CN104998640A - Pd-In/C catalyst and preparation method and application in alcohol oxygenated fuel preparing - Google Patents
Pd-In/C catalyst and preparation method and application in alcohol oxygenated fuel preparing Download PDFInfo
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Abstract
The invention discloses a Pd-In/C catalyst and a preparation method and application in alcohol oxygenated fuel preparing. The method comprises the following steps that firstly, active carbon is pretreated through a saltpeter solution under the heating condition; secondly, active component Pd is loaded to the active carbon which is subjected to pretreatment, the Pd/C catalyst is obtained, active component In is further loaded to the active carbon, and the Pd-In/C catalyst is obtained. The In metal is introduced to Pd/C to reduce the use amount of Pd, and accordingly the bio-oil purifying cost is reduced. The prepared bimetallic catalyst is applied to a hydrofining reaction of catechol with phenolic compound being maximal in bio-oil, and it is found that the catechol can be completely converted into alcohol oxygen bearing liquid fuel.
Description
Technical field
To the present invention relates in a kind of bio oil phenolic compound Hydrogenation for the method for alcohols oxygenated fuel.
Background technology
Bio oil is that living beings obtain easy accumulating and original liquid fuel easy to use by thermal cracking, condensation at relatively high temperatures.Bio oil can obtain the good liquid fuel of quality by hydrofinishing, the selection of Hydrobon catalyst is very important, the active component of common hydrogenation catalyst mainly contains the metal of VI B race and VIII race, wherein active it is preferred that noble metal catalyst Pt, Pd, Ru etc.The hydrogenation catalyst of single active component is applied on bio-oil upgrading has very large deficiency (easy inactivation, coking amount are high), bimetallic catalyst is made in the metallic combination of two kinds of active components together and often shows the character different from single active constituent catalyst, the second metal added can show collaborative effect, is greatly improved to aspects such as the activity of catalyst, selective, stability.From the sixties in 20th century, bimetallic catalyst is studied widely, is widely used in now each catalytic field, such as, at Pt/Al
2o
3in add metal Sn and once related in large quantifier elimination.In bio oil, phenolic compound is under Pd/C catalyst action, alcohols oxygen-bearing liquid fuel can be obtained through two-stage hydrogenation reaction, but the cost of Pd/C is higher, be not suitable for large-scale industrialization application, thus we are necessary the catalyst researching and developing low cost, to reduce the preparation cost of alcohols oxygen-bearing liquid fuel.
Summary of the invention
The object of the present invention is to provide in a kind of bio oil that phenolic compound Hydrogenation is for the method for alcohols oxygenated fuel, the method conversion ratio is high, and the Pd/C catalyst price that catalyst price is more traditional decreases, and easily realizes industrialization promotion.
Object of the present invention is achieved through the following technical solutions:
A preparation method for Pd-In/C catalyst, comprises the steps:
(1) in a heated condition pretreatment is carried out to active carbon with salpeter solution;
(2) first load active component palladium on active carbon after the pre-treatment, obtains Pd/C catalyst, then load active component indium further, obtains Pd-In/C catalyst.
The preparation of described Pd/C catalyst: make the active carbon after process suspend in water under agitation, heating, under the condition stirred continuously, in active carbon suspension, add palladium nitrate solution, then the NaOH aqueous solution is dripped, until pH reaches 4.0 ~ 6.0, aging 20 ~ 50min after allowing charcoal absorption 80 ~ 120min, stopping stir, then carry out suction filtration, drying, calcining (the metal component Pd so that fixing active carbon to adhere to), obtain Pd/C catalyst.
The preparation of described Pd-In/C catalyst: add deionized water in Pd/C catalyst, and stirring makes it suspend in water, heating, add indium nitrate solution, continue to stir, drip the NaOH aqueous solution and reach 4.0 ~ 6.0 to pH, adsorb 80 ~ 120min again, aging 20 ~ 50min, finally carries out suction filtration, drying, calcining, obtains Pd-In/C catalyst.
Above-mentioned aging be to make active component better be attached on carrier, prevent loss too much in upper once dipping process.
Step (2) described palladium nitrate solution and indium nitrate solution concentration are than being 5:0.1 ~ 5, and the temperature of heating is 60 ~ 90 DEG C; Baking temperature 100 ~ 140 DEG C, time 0.5 ~ 6h; The temperature 300 ~ 600 DEG C of calcining, time 0.5 ~ 6h.
The concentration of step (1) described nitric acid is 1% ~ 10%, and heating-up temperature is 50 ~ 70 DEG C, heat time more than 2.0h.
The Pd-In/C catalyst that said method obtains phenolic compound Hydrogenation in bio oil, for the application in alcohols oxygenated fuel, specifically comprises the steps:
First by Pd-In/C catalyst H
2reduction, then joins in reactor by the Pd-In/C catalyst after phenolic compound, distilled water and reduction in bio oil, and sealing, is filled with H
2air in replacement reaction kettle, continues to be filled with H
2, carry out hydrogenation reaction, obtain product, the organic matter in extraction liquid phase, solvent is isolated in extract decompression distillation, and residual organic substances is the oxygenated fuel of preparation.
Described catalyst H
2the condition of reduction is: in 600 DEG C of tube furnaces, reduce 3h.
The temperature of described hydrogenation reaction is 200 DEG C, and rotating speed is 800rpm, and the time is 2h, H
2pressure is 5.0MPa.
Compared with prior art, tool of the present invention has the following advantages:
(1) the present invention introduces indium (In) metal in Pd/C, to reduce the use amount of Pd, thus reduces the cost of bio-oil upgrading.
(2) bimetallic catalyst of preparation is applied to the hydrofining reaction of the catechol that content of phenolic compounds is the highest in bio oil by the present invention, finds that catechol can be converted into alcohols oxygen-bearing liquid fuel completely.
Accompanying drawing explanation
Fig. 1 is Pd-In/C catalyst XRD spectra prepared by embodiment 1 ~ 9.
Fig. 2 is the TPR collection of illustrative plates of the Pd-In/C catalyst that embodiment 2,6,7 obtains.
Fig. 3 (a) (b) (c) is respectively the EPMA image of the obtained Pd-In/C catalyst of embodiment 2,6,7.
Fig. 4 is the GC-MS figure before catechol reaction.
Fig. 5 is the reacted GC-MS figure of catechol.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited thereto, for the technological parameter do not indicated especially, can refer to routine techniques and carry out.
Embodiment 1
(1) pretreatment of active carbon
First sieve active carbon powder the oarse-grained carbon granules of removing, then with 5% salpeter solution, pretreatment is carried out to active carbon, both make use of the acidity of nitric acid, also make use of its oxidisability, by 170mL mass fraction be 5% nitric acid be added in 250mL there-necked flask, then the active carbon that 20g is sieved is added wherein, be heated to 60 DEG C, with digital display quick mixer stirring reaction 2h between 60-63 DEG C, mixing speed is 150r/min, then after being down to room temperature in atmosphere, filter out nitric acid, filter cake deionized water is washed till neutrality, be placed in crucible or surface plate, put into vacuum drying chamber in 100 DEG C of dry 4h, in clean there-necked flask, add deionized water and be about 150mL, take the active carbon of 10g process, stirring with quick mixer makes active carbon suspend in water, the stirring of base set is due to 500r/min, and there-necked flask is placed in heating furnace is heated to 80 DEG C stand-by.
(2) load of active component
Adopt first back loading two kinds of Metal Palladium, the method of indium, under the condition that 500rpm stirs continuously, to in stand-by 80 DEG C of active carbon suspension, add the palladium nitrate solution of the 0.025mol/L that 20mL prepares, in acid condition, every 10-15min, divide and drip the NaOH aqueous solution that mass fraction is 30% for 4-5 time, until about the pH=5.0 of maceration extract, allow charcoal absorption 90min, stop stirring rear aging 30min, aging is to make active component better be attached on carrier, prevent loss too much in upper once dipping process, catalyst after aging carries out suction filtration, dry (temperature 100 DEG C, time 3h), calcining, the condition of calcining is in Muffle furnace 400 DEG C, 2h, with the metal component Pd that fixing active carbon adheres to.
After Pd/C catalyst after calcining is cooled to room temperature in atmosphere, weigh, in the there-necked flask of drying, add deionized water and be about 150mL, add Pd/C catalyst again, and make it suspend in water with quick mixer stirring (500rpm), and there-necked flask is placed on heating furnace and is heated to 80 DEG C, add the 0.005mol/L indium nitrate solution prepared, continue rapid stirring (500rpm), 1-2 dropping mass fraction is divided to be that the NaOH aqueous solution of 30% is to maceration extract pH=5.0, catalyst is allowed to adsorb 90min again, aging 30min, catalyst after aging carries out suction filtration, dry (temperature 100 DEG C, time 3h), calcining, the condition of calcining is in Muffle furnace 400 DEG C, 2h, with fixing active component In.
(3) reduction of catalyst
Obtained catalyst activity component exists with the form of oxidation state, needs to carry out reduction treatment to it, load weighted catalyst is placed in tube furnace, uses H before using
2air in displacement tube furnace, then under the condition passing into hydrogen continuously, be rise to 600 DEG C by the temperature of tube furnace, the duration is 3h, and the catalyst after reduction is immediately for the Hydrogenation Experiment of bio oil model compound.
(4) hydrogenation reaction of bio oil model compound catechol
The hydrofinishing experiment of bio oil phenolic compound catechol carries out in 100mL batch reactor, and the maximum pressure of reactor and maximum temperature are 20MPa and 400 DEG C respectively, and pressure and temperature is all numerical monitor, and accuracy is higher.
In hydrogenation reaction, the Pd-In/C catalyst taking 1.0g catechol, 20mL distilled water and 0.25g respectively joins in reactor, after reactor is tightened, is filled with H
2do airtight test, after air-tightness is good, be filled with the H of 2MPa
2air in replacement reaction kettle, repeats ventilation five times, in reactor, is then filled with the H of 5MPa
2(under room temperature condition), hydrorefined reaction temperature is set as 200 DEG C, rotating speed is 800rpm, time is 2h, after reaction stops, question response still cool to room temperature, reacted product is taken out from reaction kettle body, and with distilled water washing reaction kettle, the means of filtration under diminished pressure are adopted to be separated solid phase and liquid phase, liquid phase productive rate is 87%, be extracted with ethyl acetate the organic matter in liquid phase, divide three extractions, decompression distillation is carried out to extract and isolates ethyl acetate, remaining organic matter is the hydrorefined product of catechol, by the product of liquid-transfering gun measured amounts, finite concentration is diluted to chromatographically pure ethyl acetate, and analyze its composition with gas chromatography-mass spectrum (GC-MS).
At reaction condition be: 200 DEG C, 5.0MPa H
2, 2.0h, 0.25g Pd-In/C, after reaction terminates, be extracted with ethyl acetate organic matter and test with GC-MS, catechol can transform completely, and comprise cyclohexanol, cyclohexanediol, cyclopentyl carbinol in product, as shown in Figure 5, this illustrates that catechol hydrogenation can occur under the catalytic action of bimetallic catalyst, mainly cyclohexanol and cyclohexanediol in product.
(5) catalyst analysis and characterizing method
The specific area of catalyst and its pore structure (BET) complete on the full-automatic specific area geographical approach process analysis, GAP analysis instrument of Micromeritics company's T ristar II, use specific surface and the pore structure of liquid nitrogen determination of adsorption method Pd-In/C catalyst, first by catalyst vacuum desorption 12h under the temperature conditions of 110 DEG C, according to Static Adsorption, desorption isotherm, by the specific area of Brunauer-Emmett-Teller (BET) theory calculate carrier, according to desorption isotherm by the distribution of Barrett-Joyner-Halanda (BJH) equivalent cylindrical model calculated hole diameters.
X-ray powder diffraction (XRD) test carries out on the XRD analysis instrument that German Bruker company, model are D8ADVANCE, experiment condition: copper target, incident ray wavelength 0.15418nm, Ni filter plate, pipe pressure 40KV, pipe stream 40mA, scanning step 0.02 degree, sweep speed 0.1 second/step, slit DS=0.5 °.
It is the EPMA-1600 analyzer of Shimadzu, Japan that electron probe microanalysis (EPMA) (EPMA) characterizes what adopt, experiment condition is: accelerating potential is 0.2kV ~ 30kV, secondary electron image resolution ratio is 6nm, is equipped with U.S. EDAX company Gensis mass spectrograph, energy resolution 128eV.
What atomic absorption spectrography (AAS) (AAS) adopted is HIT, and model is the Atomic Absorption Spectrometer of Z-2000, experiment condition: it is 247.6nm that metal Pd measures wavelength, slit width is 0.4nm, time constant is 1s, and lamp current is 10mA, and photomultiplier transit volt high pressure is 431V; It is 325.6nm that metal In measures wavelength, and slit width is 1.3nm, and time constant is 1s, and lamp current is 10mA, and photomultiplier transit volt high pressure is 294V.
What hydrogen-temperature programmed reduction (H2-TPR) analysis was selected is TPD/TPR 2900 chemical adsorption instrument of Micromeritics company, take the Pd-In/C catalyst powder powder sample of about 50mg, be placed in specific quartz tube reactor, inert gas argon gas (Ar) is filled with as protective gas using the flow velocity of 10mL/min, 300 DEG C are risen to by room temperature with the heating rate of 10 DEG C/min, and constant temperature 1h, be cooled to room temperature subsequently, reducibility gas 10%H2/Ar is filled with again with the flow velocity of 10mL/min, and rise to 750 DEG C with the heating rate of 10 DEG C/min by room temperature, and constant temperature 2h, the TCD signal of record hydrogen gas consumption, and be depicted as curve, final sample is cooled to room temperature.
GC-MS analytical instrument is Shimadzu QP 2010Plus, and chromatographic column is
(30m × 0.25mm × 0.25 μm), He is as carrier gas, and injector temperature is 270 DEG C, and ion source temperature is 200 DEG C, and split ratio is 5:1, and mass spectrographic detection range is from 20-500m/z.Analysis condition is: post case temperature 40 DEG C keep 4min, be raised to 120 DEG C with the heating rate of 4 DEG C/min, then with the heating rate of 10 DEG C/min to 280 DEG C, 280 DEG C keep 4min.All materials are all identified by mass spectral database NIST08 and NIST08s.
(6) result and discussion
The factor affecting catalyst activity can be divided into two classes: one is surface-active metal content, and two is active metal particles sizes.Wherein, in catalyst preparation process, dipping method, baking temperature are the principal elements affecting catalyst surface active tenor, because impregnation concentration size, and the length of dip time all directly affects the adhesion effect of active metal at carrier surface, and in dry run, the loss of moisture and diffusion motion directly have influence on the case depth of active metal at carrier.Therefore finding in best catalyst preparation conditions process, on the basis of embodiment 1, change the condition such as maceration extract pH value, mixing speed, adsorption time, baking temperature of preparation Pd/C and Pd-In/C process simultaneously, and analyze with reference to characterization result, draw comparatively ideal embodiment 1 ~ 9, detailed experiment parameter is in shown in table 1.
The preparation condition of table 1 catalyst
The mensuration of specific surface area of catalyst and pore structure (BET)
The measurement result of BET is shown in Table 2, and can find out, the specific surface area of catalyst of preparation is all at 800m
2/ more than g, pore volume is at 0.4 ~ 0.5cm
3between/g, once the CTP Series P d/C catalyst that Sinopec Shanghai petrochemical industry research institute successfully researches and develops was reported in document, represent the R & D Level of domestic advanced Pd/C catalyst, wherein, the specific area that the Pd/C catalyst of CTP II series measures is 900 ~ 1200m
2/ g, pore volume is all at about 0.5mL/g, the data of each group of sample relatively after, we can find, between maceration extract pH=5.0 ~ 6.0, dip time 90 ~ 100min, the pore structure of catalyst is better, specific area, pore volume is larger, that is the catalyst made under these conditions has larger space to be supplied to biological wet goods reactant to be attached with the carrying out being beneficial to reaction, and the mixing speed improving dipping process does not have greatly improved to the pore structure of catalyst, although the baking temperature improving catalyst can make the pore volume of catalyst increase, but significantly reduce its specific area.
Table 2 catalyst B ET test result
The XRD test of catalyst
According to the test philosophy of XRD, the grain size of research object determines the power of diffraction maximum, crystal grain is larger, diffraction maximum is stronger, and along with crystal grain diminishes, diffraction maximum also can die down gradually, when crystal grain is enough little, diffraction maximum then can disappear, and the diffraction maximum of metal Pd crystal grain appears in ° place, 2 θ=40.6, and the diffraction maximum of metal In crystal grain appears at ° place, 2 θ=50.2.The XRD test result of catalyst as shown in Figure 1, as can be seen from the figure, Pd-In/C catalyst in 2 θ=40.6 °, all there is obvious diffraction maximum in 50.2 ° of places, by calculating in obtained Pd-In/C catalyst, the grain size major part of metal Pd is between 13-20nm, and the grain size of metal In is then between 32-45nm; The pH=6.0 (2#) of maceration extract, Pd grain size is minimum, be about 13nm, In grain size is about 32nm, and the grain size of metal is less than the grain size of metal in catalyst time pH=6.5 (3#) in the catalyst obtained time pH=5.0 (1#), therefore during maceration extract pH=5.0 ~ 6.0, in obtained catalyst, the grain size of metal is more suitable; Improve the mixing speed (1#, 4#, 5#) in dipping process, the grain size of metal increases, experiment is had to prove, along with the raising of mixing speed, initial nuclei growth speed sharply increases, nuclei growth speed is fast, then nucleus grain size can be made to become large, and this is consistent with this experimental result; Dipping adsorption time (1#, 6#, 7#) is longer, and the catalyst deposit time is more of a specified duration, and the grain size of metal in catalyst is sharply increased; And when improving baking temperature (1#, 8#, 9#), on active carbon, the load capacity of Pd metal obviously increases, and the content of metal In declines.
Atomic absorption spectrum (AAS) is tested
How many direct performances affecting catalyst of active component Pd content, as can be seen from Table 3, metal Pd when pH=6.0 (2#) than pH=5.0 (1#), more easily be attached on active carbon in the maceration extract of 6.5 (3#), improve mixing speed (1#, 4#, 5#), Pd tenor has rising in various degree, In content is then in decline, along with dipping adsorption time (1#, 6#, prolongation 7#), active component stop adsorption time on the activated carbon increases, the load capacity of the Pd metal on active carbon can increase, raise baking temperature (1#, 8#, 9#), the content of the Pd metal on active carbon obviously increases, but the content of metal In declines.
Table 3Pd-In/C catalyst A AS test result
Temperature programmed reduction (TPR) is tested
The comprehensive test result analyzing BET, XRD, AAS, filters out 2#, 6#, 7# tri-groups of catalyst and is H
2-TPR tests, TPR collection of illustrative plates as shown in Figure 2, can find out, all there is the consumption peak of hydrogen at about 100,175,400,600 DEG C in 6#, 7# catalyst, and 2# catalyst does not exist the consumption peak of hydrogen at 175 DEG C, and the hydrogen consumption peak position of peak 1,2,3 and active carbon itself is close, and compared with peak 4, peak signal is more weak, and area is less, therefore can think that these two hydrogen consumption peaks are hydrogen consumption peaks of absorbent charcoal carrier.Analyzed from AAS, in 2#, 6#, 7# sample, the active component of load on active carbon is the highest with Pd, In tenor in 2# sample, and 6#, 7# are large for 2# catalyst TPR peak area ratio, can infer the increase along with metal In content, TPR hydrogen consumption peak area significantly increases, and describes the reducing power of metal In to Pd and serves the collaborative effect promoted, there is synergy in the combination of two kinds of noble metals, the palladium-indium alloy of proper proportion is more conducive to the carrying out of hydrogenolysis, hydrogenation reaction.
Electron probe microanalysis (EPMA) (EPMA)
In order to probe into the adhesion condition of active component on carrier, we have done electron probe microanalysis (EPMA) to 2#, 6#, 7# sample, and as shown in Figure 3, in figure, the bright spot of white represents active component, can find out that metal Pd, In have been attached on active carbon really.
From above phenetic analysis, the comparatively large (895m of specific area of 2# sample (maceration extract pH=6.0, mixing speed 500r/min, absorption 90min, baking temperature 100 DEG C) can be found
2/ g), pore structure is (0.459cm better
3/ g), metal Pd, In content are applicable to (0.343wt.%Pd, 0.107wt.%In), metal also can be uniformly distributed, the grain size of metal is also minimum, and in TPR test, hydrogen-consuming volume is maximum, and the activity of this group catalyst is best in theory, therefore we are in the Hydrobon reaction of bio oil model compound, select 2# sample as catalyst.
Claims (10)
1. a preparation method for Pd-In/C catalyst, is characterized in that, comprises the steps:
(1) in a heated condition pretreatment is carried out to active carbon with salpeter solution;
(2) first load active component palladium on active carbon after the pre-treatment, obtains Pd/C catalyst, then load active component indium further, obtains Pd-In/C catalyst.
2. method according to claim 1, is characterized in that, the preparation of described Pd/C catalyst:
The active carbon after process is made to suspend in water under agitation, heating, under the condition stirred continuously, in active carbon suspension, add palladium nitrate solution, then the NaOH aqueous solution is dripped, until pH reaches 4.0 ~ 6.0, aging 20 ~ 50min after allowing charcoal absorption 80 ~ 120min, stopping stir, then carry out suction filtration, drying, calcining, obtain Pd/C catalyst.
3. method according to claim 2, is characterized in that, the preparation of described Pd-In/C catalyst:
Deionized water is added in Pd/C catalyst, and stirring makes it suspend in water, heating, add indium nitrate solution, continue to stir, drip the NaOH aqueous solution and reach 4.0 ~ 6.0 to pH, adsorb 80 ~ 120min again, aging 20 ~ 50min, finally carries out suction filtration, drying, calcining, obtains Pd-In/C catalyst.
4. method according to claim 3, is characterized in that, step (2) described palladium nitrate solution and indium nitrate solution concentration are than being 5:0.1 ~ 5, and the temperature of heating is 60 ~ 90 DEG C, and pH is 4.0 ~ 6.0; Baking temperature 100 ~ 140 DEG C, time 1.0 ~ 6.0h; The temperature 300 ~ 700 DEG C of calcining, time 0.5 ~ 6.0h.
5. the method according to claim 1 or 2 or 3 or 4, is characterized in that, the concentration of step (1) described nitric acid is 1% ~ 10%, and heating-up temperature is 50 ~ 70 DEG C, heat time more than 2.0h.
6. the Pd-In/C catalyst that method described in any one of Claims 1 to 5 is obtained.
7. catalyst described in claim 6 in bio oil phenolic compound Hydrogenation for the application in alcohols oxygenated fuel.
8. application according to claim 7, is characterized in that, comprises the steps:
First by Pd-In/C catalyst H
2reduction, then joins in reactor by the Pd-In/C catalyst after phenolic compound, distilled water and reduction in bio oil, and sealing, is filled with H
2air in replacement reaction kettle, continues to be filled with H
2, carry out hydrogenation reaction, obtain product, the organic matter in extraction liquid phase, solvent is isolated in extract decompression distillation, and residual organic substances is the oxygenated fuel of preparation.
9. application according to claim 8, is characterized in that, described catalyst H
2the condition of reduction is: in 600 DEG C of tube furnaces, reduce 3h.
10. application according to claim 8 or claim 9, it is characterized in that, the temperature of described hydrogenation reaction is 200 DEG C, and rotating speed is 800rpm, and the time is 2h, H
2pressure is 5.0MPa.
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