CN104387223B - It is the method for aromatic hydrocarbons by two-step method catalyzed conversion lignin - Google Patents
It is the method for aromatic hydrocarbons by two-step method catalyzed conversion lignin Download PDFInfo
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Abstract
The invention discloses a kind of is the method for aromatic hydrocarbons by two-step method catalyzed conversion lignin, and it includes step: (a), in polar solvent, under hydrodepolymerization catalyst and hydrogen pressure effect, lignin hydrogenolysis obtains phenols oil mixture；B the phenols oil mixture that step (a) obtains is steamed in () rotation, under the conditions of hydrogenation deoxidation catalyst, solvent, high-temperature low-pressure, hydrogenation deoxidation reaction obtains aromatic product.The present invention also provides for a kind of hydrodepolymerization catalyst and hydrogenation deoxidation catalyst.The present invention, with inexpensive lignin as raw material, is aromatic hydrocarbons through two-step method Efficient Conversion under mild reaction conditions, and product economic worth is high, and course of reaction environmental protection has broad prospect of application.
Description
Technical field
The present invention relates to biomass technical field of new energies, particularly relating to a kind of is aromatic hydrocarbons by two-step method catalyzed conversion lignin
Method.
Background technology
The problem of environmental pollution caused after the non-renewable and burning of fossil energy so that develop renewable and environmentally friendly
The task of biomass resource extremely urgent.Lignin as a potential class rich in the new forms of energy of the high-energy-density of aromatic rings
Carrier, its current utilization is only limitted to the binding agent as low value and reinforcing agent, and most lignin is as paper waste
It is directly discharged in rivers,lakes and seas, not only causes environmental pollution but also waste resource.Lignin as high phenyl ring content and inexpensively enriches
Renewable resource, it is big that the character being difficult to dissolve due to the macromolecular structure of its complex three-dimensional causes converting difficulty, thus study into
Postpone and cannot be fully used slowly.Therefore, the chemicals that lignin is converted to energy fuel and high value the most effectively is
One of focus of current research, is also one of difficult problem.
The research of lignin depolymerization is relatively fewer, and patent CN101798052A has been issued a kind of by with natural lignin and industry
Lignin is raw material, and with support type Ni base catalyst in polar solvent methanol, ethanol, isopropanol, reaction temperature is 180-250 DEG C,
Under conditions of reactive hydrogen atmospheric pressure is 3-8MPa, selectivity obtains phenol derivatives, and the selectivity of aromatic hydrocarbon is less than 10%.
Patent CN 102701898A issued a kind of by two-step method in the tubular fixed bed reactors have conductive wire wood
Quality orients the method being converted into benzene.The method first step uses the modified zeolite molecular sieve depolymerization lignin of Ni to be liquefied phenol
Class mixture, second step Re loaded zeolite molecular sieve converts phenol mixture orientation at 200-250 DEG C and is converted into aromatic hydrocarbons.This
Process is the most complicated, and lignin pyrolytic conversion on solid catalyst in fixed bed reactors, and solid-solid reaction makes catalyst
Active sites is difficult to contact, and causes lignin conversion rate low and carbon deposit is serious.
From existing technology it can be seen that the efficiency of lignin depolymerization is low and reaction needs harsh reaction condition, and depolymerization obtains
Phenols oil easily regroup so that phenolic monomers productivity is low.Lignin hydrogenolysis needs the hydrogen of high pressure, under the reaction conditions
The benzene ring structure that lignin derives easily is hydrogenated, and therefore deoxidation process is more suitable for the second step reaction condition at high-temperature low-pressure
Under carry out.But the difficult point of this process is that the phenols oil carbon-oxygen bond bond energy that lignin gets is the highest, fracture carbon-oxygen bond needs the most severe
The condition carved, is therefore difficult to balance and can optionally rupture carbon-oxygen bond, can optionally not be hydrogenated by deoxidation reservation phenyl ring again
To aromatic hydrocarbons.In order to utilize crude benzene ring like structure abundant in lignin fully, thus obtain widely aromatic hydrocarbons chemical industry base
Plinth raw material, development Efficient Conversion lignin in liquid phase slurry bed system is that the technology of aromatic hydrocarbons is the most necessary.
Summary of the invention
Present invention is primarily intended to propose a kind of is the method for aromatic hydrocarbons by two-step method catalyzed conversion lignin, is a kind of from lignin
The middle new method preparing aromatic hydrocarbon, including, the first step be liquid phase Efficient Conversion lignin be phenols oil (lignin hydroformylation product solution),
Second step is that liquid phase high-selective and hydrogenating deoxidation lignin phenols is oily obtains aromatic hydrocarbons.
The present invention is the method for aromatic hydrocarbons by two-step method catalyzed conversion lignin, comprises the steps:
A (), under the conditions of Hydrogen Vapor Pressure 2.0-10MPa, in polar solvent, lignin is under hydrodepolymerization catalyst action
Hydrogenolysis, reaction temperature is 250-500 DEG C, and the response time is 2-24h, obtains phenols oil mixture；
B phenols oil mixture that () rotation obtains after boiling off polar solvent, under the conditions of Hydrogen Vapor Pressure 0.1-3.0MPa, is adding
Under the conditions of hydrogen dehydrogenation catalyst, solvent, high-temperature low-pressure, hydrogenation deoxidation reaction, reaction temperature under hydrogenation deoxidation catalyst effect
For 150-500 DEG C, response time 1.0-10h, obtain purpose product aromatics.
The inventive method, realizes by two-step method, lignin is catalytically conveted to aromatic product under the conditions of low hydrogen pressure.Described
Aromatic product includes main C6-C9Aromatic hydrocarbons mixture and a small amount of C6-C9Cycloalkane and alkane.
The product that the inventive method prepares includes main C6-C9Aromatic hydrocarbons mixture.Described C6-C9Aromatic hydrocarbons mixture contains benzene, first
Benzene, ethylbenzene, propyl benzene.Described C6-C9In aromatic hydrocarbons mixture, the ratio of benzene is 0-15wt%, and the ratio of toluene is 5-20wt%,
The ratio of ethylbenzene is 25-60wt%, and the ratio of propyl benzene is 30-70wt%.
Can also be containing a small amount of C in product prepared by the inventive method6-C9Cycloalkane and alkane.Wherein, the ratio of cycloalkane
Example is 0-10wt%, and the ratio of alkane is 0-5wt%.
In a specific embodiment, the first step hydrogenolysis lignin of the present invention: be firstly added lignin, metallic catalyst,
In polar solvent in high-pressure reactor.After filling the air in 3 nitrogen rear substitution reactors, it is passed through certain pressure at room temperature
Hydrogen (such as, reactive hydrogen atmospheric pressure 2.0-10MPa), (such as, reaction temperature 250-500 DEG C) is high at appropriate temperatures
Speed stirring reaction certain time (such as, 2-24 hour).It is cooled to room temperature after end, obtains the phenols oil after hydrogenolysis depolymerization and mix
Compound.Second step is that rotation boils off except the phenols oil that will concentrate after solvent, adds hydrogenation deoxidation catalyst (metallic catalyst),
In slurry reactor still, in water or alkane solvent, at suitable temperature (such as, 150-500 DEG C) and pressure (such as, hydrogen
Pressure 0.2-3.0MPa) under react certain time (such as, 1.0-10h) obtain aromatic hydrocarbons.
In the present invention, in step (a) lignin hydrogenolysis process: described lignin is natural lignin, industrial lignin.Its
In, described industrial lignin includes enzymolysis xylogen, lignosulfonate, alkali lignin.Preferably, lignin is that enzymolysis is wooden
Element.Described polar solvent is one or more in water, methanol, ethanol, isopropanol, ethylene glycol, dioxane.Preferably,
Polar solvent is water, ethanol.The metal of described hydrodepolymerization catalyst is one or more in Pd, Ru, Ni, Co.Excellent
Elect metal alloy Ru, Ni as.Described hydrodepolymerization catalyst is load type metal catalyst, including carrier and the gold that loaded thereof
Belong to.Wherein, carrier is the one of Si-Al molecular sieve, phosphate aluminium molecular sieve, silicon dioxide, aluminium sesquioxide or Carbon Materials or many
Kind.It is preferably silicon dioxide, Si-Al molecular sieve.Described reactor is batch (-type) or flow-type high pressure paste state bed reactor.Described
Reaction temperature is 250-500 DEG C, and reactive hydrogen atmospheric pressure is 2.0-10MPa, and the response time is 2-24h.
In the present invention, in step (b) phenols oil mixture deoxidation process: selected solvent is water, alkane.Described hydrogenation deoxidation
Catalyst is load type metal catalyst, including carrier and the metal that loaded thereof.Wherein, described metal center be Ru, Pd,
One or more in Ni, Fe.It is preferably metal Ru.The carrier of described hydrogenation deoxidation catalyst is Si-Al molecular sieve, phosphorus aluminum
Molecular sieve, HTS, oxide, solid acid.It is preferably acid Si-Al molecular sieve, zirconium oxysulfate.Described reaction temperature
For 150-500 DEG C.It is preferably 200-350 DEG C.Described reactive hydrogen atmospheric pressure is 0.1-3.0MPa.It is preferably 0.6-1.0MPa.Institute
Stating the response time is 1.0-10h.
The present invention also proposes a kind of aromatic hydrocarbons obtained by the invention described above preparation method.Described aromatic product includes C6-C9Aromatic hydrocarbons mixes
Compound, it comprises benzene, toluene, ethylbenzene, propyl benzene.Described aromatic hydrocarbons is C6-C9In aromatic hydrocarbons mixture, the ratio of benzene is 0-15wt%,
The ratio of toluene is 5-20wt%, and the ratio of ethylbenzene is 25-60wt%, and the ratio of propyl benzene is 30-70wt%.Described product mixes
Thing can also be containing a small amount of C6-C9Cycloalkane and alkane, wherein the ratio of cycloalkane is 0-10wt%, the ratio of alkane
Example is 0-5wt%.
In the present invention, the first step i.e., under the conditions of Hydrogen Vapor Pressure 2.0-10MPa, supports RuNi/SiO at metal2Catalyst, pole
In property etoh solvent/water, under 300 DEG C and hydrogen existence condition, hydrogenolysis depolymerization lignin is phenols oil mixture；Second step is high temperature
The most refined first step gained phenols oil mixture under the conditions of low pressure (Hydrogen Vapor Pressure 0.1-3.0MPa), at alkane or aqueous solution
In, obtain C with Ru base catalyst hydrogenation deoxidation6-C9Aromatic hydrocarbons is containing benzene, toluene, ethylbenzene, propyl benzene and a small amount of cycloalkane and chain
Alkane.Wherein, the phenols oil yield of the depolymerization gained of first step lignin reaches more than 60wt%, second step phenols oil selectivity
It is converted into the yield of aromatic hydrocarbons close to 90%.
The invention allows for a kind of hydrodepolymerization catalyst, it includes carrier and the metal loaded thereof；Wherein, described metal
It is one or more in Pd, Ru, Ni, Co；Described carrier be Si-Al molecular sieve, phosphate aluminium molecular sieve, silicon dioxide, three
Al 2 O, Carbon Materials one or more；Described hydrodepolymerization catalyst is wooden by two-step method catalyzed conversion for the present invention
Element is in the method for aromatic hydrocarbons.
Described hydrodepolymerization catalyst is: Ru/HBEA, Ni/HZSM-5, Co/MOR, RuNi/HZSM-5, RuCo/SAPO,
NiCo/SiO2, RuNiCo/C etc..In a specific embodiment, the preparation of described hydrodepolymerization catalyst: with the present invention
In as a example by used RuNi/HZSM-5, prepare via infusion process: under agitation, respectively by 0.432g ruthenium trichloride with
2.476g six water nickel nitrate is dissolved in 10mL deionized water, obtains solution A and solution B；Again solution A and solution B are added
In 4.25g HZSM-5 molecular sieve, stirred overnight, the mixture obtained is 80 DEG C of drying, then enters through tube calciner
Row calcining and reduction step, first calcine 4h with the air atmosphere of 100mL/min, subsequently 100mL/min hydrogen atmosphere also
Former 4h, obtains catalyst RuNi/HZSM-5.
The invention allows for a kind of hydrogenation deoxidation catalyst, it includes carrier and the metal loaded thereof；Wherein, described metal
It is one or more in Ru, Pd, Ni, Fe；Described carrier be Si-Al molecular sieve, phosphate aluminium molecular sieve, HTS,
One or more of oxide and solid acid；Described hydrogenation deoxidation catalyst is for of the present invention by two-step method catalyzed conversion
Lignin is in the method for aromatic hydrocarbons.
Described hydrogenation deoxidation catalyst is: Ru/SO4 2--ZrO2, Ru-Ni/HZSM-5, Ru-Pd/HMOR, Ru-Fe/MOR etc..
In a specific embodiment, the preparation of described hydrogenation deoxidation catalyst: use first as a example by representational Ru base catalyst
Aldehyde liquid phase reduction, concrete synthetic method is: weighs 0.254g tri-chloride hydrate ruthenium addition 100mL water and is made into ruthenium trichloride
Solution, is then added dropwise over solution in the HZSM-5 carrier of 2.0g.This suspension mixture is stirred at room temperature under magnetic stirring
After 5.0h, dropping sodium hydroxide solution regulation pH value is the formalin dripping 5mL37% after 11, adds in 60 DEG C of oil baths
Hot reflux reaction 4h.After being down to room temperature, filtering catalyst is washed to gained catalyst after neutrality at 80 DEG C of dry 12h.
The present invention innovation and beneficial effect include: the technology main depolymerization lignin of prior art lignin conversion be relative worth relatively
Low phenols oil mixture.Being different from prior art, the target product prepared by the inventive method is important industrial base
Plinth raw material C6-C9Aromatic hydrocarbons mixture, it comprises benzene, toluene, ethylbenzene, propyl benzene, possibly together with a small amount of cycloalkane and alkane.
The realization of the present invention is to be obtained by design two-step catalysis method Efficient Conversion lignin in the liquid phase, is to make full use of lignin
The construction features of raw material, a kind of new response path of design targetedly and catalyst system and catalyzing.
In prior art, the difficult point of lignin conversion is that lignin is difficult to dissolve thus active center is difficult to touch site.And this
Bright utilizing under condition of high voltage, the conversion ratio utilizing the C-O key of RuNi alloy efficient hydrogenolysis lignin to obtain phenols oil obtains 60wt%
Above, it is achieved that the breakthrough of the efficient depolymerization of lignin in liquid solution.
Aromatic hydrocarbons is the bulk chemical that a very important market demand of class is high, and in prior art, phenols innage effect turns in the liquid phase
The process difficulty turning to aromatic hydrocarbons is big.And the New Policy of the inventive method is: utilize Ru center first selectivity fracture phenols chemical combination
The methoxyl group of thing obtains the derivant of methanol and phenol, and the derivant of phenol is hydrogenated to cyclic alcohol, and cyclic alcohol is de-on acidic molecular sieve
Water generates cyclenes, and cyclenes selective dehydrogenation under the conditions of high temperature low hydrogen pressure generates aromatic hydrocarbons.By in finely regulating metal center, acid
The heart, temperature, pressure and dicyandiamide solution, present invention achieves the deoxidation process of high selectivity and atom economy, phenols oil
Conversion ratio to aromatic hydrocarbon reaches 100%, and selectivity reaches more than 90%.The present invention is with inexpensive lignin as raw material, through two
Footwork Efficient Conversion under mild reaction conditions is aromatic hydrocarbons, and product economy is worth high and chemical reaction process environmental protection, possesses wide
Wealthy application prospect
Accompanying drawing explanation
Fig. 1 represent step (a) lignin depolymerization after the gas chromatogram (ethanol is solvent) of phenols oil product.
Fig. 2 represent step (a) lignin depolymerization after the gas chromatogram (ethanol is solvent) of gaseous product.
Fig. 3 represents that step (b) phenols oil mixture selectivity deoxidation is the products distribution of aromatic hydrocarbons, and catalyst is ruthenium/zirconium oxysulfate.
Fig. 4 represents that phenols oil mixture is selectively converted to the reaction mechanism figure of aromatic hydrocarbon.
Detailed description of the invention
In conjunction with specific examples below and accompanying drawing, the present invention is described in further detail, and the protection content of the present invention is not limited to
In following example.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and advantage
All it is included in the present invention, and with appending claims as protection domain.Implement the process of the present invention, condition, examination
Agent, experimental technique etc., outside the lower content mentioned specially, be universal knowledege and the common knowledge of this area, the present invention
Content is not particularly limited.
One of innovation of the present invention is embodied in, and the process that selectivity deoxidation is aromatic hydrocarbons of phenols oil, response path is as shown in Figure 4.Benzene
Phenol, the derivant such as 2-methoxyphenol needs selective excision oxygen-containing functional group and retains phenyl ring and could realize the quantitative raw of aromatic hydrocarbons
Become.This path is that in many parallel reactions, the ether-oxygen bond of Ru hydrogenolysis phenols oil obtains methanol and corresponding phenol under the atmosphere of hydrogen,
Phenol continues hydrogenation and generates corresponding cyclic alcohol, and cyclic alcohol is dehydrated on acid centre and generates corresponding cyclenes subsequently, and cycloolefin is low at high temperature
Pressure selective dehydrogenation generates aromatic hydrocarbon.Realize these a series of waterfall type response paths to need to regulate and control subtly in metal center, acid
Each factors such as the heart, temperature, pressure and dicyandiamide solution, innovate the above-mentioned reaction scheme of proposition by the present invention thus realize optionally
Generate aromatic hydrocarbons.
Embodiment 1
Representative lignin enzymolysis xylogen raw material used by the present embodiment is purchased from Shandong Longli Biology Science and Technology Co., Ltd, logical
Cross enzymolysis process and obtain lignin raw material to the cellulose removing discarded corn cob raw material.The component of enzymolysis xylogen used and
As shown in table 1, the content of Klason lignin is 80wt%, and sugar contains 3wt%, and ash contains 5wt% in the composition distribution of element,
Moisture contains 12wt%.Elementary composition middle C content is 62.4wt%, and O content is 31.8wt%, and H content is 5.34wt%, N
Content is that 0.45wt%, S content is less than detection limit (ppm).
Table 1: the component of the lignin used and elementary composition distribution
| Component | Klason lignin | Ash | Moisture | Residue sugar | - |
| (wt%) | 80 | 5 | 12 | 3 | - |
| Elementary composition | C | O | N | H | S |
| (wt%) | 62.4 | 31.8 | 0.45 | 5.34 | - |
Catalyst used is preferred RuNi/SiO2, to be prepared by infusion process, concrete grammar is, weighs 5.0g silicon dioxide
Carrier, add solution of ruthenium trichloride (30mL, 0.4g/mL) and nickel nitrate solution (50mL, 0.5g/mL) at room temperature
Reacted 2 days by magnetic agitation.After solvent volatilizees, the catalyst of gained is put in tube furnace, in the air atmosphere of flowing
550 DEG C of calcining 3.0h, in the hydrogen atmosphere of flowing, 300 DEG C of reduction 4.0h obtain RuNi/SiO subsequently2Catalyst.
In the present embodiment, it is firstly added 5.0g enzymolysis xylogen, 0.5g RuNi/SiO2, etoh solvent 100mL is in reaction under high pressure
In device slurry device (300mL), fill the air that 3 nitrogen eliminates in reactor and be filled with the hydrogen of 5.0MPa at room temperature and start
Mechanical agitation (mixing speed 1000rpm).Room temperature is naturally cooled to after reacting 8h at 260 DEG C.Take out in reactor
Liquid product adds 1.0g dodecane as interior scalar quantity, and liquid product enters GC and MS to carry out qualitative and quantitative analysis and calculate
Liquid yield, the collection of gas airbag goes out gas recovery ratio to GC analytical calculation.The total recovery of lignin is liquid yield and gas
Yield sum.Table 2 lists enzymolysis xylogen (aqueous, methanol, ethanol, isopropanol, ethylene glycol, first in different solvents
Alcohol/ethanol, ethanol/ethylene glycol) performance test.Result shows: RuNi/SiO2The lignin depolymerization efficiency in ethanol of catalysis
The highest, reach 60wt%.The raw material corn cob enzymolysis xylogen selected according to the present embodiment, principal product is the mixed of phenol derivatives
Compound, its comprise 4-ethyl-phenol (8.4%), 2-methoxyl group-4-ethyl-phenol (11.2%), guaiaci lignum phenolic group methanol (4.6%),
4-propyl group-2,6-syringol (10.2%), 4-hydroxyl propyl benzene acetoacetic ester (21.8%), 2-methoxyl group-4-acetyl phenol
(13.3%), the selectivity of 6 kinds of products always reaches 69.3%.
Table 2:RuNi/SiO2The lignin depolymerization in different solvents of catalysis and primary product distribution
As can be seen from the above table, in neat solvent ethanol, the conversion ratio of lignin is the highest, and product is mainly phenol derivatives mixture.
Fig. 1 is phenolic product distribution and the gas chromatogram (ethanol is solvent) of composition after lignin depolymerization, dividing of concrete phenolic product
Cloth sees the product structure figure of Fig. 1.Passing through internal standard area method with the dodecane added for internal standard and calculate the yield of liquid, ethanol is molten
In agent, the yield of phenol mixture reaches 60wt%.Gaseous product after lignin depolymerization is analyzed that (gas chromatogram sees
Fig. 2), concrete analysis is listed in table 3, and the concentration of methane is up to 1100ppm, also CO (890ppm) and CO2
(35ppm).Methane may be from the elimination reaction of the methoxyl group in lignin structure, and CO and CO2Essentially from phenols
The decarbonylation base of-COOH carried in compound ,-COOR functional group or decarboxylation reaction.
Table 3: the content of gaseous product after lignin depolymerization
| Gas | Methane | CO | CO2 |
| Content (ppm) | 1100 | 890 | 35 |
Embodiment 2
Catalyst is: Ru/HBEA, Ni/HZSM-5, Co/MOR, RuNi/HZSM-5, RuCo/SAPO, NiCo/SiO2、
RuNiCo/C etc..
The preparation of catalyst: as a example by RuNi/HZSM-5 used in the present invention, prepare via infusion process: under agitation,
Respectively 0.432g ruthenium trichloride and 2.476g six water nickel nitrate are dissolved in 10mL deionized water, obtain solution A and solution B；
Solution A and solution B being added in 4.25g HZSM-5 molecular sieve, stirred overnight, the mixture obtained is 80 DEG C of bakings again
Dry, then carry out calcining and reduction step through tube calciner, first calcine 4h with the air atmosphere of 100mL/min, exist subsequently
The hydrogen atmosphere reduction 4h of 100mL/min, obtains catalyst RuNi/HZSM-5.
In the present embodiment, adding 5.0g organosolv lignin, 0.5g metal is catalyst-loaded, and 100mL solvent is in batch (-type) slurry bed system
In reactor (300mL), fill the air that 3 nitrogen eliminates in reactor and be filled with the hydrogen of 5.0MPa at room temperature and start machine
Tool stirring (mixing speed 800rpm).Room temperature is naturally cooled to after reacting 10h at 280 DEG C.Take out the liquid in reactor
State product addition 1.0g dodecane is as interior scalar quantity, and liquid product enters GC and MS detector and carries out qualitative and quantitative analysis meter
Calculating liquid yield, the collection of gas airbag goes out gas recovery ratio to GC analytical calculation.The total recovery of lignin be liquid yield and
Gas recovery ratio sum.
Use different metal center Ru, Ni, Co, RuNi, RuCo, NiCo, RuNiCo and acidic molecular sieve (HBEA,
HZSM-5、HMOR)、Al2O3、SAPO、SiO2, activated carbon as catalyst (seeing table 4), from data, RuNi/Al2O3
The lignin conversion rate of catalysis is up to 43%, and principal product and the embodiment 1 of depolymerization product phenols are basically identical.
Table 4: organosolv lignin is at the catalyst-loaded disaggregation assay of different metals
Embodiment 3
The phenols oil that the present embodiment utilizes the reaction of the lignin first step to obtain carries out deoxidation treatment further, uses Ru to be supported on
Acid carrier is as catalyst.Ru base catalyst uses formaldehyde liquid phase reduction, and concrete synthetic method is: weigh 0.254g
Three chloride hydrate rutheniums add 100mL water and are made into solution of ruthenium trichloride, and then solution be added dropwise over the different acid load of 2.0g
In body.After this suspension mixture is stirred at room temperature 5.0h under magnetic stirring, dropping sodium hydroxide solution regulation pH value is 11
The formalin of rear dropping 5mL37%, in 60 DEG C of oil bath heating reflux reaction 4h.After being down to room temperature, filtering catalyst water
It is washed till gained catalyst after neutrality at 80 DEG C of dry 12h.
Representative reactions in the present embodiment is, obtains the rotation of previous step lignin conversion phenols oil and be evaporated off molten in mix embodiment 1
Agent, the acid carrier catalyst of 0.2g Ru base, solvent 100mL water is in intermittent high-pressure reactor (300mL).Fill 3
After air in secondary nitrogen replacement reaction kettle, it is passed through 8bar hydrogen at room temperature and reacts 3.0h at 240 DEG C subsequently, be cooled to room
Liquid product in temperature extractive reaction still.Product liquid enters GC and MS thus qualitatively and quantitatively oily the turning of analytical calculation phenols
Rate and the selectivity of various aromatic hydrocarbons.
It is the research of aromatic hydrocarbons that table 5:Ru is supported on deoxidation phenols oil on different acid carriers
Analyzed by table 5 data (by modulation acid carrier, temperature, pressure, and response time) and understand, the life of aromatic hydrocarbons
Become to tend to the carrier that high temperature, low pressure, suitable response time and peracid are strong.When temperature is less than 200 DEG C and hydrogen pressure
During higher than 10bar long response time (more than 3h), the hydrogenation aggravation of aromatic ring and principal product major part be hydrogenated to cycloalkane and
It is difficult to retain phenyl ring.And under high-temperature low-pressure, the highest arenes selectivity results from ruthenium/zirconium oxysulfate catalyst, temperature is
240 DEG C, pressure is 8bar hydrogen, the yield of aromatic hydrocarbons (benzene, toluene, ethylbenzene, propyl benzene) close to 90%, detailed hydrocarbon
Class product analysis refers to Fig. 3.
Claims (7)
1. one kind is the method for aromatic hydrocarbons by two-step method catalyzed conversion lignin, it is characterised in that said method comprising the steps of:
A (), under the conditions of Hydrogen Vapor Pressure 2.0-10MPa, in polar solvent, hydrodepolymerization reaction under hydrodepolymerization catalyst action, reaction temperature is 250-500 DEG C, and the response time is 2-24h, and lignin hydrogenolysis obtains phenols oil mixture；
B the phenols oil mixture that step (a) obtains is steamed in () rotation, under the conditions of Hydrogen Vapor Pressure 0.1-3.0MPa, in a solvent, hydrogenation deoxidation reaction under hydrogenation deoxidation catalyst effect, reaction temperature is 150-500 DEG C, response time 1.0-10h, obtains aromatic product；
Wherein, described hydrodepolymerization catalyst includes carrier and the metal loaded thereof；Wherein, described metal is one or more in Pd, Ru, Ni, Co；Described carrier be Si-Al molecular sieve, phosphate aluminium molecular sieve, silicon dioxide, aluminium sesquioxide, Carbon Materials one or more；
Described hydrogenation deoxidation catalyst includes carrier and the metal loaded thereof；Wherein, described metal is Ru；Described carrier is one or more of Si-Al molecular sieve, phosphate aluminium molecular sieve, HTS, oxide and solid acid.
2. the method for claim 1, it is characterised in that the product that described method prepares includes C6-C9Aromatic hydrocarbons mixture；Described C6-C9Aromatic hydrocarbons mixture includes benzene, toluene, ethylbenzene, propyl benzene；Wherein, the ratio of benzene is 0-15wt%, and the ratio of toluene is 5-20wt%, and the ratio of ethylbenzene is 25-60wt%, and the ratio of propyl benzene is 30-70wt%.
3. method as claimed in claim 2, it is characterised in that the product that described method prepares can also include C6-C9Cycloalkane and alkane；Wherein, the ratio of cycloalkane is 0-10wt%, and the ratio of alkane is 0-5wt%.
4. the method for claim 1, it is characterised in that in described step (a), described lignin includes natural lignin, industrial lignin；Wherein, described industrial lignin includes enzymolysis xylogen, lignosulfonate, alkali lignin.
5. the method for claim 1, it is characterised in that in described step (a), described polar solvent is one or more in water, methanol, ethanol, isopropanol, ethylene glycol, dioxane.
6. the method for claim 1, it is characterised in that in described step (a), described reactor is batch (-type) or flow-type high pressure paste state bed reactor.
7. the method for claim 1, it is characterised in that in described step (b), solvent is water, alkane.
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| CN105461498B (en) * | 2015-11-30 | 2017-08-11 | 华南农业大学 | It is a kind of to improve the hydrogen utilization rate that hydrogenation deoxidation reacts under guaiacol normal pressure, the method for reduction carbon atom loss |
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