CN106316733B - The method of alcohol compound aromatisation aromatic hydrocarbons - Google Patents

The method of alcohol compound aromatisation aromatic hydrocarbons Download PDF

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CN106316733B
CN106316733B CN201510345786.5A CN201510345786A CN106316733B CN 106316733 B CN106316733 B CN 106316733B CN 201510345786 A CN201510345786 A CN 201510345786A CN 106316733 B CN106316733 B CN 106316733B
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alcohol
aromatic hydrocarbons
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alcohol compound
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宋奇
郑均林
孔德金
徐旋
姜向东
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a kind of methods of alcohol compound aromatisation aromatic hydrocarbons to make C under aromatization conditions4~6Alcohol is contacted with catalyst generates the arene stream containing benzene, toluene and dimethylbenzene;The catalyst is selected from compound Zirconium oxide XaOb/ZrO2;Wherein, X is selected from least one of tungsten, molybdenum, cerium, lanthanum or manganese, and a and b are stoichiometric number;In the compound Zirconium oxide, based on parts by weight, XaObDosage be 0.1~40 part, ZrO2Dosage be 60~99.9 parts.This method can be used for non-fossil sources aromatic hydrocarbons field.

Description

The method of alcohol compound aromatisation aromatic hydrocarbons
Technical field
The present invention relates to a kind of methods of alcohol compound aromatisation aromatic hydrocarbons.
Background technique
Biomass is the renewable resource that nature is widely present, and has the characteristics that neutral carbon is environmentally friendly.The whole world is raw The annual yield of substance is about 200,000,000,000 tons, and rich reserves are from a wealth of sources, cheap and easy to get.Go out from reproducible biomass resource Hair is prepared with the extensive concern that widely applied aromatic hydrocarbon product causes scientific circles and industry.
Cellulose and hemicellulose are one of main compositions of biomass, and internal structural unit is pentose and six carbon Sugar, such as glucose and fructose.From pentose and hexose by reformation, the pure and mild carbon six of light dydrocarbon can be obtained Alcohol, the two have application in field of medicaments and perfume industry.Still further aspect, the pure and mild six carbon alcohol of five carbon can obtain carbon by conversion Five and carbon six alkene, double bond can further be alkylated to obtain more products under the action of acid catalyst.Such as Amylene can form amylbenzene or toluene with aromatic hydrocarbons such as benzene, toluene, further be cyclized available methyl substituted naphthalene.
Currently, benzene, toluene and dimethylbenzene are the important basic organic chemical industry raw materials of social development, its own or process are again Production can derive multiple product chain, and product is widely used in many necks such as polyester, chemical fibre, rubber, medicine and fine chemistry industry Domain, domestic consumption amount reach up to ten million tons, have great influence to the national economic development.Benzene is that a kind of basic petrochemical industry of multipurpose is former Material can produce numerous products, including ethyl benzene/styrene, cumene/phenol derived from it etc..Paraxylene is mainly used for Terephthalic acid (TPA) is manufactured, it is poly- cruel for producing by terephthalic acid (TPA) (PTA) or diethyl terephthalate (DMT) intermediate Fiber such as polyethylene terephthalate (PET), resin and film.These three types of aromatic hydrocarbons are typical light aromatics, are abbreviated as BTX.The production of BTX depends on non-renewable fossil resource both at home and abroad at present, such as can be by a catalyst by petroleum By adding the technical process such as hydrogen, reformation, aromatic hydrocarbons conversion and separation to obtain.But fossil resource reserves are limited and non-renewable, So that more being seen with the cost that petroleum is main refining raw material production aromatic hydrocarbons surging.In addition, continually developing for fossil resource utilizes production Raw a large amount of greenhouse gas emissions, caused a series of environmental problems are on the rise, therefore develop raw from renewable resource route Produce that aromatic hydrocarbons is significant and application value.
Six alcohol of carbon pure and mild for biomass-based light dydrocarbon can be further oxidized to aldehyde and perhaps acid or be dehydrated into alkene. But it is rarely reported at present and the pure and mild six alcohol aromatization of carbon of light dydrocarbon is turned into aromatic hydrocarbons.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of alcohol compound aromatisation aromatic hydrocarbons.Such alcohol compound can It is obtained by the biomass material of rich reserves from a wealth of sources, it can be with large scale preparation.It is raw that this method increase traditional aromatic hydrocarbons Production method can be used as the supplement of fossil resource production aromatic hydrocarbons, with the high-efficient and easy industrialization amplification of at low cost, aromatisation Feature.
For achieving the above object, The technical solution adopted by the invention is as follows: a kind of alcohol compound aromatisation system is fragrant The method of hydrocarbon makes C under aromatization conditions4~6Alcohol is contacted with catalyst generates the arene stream containing benzene, toluene and dimethylbenzene;
The catalyst is selected from compound Zirconium oxide XaOb/ZrO2;Wherein, X in tungsten, molybdenum, cerium, lanthanum or manganese at least One kind, a and b are stoichiometric number;In the compound Zirconium oxide, based on parts by weight, XaObDosage be 0.1~40 part, ZrO2Dosage be 60~99.9 parts.
In above-mentioned technical proposal, the C4~6Alcohol is selected from n-butyl alcohol, 2- butanol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 1,2- penta Glycol, 1,3- pentanediol, 1,4- pentanediol, 1,5- pentanediol, 1- hexanol, 2- hexanol, 3- hexanol, 1,2- hexylene glycol, 1,3- oneself At least one in glycol, 1,4- hexylene glycol, 1,5- hexylene glycol, 1,6-HD, 1,2,3- hexanetriol, sorbierite or xylitol Kind.
In above-mentioned technical proposal, it is preferable that the C4~6Alcohol comes from biological material.
In above-mentioned technical proposal, it is preferable that the C4~6Alcohol is in glucose, cellobiose, hemicellulose or lignin At least one.
In above-mentioned technical proposal, it is preferable that the C4~6Alcohol comes from bagasse, glucose, timber, corn stalk or straw straw At least one of.
In above-mentioned technical proposal, it is preferable that in the compound Zirconium oxide, based on parts by weight, XaObDosage be 1~ 40 parts, ZrO2Dosage be 60~99 parts.
In above-mentioned technical proposal, it is preferable that the aromatization conditions are as follows: 300~800 DEG C of reaction temperature, Hydrogen Vapor Pressure with Gauge pressure 0.1~5MPa of meter, raw material weight air speed 0.3~10 hour-1.It is highly preferred that the aromatization conditions are as follows: reaction temperature 300~650 DEG C, Hydrogen Vapor Pressure 0.5~4MPa in terms of gauge pressure, raw material weight air speed 0.3~5 hour-1
Heretofore described compound Zirconium oxide XaOb/ZrO2;Wherein, X in tungsten, molybdenum, cerium, lanthanum or manganese at least One kind, a and b are stoichiometric number, this is related with the chemical valence of selected metal.When selected metal determines, each subscript has Determining numerical value.Infusion process or the precipitation method known in the art can be used in its preparation.Infusion process is by tungsten, molybdenum, cerium, lanthanum or manganese It is impregnated on zirconium oxide in the form of salting liquid, dipping outwells surplus liquid after 12~48 hours, 100~200 DEG C of drying process will Moisture, which is evaporated, leaves active component, using other up to the carrier catalysis of high degree of dispersion after roast, activation procedure processing.It is heavy Shallow lake method can by the way that the aqueous metal solution of the aqueous metal salt of tungsten, molybdenum, cerium, lanthanum or manganese, zirconium and precipitating reagent ammonium hydroxide are added simultaneously, Generate solid precipitating.The precipitating of generation is washed, filtering, dry, catalyst can be obtained in roasting after at 400~600 DEG C.
As an embodiment of the invention, raw material of the present invention is biomass-based alcoholic compound.Such alcoholization Closing object can be obtained by biomass material from a wealth of sources, rich reserves, can be with large scale preparation.For example, n-butanol and isobutyl Alcohol can obtain (Chinese patent CN201210509488.1 by the method for fermentation of biomass;CN201280029221.0; CN201110396100.7);The sugar alcohols such as sorbierite and xylitol can be obtained, i.e., by the modes such as hydrocellulose or squeezing sugar After obtaining the sugar such as glucose, sucrose, cellobiose and fructose, by adding hydrogen to obtain sorbierite and xylitol (Conversion of Cellulose into Sorbitol over Carbon Nanotube-Supported Ruthenium Catalyst, Catalysis Letters, 133 (1), 167-174,2009;Glucose Hydrogenation to Sorbitol over A Skeletal NiP Amorphous Alloy Catalyst (Raney NiP), Journal of Catalysis, 191 (1), 257-260,2000;).In addition, the monohydric alcohol and polyalcohol of four~carbon of carbon six, can also by aqueous-phase reforming glucose and The aqueous-phase reformings such as the carbohydrates such as fructose and sugar alcohol such as sorbierite, mannitol obtain.(Catalytic conversion of Biomass to monofunctional hydrocarbons and targeted liquid-fuel classes, Science.2008,322 (5900): 417-21.)
The present invention provides one to prepare the new way of aromatic hydrocarbons from biomass-based alcoholic compound, after being converted with saccharide compound Hexanol and amylalcohol as aromatisation platform.Using the method for the present invention, feed stock conversion can reach 99%, benzene,toluene,xylene The selectivity of target product achieves preferable technical effect up to 93%.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
5 grams are weighed through the WO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 3/97, it is packed into fixed bed reactors.Reaction substrate is n-butyl alcohol, weight space velocity 0.5 hour-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 97%, BTX is 88%.
[embodiment 2]
5 grams are weighed through the WO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 5/95, it is packed into fixed bed reactors.Reaction substrate be 2- butanol, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 90%, BTX is 93%.
[embodiment 3]
Aqueous-phase reforming glucose prepares amylalcohol: loading 5 grams in fixed bed reactors and takes PtRe/C prepared by infusion process Catalyst, the ratio that tenor is 5%, Pt and Re in the catalyst is 50:50.Temperature reaction device, in 350 in nitrogen atmosphere DEG C keep 2 hours, cool to 210 DEG C later, nitrogen atmosphere weight space velocity be 1h-1Under conditions of put into the glucose of 40% concentration Aqueous solution carries out liquid phase reforming reaction.The raw material is after catalyst bed, and product stream is cooling to be collected, and the oil on upper layer is mutually through excessive It is 2- amylalcohol that analysis characterization, which identifies primary product,.Reaction conversion ratio is 99%, and the selectivity of amylalcohol is 85%.
5 grams are weighed through the WO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 20/80, it is packed into fixed bed reactors.Reaction substrate be 2- amylalcohol, weight space velocity 3.5 hours-1, Hydrogen Vapor Pressure 2.0MPa, flow 20ml min-1, 380 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 91%, BTX is 86%.
[embodiment 4]
5 grams are weighed through the MoO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 20/80, it is packed into fixed bed reactors.Reaction substrate be 2- amylalcohol, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 480 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 92%, BTX is 84%.
[embodiment 5]
5 grams are weighed through the CeO for removing water 12 hours dry at 120 DEG C2/ZrO2The share ratio of catalyst, metal oxide is 10/90, it is packed into fixed bed reactors.Reaction substrate be 3- amylalcohol, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 88%, BTX is 89%.
[embodiment 6]
5 grams are weighed through the WO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 15/85, it is packed into fixed bed reactors.Reaction substrate be 1- amylalcohol, weight space velocity 5.0 hours-1, Hydrogen Vapor Pressure 3.0MPa, flow 20ml min-1, 500 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 92%, BTX is 85%.
[embodiment 7]
5 grams are weighed through the MoO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 13/87, it is packed into fixed bed reactors.Reaction substrate is 1,2- pentanediol, weight space velocity 1.5 hours-1, Hydrogen Vapor Pressure 1.5MPa, Flow 20ml min-1, 420 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction As a result quantitative analysis is carried out.The selectivity that reaction substrate conversion ratio is 90%, BTX is 89%.
[embodiment 8]
5 grams are weighed through the La for removing water 12 hours dry at 120 DEG C2O3/ZrO2Catalyst, the share ratio of metal oxide It is 15/85, is packed into fixed bed reactors.Reaction substrate is 1,2- pentanediol, weight space velocity 1.5 hours-1, Hydrogen Vapor Pressure 1.5MPa, flow 20ml min-1, 440 DEG C of temperature.After reaction, qualitative analysis, chromatography are carried out to reaction result using mass spectrum Quantitative analysis is carried out to reaction result.The selectivity that reaction substrate conversion ratio is 95%, BTX is 92%.
[embodiment 9]
5 grams are weighed through the WO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 10/90, it is packed into fixed bed reactors.Reaction substrate be 1- hexanol, weight space velocity 1.5 hours-1, Hydrogen Vapor Pressure 1.5MPa, flow 20ml min-1, 390 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 98%, BTX is 91%.
[embodiment 10]
5 grams are weighed through the WO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 40/60, it is packed into fixed bed reactors.Reaction substrate be 1- hexanol, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.5MPa, flow 40ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 99%, BTX is 89%.
[embodiment 11]
5 grams are weighed through the MoO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 30/70, it is packed into fixed bed reactors.Reaction substrate 2- hexanol, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 2.5MPa, flow 40ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 97%, BTX is 89%.
[embodiment 12]
5 grams are weighed through the MnO for removing water 12 hours dry at 120 DEG C3/ZrO2The share ratio of catalyst, metal oxide is 8/92, it is packed into fixed bed reactors.Reaction substrate be 3- hexanol, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.5MPa, flow 40ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction result Carry out quantitative analysis.The selectivity that reaction substrate conversion ratio is 92%, BTX is 89%.
[embodiment 13]
5 grams are weighed through the MnO for removing water 12 hours dry at 120 DEG C2-WO3/ZrO2Catalyst, the share ratio of metal oxide Example is 8/92, is packed into fixed bed reactors.Reaction substrate is 1,2- hexylene glycol, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.5MPa, flow 40ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis, chromatography are carried out to reaction result using mass spectrum Quantitative analysis is carried out to reaction result.The selectivity that reaction substrate conversion ratio is 93%, BTX is 89%.
[embodiment 14]
5 grams are weighed through the La for removing water 12 hours dry at 120 DEG C2O3-WO3/ZrO2Catalyst, the share of metal oxide Ratio is 8/92, is packed into fixed bed reactors.Reaction substrate is 1,2- hexylene glycol, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.5MPa, flow 40ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis, chromatography are carried out to reaction result using mass spectrum Quantitative analysis is carried out to reaction result.The selectivity that reaction substrate conversion ratio is 87%, BTX is 84%.
[embodiment 15]
5 grams are weighed through the CeO for removing water 12 hours dry at 120 DEG C2-WO3/ZrO2Catalyst, the share ratio of metal oxide Example is 8/92, is packed into fixed bed reactors.Reaction substrate be 1- amylalcohol, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.5MPa, stream Measure 40ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography ties reaction Fruit carries out quantitative analysis.The selectivity that reaction substrate conversion ratio is 89%, BTX is 91%.
[embodiment 16]
50 grams of celluloses are weighed, 300 milliliters of water are merged, the Ni/C catalyst of 2 grams of 10%Ni load capacity are added, 240 It is reacted 1 hour at DEG C, cooling to take out reaction solution, by analysis, the conversion ratio of cellulose is 96%, and the yield of sorbierite is 75%.
5 grams are weighed through the CeO for removing water 12 hours dry at 120 DEG C2-WO3Catalyst is packed into fixed bed reactors.React bottom Object is sorbierite, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates Afterwards, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is The selectivity of 98%, BTX are 85%.
1 embodiment of table summarizes
Embodiment Substrate Catalyst Conversion ratio/% BTX selectivity/%
1 N-butyl alcohol WO3/ZrO2 97 88
2 2- butanol WO3/ZrO2 90 93
3 2- amylalcohol WO3/ZrO2 91 86
4 2- amylalcohol MoO3/ZrO2 92 84
5 3- amylalcohol CeO2/ZrO2 88 89
6 1- amylalcohol WO3/ZrO2 92 85
7 1,2- pentanediol MoO3/ZrO2 90 89
8 1,2- pentanediol La2O3/ZrO2 95 92
9 1- hexanol WO3/ZrO2 98 91
10 1- hexanol WO3/ZrO2 99 89
11 2- hexanol MoO3/ZrO2 97 89
12 3- hexanol MnO2/ZrO2 92 89
13 1,2- hexylene glycol MnO2-WO3/ZrO2 93 89
14 1,2- hexylene glycol La2O3-WO3/ZrO2 87 84
15 1- amylalcohol CeO2-WO3/ZrO2 89 91
16 Sorbierite CeO2-WO3 98 85

Claims (8)

1. a kind of method of alcohol compound aromatisation aromatic hydrocarbons makes C under aromatization conditions4~6Alcohol contacts generation with catalyst Arene stream containing benzene, toluene and dimethylbenzene;
The catalyst is selected from compound Zirconium oxide XaOb/ZrO2;Wherein, X is selected from least one of tungsten, molybdenum, cerium, lanthanum or manganese, A and b is stoichiometric number;In the compound Zirconium oxide, based on parts by weight, XaObDosage be 0.1~40 part, ZrO2's Dosage is 60~99.9 parts.
2. the method for alcohol compound aromatisation aromatic hydrocarbons according to claim 1, feature with the C4~6Alcohol is selected from 1- Butanol, 2- butanol, 1- amylalcohol, 2- amylalcohol, 3- amylalcohol, 1,2- pentanediol, 1,3- pentanediol, 1,4- pentanediol, 1,5- pentanediol, 1- hexanol, 2- hexanol, 3- hexanol, 1,2- hexylene glycol, 1,3- hexylene glycol, 1,4- hexylene glycol, 1,5- hexylene glycol, 1,6-HD, At least one of 1,2,3- hexanetriol, sorbierite or xylitol.
3. the method for alcohol compound aromatisation aromatic hydrocarbons according to claim 1, it is characterised in that the C4~6Alcohol comes spontaneous Material.
4. the method for alcohol compound aromatisation aromatic hydrocarbons according to claim 1, it is characterised in that the C4~6Alcohol comes from Portugal At least one of grape sugar, cellobiose, hemicellulose or lignin.
5. the method for alcohol compound aromatisation aromatic hydrocarbons according to claim 1, it is characterised in that the C4~6Alcohol is from sweet At least one of bagasse, glucose, timber, corn stalk or straw straw.
6. the method for alcohol compound aromatisation aromatic hydrocarbons according to claim 1, it is characterised in that the compound zirconium oxidation In object, based on parts by weight, XaObDosage be 1~40 part, ZrO2Dosage be 60~99 parts.
7. the method for alcohol compound aromatisation aromatic hydrocarbons according to claim 1, it is characterised in that the aromatization conditions Are as follows: 300~800 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure, raw material weight air speed 0.3~10 hour-1
8. the method for alcohol compound aromatisation aromatic hydrocarbons according to claim 1, it is characterised in that the aromatization conditions Are as follows: 300~650 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.5~4MPa in terms of gauge pressure, raw material weight air speed 0.3~5 hour-1
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