aqueous phase to prepare monobenzene ring phenol compounds. A base compound is added in the reaction. The metal nanoparticle catalyst can be one or more of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag or Au in any ratio. The method has mild reaction conditions, low energy consumption, low cost, high operational safety and easy separation of products.
Description
Technical field
The present invention relates to a kind of catalyzed conversion xylogen and prepare the method for single phenyl ring phenolic cpd.
Background technology
Biomass mainly comprise agriculture straw and forest biomass two big classes.At occurring in nature, xylogen is the important component part (accounting for the weight of 15-30%, 40% energy) of biomass, and all regenerate with 50,000,000,000 tons speed every year.The pulp and paper industry of xylogen is isolated about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant; Obtain the lignin product about 5,000 ten thousand tons simultaneously; But up to now; Surpass 95% xylogen still directly enter rivers with " black liquor " or concentrate after burn, seldom be utilized effectively, cause the wasting of resources and environmental pollution.Xylogen is the polymkeric substance that the monomer by phenyl propane derivative constitutes, and is a kind of complicated phenol polymer that is formed by four kinds of alcohol monomers (to tonquinol, lubanol, 5-hydroxyl lubanol, sinapyl alcohol), and structure is relatively stable, and the challenge of development and use is bigger.Xylogen is through selecting the chemical reaction of scission of link; Can produce fine chemicals (compounds such as phenol, alcohol, aldehyde, acid, ester) and bulk chemical (three benzene-like compounds) and the biofuel of sulfur-bearing not, so xylogen can be considered the critical materials of exploitation biomass energy.
The trans-utilization of xylogen focuses mostly in fields such as biological chemistry and engineering processing.The route of catalyzed conversion adopts high temperature, highly compressed reaction conditions more, and energy consumption is high; Have groups such as ether, phenol, ester in the lignin structure, under the hot conditions, generate a large amount of by products, separating difficulty is big.Through the exploitation high-selectivity catalyst, can select a certain type of chemical bond of activation fracture, realize target formula production chemical, Atom economy is high; Catalysis process can reduce the use of solvent and additive in the production process, simplifies the product separating step, reduces waste discharge, is the environmental friendliness route.
It is raw material that document (Appl.Biochem.Biotechnol., 1988,17,151) adopts solvent-borne type xylogen (Organosolv lignin), with Co-Mo/Al
2O
3Be catalyzer, temperature of reaction is 673K-723K, and pressure is 10MPa-15MPa, and the yield of phenol is 10%.Patent US 4647704 discloses a kind of Ni-W/SiO
2-Al
2O
3Loaded catalyst, temperature of reaction are 573K-723K, and reaction pressure is 3.5MPa-24MPa, and the yield of phenolic cpd is 30%.Document (Energy Fuels 1993,7,426) report adopts Mo catalyst based, and temperature of reaction is 673K, and reaction pressure is 7MPa-10MPa, and the total recovery of the generation phenols of catalyzed conversion xylogen, benzene class, naphthalene class and cyclohexanes compound is 61%.Patent CN200810030705.2 discloses a kind of method of preparing vanillin from alkali bamboo lignin, under 300 ℃-800 ℃ temperature of reaction, is catalyzer with metals such as Pd, Cu, Ag, do not see have transformation efficiency and optionally the report.Article (biomass chemical engineering, 2009 (6), 31-35) report nano-TiO
2The photocatalytic oxidation degradation alkali lignin can obtain small-molecule substances such as Syringa oblata Lindl. radical derivative, Vanillin, guaiacyl verivate.
More than the reaction high-temperature high-voltage reaction conditions that adopt are carried out in fixed-bed reactor more, are main with cleavage reaction product.Mostly these catalyzer are the direct use that hydrogenation such as hydrogenating desulfurization and hydrodenitrification take off the heteroatoms catalyzer, have the performance that certain sulphur-nitrogen resistant is poisoned, though in the hydrogenation deoxidation reaction of biomass, certain activity is arranged, reaction efficiency is lower.The reaction of solid catalyst in solid lignin and the fixed-bed reactor, real is intermittent reaction, can't realize the continuous flow reaction; And along with the carrying out in reaction times, coking is aggregated in and forms carbon distribution on the beds, increases catalyst recovery utilization and the isolating difficulty of product.
Summary of the invention
Technical problem to be solved by this invention is to adopt highly active nano-particle catalyst; Under mild reaction conditions, be raw material with the waste alkali lignin in the industrial production, react through hydrocracking; Manufacture order phenyl ring phenolic cpd, primary product are phenol and cresols compound.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of catalyzed conversion xylogen prepares the method for single phenyl ring phenolic cpd; In temperature of reaction is that 90 ℃-180 ℃, hydrogen pressure are under the condition of 1.0MPa-10.0MPa, and under the effect of catalyst with metal nanoparticles, in aqueous phase, hydrogenation degraded alkali lignin prepares single phenyl ring phenolic cpd.
Add in the reaction system bases compound is arranged; Described catalyst with metal nanoparticles can be a kind of or any ratio among Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag or the Au;
Said catalyst with metal nanoparticles is non-loading type, is scattered in the catalyst with metal nanoparticles of aqueous phase that it is a metal water colloidal sol catalyzer.
Xylogen is the structure in fine and close few hole, and the hydrogen bonded in bases compound and the structure weakens the effect of hydrogen bond, promotes the loosening of lignin structure, and adding the bases compound is to achieve these goals.Adoptable bases compound is one or more in Quilonum Retard, salt of wormwood, yellow soda ash, saleratus, sodium hydrogencarbonate, Lithium Hydroxide MonoHydrate, sodium hydroxide, Pottasium Hydroxide, Natural manganese dioxide, quicklime or the barium oxide; Be preferably in salt of wormwood, sodium hydroxide or the quicklime, be preferably salt of wormwood.The weight ratio of the usage quantity of said bases compound and the add-on of xylogen is 1: 1-1: 20, be preferably 1: 1-1: and 10, be preferably 1: 1-1: 2.
Under mild conditions, the catalytic activation xylogen needs the catalyzer of greater activity.Nano metal from particle catalyst owing to have high surface energy and a high surface imperfection, active higher in catalyzed reaction; Nanometer metal particle catalyst has the easily separated property of heterogeneous catalyst and the polymolecularity and the easy diffustivity of homogeneous catalyst, helps taking place with fully contacting of xylogen substrate catalyzed reaction.Catalyst with metal nanoparticles can be preferably nanometer Au, Ru and Ni catalyzer for a kind of or any ratio among Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag or the Au, is preferably Au.
Reaction needed adopts still formula whisking appliance with catalyzer, xylogen and hydrogen thorough mixing.Temperature of reaction is 90 ℃-180 ℃, and temperature of reaction is preferably 110 ℃-140 ℃, is preferably 120 ℃; Hydrogen reaction pressure is 1.0MPa-10.0MPa, and hydrogen pressure is preferably 4.0MPa-8.0MPa; Be preferably 6.0MPa.Reaction product is through behind the compartment analysis, and primary product is phenol, cresols, methyl catechol and Syringa oblata Lindl. alcohol.
The conventional production methods of phenol products is a raw material with the fossil resource, and cost is higher.With Biological resources is this compounds of raw material production, and cost is low, and quality product is high, and Sustainable development.
The technical superiority that the present invention has is: (1) reaction conditions is gentle, and energy consumption is low, and cost is low, and processing safety is high; (2) the single benzene ring type compounds of highly-selective preparation; (3) product separates simple.
Embodiment
The following example will help to understand the present invention, but content of the present invention is not limited thereto.
Embodiment 1
Preparation Au nano-particle catalyst.The hydration HAuCl that under constantly stirring, in 100 milliliters water, adds 1 milliliter 1% (weight)
43H
2O.After 10 minutes, add the hydration Trisodium Citrate of 1 milliliter 1% (weight).After adding 10 minutes, add 0.075% (weight) NaBH of 1 milliliter again
4, solution was constantly stirred 5 minutes, store for future use.
The catalyzer of preparation is changed in 300 milliliters of reaction kettles, add 5.0 gram alkali lignins (kraft lignin) and 3.0 gram salt of wormwood, feed hydrogen exchange three times, be heated to 120 ℃, open the hydrogen inlet valve, the pressure maintaining valve of inlet mouth is adjusted to 6.0MPa.React after 10 hours, stopped reaction, cooling, regulating pH value is 7, with ethyl acetate extraction three times, each 50mL, after the merging, employing gas chromatographic analysis products distribution is removed ETHYLE ACETATE with revolving steaming, is weighed as the product gross weight.In hydrogenation reaction, it is less that the increase of molecular weight of product accounts for the ratio of product weight, so transformation efficiency can be from product weight and the ratio calculation that adds xylogen weight.Analytical results is seen table 1.
Embodiment 2
Preparation Ni nano-particle catalyst.(1) being formulated as of Hydrazine Hydrate 80/NaOH solution: in 85% Hydrazine Hydrate 80 100mL solution, dripping 1.0M NaOH solution to pH value is 13.(2) with the 150mL normal hexane, the 30g Surfactant CTAB, the 40mL n-hexyl alcohol mixes, and stirs down, drips Hydrazine Hydrate 80/NaOH solution to clarification, is the Hydrazine Hydrate 80 microemulsion.(3) preparation 0.5M NiCl
2Solution 100mL.(4) with the 150mL normal hexane, the 30g Surfactant CTAB, the 30mL n-hexyl alcohol mixes, and stirs down, drips 0.5M NiCl
2Solution is NiCl to clarification
2Microemulsion.(5), it is in 70 ℃ the oil bath that NiCl2 microemulsion bottle is inserted temperature, adds the Hydrazine Hydrate 80 microemulsion rapidly, continue to stir after 1 hour, and cooling, subsequent use.Measure the 100mL catalyst solution, adopt the reaction method of embodiment 1.Reaction result is seen table 1.
Embodiment 3
Preparation Ru nano-particle catalyst.Take by weighing PVP K-301.8g and be dissolved in the 100ml water, stirred 15 minutes.Take by weighing RuCl
3XH
2O 120mg is dissolved in the 4mL water, and mixes with PVP solution, and temperature of reaction is 90 ℃, and the time is 12 hours, and hydrogen flowing quantity is 30mL/min, and cooling is subsequent use.Adopt the reaction method of embodiment 1.Reaction result is seen table 1.
Embodiment 4
Adopt the catalyzer of embodiment 1, difference is to add in the reaction 1.2g CaO replacement 3.0 gram salt of wormwood.Reaction result is seen table 1.
Embodiment 5
Preparation of Catalyst and reaction conditions are with embodiment 1, and only changing temperature of reaction is 90 ℃.Reaction result is seen table 1.
Embodiment 6
Preparation of Catalyst and reaction conditions are with embodiment 1, and only changing temperature of reaction is 180 ℃.Reaction result is seen table 1.
Embodiment 7
Preparation of Catalyst and reaction conditions are with embodiment 1, and only changing reaction pressure is 10MPa.Reaction result is seen table 1.
Embodiment 8
Preparation of Catalyst and reaction conditions are with embodiment 1, and only changing reaction pressure is 1.0MPa.Reaction result is seen table 1.
Embodiment 9
Adopt the catalyzer of embodiment 1, the consumption that only changes salt of wormwood is 0.5 gram.Reaction result is seen table 1.
Embodiment 10
Adopt the catalyzer of embodiment 1, the consumption that only changes salt of wormwood is 5.0 grams.Reaction result is seen table 1.
Can find out from above reaction result.It is different that the employing different catalyst obtains the growing amount of cresols, and the growing amount of by product methyl catechol and Syringa oblata Lindl. alcohol can be regulated through adding different catalyst.Under low temperature and the low pressure reaction condition, the gross weight of product is less, and methyl catechol and Syringa oblata Lindl. alcohol growing amount is high in the product; Under the high-temperature high-voltage reaction condition, product is main with phenol and cresols.The growing amount of the consumption remarkably influenced product of alkali, the alkali usage quantity is low excessively, is unfavorable for the conversion of product.With data by MoM and MEI; Adopt method of the present invention, reaction conditions is gentle, and the overall selectivity of phenolic cpd is brought up to more than 70%; The transformation efficiency of substrate reaches 50%; And reaction a small amount of methyl catechol of by-product and Syringa oblata Lindl. alcohol, the overall selectivity of product reaches more than 90%, obviously is superior to existing reaction result.
Claims (10)
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