CN106423241B - A kind of preparation of ion liquid modified tungsten carbide and its application in straw degradative - Google Patents
A kind of preparation of ion liquid modified tungsten carbide and its application in straw degradative Download PDFInfo
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Abstract
The present invention relates to a kind of ion liquid modified tungsten carbide catalysts and preparation method and application.Base metal precursor salt is impregnated on high-area carbon using ion liquid modified dipping method, temperature programming is carbonized in the mixed gas of methane and hydrogen after drying, and the base metal tungsten carbide of the high degree of dispersion on high-area carbon can be obtained.The ion liquid modified transition metal tungsten carbide prepared with the method shows the performance better than unmodified catalyst in the liquefaction degradation of stalk full constituent, the modification of ionic liquid restrained effectively the reunion of metal active constituent, the crystal form for changing tungsten carbide catalyst makes its catalytic degradation stalk performance boost to better than precious metals pt/C catalytic activity.
Description
Technical field
The present invention relates to the catalyst for the liquefaction degradation of stalk full constituent, it is specifically a kind of using ionic liquid as
Modifying agent, using carbon material as carrier, dual element metallic carbide tungsten is that the catalyst of active component is degraded in the liquefaction of stalk full constituent
In application.
Technical background
Transition metal carbide is that one kind that carbon atom enters the lattice of transition metal and formed has similar noble metal
Compound is filled between matter, because carbide surface electronic structure is similar to Pt race element, thus the catalytic activity with " eka-platinium ",
The fields such as catalytic hydrogenation, alkane hydrogenolysis, denitrogenation, desulfurization and ammonolysis craft show preferable catalytic effect, cause people in recent years
Extensive concern and research.Preparation method mainly has the hot hydrogen reduction of temperature-programmed reaction method, chemical vapour deposition technique, carbon
Method, wherein temperature-programmed reaction method is most widely used, and the carbide material catalytic performance for the unsupported/support type prepared is most
It is good.
Transition metal carbide also showed very high biomass catalyzing Degradation and Transformation in terms of biomass in recent years
Performance.Numerous research and application have been done in this respect by the Zhang Tao team of the Dalian Chemistry and Physics Institute, and patent CN101428213 is disclosed
A kind of charcoal load carbonization class noble metal catalyst, is used for cellulose hydrogenation hydrolyzation and prepares in D-sorbite and mannitol reaction,
Higher product yield is obtained；Patent CN101648140, CN102049273, WO2010/017681 (US8338326),
WO2010/045766, WO2011/050691 (US8889585) and US8692032 disclose distinct methods or condition preparation
Tungsten carbide catalyst converts preparing ethylene glycol for cellulose, has obtained extraordinary cellulose transformation efficiency and ethylene glycol produces
Rate, yield reach as high as 74.4%；University Of Tianjin Li Yongdan professor seminar (document: Angew.Chem.Int.Ed.2014,
53,7310-7315 and ACS Catal.2015,5,4803-4813) preparation molybdenum carbide catalyst be degraded in lignin alcoholysis
Biggish achievement is also achieved in terms of the chemicals of low molecular weight.
But these researchs are spreading out to the more small molecule of the one-component cellulose or lignin of biomass or its degradation
Biology carry out catalyzed conversion research, and it is rare using transition metal carbide catalyst to biomass full constituent carry out degradation grind
The report studied carefully.And today increasingly serious in energy crisis, renewable biomass such as liquefaction of corn straw is degraded to low-carbon chemicals
Or lower carbon number hydrocarbons is very important as liquid fuel or fuel additive.Secondly, these results of study are shown, only by carbon
Compound, which is supported on the carrier with special construction (unordered mesoporous), can just get higher biomass components degradation effect, this is
Because the carrier of special construction can effectively prevent the reunion of carbide active component, keep more active catalyst sites sudden and violent
It exposes outside, to make catalyst that there is high activity and high stability.But this undoubtedly to limit common carrier (such as microporous activated
Charcoal) use.
The ionic liquid green solvent novel as one kind, while the still new stabilizer of metal nano catalyst, it is many
More high activities, high stability metal nano catalyst be produced and for (book chapter: Topic in various reactions
Organometa.Chem.,2015,51:17-51).This is mainly due to ionic liquids to be made of zwitterion, can be in space
Certain " macromolecular network structure " is formed, so they not only have electronic effect, but also has steric effect prepared to stablize
Metallic particles, to can effectively prevent the reunion of metallic particles.It can be seen that ionic liquid can be used for load type carbon compound
The preparation of catalyst effectively prevents the reunion of carbide active component.
Summary of the invention
The purpose of the present invention is to provide a kind of low cost and high performance ion liquid modified biomass straw full constituents
Liquefy the catalyst degraded, and carrier is carbon material, and active component is transition metal tungsten carbide.Such catalyst has Gao Bibiao
Area, active component high degree of dispersion and steady load have certain actual application prospect in the high-area carbon surface the advantages that.
To achieve the above object, the technical solution of the present invention is as follows:
A kind of biomass straw full constituent liquefaction degradation catalyst, is represented by Ay-WxC/S-IL catalyst, wherein Ay-
WxC is metal active constituent, one of A Ni, Co, Fe or Zn, WxC is tungsten carbide, and S is high-area carbon, and IL is ionic liquid,
The load capacity of metal is 2-50wt% in catalyst, wherein 0 < x≤2,0≤y≤2.
The ionic liquid (IL) is disubstituted imidazole type water soluble ion liquid, and structural formula is as follows:
Wherein: R is alkyl, C selected from H, C1-C126H5CH2-、CH2=CH- and CH2=CH-CH2Any one, X-
For selected from I-、Br-、Cl-、HCOO-、CH3COO-、NO3 -、HSO4 -、BF4 -、CH3SO3 -、CH3SF3 -、(CH3)2PO4 -、(CH3CH2)2PO4 -、CH3SO4 -、CH3CH2SO4 -And SCN-Any one.
The catalyst carrier is high-area carbon, including active carbon, carbon black and the various carbon materials of graphene.Wherein high-area carbon packet
Include the high-area carbon of acidification and the high-area carbon of not-acidified processing.
The acid concentration of the acidification is 0-15mol/L, preferably 1-5mol/L, and acid used in the acidification is nitre
One of acid, hydrochloric acid, sulfuric acid, hydrofluoric acid.
The catalyst is supported the ionic liquid solution of active metal tungsten and A substep on carrier using infusion process, gold
Belong to the preferred load capacity of tungsten in 10-50wt%, the preferred load capacity of metal A is in 0-5wt%.
Catalyst precursor after dipping is after 80-120 DEG C dry, in the gaseous mixture of hydrogen and nitrogen, hydrogen or first
The volume content of hydrogen is 5- in the gaseous mixture of progress temperature programming carbonization in the gaseous mixture of alkane and hydrogen, hydrogen and nitrogen
The volume content of methane is 10-50%, preferably 10-25% in the gaseous mixture of 100%, preferably 5-20%, methane and hydrogen；
Carburizing temperature is 600-950 DEG C, and preferably 700-800 DEG C, carbonization time is no less than 1 hour.
The stalk full constituent catalytic liquefaction degradation process carries out in closed batch type high pressure reactor, reaction raw materials straw
The mass ratio of stalk and solvent is 1:50-1:25, and the mass ratio of stalk and catalyst is 2:1-10:1, mixing speed 500-
1000r/min, initial hydrogen pressure is 0-2.5MPa in reaction kettle at room temperature, and reaction temperature is 200-340 DEG C, and the reaction time is
0-12 hours.
The solvent is that one or more of water, methanol, ethyl alcohol, isopropanol, n-butanol, sec-butyl alcohol and n-amyl alcohol are mixed
It closes.
The stalk is untreated corn stover and passes through pretreated corn stover.
The ionic liquid is by taking 1- ethyl-3-methylimidazole formates ([EMIM] [HCOO]) as an example, and metal A is with metallic nickel
For, high-area carbon is acidified the acid of carrier by taking nitric acid as an example, solvent is by taking ethyl alcohol as an example by taking normal activated carbon as an example.
The preparation process of the catalyst is as follows:
The soluble ammonium salt of transition metal tungsten is dissolved in the aqueous solution of water or ionic liquid to (quality of ionic liquid is
3.0%, PH is adjusted to being greater than 12 with sodium hydroxide, is stirred at room temperature and is impregnated on active carbon, by 100 DEG C of drying, 450 DEG C overnight
One-component dipping is completed in roasting.Then the soluble nitrate of metallic nickel is dissolved in the aqueous solution of water or ionic liquid, room temperature
Stirring dipping, 100 DEG C of drying, 450 DEG C of roastings obtain dual-component catalyst presoma.The presoma is subjected to temperature programming carbon
Change, unmodified or ion liquid modified different transition metal tungsten carbide catalysts can be prepared.
Advantages of the present invention
1. the modification of ionic liquid greatly improves the crystal form of catalyst activity component, make it have preferably activity and
Stability is compared to unmodified catalyst.
2. the catalyst is due to, as active component, adding a small amount of nickel, cobalt, iron and zinc transition metal using base metal tungsten
It is low in cost as the second component, and have many advantages, such as that specific surface area is high, stability is good, prepares simple, actual application prospect
It is wide.
3. such catalyst has corn stover full constituent catalytic liquefaction close or higher with commercial noble metal catalyst
Degrading activity, biomass liquefying rate is high, and lignin degradation monomer product yield is up to 33.4% in product after degradation, cellulose
With hemicellulose degradation monomer product yield up to 46.1%.
4. it is from a wealth of sources using the renewable biomass stalk in nature as raw material, it is excellent with low raw-material cost
Point.
Detailed description of the invention
Fig. 1 is the XRD spectra of the embodiment of the present invention 2, embodiment 3 and comparative example 1.
Fig. 2 is the SEM figure of the present embodiment 2 and embodiment 3
Fig. 3 is corn stover degradation monomer product figure
Specific embodiment
The present invention is further illustrated below with reference to embodiment.It is noted that these embodiments only for the purpose of illustration hair
It is bright, it is all not meant to limit the scope of the invention in any way.
1 pretreatment of raw material of embodiment
It weighs 9.30g disodium ethylene diamine tetraacetate and 3.40g Boratex is put into together in 500mL beaker, a small amount of steam is added
Distilled water after heating for dissolving, adds 15g lauryl sodium sulfate and 5mL ethylene glycol ethyl ether；Weigh 2.28g anhydrous phosphoric acid hydrogen two
Sodium is placed in another beaker, is added after a small amount of distilled water dissolves by heating slightly, is poured into the first beaker, be diluted in volumetric flask
500mL, as neutral detergent, get ready with to be used.Corn stover is cleaned, dries, is crushed with discontinuous grinding mill, is sieved
Diameter is less than 120 mesh powders, drying out.It weighs less than 120 mesh powder 2g, neutral detergent solution 100mL is measured, by two
Person mixes with oil bath heating, is allowed to (130 DEG C or so) the reflux 1h that boil, and closes reactor, continues reflux a little while, after cooling will
Solution is filtered together with not molten object, is washed with deionized water not molten object to no foam, then washed 3 times with acetone, will not molten object
It is transferred in glass culture dish completely, dries, pulverize and sieve the corn stalk that removing center detergent dissolved matter (NDS) can be obtained
Stalk powder is used for degradation experiment.
2 catalyst preparation of embodiment
It weighs 0.5918g ammonium metatungstate and is dissolved in distilled water/[EMIM] [HCOO] mixed liquor (using sodium hydroxide adjusting PH
To in 12), obtained clear solution is stirred at room temperature and is impregnated on active carbon (AC) carrier of 1g, then 80 DEG C of vacuum drying
One pack system WO is made in 12h, 450 DEG C of roasting 4h3/ AC presoma；Then 0.1463g nickel nitrate is dissolved in steaming in the same way
Distilled water/[EMIM] [HCOO] mixed liquor, and it is impregnated into WO3On/AC presoma, bi-component NiO-WO is obtained3/ AC-IL forerunner
Body.By NiO-WO3/ AC-IL presoma is raised to 450 DEG C from room temperature with the rate of 10 DEG C/min in hydrogen atmosphere, then 15%
700 DEG C are raised to the rate of 1 DEG C/min in methane/hydrogen (v/v) atmosphere, keeps 1h at such a temperature, after being cooled to room temperature,
It is passed through 1% oxygen/nitrogen (v/v) purging passivation 12h.The loading of catalyst W is 30wt%, and the loading of Ni is 2wt%,
Labeled as Ni-W2C/AC-IL, Fig. 1 XRD diagram show that ion liquid modified catalyst is available under same preparation condition
It is different from the crystal form of unmodified catalyst, this is the main reason for improving catalyst activity.Fig. 2 SEM figure shows ionic liquid
Modification can actually make catalyst metals active component more it is small it is more uniform be dispersed in activated carbon surface, ionic liquid plays
The effect of dispersing agent.
3 catalyst preparation of embodiment
With embodiment 2, difference from Example 2 is method for preparing catalyst, does not add ionic liquid in maceration extract
[EMIM] [HCOO], the catalyst are labeled as Ni-W2C/AC。
4 catalyst preparation of embodiment
It weighs 0.5918g ammonium metatungstate and is dissolved in distilled water/[EMIM] [HCOO] mixed liquor (using sodium hydroxide adjusting PH
To in 12), obtained clear solution is stirred to the activity for being impregnated into 1g after 70 DEG C of reflow treatment 4h of 5mol/L nitric acid at room temperature
On charcoal (AC) carrier, then 80 DEG C of vacuum drying 12h, 450 DEG C of roasting 4h, are made one pack system WO3/ AC presoma；Then with same
0.1463g nickel nitrate is dissolved in distilled water/[EMIM] [HCOO] mixed liquor by the method for sample, and is impregnated into WO3/ AC presoma
On, obtain bi-component NiO-WO3/ AC-IL presoma.By NiO-WO3/ AC-IL presoma is in hydrogen atmosphere with 10 DEG C/min's
Rate is raised to 450 DEG C from room temperature, then is raised to 700 DEG C in 15% methane/hydrogen (v/v) atmosphere with the rate of 1 DEG C/min, at this
At a temperature of keep 1h, after being cooled to room temperature, be passed through 1% oxygen/nitrogen (v/v) purging passivation 12h.Catalyst W's supports
Amount is 30wt%, and the loading of Ni is 2wt%, is labeled as Ni-W2C/AC-IL-5M。
1 catalyst preparation of comparative example
Ni-W is prepared using the method for co-impregnation2C/AC catalyst: 0.5918g ammonium metatungstate and 0.1463g are weighed respectively
Nickel nitrate is dissolved in distilled water, and obtained clear solution is stirred at room temperature and is impregnated on active carbon (AC) carrier of 1g, then
80 DEG C of vacuum drying 12h, be made catalyst precursor, by catalyst precursor in hydrogen atmosphere with the rate of 10 DEG C/min from
Room temperature is raised to 450 DEG C, then is raised to 700 DEG C in 15% methane/hydrogen (v/v) atmosphere with the rate of 1 DEG C/min, at such a temperature
1h is kept, after being cooled to room temperature, is passed through 1% oxygen/nitrogen (v/v) purging passivation 12h.The loading of catalyst W is
The loading of 30wt%, Ni are 2wt%, are labeled as Ni-W2C/AC-co。
2 catalyst preparation of comparing embodiment
The catalyst is commercialization Pt/C catalyst, and Pt loading is 10%.
The evaluation of 5 catalyst of embodiment
Corn stover full constituent liquefaction degradation reaction of the invention be in the batch type high pressure reactor of a 25mL into
Capable.Catalyst and 6mL dehydrated alcohol 100mg corn stover, 50mg made above is added in reaction kettle, is passed through hydrogen and is set
After changing 3-5 gas, gas is flushed with hydrogen to 2MPa, is stirred with the revolving speed of 700rpm, while being warming up to 320 DEG C of reaction 8h.Reaction
After, it is down to room temperature, is centrifugated out catalyst, takes liquid to carry out on gaseous mass analyzer qualitative, and in gas chromatograph
It is upper to use inner mark method ration.The monomer product obtained by gas chromatographic analysis is as shown in figure 3, mainly by dihydric alcohol, furfural class, furan
The low carbon compounds such as class of muttering and phenols composition.Total degradation monomer yield is as shown in table 1, the results show that the modification of ionic liquid
It can be improved the biomass full constituent degradation efficiency of catalyst.
Table 1 is 5 different catalysts of the embodiment of the present invention to corn stover catalytic liquefaction degradation results
Claims (7)
1. a kind of ion liquid modified tungsten carbide catalyst, it is characterised in that: catalyst formula Ay-WxC/S-IL expression,
Wherein Ay-WxC is metal active constituent, one of A Ni, Co, Fe or Zn, WxC is tungsten carbide, and S is that the charcoal of acidification carries
Body, IL are disubstituted imidazole type water soluble ion liquid, it is characterised in that the disubstituted imidazole type water soluble ion liquid
Structural formula is as follows:
Wherein: R is alkyl, C selected from H, C1-C126H5CH2-、CH2=CH- and CH2=CH-CH2Any one, X-For choosing
From I-、Br-、Cl-、HCOO-、CH3COO-、NO3 -、HSO4 -、BF4 -、CH3SO3 -、CH3SF3 -、(CH3)2PO4 -、(CH3CH2)2PO4 -、
CH3SO4 -、CH3CH2SO4 -And SCN-Any one；
The load capacity of metal is 2-50wt% in the catalyst, wherein 0 < x≤2,0≤y≤2；
The preparation of the catalyst is will to add the soluble salt solutions step impregnation of the active metal tungsten and A of ionic liquid in load
On body, wherein the solution of the tungsten containing active metal adjusts PH >=12 with sodium hydroxide.
2. catalyst according to claim 1, it is characterised in that: the high-area carbon of the acidification is the work of acidification
The various carbon materials of graphene of property charcoal, the carbon black of acidification and acidification.
3. catalyst according to claim 2, it is characterised in that the acid concentration of the acidification is 0-15mol/L, institute
Stating acidification acid used is one of nitric acid, hydrochloric acid, sulfuric acid, hydrofluoric acid.
4. a kind of preparation method of catalyst described in claim 1, it is characterised in that: the active metal tungsten of ionic liquid will be added
With the soluble salt solutions step impregnation of A on carrier, wherein the soluble salt solutions of the tungsten containing active metal need to use hydroxide
Sodium adjusts PH >=12, and after 80-120 DEG C dry, 450 DEG C of roastings obtain catalyst precursor, then in the mixed of hydrogen and nitrogen
It closes and carries out temperature programming carbonization in the gaseous mixture of gas, hydrogen or methane and hydrogen, the body of hydrogen in the gaseous mixture of hydrogen and nitrogen
Content is accumulated as 5-100%, the volume content of methane is 10-50% in the gaseous mixture of methane and hydrogen；Carburizing temperature is 600-950
DEG C, carbonization time >=1 hour.
5. ion liquid modified tungsten carbide catalyst described in a kind of claim 1 is in the direct catalytic liquefaction degradation of stalk full constituent
Application in reaction, it is characterised in that: the liquefaction degradation reaction carries out in closed batch type high pressure reactor, reaction raw materials
The mass ratio of stalk and solvent is 1:50-1:25, and the mass ratio of stalk and catalyst is 2:1-10:1, mixing speed 500-
1000r/min, initial hydrogen pressure is 0-2.5MPa in reaction kettle at room temperature, and reaction temperature is 200-340 DEG C, and the reaction time is
0-12 hours.
6. applying according to claim 5, it is characterised in that reaction dissolvent be water, methanol, ethyl alcohol, isopropanol, n-butanol,
The mixing of one or more of sec-butyl alcohol and n-amyl alcohol.
7. applying according to claim 5, it is characterised in that reaction raw materials stalk is untreated corn stover and process
Pretreated corn stover.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610832491.5A CN106423241B (en) | 2016-09-19 | 2016-09-19 | A kind of preparation of ion liquid modified tungsten carbide and its application in straw degradative |
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| CN201610832491.5A CN106423241B (en) | 2016-09-19 | 2016-09-19 | A kind of preparation of ion liquid modified tungsten carbide and its application in straw degradative |
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| CN106423241B true CN106423241B (en) | 2019-10-18 |
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| CN101648140A (en) * | 2008-08-14 | 2010-02-17 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst, preparation thereof and application thereof in reaction for preparing glycol from cellulose |
| CN102476980A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Application of tungsten-based catalyst in lignin catalytic hydrogenation for producing aromatic compound |
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| CN101648140A (en) * | 2008-08-14 | 2010-02-17 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst, preparation thereof and application thereof in reaction for preparing glycol from cellulose |
| CN102476980A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Application of tungsten-based catalyst in lignin catalytic hydrogenation for producing aromatic compound |
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