CN112844466B - Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof - Google Patents
Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a green biomass charcoal modified molecular sieve supported metal catalyst, and a preparation method and application thereof. The preparation method of the catalyst comprises the following steps: (1) adding biochar and a molecular sieve into a mixed solvent of ethanol and water, and uniformly mixing to obtain a mixed solution; wherein the biochar is at least one of pine nut shell biochar, rice hull biochar, eucalyptus chip biochar and chlorella biochar; (2) adding nickel salt and vanadium salt into the mixed solution, standing, aging and drying after the mixture is uniform to obtain a catalyst precursor; (3) and grinding, crushing and sieving the catalyst precursor, and then reducing the catalyst precursor in a reducing gas atmosphere to obtain the green biomass carbon modified molecular sieve supported metal catalyst. The activity of the catalyst modified by the biochar obtained in the invention is obviously improved, the quality improving effect of the bio-oil can be enhanced, and the catalyst can be used for catalyzing the bio-oil or the guaiacol for hydrodeoxygenation to prepare aromatic hydrocarbon.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a green biomass charcoal modified molecular sieve supported metal catalyst and a preparation method and application thereof.
Background
The production of green industrial chemicals from renewable pyrolysis bio-oil has broad prospects, such as aromatics of benzene, toluene, xylene (BTX) and the like can be converted into chemicals of high-octane gasoline, synthetic rubber and the like through downstream processing. However, BTX is currently mainly refined from fossil resources, and considering the urgent need for aromatics and the requirements for energy conservation and environmental protection, an alternative method for obtaining aromatics from bio-oil is promising and economical. However, the crude bio-oil has high oxygen content, still has the defects of high acidity, low stability, low calorific value and the like, and the refining by catalytic hydrodeoxygenation is an effective method for improving the quality of the bio-oil.
At present, the common biological oil hydrodeoxygenation needs high reaction temperature and pressure requirements, and has the problems of high equipment requirements, high alkyl loss rate, high hydrogen consumption and the like. Therefore, the continuous hydrodeoxygenation of the bio-oil under the normal pressure is favored. The hydrodeoxygenation catalyst is a key, the molecular sieve supported metal catalyst is a high-efficiency bio-oil hydrodeoxygenation catalyst, however, under mild conditions, strong adsorption of a phenolic compound by a molecular sieve can cause product selectivity reduction and catalyst deactivation, and therefore, the molecular sieve catalyst is required to be modified by an auxiliary agent. The pyrolytic biochar is a high-quality catalyst organic modification auxiliary agent due to the advantages of low cost, high yield, easiness in preparation, greenness, sustainability and the like. Therefore, the molecular sieve supported metal hydrodeoxygenation catalyst modified by the green biomass charcoal has important significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a green biomass charcoal modified molecular sieve supported metal catalyst.
The invention also aims to provide the green biomass charcoal modified molecular sieve supported metal catalyst prepared by the method.
The invention further aims to provide application of the green biomass charcoal modified molecular sieve supported metal catalyst.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a green biomass charcoal modified molecular sieve supported metal catalyst comprises the following steps:
(1) adding biochar and a molecular sieve into a mixed solvent of ethanol and water, and uniformly stirring and mixing to obtain a mixed solution; wherein the biochar is at least one of pine nut shell biochar, rice hull biochar, eucalyptus chip biochar and chlorella biochar;
(2) adding nickel (Ni) salt and vanadium (V) salt into the mixed solution obtained in the step (1), uniformly stirring and mixing, then carrying out ultrasonic treatment, standing at room temperature for aging, and drying to obtain a catalyst precursor;
(3) grinding and crushing the catalyst precursor obtained in the step (2), sieving, reducing for 3-5 h (preferably for 3h) in a reducing gas atmosphere at 450-550 ℃ (preferably 500 ℃), then heating to 600-700 ℃ (preferably 650 ℃) to reduce for 2-4 h (preferably for 2h), and cooling to obtain the green biomass charcoal modified molecular sieve supported metal catalyst.
The mass ratio of the biochar to the molecular sieve in the step (1) is 1: 4-16; preferably 1: 8.
The biochar in the step (1) is preferably pine nut shell biochar.
The particle size of the biochar in the step (1) is preferably 200 meshes.
The molecular sieve in the step (1) is an H-type beta molecular sieve (H beta molecular sieve); preferably the silicon-aluminum ratio is 25, and the specific surface area is more than or equal to 650m2Beta molecular sieve type H/g.
The stirring conditions in the step (1) are as follows: shaking the mixture for 2 to 6 hours in a shaking table with the temperature of 50 to 60 ℃ and the rpm of 180; preferably: shaking the mixture for 2 hours on a shaker at 50 ℃ and 180 rpm.
The pine nut shell biochar, the rice hull biochar and the eucalyptus chip biochar in the step (1) can be obtained by conventional commercial sale or prepared by conventional methods in the field; preferably prepared by the following method:
crushing pine nut shells, rice hulls or eucalyptus wood chips, sieving, drying, and then carrying out pyrolysis reaction under the condition of 500-750 ℃ (preferably 650 ℃), so as to obtain the pine nut shell biochar, the rice hull biochar or the eucalyptus wood chip biochar.
And the sieving is to sieve by a sieve of 20-80 meshes.
The drying conditions are as follows: drying at 105-115 ℃ for 12-24 h; preferably: drying at 110 deg.C for 24 h.
The pyrolysis time is 10-30 min; preferably 10 min.
The chlorella biochar in the step (1) can be obtained by conventional commercial purchase or prepared by conventional methods in the field; preferably prepared by the following method: mixing chlorella and pyroligneous, carrying out hydrothermal pyrolysis reaction under the conditions of sealing and 160-200 ℃ (preferably 170 ℃), cooling, filtering and drying to obtain the chlorella biochar.
The mass ratio of the chlorella to the pyroligneous is 1: 8-12; preferably 1: 10.
The hydrothermal pyrolysis reaction time is 4-8 h; preferably 5 h.
The drying conditions are as follows: drying at 80-100 ℃ for 12-24 h; preferably: drying at 80 ℃ for 12 h.
The pyroligneous liquor can be obtained by conventional commercial purchase or by biomass pyrolysis; preferably a liquid product obtained after continuous pyrolysis of pine nut shells; more preferably by the following method: crushing, sieving and drying pine nut shells, then carrying out pyrolysis reaction under the condition of 500-750 ℃ (preferably 650 ℃), collecting liquid products, and carrying out centrifugal separation to obtain pyroligneous liquor.
The pyrolysis reaction time is 10-30 min; preferably 10 min.
The ethanol in the step (1) is preferably absolute ethanol.
The water in the step (1) is preferably distilled water.
The volume ratio of the ethanol to the water in the step (1) is 1: 5-10; preferably 1: 5.
The total mass ratio of the mixed solvent to the biochar and the molecular sieve in the step (1) is 20: 1.
The nickel (Ni) salt in the step (2) is soluble nickel salt; preferably Ni (NO)3)2·6H2O。
The nickel element in the nickel salt in the step (2) accounts for 15-30% of the mass of the molecular sieve supported metal catalyst modified by the green biomass charcoal; preferably accounts for 20% of the mass of the green biomass charcoal modified molecular sieve supported metal catalyst.
The vanadium salt in the step (2) is soluble vanadium salt; preferably NH4VO3。
The vanadium element in the vanadium salt in the step (2) accounts for 5-15% of the mass of the green biomass carbon modified molecular sieve supported metal catalyst; preferably accounts for 10% of the mass of the green biomass charcoal modified molecular sieve supported metal catalyst.
The mixing conditions in the step (2) are as follows: shaking the mixture in a shaking table at 50-60 ℃ and 180rpm for 2-6 h; preferably: shaking the mixture for 2 hours on a shaker at 50 ℃ and 180 rpm.
The ultrasonic conditions in the step (2) are as follows: ultrasonic treatment is carried out for 0.5-1h at 20kHz and 150 w; preferably: 20kHz and 150w of ultrasonic treatment are carried out for 0.5 h.
The standing and aging time in the step (2) is 12-24 hours; preferably 12 h.
The drying conditions in the step (2) are as follows: drying at 105-115 ℃ for 12-24 h; preferably: drying at 110 deg.C for 12 h.
The reducing gas in the step (3) is H2Or H2And N2The mixed gas of (3); preferably H2And N2The resulting reducing gases were mixed in a volume ratio of 1: 9.
The flow rate of the reducing gas in the step (3) is 100-300 mL/min; preferably 200 mL/min.
The temperature rising speed in the step (3) is 5-20 ℃/min; preferably 20 deg.C/min.
The cooling in step (3) is preferably in the range of N2Cooling in the air flow.
A green biomass charcoal modified molecular sieve supported metal catalyst is prepared by any one of the methods.
The green biomass charcoal modified molecular sieve supported metal catalyst is applied to preparation of aromatic hydrocarbons by catalyzing hydrogenation and deoxidation of bio-oil and/or guaiacol.
The aromatic hydrocarbon comprises at least one of benzene, toluene and xylene (BTX); preferably benzene.
The temperature of the catalysis is 320-410 ℃; preferably 350-410 ℃; further preferably 350-380 ℃; still more preferably 380 ℃.
The mass space velocity of the catalysis is 0.3/h-2/h; preferably 0.5/h to 1/h; more preferably 0.5/h.
The catalysis time is 0-2 h (excluding 0); preferably 0.5-1.5 h; preferably 0.5 to 1 hour.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention synthesizes a green biomass carbon modified molecular sieve supported metal catalyst, which is prepared by adding pyrolytic biochar (pine nut shell biochar (PB), rice hull biochar (RB), eucalyptus wood chip biochar (EB) and Chlorella Biochar (CB)) into a molecular sieve carrier according to a certain proportion, and loading metal Ni and metal V after mixed impregnation, ultrasonic treatment, aging and high-temperature reduction.
(2) The biochar modified molecular sieve supported metal catalyst synthesized by the invention can be used for catalyzing biological oil and guaiacol for hydrodeoxygenation to prepare high-value aromatic chemicals (BTX), and has the following advantages: the catalytic activity of the modified biological carbon is obviously improved, higher aromatic hydrocarbon yield is obtained under normal pressure, and the quality improving effect of biological oil can be enhanced; secondly, the pyrolytic biochar is a cheap, easily-obtained, green and renewable organic modifier, and the biochar modified catalyst can reduce the cost of the catalyst, improve the performance of the catalyst and promote the sustainable development of the catalyst; and the green charcoal modified catalyst has great significance in catalyzing the biological oil to prepare the high-value aromatic hydrocarbon product through hydrodeoxygenation in developing renewable energy sources, replacing fossil fuels and protecting the environment.
Drawings
FIG. 1 shows an organismFixed bed reaction device diagram for preparing aromatic hydrocarbon by oil normal pressure catalytic hydrodeoxygenation (in the diagram, 1: hydrogen (H)2) A bottle; 2: an air valve; 3: a gas flow meter; 4: a constant flow pump; 5: bio-oil/guaiacol feed bottles; 6: a gasification chamber; 7: a stainless steel tube reactor; 8: heating furnace; 9: a catalyst; 10: quartz wool; 11: a condenser tube; 12 acetone collection bottle; 13: an air bag; 14: a temperature flow controller).
FIG. 2 is a flow chart of the present invention for synthesizing green biochar-modified catalyst.
Fig. 3 is a XRD comparison pattern of green biochar modified catalyst.
FIG. 4 is a TEM image and EDS spectra of a biochar-modified and unmodified catalyst, comparing particle size distribution; wherein a, b and c are TEM images and particle size diagrams of the catalyst H beta/Ni-V, PB/Ni-V, PB-H beta-8/Ni-V respectively; d. e and f are EDS spectra of the catalyst H beta/Ni-V, PB/Ni-V, PB-H beta-8/Ni-V, respectively.
FIG. 5 is a graph showing the yields of various products from the hydrodeoxygenation of guaiacol with different proportions and types of biochar-modified catalysts.
FIG. 6 is a graph showing the effect of different reaction conditions on the preparation of aromatics by hydrodeoxygenation of guaiacol catalyzed by a biochar-modified catalyst PB-H beta-8/Ni-V.
FIG. 7 is a graph showing the effect of stability and regeneration performance of a biochar-modified catalyst in the preparation of aromatics by the hydrodeoxygenation of guaiacol.
FIG. 8 is a graph of the yield of aromatics from hydrodeoxygenation of real bio-oil catalyzed by a bio-char modified catalyst.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The following examples are given without reference to specific experimental conditions, and are generally in accordance with conventional experimental conditions. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
Example 1 modification of Hbeta molecular Sieve Metal catalysts with different types of biochar and different proportions of pine nut Shell carbon
Catalyst preparation (synthetic flow is shown in figure 2)
(1) Preparing charcoal of biological carbon:
pine nut shell biochar (PB), rice hull biochar (RB) and eucalyptus chip biochar (EB):
drying the crushed biomass raw materials (20-80 meshes) of the pine nut shells, the rice husks and the eucalyptus wood chips at 110 ℃ for 24 hours, and then carrying out continuous pyrolysis on the biomass raw materials in a conventional continuous pyrolysis reactor to obtain the pyrolytic biochar, wherein the pyrolysis temperature is 650 ℃, and the pyrolysis residence time is 10 min.
② Chlorella Biochar (CB):
the chlorella carbon is obtained by adopting a hydrothermal pyrolysis method, 15g of chlorella (China tobacco platform, Haichio-marginata, Biotech Co., Ltd.) and 150g of pyroligneous liquor (obtained by centrifugally separating a liquid product obtained by continuous pyrolysis of the pine nut shells) are mixed and sealed in a 300mL stainless steel high-pressure reaction kettle for pyrolysis, the hydrothermal temperature is 170 ℃, the pyrolysis time is 5 hours, a solid product after pyrolysis is cooled, filtered, dried at 80 ℃ for 12 hours and then collected.
And (3) sieving the obtained pine nut shell biochar, rice hull biochar, eucalyptus chip biochar and chlorella biochar with a 200-mesh sieve, and sealing and storing to prepare the modified catalyst.
(2) Preparing different types of biochar modified catalysts:
preparation of carbon-doped molecular sieve carrier: respectively weighing 0.6667g of different types of biochar (pine nut shell biochar, rice hull biochar, eucalyptus chip biochar and chlorella biochar) and 5.3333g H type beta molecular sieve (catalyst factory of Tianjin Nankai university in China, silicon-aluminum ratio 25, powder, specific surface area more than or equal to 650 m) in the step (1)2(ii)/g; also known as H β molecular sieve) (mass ratio 1:8, the total mass is 6g), adding the mixture into a 250mL beaker, adding 100g of distilled water and 20g of absolute ethyl alcohol, and stirring and shaking uniformly to obtain a mixed solution;
secondly, loading cheap transition metal Ni nickel and metal V vanadium: 8.49g of Ni (NO) were weighed3)2·6H2O and 1.97g NH4VO3(metal precursor) to the above mixed solution, the metal in this stepNi loading was 20 wt.% mass fraction, V loading was 10 wt.%; the mixture is stirred uniformly, then is shaken uniformly for 2h in a shaking table with 50 ℃ and 180rpm, is taken out and is treated by ultrasonic waves (20kHz and 150w) for 0.5h, is kept stand and aged for 12h at room temperature, and is transferred to a 110 ℃ oven to be kept for 12h for complete drying after the aging is finished.
③ reduction and activation: crushing and grinding the dried sample, sieving with a 40-mesh sieve, filling into a quartz reaction tube, and introducing a reducing gas H2/N2(10%/90% (v/v), gas flow 200mL/min), reducing for 3h when the temperature is programmed to 500 ℃, wherein the temperature rise speed is 20 ℃/min; then the temperature is raised to 650 ℃ again, and the reduction is further carried out for 2 h. Sample after high temperature reduction in N2Cooling in airflow, sealing and storing to prepare the green biomass carbon modified molecular sieve supported metal catalyst, and respectively naming the green biomass carbon modified molecular sieve supported metal catalyst as follows: PB-Hbeta-8/Ni-V, RB-Hbeta-8/Ni-V, EB-Hbeta-8/Ni-V, CB-Hbeta-8/Ni-V.
The preparation of the carbon-doped molecular sieve carrier in the step (2) can be carried out by adopting a mechanical mixing mode; in the embodiment of the invention, the molecular sieves PB and H beta are mixed according to the mass ratio of 1:8 (total mass 6g), mixing by mechanical stirring: shaking at 50 deg.C and 180rpm for 2 h.
(3) Preparing biochar modified catalysts in different proportions:
according to the method of the steps (1) and (2), the pine nut shell biochar (PB) and the H beta molecular sieve are respectively screened according to the mass ratio of 1: 4. 1: 16 (the total mass is 6g), synthesizing biochar modified catalysts with different proportions, and naming the biochar modified catalysts as PB-Hbeta-4/Ni-V, PB-Hbeta-16/Ni-V; wherein, the carbon-doped molecular sieve carrier is prepared by adopting the same mechanical mixing mode.
(4) Blank comparison catalyst without adding biochar and H beta molecular sieve
Synthesizing a catalyst which is not modified by adding any biochar according to the method in the step (2) and is named as H beta/Ni-V;
secondly, according to the methods in the steps (1) and (2), pine nut shell biochar is independently adopted as a carrier (6g), H beta molecular sieve is not added, and a catalyst without the H beta molecular sieve is synthesized and named as PB/Ni-V.
(5) XRD analysis of green biochar modified catalyst
The synthesized H β/Ni-V, PB/Ni-V and PB-H β -8/Ni-V were analyzed by an X-ray diffractometer (instrument, Rigaku Ultima-IV diffractometer, japan, recorded with CuK α radiation source (λ 0.1542nm) in the 2 θ range of 5 ° to 90 ° and a scan rate of 10 °/min), and the results are shown in fig. 3; meanwhile, the species and content of the elements of the catalyst were analyzed by an energy spectrometer (EDS) under a Transmission Electron Microscope (TEM) (obtained on a Talos-L120C (Thermo Fisher scientific) instrument operating at 200kV, and the catalyst sample was ultrasonically dispersed in deionized water for 30 minutes and then subjected to sample preparation for observation), and the results are shown in fig. 4.
(II) evaluation of microreflector
(1) The device required by the reaction can be carried out by adopting the existing device or equipment which can realize the normal-pressure catalytic hydrodeoxygenation of the bio-oil or the guaiacol to prepare the aromatic hydrocarbon, and the aim can also be realized by a reassembled device. The fixed bed reaction device for preparing the aromatic hydrocarbon by the normal-pressure catalytic hydrodeoxygenation of the bio-oil (or the guaiacol) can be added with a condensing pipe and a collecting device on the basis of an FTS-3020 Fischer-Tropsch synthesis evaluation device (FTS-3020, model number of the first Authority Industrial development Co., Tianjin City), and is specifically shown in figure 1:
the aromatic hydrocarbon fixed bed reaction device comprises a hydrogen cylinder 1, a gasification chamber 6, a constant flow pump 4, a temperature and flow controller 14, a stainless steel tube reaction 7 and a heating furnace 10; the hydrogen cylinder 1 is connected with one end of the gasification chamber 6 through the gas valve 2 and the gas flowmeter 3 in sequence; the other end of the gasification chamber 6 is connected with a stainless steel tube reactor 7; the gasification chamber 6 is connected with a constant flow pump 4 and a temperature and flow controller 14; the constant flow pump 4 is connected with the temperature and flow controller 14; a bio-oil/guaiacol feeding bottle 5 is connected below the constant flow pump 4; the stainless steel tube connecting reactor 7 is arranged in a heating furnace 8; the heating furnace 8 is connected with a temperature and flow controller 14; a condensing pipe 11 is connected below the stainless steel pipe connecting reactor 7; the catalyst 9 is arranged in the connecting stainless steel tube reactor 7; quartz wool 10 is arranged at two ends of the catalyst 9 and used for fixing the catalyst; the lower end of the quartz wool 10 is supported and positioned by a wire mesh; the condensation pipe 11 is connected with an acetone collecting bottle 12; the acetone collecting bottle 12 is connected with an air bag 13.
(2) Conditions of the experiment
Reaction temperature: 350 ℃; the gasification temperature of the raw materials is as follows: 230 ℃; mass space velocity (mass of raw material passing unit mass of catalyst in unit time, 0.5g/2g/0.5h, i.e. 0.5/h): 0.5/h; h2Flow rate: 133 mL/min; the amount of the catalyst is 2 g; guaiacol feed: 1 g/h; hydrogen-to-guaiacol ratio (molar ratio of hydrogen to guaiacol): 40; the reaction time is as follows: 0.5 h; condensation temperature: -15 ℃;
(3) procedure for the preparation of the
The hydrodeoxygenation reaction of guaiacol is carried out in a fixed bed stainless steel tube (length is 350mm, diameter is 10mm) reactor under normal pressure conditions, and specifically comprises the following steps:
2g of the synthesized catalyst is respectively weighed and placed in the center of a stainless steel tube reactor, a layer of quartz cotton is respectively filled in the upper part and the lower part of the catalyst for fixation, and the lower end of the catalyst is supported and positioned by a wire mesh. Before the reaction, the catalyst was heated at 450 ℃ and 150mL/min of H2Reducing in situ for 15min under the condition. In the formal reaction process, a constant flow pump is used for continuously conveying 0.5g of guaiacol to a gasification chamber at a constant speed within 0.5h of reaction time at a mass space velocity of 0.5/h. The gasification chamber is maintained at 230 ℃, the reaction mass is fully gasified in the gasification chamber and is mixed with pure H2(133mL/min) to obtain a gas-phase mixture, wherein the hydrogen recovery ratio (molar ratio) is 40. And then, the gas-phase material is conveyed to a stainless steel tube reactor with the temperature of 350 ℃ to perform gas-solid heterogeneous reaction with a catalyst, so that the catalytic hydrogenation, deoxidation and quality improvement process is realized. And discharging a reaction product from the lower end of the reaction tube, introducing the reaction product into a-15 ℃ condensation tube and an acetone solution collecting bottle for collection, and collecting and analyzing gas components in tail gas by using an air bag. After the overall reaction reached 0.5H, the feed was stopped and H was continued for 5 minutes2To purge residual reactants in the lines. The liquid product collected mainly was subjected to a GC-MS (Shimadzu QP2010 Ultra, Japan) equipped with a RTX-Wax column (30 m.times.0.25 mm.times.0.25 μm), an inlet gas temperature of 240 ℃ and a helium purge, an inlet gas temperature of 0.5 μ L, a temperature raising program of 35 ℃ for 10 minutes and then 10 μ LHeating to 150 deg.C/min, heating to 200 deg.C at 5 deg.C/min for 5min, and heating to 240 deg.C at 10 deg.C/min. Identification of the fractions by NIST11s library search) the product composition was analyzed and feedstock conversion and individual product yields were calculated (3 replicates). See table 1 below.
TABLE 1 conversion of starting materials and yield of the individual products
In the table, BTX: benzene, toluene and xylene; the same applies below.
It can be seen from table 1 and fig. 5 that the hydrodeoxygenation activities of different types of biochar modified catalysts are improved, more target product aromatic hydrocarbons BTX can be effectively produced, and the generation of oxygen-containing phenol products is reduced. Wherein, the pine nut shell biochar modified catalyst obtains the highest yield of aromatic hydrocarbon BTX, which exceeds 50 percent. In addition, the modification of the pine nut shell biochar with different proportions can also achieve the effect of improving the activity of the catalyst, but when more or less biochar is added, the yield of aromatic hydrocarbon is reduced, wherein when the mass ratio of the biochar to the H beta is 1:8, the PB-H beta-8/Ni-V obtained by modification is the optimal biochar adding proportion, so that the generation of the aromatic hydrocarbon BTX is most facilitated, and the yield reaches 54.24%. Therefore, the addition of the biochar has a remarkable optimization and modification effect on the molecular sieve supported metal catalyst.
Example 2 reaction Condition Effect of the preferred biochar modified catalyst PB-Hbeta-8/Ni-V on the preparation of aromatics by the Hydrodeoxygenation of guaiacol
According to the results of example 1, the catalyst PB-H β -8/Ni-V prepared in example 1 was selected to perform catalytic hydrodeoxygenation on guaiacol under different temperature and different mass space velocities.
(I) reaction temperature
(1) The experimental conditions were fixed: temperature of raw material gasificationDegree: 230 ℃; mass airspeed: 0.5/h; h2Flow rate: 133 mL/min; the amount of the catalyst is 2 g; guaiacol feed: 1 g/h; hydrogen-to-guaiacol ratio (molar ratio of hydrogen to guaiacol): 40; the reaction time is 0.5 h; condensation temperature: -15 ℃;
(2) temperature conditions: the PB-Hbeta-8/Ni-V is used for carrying out hydrodeoxygenation on guaiacol at 320 ℃, 350 ℃, 380 ℃ and 410 ℃ respectively, and the hydrodeoxygenation is recorded as 320 ℃, 350 ℃, 380 ℃ and 410 ℃.
(3) Procedure for the preparation of the
The aromatic hydrocarbon is prepared by catalytic hydrogenation and deoxidation of guaiacol according to the operation steps of the step (3) of the example 1 under different temperature conditions.
(II) reaction Mass space velocity
(1) The experimental conditions were fixed: reaction temperature: 380 ℃; the gasification temperature of the raw materials is as follows: 230 ℃; h2Flow rate: 133 mL/min; the amount of the catalyst is 2 g; guaiacol feed: 1 g/h; hydrogen-to-guaiacol ratio (molar ratio of hydrogen to guaiacol): 40; the reaction time is 0.5 h; condensation temperature: -15 ℃;
(2) mass space velocity (WHSV) conditions: PB-H beta-8/Ni-V is used for carrying out hydrodeoxygenation on guaiacol under the conditions that the mass space velocity is 0.3/H, 0.5/H, 1/H and 2/H respectively, and the mass space velocity is marked as WHSV-0.3, WHSV-0.5, WHSV-1 and WHSV-2 respectively.
(3) Procedure for the preparation of the
The aromatic hydrocarbon is prepared by catalytic hydrogenation and deoxidation of guaiacol according to the operation steps of the step (3) of the example 1 and changing different space velocity conditions.
The results of the effect of the different reaction temperature and mass space velocity conditions are shown in Table 2 below.
TABLE 2 results of the influence of different reaction temperature and Mass space velocity conditions
Table 2 and fig. 6 show that:
under the conditions of temperature gradient of 320 ℃, 350 ℃, 380 ℃ and 410 ℃, the conversion rate of guaiacol reaches 100 percent, the appropriate increase of the reaction temperature is more beneficial to the guaiacol to realize the hydrodeoxygenation to prepare an aromatic hydrocarbon BTX product, and when the reaction temperature reaches 380 ℃, the highest aromatic hydrocarbon yield is obtained and reaches 61.22 percent. However, when the temperature is increased to 410 ℃, the selectivity of the aromatic hydrocarbon is reduced, mainly because the cracking reaction is caused by the excessively high reaction temperature, and the yield of the aromatic hydrocarbon is reduced. Under the action of the biochar modified catalyst, 380 ℃ is the optimal reaction temperature for catalytic hydrodeoxygenation under normal pressure.
Under the conditions of mass space velocity gradient of 0.3/h, 0.5/h, 1/h and 2/h, the yield of aromatic hydrocarbon BTX is in a trend of rising first and then falling, the conversion rate of the space velocity within 1/h reaches 100%, and the yield of high-value aromatic hydrocarbon compounds in the product is highest when the space velocity is 0.5/h, so that the method has the most reasonable economy. In conclusion, the reaction temperature is preferably 380 ℃ and the reaction mass space velocity is preferably 0.5/h.
Example 3 stability and regeneration Performance Effect of biochar modified catalysts
According to the experimental results of examples 1 and 2, the pine nut shell biochar modified catalyst PB-Hbeta-8/Ni-V prepared in example 1 is preferably selected, the experimental conditions of example 2 are preferably that the reaction temperature is 380 ℃ and the reaction mass space velocity is 0.5/H, and the influence of the stability and the regeneration performance of the catalyst is evaluated according to the experimental method of example 1. Testing the stability of the catalyst by prolonging the duration of the hydrodeoxygenation reaction; the method is characterized in that the regeneration performance of the catalyst is explored through three times of in-situ activation regeneration, and specifically comprises the following steps:
(1) the experimental conditions are as follows: the gasification temperature of the raw materials is as follows: 230 ℃; mass airspeed: 0.5/h; h2Flow rate: 133 mL/min; the amount of the catalyst is 2 g; guaiacol feed: 1 g/h; hydrogen-to-guaiacol ratio (molar ratio of hydrogen to guaiacol): 40; the reaction time is 2 h; condensation temperature: -15 ℃;
(2) evaluation of catalyst stability: the hydrodeoxygenation reaction was continuously carried out on a fixed bed reactor for 2 hours, the same operation as the experimental procedure of example 1 was used, independent test groups were set every 0.5 hour and respectively recorded as 0-0.5 hour, 0.5-1 hour, 1-1.5 hour and 1.5-2 hours, and products were collected every 0.5 hour for analysis and comparison to evaluate the stability of the catalyst.
(3) Evaluation of catalyst regeneration Performance: the catalyst after the hydrodeoxygenation reaction for 2 hours is subjected to reaction with pure H at the temperature of 500 DEG C2And (133mL/min) reducing in situ in the reaction tube for 0.5h to obtain a regenerated catalyst. When the reactor temperature dropped to the desired 380 ℃, the feeds were repeated and the reaction was allowed to proceed for 0.5 h. The above cyclic regeneration procedure was repeated, 3 regeneration runs were conducted, and the catalyst regeneration performance was evaluated and recorded as primary regeneration, secondary regeneration, and tertiary regeneration, respectively.
The effect of catalyst stability and regeneration performance is shown in table 3 below.
TABLE 3 stability and regeneration Properties of the catalysts
As can be seen from Table 3 and FIG. 7, the catalyst maintains 100% conversion rate in the two-hour reaction process, has good stability, the yield of the aromatic BTX compound shows a trend of increasing first and then decreasing with the extension of the reaction time, and the highest yield of the aromatic hydrocarbon is obtained within the reaction time period of 0.5-1h, and reaches 69.17%. And then, three regeneration experiments show that the biochar modified catalyst can stably maintain 100% of conversion rate after being treated under the regeneration conditions, in addition, the yield of the aromatic hydrocarbon high-value product is obviously improved and is improved from 26.83% to 60.85%, and the stability is maintained at about 60% higher, so that the biochar modified catalyst has good regeneration performance and can efficiently convert materials to aromatic hydrocarbon products.
Example 4 hydrodeoxygenation Effect of biochar-modified catalysts on real pyrolysis bio-oil
According to the experimental results of examples 1 and 2, the pine nut shell biochar modified catalyst PB-H beta-8/Ni-V prepared in example 1 is preferably selected, the experimental conditions of example 2 are preferably that the reaction temperature is 380 ℃ and the reaction mass space velocity is 0.5/H, and the effect of the modified catalyst on the hydrodeoxygenation reaction of real bio-oil (conventional commercial bio-oil) is evaluated according to the experimental method of example 1. In this embodiment, the pyrolysis bio-oil (i.e., the real bio-oil) is a heavy oil component separated from the pyrolysis liquid-phase product, and has a high viscosity, and is prepared according to a mass ratio of 90% bio-oil/10% acetone, so as to improve the fluidity of the pyrolysis bio-oil and ensure that the material is smoothly pumped and conveyed. And (3) collecting a product obtained after the catalytic reaction of the modified catalyst for analysis by taking the real biological oil as a reference.
The experimental conditions are as follows: reaction temperature: 380 ℃; vaporization temperature of raw material: 280 ℃; mass airspeed: 0.5/h; h2Flow rate: 133 mL/min; the amount of the catalyst is 2 g; feeding biological oil: 1 g/h; hydrogen-to-guaiacol ratio (molar ratio of hydrogen to guaiacol): 40; condensation temperature: -15 ℃.
TABLE 4 Main Components before and after the catalytic reaction of the bio-oil
As shown in Table 4 and FIG. 8, guaiacol (59.3%) in the real bio-oil was the main component, accompanied by 23.4% phenols, 9.2% ketones, and 2.2% anisole, etc., which are the main oxygen-containing components in the bio-oil, and no aromatic hydrocarbon products were found in the crude bio-oil. Through the catalytic hydrodeoxygenation reaction of the green biochar modified catalyst, oxygen-containing substances such as guaiacol, phenols and the like are effectively converted into aromatic hydrocarbon BTX products. In the process, the yield of the aromatic hydrocarbon product reaches 44.93%, and in addition, 12.2% of methane and a very small amount of phenols are obtained. The biological carbon modified catalyst can effectively catalyze the real biological oil hydrodeoxygenation reaction, can realize higher conversion rate and aromatic hydrocarbon yield, and achieves the application purpose of producing high-value aromatic hydrocarbon BTX products by biological oil quality improvement.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a green biomass charcoal modified molecular sieve supported metal catalyst is characterized by comprising the following steps:
(1) adding biochar and a molecular sieve into a mixed solvent of ethanol and water, and uniformly stirring and mixing to obtain a mixed solution; wherein the biochar is at least one of pine nut shell biochar, rice hull biochar, eucalyptus chip biochar and chlorella biochar;
(2) adding nickel salt and vanadium salt into the mixed solution obtained in the step (1), stirring and mixing uniformly, then carrying out ultrasonic treatment, standing at room temperature for aging, and drying to obtain a catalyst precursor;
(3) grinding, crushing and screening the catalyst precursor obtained in the step (2), reducing for 3-5 h at 450-550 ℃ in a reducing gas atmosphere, heating to 600-700 ℃ for reducing for 2-4 h, and cooling to obtain a green biomass charcoal modified molecular sieve supported metal catalyst;
the molecular sieve in the step (1) has a silicon-aluminum ratio of 25 and a specific surface area of more than or equal to 650m2H-type beta molecular sieve,/g;
the mass ratio of the biochar to the molecular sieve in the step (1) is 1: 4-16;
the pine nut shell biochar, the rice hull biochar and the eucalyptus chip biochar in the step (1) are prepared by the following methods:
crushing, screening and drying pine nut shells, rice hulls or eucalyptus wood chips, and then carrying out pyrolysis reaction at 500-750 ℃ to obtain pine nut shell biochar, rice hull biochar or eucalyptus wood chip biochar;
the sieving is to sieve by a sieve of 20-80 meshes;
the drying conditions are as follows: drying at 105-115 ℃ for 12-24 h
The pyrolysis time is 10-30 min;
the chlorella biochar in the step (1) is prepared by the following method: mixing chlorella and pyroligneous, carrying out hydrothermal pyrolysis reaction under the conditions of sealing and 160-200 ℃, cooling, filtering and drying to obtain the chlorella charcoal;
the wood vinegar is obtained by the following method: crushing, screening and drying pine nut shells, then carrying out pyrolysis reaction at 500-750 ℃, collecting liquid products, and carrying out centrifugal separation to obtain pyroligneous;
the mass ratio of the chlorella to the pyroligneous is 1: 8-12;
the hydrothermal pyrolysis reaction time is 4-8 h;
the drying conditions are as follows: drying at 80-100 ℃ for 12-24 h;
the vanadium element in the vanadium salt in the step (2) accounts for 5-15% of the mass of the green biomass carbon modified molecular sieve supported metal catalyst;
the nickel element in the nickel salt in the step (2) accounts for 15-30% of the mass of the molecular sieve supported metal catalyst modified by the green biomass charcoal.
2. The preparation method of the green biomass charcoal modified molecular sieve supported metal catalyst according to claim 1, characterized in that:
the nickel salt in the step (2) is soluble nickel salt;
the vanadium salt in the step (2) is soluble vanadium salt.
3. The preparation method of the green biomass charcoal modified molecular sieve supported metal catalyst according to claim 2, characterized in that:
the nickel salt in the step (2) is Ni (NO)3)2·6H2O；
The vanadium salt in the step (2) is NH4VO3。
4. The preparation method of the green biomass charcoal modified molecular sieve supported metal catalyst according to claim 1, characterized in that:
the mass ratio of the biochar to the molecular sieve in the step (1) is 1: 8;
the nickel element in the nickel salt in the step (2) accounts for 20% of the mass of the green biomass charcoal modified molecular sieve supported metal catalyst;
and (3) the vanadium element in the vanadium salt in the step (2) accounts for 10% of the mass of the green biomass carbon modified molecular sieve supported metal catalyst.
5. The preparation method of the green biomass charcoal modified molecular sieve supported metal catalyst according to claim 1, characterized in that:
the particle size of the biochar in the step (1) is 200 meshes;
the stirring conditions in the step (1) are as follows: shaking the mixture for 2 to 6 hours in a shaking table with the temperature of 50 to 60 ℃ and the rpm of 180;
the volume ratio of the ethanol to the water in the step (1) is 1: 5-10;
the total mass ratio of the mixed solvent, the biological carbon and the molecular sieve in the step (1) is 20: 1;
the mixing conditions in the step (2) are as follows: shaking the mixture in a shaking table at 50-60 ℃ and 180rpm for 2-6 h;
the ultrasonic conditions in the step (2) are as follows: ultrasonic treatment is carried out for 0.5-1h at 20kHz and 150 w;
the standing and aging time in the step (2) is 12-24 hours;
the drying conditions in the step (2) are as follows: drying at 105-115 ℃ for 12-24 h;
the reducing gas in the step (3) is H2Or H2And N2The mixed gas of (3);
the flow rate of the reducing gas in the step (3) is 100-300 mL/min;
the temperature rising speed in the step (3) is 5-20 ℃/min;
the cooling in the step (3) is in N2Cooling in the air flow.
6. A green biomass charcoal modified molecular sieve supported metal catalyst is characterized in that: prepared by the method of any one of claims 1 to 5.
7. The use of the green biomass charcoal modified molecular sieve supported metal catalyst of claim 6 in catalyzing the hydrodeoxygenation of bio-oil and/or guaiacol to produce aromatics.
8. Use according to claim 7, characterized in that:
the aromatic hydrocarbon is at least one of benzene, toluene and xylene;
the temperature of the catalysis is 320-410 ℃;
the mass space velocity of the catalysis is 0.3/h-2/h;
the catalysis time is 0-2 h, and 0 is not included.
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