CN1301241C - Method for preparing vanillin - Google Patents
Method for preparing vanillin Download PDFInfo
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- CN1301241C CN1301241C CNB2005101008410A CN200510100841A CN1301241C CN 1301241 C CN1301241 C CN 1301241C CN B2005101008410 A CNB2005101008410 A CN B2005101008410A CN 200510100841 A CN200510100841 A CN 200510100841A CN 1301241 C CN1301241 C CN 1301241C
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- food grade
- vanillin food
- vanillin
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- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 235000012141 vanillin Nutrition 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title abstract description 9
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 13
- 238000006552 photochemical reaction Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 230000015556 catabolic process Effects 0.000 claims abstract description 4
- 235000013305 food Nutrition 0.000 claims description 43
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 235000019357 lignosulphonate Nutrition 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000004237 preparative chromatography Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 10
- 229920005610 lignin Polymers 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000006277 sulfonation reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 150000008054 sulfonate salts Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 230000000593 degrading effect Effects 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 150000003384 small molecules Chemical class 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000004537 pulping Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 6
- 229960001867 guaiacol Drugs 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- BPMFZUMJYQTVII-UHFFFAOYSA-N guanidinoacetic acid Chemical compound NC(=N)NCC(O)=O BPMFZUMJYQTVII-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- -1 methoxyl group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 241000732800 Cymbidium Species 0.000 description 1
- 241000190019 Guaiacum Species 0.000 description 1
- 235000004440 Guaiacum sanctum Nutrition 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing vanillin, which is characterized in that sulfonation is carried out on lignin in pulp-making waste liquid to obtain lignin sulfonate salt, and the salt is dissolved in water. The obtained solution is placed in a photochemical reaction vessel, and degradation of photocatalytic oxidation is carried out by using an ultraviolet lamp to carry out irradiation within a temperature range between normal temperature and 80 DEG C and leading air or oxygen into the vessel under the function of semiconductor photochemical catalysts to obtain products. The present invention overcomes the problems which exist in current methods for preparing vanillin at home and abroad and develops a preparation method having the advantages of low cost, simple technology, moderate reaction condition and no secondary pollution. The present invention reduces environmental pollution in paper-making industry and simultaneously carries out comprehensive application on pulp-making waste liquid, and vanillin with high added value can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of vanillin food grade,1000.000000ine mesh, relate in particular to a kind of method for preparing vanillin food grade,1000.000000ine mesh by the photochemical catalysis xylogen.
Background technology
Vanillin food grade,1000.000000ine mesh (Vanillin) is the kind of output maximum in the perfume industry, its chemistry 3-methoxyl group by name-4-hydroxy benzaldehyde.The purposes of vanillin food grade,1000.000000ine mesh is very extensive, except being the major ingredient of the cream vanilla generally liked of people, also as perfume material, correctives or fixative, wherein food department consumptions such as cake, biscuit, candy, beverage and roasted seeds and nuts are in the majority in food, daily use chemicals, tobacco industry.
Chinese cymbidium have the branch of natural product and sintetics.Natural product are mainly extracted from XIANGJIALANDOU, and the vanillin food grade,1000.000000ine mesh that obtains is 3,000 dollars/kilogram, and not only rare, the limited amount of raw material but also cost an arm and a leg far can not satisfy the growing market requirement.So vanillin food grade,1000.000000ine mesh product is in the market mainly obtained by chemical synthesis.Synthesis method commonly used has two kinds, and the one, the xylogen method that adopt in the U.S., Canada and West Europe, promptly to be that raw material is synthetic obtain the xylogen from pulping waste liquor, and this preparation method's alkali consumption is huge, so the cost costliness; Another kind is the nitroso process that China selects for use, be to use nitroso-group N after methyl catechol (guaiacol) and the aldehyde condensation, the accelerine oxidation obtains vanillin food grade,1000.000000ine mesh, because the raw material Ortho Anisidine of preparation methyl catechol needs import, therefore methyl catechol costs an arm and a leg, the production cost height, the by product P-aminodimethylaniline for preparing the reaction generation of vanillin food grade,1000.000000ine mesh in addition can cause serious environmental to be polluted, and therefore the vanillin food grade,1000.000000ine mesh preparation method of present domestic use lacks competitive capacity.
Paper-making effluent is one of present main environmental pollution thing, wherein pollutes the most serious with pulping waste liquor especially.Xylogen is the main component of pulping waste liquor, if therefore can make full use of the pollution that these xylogen will reduce environment, and turns waste into wealth.
The heterogeneous photocatalysis oxidation technique of semi-conductor is one of field the most active in the our times water treatment research, has the reaction conditions gentleness, advantages such as speed is fast, efficient is high, the simple cleaning of technology, non-secondary pollution.
Summary of the invention
The objective of the invention is to utilize the heterogeneous photocatalysis oxidation technique of semi-conductor to develop a kind of is the preparation method of vanillin food grade,1000.000000ine mesh of the with low cost and environmental protection of raw material with the xylogen in the pulping waste liquor.
The present invention obtains sulfonated lignin with the xylogen sulfonation in the pulping waste liquor, carries out photocatalytic oxidation degradation then under the effect of semiconductor light-catalyst, obtains vanillin food grade,1000.000000ine mesh, this preparation method's starting material are cheap, technology is simple, and non-secondary pollution, thereby has realized purpose of the present invention.
The preparation method of vanillin food grade,1000.000000ine mesh of the present invention, it is characterized in that in photochemical reaction device, the lignosulfonic acid salt brine solution is having semiconductor light-catalyst and is passing under the air or oxygen condition, carry out photocatalytic oxidation degradation with UV-lamp in the temperature range internal irradiation of normal temperature to 80 ℃, separate, obtain product, the sulfonated lignin quality is 5%～50% of a quality in the described lignosulfonic acid salt brine solution, and described semiconductor light-catalyst consumption is 0.5%～1% of an above-mentioned quality.
Described sulfonated lignin can be buied from city's field boundary, are preferably 10% of quality, and described photochemical reaction device can adopt commercially available device, preferably adopt the device shown in the figure (1), and described semiconductor light-catalyst can be TiO
2Or ZnO or Fe
2O
3Deng, preferably stir after the adding or ultra-sonic dispersion is suspended in the solution photocatalyst, the ratio that the preferably every 100mL solution of the power of described ultraviolet lamp is 100 watts, the described photocatalytic oxidation degradation reaction times is 9～11 hours, preferably 10 hours, described separation can be adopted conventional separation method, for example use chloroform, organic solvent such as benzene or dimethylbenzene extracts and with preparative chromatography post separation etc., described product also comprises vanillin food grade,1000.000000ine mesh precursor such as guaiacol except mainly being the vanillin food grade,1000.000000ine mesh, lignum-vitae guanidine-acetic acid and 1-hydroxyl-3-(4-hydroxyl-3-methoxyl group) phenyl-acetone etc. and lignin degrading and other small molecules products.
The present invention adopts novel conductor photocatalysis oxidation technology that the main component xylogen of pulping waste liquor is carried out oxidative degradation, when reducing the paper industry environmental pollution, can fully utilize pulping waste liquor again, obtain to have the high value-added product vanillin food grade,1000.000000ine mesh.This method technology is simple, reaction conditions gentleness, and non-secondary pollution.
Description of drawings
Fig. 1: photochemical reaction device structural representation.
Fig. 2: the document figure (figure below) of isolating vanillin food grade,1000.000000ine mesh mass spectrum (last figure) and vanillin food grade,1000.000000ine mesh in the reaction product.
Embodiment
Following examples are to further specify of the present invention, are not limitations of the present invention.
Embodiment 1
Adopt photochemical reaction device shown in Figure 1, this device is with reaction tubes 2 two portions members of water-bath chuck in conjunction with forming by a silica glass inner sleeve 1 and.Space A can place a tubular light source in the pipe of silica glass inner sleeve 1, vertically be sintered to fix a silica glass inlet pipe 3 along tube wall one side in the pipe, this pipe extends to the inner sleeve bottom always and passes its central authorities and communicates with the space B of pipe outside, and this tubule can be used for feeding gaseous substance in reaction solution.Two-layer inside and outside the reaction tubes of band water-bath chuck 2 minutes, constitute the water-bath chuck C of a sealing, water-bath chuck C leaves water-in 5 in the bottom, leave water outlet 6 on top, be used for being used for the homothermic fluid medium to chuck feeding recirculated water or other, also have a glass escape pipe 4 that is bent upwards, this pipe to pass water-bath chuck C in the upper end of reaction tubes and communicate, be used for discharging the gaseous substance that the quartzy inlet pipe by silica glass inner sleeve 1 part feeds to reaction medium with the B space of reaction tubes internal layer.
Space A places the ultraviolet light source of 1000 watts of tubuloses in the pipe of silica glass inner sleeve 1 in above-mentioned photochemical reaction device shown in Figure 1, get the 100g sulfonated lignin and put into the B space of the reaction tubes 2 of band water-bath chuck, inject the 1000mL water dissolution, add 10g TiO
2Stir by silica glass inlet pipe 3 to reaction solution feeding sufficient amount of oxygen with magnetic stirrer, water-bath chuck C feeds recirculated water, open ultraviolet lamp, normal temperature reacts after 10 hours down, with chloroform extraction, separate with the preparative chromatography post then, can get about vanillin food grade,1000.000000ine mesh 0.5g and a certain amount of vanillin food grade,1000.000000ine mesh precursor, lignin degrading and some other small molecules products.
Embodiment 2
Photochemical reaction device structure that is adopted and principle of work are with embodiment 1.
Get the 100g sulfonated lignin, use the 1000mL water dissolution, add the 5g nano-TiO
2Ultra-sonic dispersion 20 minutes, inject figure (1) apparatus for photoreaction then, stir and feed sufficient amount of oxygen with magnetic stirrer, open 1000 watts of ultraviolet lamps, normal temperature reacts after 9 hours, with chloroform extraction down, separate with the preparative chromatography post, can get about vanillin food grade,1000.000000ine mesh 1g and a certain amount of vanillin food grade,1000.000000ine mesh precursor, lignin degrading and some other small molecules products.
Embodiment 3
Photochemical reaction device structure that is adopted and principle of work are with embodiment 1.
Get the 100g sulfonated lignin, use the 1000mL water dissolution, add 5g TiO
2, ultra-sonic dispersion 20 minutes.Inject the apparatus for photoreaction of figure (1) then, stir and feed the capacity air with magnetic stirrer, open 1000 watts of ultraviolet lamps, 50 ℃ the reaction 11 hours after, with chloroform extraction, separate with the preparative chromatography post, can get about vanillin food grade,1000.000000ine mesh 1.2g and a certain amount of vanillin food grade,1000.000000ine mesh precursor, lignin degrading and some other small molecules products.
Embodiment 4
Photochemical reaction device structure that is adopted and principle of work are with embodiment 1.
Get the 50g sulfonated lignin, use the 1000mL water dissolution, add the 5g nano-TiO
2Ultra-sonic dispersion 20 minutes, inject the apparatus for photoreaction of figure (1) then, stir and feed the capacity air with magnetic stirrer, open 1000 watts of ultraviolet lamps, after 10 hours, extract with benzene 50 ℃ of reactions, separate with the preparative chromatography post, can get about vanillin food grade,1000.000000ine mesh 0.7g and a certain amount of vanillin food grade,1000.000000ine mesh precursor, lignin degrading and some other small molecules products.
Embodiment 5
Photochemical reaction device structure that is adopted and principle of work are with embodiment 1.
Get the 500g sulfonated lignin, use the 1000mL water dissolution, add the 5g nano-TiO
2, ultra-sonic dispersion 20 minutes injects the apparatus for photoreaction of scheming (1) then, stirs and feeding capacity air with magnetic stirrer, opens 1000 watts of ultraviolet lamps.,, separate after 10 hours 80 ℃ of reactions, can get about vanillin food grade,1000.000000ine mesh 3g and a certain amount of vanillin food grade,1000.000000ine mesh precursor, lignin degrading and some other small molecules products with the preparative chromatography post with xylene extraction.
Embodiment 6
Photochemical reaction device structure that is adopted and principle of work are with embodiment 1.
Getting the 100g sulfonated lignin puts in the apparatus for photoreaction of figure (1), use the 1000mL water dissolution, add 10g ZnO, stir and feed the capacity air with magnetic stirrer, open 1000 watts of ultraviolet lamps, react 10 hours at normal temperatures after, with chloroform extraction, separate with the preparative chromatography post, can get about vanillin food grade,1000.000000ine mesh 0.4g and a certain amount of vanillin food grade,1000.000000ine mesh precursor, lignin degrading and some other small molecules products.
Embodiment 7
Photochemical reaction device structure that is adopted and principle of work are with embodiment 1.
Get the 100g sulfonated lignin and put in the apparatus for photoreaction, use the 1000mL water dissolution, add 10g Fe
2O
3, stir and feeding capacity air with magnetic stirrer, open 1000 watts of ultraviolet lamps, after reacting 10 hours at normal temperatures, with chloroform extraction, separate with the preparative chromatography post, can get about vanillin food grade,1000.000000ine mesh 0.2g and a certain amount of vanillin food grade,1000.000000ine mesh precursor, lignin degrading and some other small molecules products.
Embodiment 8
The bibliographic reference figure (Fig. 2 figure below) of vanillin food grade,1000.000000ine mesh compares in the mass spectrum (the last figure of Fig. 2) of the vanillin food grade,1000.000000ine mesh that embodiment 1～7 is obtained and the Computer Database.Vanillin food grade,1000.000000ine mesh and the vanillin food grade,1000.000000ine mesh in the document that proof embodiment obtains are same substances.Its main peaks ownership: mass-to-charge ratio 152 places are molecular ion peaks of vanillin food grade,1000.000000ine mesh, and base peak 151 is that molion loses the quasi-molecular ions that forms behind the H.The 28th, from the C ≡ O in the aldehyde radical
+Quasi-molecular ions.The 137th, molion loses the fragmention behind the methyl on the methoxyl group.The 123rd, molion loses a fragment ion peak behind the aldehyde radical.The 109th, the methoxyl group of molion loses a methyl and the fragmention that carbonyl forms.
Claims (4)
1. the preparation method of a vanillin food grade,1000.000000ine mesh, it is characterized in that in photochemical reaction device, the lignosulfonic acid salt brine solution is having semiconductor light-catalyst and is passing under the air or oxygen condition, carry out photocatalytic oxidation degradation with UV-lamp in the temperature range internal irradiation of normal temperature to 80 ℃, separate, obtain product, the sulfonated lignin quality is 5%～50% of a quality in the described lignosulfonic acid salt brine solution, and described semiconductor light-catalyst consumption is 0.5%～1% of an above-mentioned quality.
2. according to the preparation method of a kind of vanillin food grade,1000.000000ine mesh of claim 1, the quality that it is characterized in that described sulfonated lignin is 10% of a quality, and described semiconductor light-catalyst is TiO
2Or ZnO or Fe
2O
3, add the back and stir or ultra-sonic dispersion.
3. according to the preparation method of a kind of vanillin food grade,1000.000000ine mesh of claim 1 or 2, the power that it is characterized in that described ultraviolet lamp is the ratio of 100 watts of every 100mL solution, the described photocatalytic oxidation degradation reaction times is 9～11 hours, described separation is to extract with organic solvent, and separates with the preparative chromatography post.
4. according to the preparation method of a kind of vanillin food grade,1000.000000ine mesh of claims 3, it is characterized in that the described photocatalytic oxidation degradation reaction times is 10 hours, described organic solvent is chloroform, benzene or dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101008410A CN1301241C (en) | 2005-10-28 | 2005-10-28 | Method for preparing vanillin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101008410A CN1301241C (en) | 2005-10-28 | 2005-10-28 | Method for preparing vanillin |
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|---|---|
| CN1757623A CN1757623A (en) | 2006-04-12 |
| CN1301241C true CN1301241C (en) | 2007-02-21 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237371B (en) * | 2015-11-13 | 2017-03-22 | 南京工业大学 | Method for preparing vanillin by catalytic oxidative degradation of lignin |
| CN106188164B (en) * | 2016-06-29 | 2018-04-06 | 中国矿业大学 | A kind of method of photocatalytic oxidation degradation biomass preparative organic chemistry product |
| CN106906685B (en) * | 2017-02-28 | 2018-12-07 | 齐鲁工业大学 | A method of high added value phenol products are prepared by black liquor of pulp making |
| CN108863747A (en) * | 2018-07-16 | 2018-11-23 | 南京雪郎化工科技有限公司 | A kind of preparation method of vanillic aldehyde |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2164511C1 (en) * | 2000-04-03 | 2001-03-27 | Институт химии и химической технологии СО РАН | Method for production of aromatic aldehydes from lignin-containing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2164511C1 (en) * | 2000-04-03 | 2001-03-27 | Институт химии и химической технологии СО РАН | Method for production of aromatic aldehydes from lignin-containing material |
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