CN107286006B - Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin - Google Patents
Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin Download PDFInfo
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- CN107286006B CN107286006B CN201710429859.8A CN201710429859A CN107286006B CN 107286006 B CN107286006 B CN 107286006B CN 201710429859 A CN201710429859 A CN 201710429859A CN 107286006 B CN107286006 B CN 107286006B
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- 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
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- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- 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
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- 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
Abstract
The invention discloses a method for preparing vanillone and acetosyringone by catalyzing alcoholysis of lignin, which comprises the steps of carrying out microwave alcoholysis on lignin serving as a raw material in an alcohol solvent containing a supported metal catalyst, cooling, filtering and washing to obtain a liquid product mainly containing the vanillone and the acetosyringone, wherein the supported metal catalyst consists of an active center Co and a carrier; the invention provides an environment-friendly and low-price supported metal catalyst by improving the traditional lignin degradation method, realizes the high-efficiency degradation of lignin under the microwave heating condition, and prepares two types of compounds with higher yield: vanillone and acetosyringone; the method has the advantages of mild reaction conditions, short heating time and high reaction efficiency.
Description
Technical Field
The invention relates to the technical field of lignin utilization, in particular to a method for preparing vanillone and acetosyringone by catalyzing alcoholysis of lignin.
Background
Nowadays, the problems of the world energy consumption crisis, the serious environmental pollution and the like are increasingly concerned. The large amount of fossil fuels such as coal are used by human beings, so that the condition that energy is exhausted is caused, and the discharged waste gas and waste water seriously pollute the environment. Biomass energy is a new energy source with better development prospect, is renewable energy source in which solar energy is stored in plants in a chemical energy form, and is known as the best renewable energy source.
Biomass is composed primarily of cellulose, hemicellulose, and lignin. Lignin is a natural organic high molecular compound, second only in number to cellulose, and it is estimated that 1500 million tons of lignin are produced by plant growth worldwide every year. As a byproduct of the wood hydrolysis industry and the paper industry, the wood hydrolysis industry and the paper industry cannot be fully utilized, and become environmental pollutants, and seriously pollute the environment. Therefore, although the lignin resource is quite abundant, reasonable utilization is urgently needed.
The catalytic liquefaction of lignin is an important method for lignin degradation due to the relatively mild reaction conditions and relatively low reaction energy consumption. The solvent and the catalyst play an important role in the normal-pressure catalytic liquefaction of the lignin, so that the conversion rate of the lignin can be improved, and the product selectivity can be improved.
Chinese patent (CN 102295547A) reacts an oxidant with lignin in an alkaline solution, and after the reaction is finished, the reaction solution is acidified, extracted, concentrated and re-rectified to obtain the vanillone and the acetosyringone, and the purity of the vanillone and the acetosyringone is respectively 97.3 percent and 98.2 percent by gas chromatography analysis. After investigation, the vanillone and the acetosyringone are not only widely applied to the perfume industry, but also are important organic synthesis raw materials, can be used for synthesizing medicaments in medicine, and have important value. Transition metal catalysts such as cobalt, copper, iron, zinc and the like are good redox catalysts, so that the selection of a proper supported metal catalyst is of great importance in improving the selectivity and yield of products.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for preparing vanillone and acetosyringone under the action of a supported metal catalyst by using alcohols as a solvent under microwave-assisted heating.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for preparing vanillone and acetosyringone by catalyzing and alcoholyzing lignin is characterized in that the lignin is used as a raw material, microwave alcoholysis is carried out in an alcohol solvent containing a supported metal catalyst, and a liquid product mainly containing the vanillone and the acetosyringone is obtained by cooling, filtering and washing, wherein the supported metal catalyst is composed of an active center Co and a carrier.
Fe is introduced into the supported metal catalyst as an auxiliary agent, and the carrier is Al2O3、CeO2、ZrO2In MgOOne of (1) and (b). Fe is used as a catalyst promoter, so that more electron holes can be provided, the catalytic activity of Co can be improved, the C-H or C-C bond fracture of lignin is promoted, and the yield of a target product is improved. The four carriers are different in acid-base property, and the depolymerization effect can be compared.
The alcohol solvent is isopropanol. Alcohol solvents are used in lignin degradation applications due to their dissolution and hydrogen donating effects.
The method for preparing the vanillone and the acetosyringone by catalyzing and alcoholyzing the lignin comprises the following operation steps:
1) preparing a supported metal catalyst by adopting an impregnation method;
2) weighing lignin and an alcohol solvent with certain mass, adding the lignin and the alcohol solvent into a reaction tank, mixing, adding a supported metal catalyst with certain mass, mixing, putting the reaction tank into a microwave reactor, and reacting for 5-60 min under the conditions that the temperature is 100-180 ℃ and the microwave power is 600W;
3) and after the reaction is finished, taking out the reaction tank for natural cooling, filtering the product and washing the product by using a solvent to obtain a liquid product mainly containing the vanillone and the acetosyringone.
The mass ratio of the lignin to the supported metal catalyst in the step 2) is 1: 0.3-1; from the experimental results, it can be seen that: when the mass ratio of the catalyst is 0.3-1, the yield of the final product shows curve change, so that the dosage of the catalyst and the yield of the final product have direct influence; when the amount of the catalyst is less than 0.3, the yield of the final product is remarkably reduced, and when the amount of the catalyst is more than 0.8, the yield of the product is also remarkably reduced.
The method for preparing the supported metal catalyst by the impregnation method comprises the following steps:
1) weighing Co (NO)3)2·6H2Placing the O in a beaker, fully diluting the O into a solution by using deionized water, soaking the solution on the carrier in an equal volume, and stirring and soaking the solution for 24 hours at room temperature;
2) put into a drying oven 85°Drying for 12 h to obtain a catalyst precursor, and performing 500 times of drying on the catalyst precursor in a muffle furnace in an air atmosphere°C, calcining for 4 hours;
3) the calcined catalyst was brought to 90 mL/min H2Reducing for 1.5 h under the atmosphere, wherein the reduction temperature is 550°And C, obtaining the Co-loaded metal catalyst.
The supported metal catalyst of the invention has a Co loading amount of 5%, and the molar ratio of Co to Fe in the supported metal catalyst is 1: 0.3-0.8, and experimental results show that: when the molar ratio of Co to Fe in the supported metal catalyst is 1:0.3, the yield of the final product reaches a peak value, and when the molar ratio exceeds 0.3 or is less than 0.3, the yield of the final product is reduced.
The invention has the advantages that: the invention provides an environment-friendly and low-price supported metal catalyst by improving the traditional lignin degradation method, realizes the high-efficiency degradation of lignin under the microwave heating condition, and prepares two types of compounds with higher yield: vanillone and acetosyringone; the method has the advantages of mild reaction conditions, short heating time, high reaction efficiency and the like.
Drawings
FIG. 1 shows the effect of different supported catalysts on the distribution of high efficiency production of vanillone and acetosyringone by lignin alcoholysis in examples 3-5 of the present invention;
FIG. 2 is a graph showing the effect of Co/Fe molar ratio on the distribution of acetophenones and acetosyringone produced efficiently by lignin alcoholysis in examples 6-8 of the present invention;
FIG. 3 is a graph showing the effect of catalyst dosage on distribution of high efficiency production of vanilloethanone and acetosyringone by lignin alcoholysis in examples 9-11 of the present invention;
FIG. 4 is a graph showing the effect of reaction temperature on the distribution of the efficient production of vanillone and acetosyringone by lignin alcoholysis in examples 12-16 of the present invention;
FIG. 5 is a graph showing the effect of reaction time on the distribution of the efficient production of vanillone and acetosyringone by lignin alcoholysis in examples 17-20 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the following description of the drawings and the detailed description.
Example 1: weighing 1 g of lignin and 16 mL of isopropanol, mixing, adding into a reaction tank, placing the reaction tank into a microwave reactor, setting the microwave power at 600W, and reacting for 30 min at a certain reaction temperature of 120 ℃. And after the reaction is finished, taking out the digestion tank, and naturally cooling. The product was filtered and washed with isopropanol as a solvent, and the liquid product obtained after filtration was dissolved to 20 mL with isopropanol as a whole, and the liquid product was examined.
Example 2
a. 2.47 g Co (NO) are weighed3)2·6H2Placing O in a beaker, fully diluting with deionized water to obtain a solution, and soaking in 10 g of Al in equal volume2O3The support was immersed for 24 hours at room temperature with stirring. Then put into a drying oven 85°Drying for 12 h to obtain a catalyst precursor, and performing 500 times of drying on the catalyst precursor in a muffle furnace in an air atmosphere°And C, 4 h of calcination. Finally, the calcined catalyst was placed in a 90 mL/min H2Reducing for 1.5 h under the atmosphere, wherein the reduction temperature is 550°C, obtaining the catalyst 5 percent Co/Al2O3。
b. Weighing 1 g of lignin and 16 mL of isopropanol, mixing, adding into a reaction tank, and adding 0.5 g of catalyst 5% Co/Al2O3Mixing the materials in a reaction tank, placing the reaction tank into a microwave reactor, setting the microwave power at 600W, and reacting for 30 min at a certain reaction temperature of 120 ℃. And after the reaction is finished, taking out the digestion tank, and naturally cooling. The product was filtered and washed with isopropanol as a solvent, and the liquid product obtained after filtration was dissolved to 20 mL with isopropanol as a whole, and the liquid product was examined.
Examples 3 to 5
a. 5% Co/ZrO2、5% Co/CeO 25% Co/MgO catalyst preparation the procedure used step a in example 2, except that different supports of ZrO were used respectively2、CeO2And MgO to prepare the catalyst.
b. Degradation of lignin with catalyst in isopropanol solvent step b of example 2 was used, except that the catalyst type added was 5% Co/ZrO/Co2、5% Co/CeO2、5% Co/MgO。
And (3) qualitatively detecting the liquid product by adopting GC/MS (gas chromatography-mass spectrometry), and directly obtaining the peak area relation of two products (the vanillone and the acetosyringone) with higher yield in the liquid product. The results of the effect of different catalysts on the distribution of the lignin alcoholysis products are shown in FIG. 1.
Example 6
a. 2.47 g Co (NO) are weighed3)2·6H2O in a beaker, and 1.80 g of Fe (NO) was weighed3)3·9H2Placing O in a beaker, fully diluting with deionized water to obtain a solution, and soaking in 10 g of Al in equal volume2O3The support was immersed for 24 hours at room temperature with stirring. Then put into a drying oven 85°Drying for 12 h to obtain a catalyst precursor, and performing 500 times of drying on the catalyst precursor in a muffle furnace in an air atmosphere°And C, 4 h of calcination. Finally, the calcined catalyst was placed in a 90 mL/min H2Reducing for 1.5 h under the atmosphere, wherein the reduction temperature is 550°C, obtaining Co-Fe/Al2O3The bimetallic catalyst has Co loading of 5% and Co/Fe molar ratio of 1: 0.5.
b. Weighing 1 g of lignin and 16 mL of isopropanol, mixing, adding into a reaction tank, and adding 0.5 g of bimetallic catalyst Co-Fe/Al2O3Mixing the materials in a reaction tank, placing the reaction tank into a microwave reactor, setting the microwave power at 600W, and reacting for 30 min at a certain reaction temperature of 120 ℃. And after the reaction is finished, taking out the digestion tank, and naturally cooling. The product was filtered and washed with isopropanol as a solvent, and the liquid product obtained after filtration was dissolved to 20 mL with isopropanol as a whole, and the liquid product was examined.
Examples 7 to 8:
a. the Co load is 5 percent, the Co/Fe molar ratio is 1:0.3, the bimetallic catalyst Co-Fe/Al of 1:0.82O3The procedure was as in a in example 6 except that 1.08 g and 2.89 g of Fe (NO) were weighed out separately3)3·9H2O with 2.47 g Co (NO)3)2·6H2And mixing the O salt solution to prepare the catalyst.
b. The degradation step of lignin and catalyst in isopropanol solvent adoptsExample 2, except that the catalyst type was a bimetallic catalyst Co-Fe/Al with a Co loading of 5% and Co/Fe molar ratios of 1:0.3 and 1:0.8, respectively2O3。
And (3) qualitatively detecting the liquid product by adopting GC/MS (gas chromatography-mass spectrometry), and directly obtaining the peak area relation of two products (the vanillone and the acetosyringone) with higher yield in the liquid product. The results of the effect of different catalysts on the distribution of the lignin alcoholysis products are shown in FIG. 2.
Example 9: weighing 1 g of lignin and 16 mL of isopropanol, mixing, adding into a reaction tank, and adding Co loading: 5%, Co/Fe molar ratio: 1:0.3 bimetallic catalyst Co-Fe/Al2O3Mixed together in a reaction tank and the amount of the catalyst used was 0.3 g. And (3) placing the reaction tank into a microwave reactor, setting the microwave power to be 600W, and reacting for 30 min at a certain reaction temperature of 120 ℃. And after the reaction is finished, taking out the digestion tank, and naturally cooling. The product was filtered and washed with isopropanol as a solvent, and the liquid product obtained after filtration was dissolved to 20 mL with isopropanol as a whole, and the liquid product was examined.
Examples 10 to 11: the procedure of example 9 was followed except that the catalysts were added in amounts of 0.8 g and 1 g, respectively.
And (3) qualitatively detecting the liquid product by adopting GC/MS (gas chromatography-mass spectrometry), and directly obtaining the peak area relation of two products (the vanillone and the acetosyringone) with higher yield in the liquid product. The results of the effect of different catalysts on the distribution of the lignin alcoholysis products are shown in FIG. 3.
Example 12: weighing 1 g of lignin and 16 mL of isopropanol, mixing, adding into a reaction tank, and adding Co loading: 5%, Co/Fe molar ratio: 1:0.3 bimetallic catalyst Co-Fe/Al2O3Mixed together in a reaction tank and the amount of the catalyst used was 0.8 g. And (3) placing the reaction tank into a microwave reactor, setting the microwave power to be 600W, and reacting for 30 min at a certain reaction temperature of 100 ℃. And after the reaction is finished, taking out the digestion tank, and naturally cooling. The product was filtered and washed with isopropanol as a solvent, and the liquid product obtained after filtration was dissolved to 20 mL with isopropanol as a whole, and the liquid product was examined.
Examples 13 to 16: the procedure of example 12 was followed for the degradation of lignin and catalyst in isopropanol solvent, except that the reaction temperatures were 120 ℃, 140 ℃, 160 ℃ and 170 ℃, respectively.
And (3) qualitatively detecting the liquid product by adopting GC/MS (gas chromatography-mass spectrometry), and directly obtaining the peak area relation of two products (the vanillone and the acetosyringone) with higher yield in the liquid product. The results of the effect of different catalysts on the distribution of the lignin alcoholysis products are shown in FIG. 4.
Example 17: weighing 1 g of lignin and 16 mL of isopropanol, mixing, adding into a reaction tank, and adding Co loading: 5%, Co/Fe molar ratio: 1:0.3 bimetallic catalyst Co-Fe/Al2O3Mixed together in a reaction tank and the amount of the catalyst used was 0.8 g. And (3) placing the reaction tank into a microwave reactor, setting the microwave power to be 600W, and reacting for 5 min at a certain reaction temperature of 140 ℃. And after the reaction is finished, taking out the digestion tank, and naturally cooling. The product was filtered and washed with isopropanol as a solvent, and the liquid product obtained after filtration was dissolved to 20 mL with isopropanol as a whole, and the liquid product was examined.
Examples 18 to 20: the procedure of example 17 was followed for the degradation of lignin and catalyst in isopropanol solvent, except that the reaction times were 15 min, 45 min, and 60 min, respectively.
And (3) qualitatively detecting the liquid product by adopting GC/MS (gas chromatography-mass spectrometry), and directly obtaining the peak area relation of two products (the vanillone and the acetosyringone) with higher yield in the liquid product. The results of the effect of different catalysts on the distribution of the lignin alcoholysis products are shown in FIG. 5.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and any combination or equivalent changes made on the basis of the above-mentioned embodiments are also within the scope of the present invention.
Claims (1)
1. A method for preparing vanillone and acetosyringone by catalyzing and alcoholyzing lignin is characterized in that the method takes lignin as a raw material, carries out microwave alcoholysis in an alcohol solvent containing a supported metal catalyst,cooling, filtering and washing to obtain a liquid product mainly containing the vanillone and the acetosyringone, wherein the supported metal catalyst consists of an active center Co and a carrier; fe is introduced into a load type metal catalyst as an auxiliary agent, and the carrier is Al2O3、CeO2、ZrO2MgO; the alcohol solvent is isopropanol; the loading amount of Co in the supported metal catalyst is 5%, and the molar ratio of Co to Fe in the supported metal catalyst is 1: 0.3-0.8;
the method comprises the following operation steps:
1) preparing a supported metal catalyst by adopting an impregnation method;
2) weighing lignin and an alcohol solvent with certain mass, adding the lignin and the alcohol solvent into a reaction tank, mixing, adding a supported metal catalyst with certain mass, mixing, putting the reaction tank into a microwave reactor, and reacting for 5-60 min under the conditions that the temperature is 100-180 ℃ and the microwave power is 600W, wherein the mass ratio of the lignin to the supported metal catalyst is 1: 0.3-1;
3) and after the reaction is finished, taking out the reaction tank for natural cooling, filtering the product and washing the product by using a solvent to obtain a liquid product mainly containing the vanillone and the acetosyringone.
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| CN109824497B (en) * | 2019-03-06 | 2020-10-27 | 华南理工大学 | Method for preparing single benzene ring compound by degrading alkali lignin through microwave synergistic metalloporphyrin catalytic oxidation |
| CN110639604B (en) * | 2019-09-09 | 2022-04-22 | 华南理工大学 | Black liquor lignin hydrogenolysis catalyst and preparation method and application thereof |
| CN111302910B (en) * | 2020-03-13 | 2023-01-13 | 中国科学院广州能源研究所 | Method for producing acetophenone and acetic acid by biomass directional catalysis |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875343A (en) * | 2012-10-31 | 2013-01-16 | 南京林业大学 | Method for preparing aromatic aldehyde compound by catalyzing and degrading lignin with loaded solid acid |
| CN103508857A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for depolymerizing lignin into aromatic compounds under conditions of no additional hydrogen |
| CN103724189A (en) * | 2013-10-10 | 2014-04-16 | 华南理工大学 | Method for preparing monophenol compound by liquefying and degrading lignin through microwave concerted catalysis |
| CN105503540A (en) * | 2014-09-24 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for preparation of benzene ring phenol compound from alkali lignin |
| CN106565435A (en) * | 2016-10-27 | 2017-04-19 | 华南理工大学 | Method of selectively preparing aromatic aldehydes and aromatic methyl esters by degrading lignin with microwave assistance |
-
2017
- 2017-06-09 CN CN201710429859.8A patent/CN107286006B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508857A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for depolymerizing lignin into aromatic compounds under conditions of no additional hydrogen |
| CN102875343A (en) * | 2012-10-31 | 2013-01-16 | 南京林业大学 | Method for preparing aromatic aldehyde compound by catalyzing and degrading lignin with loaded solid acid |
| CN103724189A (en) * | 2013-10-10 | 2014-04-16 | 华南理工大学 | Method for preparing monophenol compound by liquefying and degrading lignin through microwave concerted catalysis |
| CN105503540A (en) * | 2014-09-24 | 2016-04-20 | 中国科学院大连化学物理研究所 | Method for preparation of benzene ring phenol compound from alkali lignin |
| CN106565435A (en) * | 2016-10-27 | 2017-04-19 | 华南理工大学 | Method of selectively preparing aromatic aldehydes and aromatic methyl esters by degrading lignin with microwave assistance |
Non-Patent Citations (3)
| Title |
|---|
| "Stabilizing cobalt catalysts for aqueous-phase reactions by strong metal-support interaction";Jechan L. et al;《Journal of Catalysis》;20150717;第330卷;第19-27页 * |
| "微波辅助木质素催化酸解机理研究";周强等;《太阳能学报》;20160630;第37卷(第6期);第1542-1546页 * |
| "微波辅助木质素醇解制备芳香化合物";刘娜娜等;《东南大学学报（自然科学版）》;20170531;第47卷(第3期);第529、532-533页 * |
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