CN109569612A - It is a kind of using active carbocoal as nanometer binary metal-base catalytic cracking of tar catalyst of carrier and preparation method thereof - Google Patents
It is a kind of using active carbocoal as nanometer binary metal-base catalytic cracking of tar catalyst of carrier and preparation method thereof Download PDFInfo
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- CN109569612A CN109569612A CN201811593563.0A CN201811593563A CN109569612A CN 109569612 A CN109569612 A CN 109569612A CN 201811593563 A CN201811593563 A CN 201811593563A CN 109569612 A CN109569612 A CN 109569612A
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- semicoke
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
Abstract
It is a kind of using active carbocoal as nanometer binary metal-base catalytic cracking of tar catalyst of carrier and preparation method thereof, belong to the technical field of metallic catalyst.The present invention will effectively improve Ni-based activity and resistance to deactivation.The method of the present invention: one, nickel salt and molysite or nickel salt and magnesium salts will be prepared into a nanometer mixed metal powder；Two, semicoke hydrochloric acid solution soaking and washing, deionized water are washed till pH value neutrality, then dry；Three, it in the mixed powder and step 2 treated semicoke addition deionized water obtained step 1, stirs evenly；Four, then dry, under carrier gas protection, baking processing, carrier gas protection decline is warmed to room temperature；Obtain loaded nano binary metal char catalyst.Compared with the prior art, nano metal particles are easier to be supported on carrier inside the present invention, increase active site, reduce duct blocking, and catalytic pyrolysis performance is good, and tar conversion is high, can reach 90% or more, simple process is easily controllable.
Description
Technical field
The invention belongs to the technical fields of metallic catalyst；More particularly to a kind of using active carbocoal as the nanometer binary of carrier
Metal Substrate catalytic cracking of tar catalyst and preparation method thereof.
Background technique
Biomass energy reserves are big, distribution is wide, CO2Zero-emission is the cleaning that uniquely can be stored and transport in renewable energy
The energy.It is fuel gas, then cogeneration of heat and power that biomass pyrogenation gasification, which can will be contained in the chemical energy Efficient Conversion in biomass,
It generates electricity (DHP), it is considered to be solve the effective way of current international energy crisis and environmental problem.
However, biomass pyrogenation gasification process generates the impurity such as tar, solid particle and nitrogen sulfide simultaneously, wherein tar
Content accounts for 80% or more total impurities.Tar Yi Yushui, flying dust etc., which combine, forms corrosive thick liquid, long-term accumulation blocking
Pipeline is serious using equipment damage to combustion gas.In addition, organic rich in polycyclic aromatic hydrocarbon (PAH), phenol and phenolic compound etc. in tar
Object, has carcinogenicity and strong and stimulating smell, and discharge atmosphere causes serious secondary pollution, is detrimental to health, therefore biomass
The critical issue of pyrolytic gasification technology development.
In burnt oil treatment process, tar conversion can be small molecule compound by deep catalytic cracking technology, burnt in removing
It also can increase while oily using micro-molecular gas component.Deep catalytic cracking technology is also considered as with good development prospect
Tar processing method.
Nickel-base catalyst has significant catalytic cracking of tar efficiency, but its main problem is nickel in catalytic pyrolysis process
Easy in inactivation.Studies have shown that nickel inactivation essence is the sharply reduction of metal surface catalytic site, burnt derived from carbon distribution covering and nickel crystallite
Knot.
Adulterate the co-catalysis metal such as Fe, Mg in conventional nickel-metal structure and construct binary metal catalyst, promote nickel with
Interaction (forming metal alloy) between aided metal, not only effectively increases the catalytic pyrolysis efficiency of tar, but also to nickel
Area carbon and it is grained sintered also have certain inhibiting effect, enhance the resistance to deactivation of nickel metal.
Micro/meso porous pore structure abundant and huge specific surface area, have it as carrier inside biological semicoke
Primary condition；Semicoke surface is rich in alkali metal inorganic salts and activity is higher, and there is certain catalytic cracking of tar ability (to urge for itself
Change site)；Semicoke belongs to the by-product of biomass pyrogenation gasification process, compared to Al2O3It is more cheap and easy to get with dolomite.Cause
This, biomass semicoke has the good potentiality as nickel catalyst agent carrier.To sum up, semicoke loads binary metal catalyst in coke
Oily catalytic pyrolysis reforming art is with important application prospects.
Hu Mian, (Hu Mian, Central China University of Science and Technology's doctoral thesis, 2015.) are prepared for semicoke using traditional infusion process and load
Fe-Ni catalyst is used for the research of catalytic pyrolysis of biomass.But the process of preparation is cumbersome, and the metal particle size prepared is big,
It is active insufficient, it causes effectively to be catalyzed area small.
CN 107715884A discloses a kind of method of novel metal load type biomass half char catalyst.With metal
The aqueous solution incipient impregnation biomass presoma of active component soluble salt is heated to 600-700 DEG C after dry and is pyrolyzed, with
Obtain metal load type biomass half char catalyst.This method is different from conventional " first making burnt method ", can be known as and " first soak
Stain method ".The metallic that this method is prepared is present in carrier surface mostly, cannot make full use of the pore structure of carrier.
The metallic that the preparation method of these catalyst is prepared is mostly micron level, much larger than the average hole of semicoke
Diameter cannot effectively utilize the pore structure of carrier, can block the duct of carrier, most metallic is all supported on carrier
Surface, the conversion ratio of tar analogies toluene are 80% or so.
Summary of the invention
It is an object of the invention to prepare semicoke metal supported catalyst to traditional infusion process to improve, prepare in advance
Nano particle metal-powder is impregnated again out, and uses Ni-Fe, and Ni-Mg nanometers of binary metals effectively improve Ni-based activity
And resistance to deactivation.
A kind of in the present invention by the nanometer binary metal-base catalytic cracking of tar catalyst of carrier of active carbocoal is with nickel
Salt, molysite (or magnesium salts) and semicoke are that specifically first nickel salt is prepared into molysite (or magnesium salts) and is received made of raw material
Rice mixed metal powder, is mixed together with the semicoke after pickling processes with deionized water, made of baking after dry；Wherein, former
The mass ratio of nickel salt, molysite and semicoke is (1.58~3.15): (2.3~4.6): 10 in material；Nickel salt, magnesium salts and semicoke in raw material
Mass ratio be (1.58~3.15): (1.41~3.5): 10；Specific preparation method is completed by following step:
Step 1: being prepared into and being received using high-molecular gel method using nickel salt and molysite or nickel salt and magnesium salts as presoma
Rice mixed metal powder；
Step 2: semicoke hydrochloric acid solution soaking and washing, deionized water is washed till pH value neutrality, then dries；
Step 3: mixed powder and step 2 treated semicoke that step 1 is obtained are added in deionized water, stirring
Uniformly；
Step 4: then drying, under carrier gas protection, baking processing, carrier gas protection decline is warmed to room temperature；Complete.
It further limits, above-mentioned nickel salt is nickel nitrate, and above-mentioned molysite is ferric nitrate, and above-mentioned magnesium salts is magnesium nitrate
It further limits, calcination temperature is 400 DEG C -500 DEG C in step 1, time 30min.
It further limits, above-mentioned semicoke is the semicoke as made of the pyrolysis of pine sawdust, stalk, rice husk and sewage sludge biomass
One of or in which several any ratios mixing.
It further limits, above-mentioned semicoke partial size is 40-60 mesh.
It further limits, is dried for 24 hours at 100 DEG C -110 DEG C in step 2.
It further limits, the carrier gas in step 4 is the nitrogen or argon gas of 99.9% or more bulk purity.
It further limits, is dried for 24 hours at 100 DEG C -110 DEG C in step 4.
It further limits, stoving temperature is 400 DEG C -600 DEG C in step 4, calcining time 0.5h-2h.
Metal particle size in the present invention is smaller, is Nano grade, and partial size can reach 4-5nm.
Nano metal particles are easier to be supported on carrier inside in the present invention, increase active site, reduce duct blocking；
Nano metal particles are not only present in carrier surface, while existing in the internal pore structure of carrier, reduce duct blocking.
Ni-based catalytic activity and resistance to deactivation are effectively raised in the present invention.
The method of the present invention obtains catalyst and the catalytic pyrolysis performance of tar is improved, and the conversion ratio of tar improves, reachable
To 90% or more, it is more converted into small molecule compound containing C after catalytic reforming, is effectively improved using gas component.
Condition of the invention is controllable, convenient for application.
Detailed description of the invention
Fig. 1 is the physical characterization result and performance evaluation figure of catalyst.
Specific embodiment
Embodiment 1: using active carbocoal as the nanometer binary metal-base catalytic cracking of tar catalyst of carrier in the present embodiment
It is to be completed by following step:
Step 1: 4.6g ferric nitrate is added in the beaker of 100mL deionized water, through electromagnetic agitation by 3.15g nickel nitrate
With ultrasonic disperse it is each after form uniform and stable solution, under stiring by 5g acrylamide and 1gN, N- methylene bisacrylamide phthalein
Amine is added in beaker, and configured solution is put into thermostat water bath, and 0.05g persulfuric acid is added and presses, and is made uniform and stable solidifying
Glue.Gel is dried to obtain xerogel at 90 DEG C of vacuum oven, and xerogel is placed in the Noah's ark of tube furnace, in the guarantor of nitrogen
It is heated to 400 DEG C under shield with the heating rate of 5 DEG C/min to be calcined, constant temperature 30min obtains mixed powder after calcining；
Step 2: the hydrochloric acid solution soaking and washing of 10g semicoke 1mol/L, deionized water is washed till pH value neutrality, then sets
In drying box, dried for 24 hours at 100 DEG C；
Step 3: mixed powder and step 2 treated semicoke that step 1 is obtained are added in 100mL deionized water,
It stirs evenly；
Step 4: being subsequently placed in drying box, drying for 24 hours, is protected in the nitrogen that bulk purity is 99.98% at 100 DEG C
Processing 1h is baked under shield, at 400 DEG C, carrier gas protection decline warms to room temperature；Complete.
Comparative example 1: by nickel nitrate 3.15g, ferric nitrate 4.6g and 10g semicoke are mixed into solution, stir evenly.Solution is set
In drying box, 100 DEG C of dryings are for 24 hours.Further progress at dried carrier under nitrogen protection 400 DEG C is baked, the time
In 1h.
Embodiment 2: using active carbocoal as the nanometer binary metal-base catalytic cracking of tar catalyst of carrier in the present embodiment
It is to be completed by following step:
Step 1: 2.81g magnesium nitrate is added in the beaker of 100mL deionized water by 3.15g nickel nitrate, stirred through electromagnetism
Each rear uniform and stable solution of formation of ultrasonic disperse is mixed and stirred, under stiring by 5g acrylamide and 1gN, N- methylene bisacrylamide
Phthalein amine is added in beaker, and configured solution is put into thermostat water bath, and 0.05g persulfuric acid is added and presses, is made uniform and stable
Gel.Gel is dried to obtain xerogel at 90 DEG C of vacuum oven, xerogel is placed in the Noah's ark of tube furnace, in nitrogen
It is heated to 400 DEG C under protection with the heating rate of 5 DEG C/min to be calcined, constant temperature 30min obtains mixed powder after calcining
Body；
Step 2: the hydrochloric acid solution soaking and washing of 10g semicoke 1mol/L, deionized water is washed till pH value neutrality, then sets
In drying box, dried for 24 hours at 100 DEG C；
Step 3: mixed powder and step 2 treated semicoke that step 1 is obtained are added in 100mL deionized water,
It stirs evenly；
Step 4: being subsequently placed in drying box, drying for 24 hours, is protected in the nitrogen that bulk purity is 99.98% at 100 DEG C
Processing 1h is baked under shield, at 400 DEG C, carrier gas protection decline warms to room temperature；Complete.
Comparative example 2: by nickel nitrate 3.5g, magnesium nitrate 2.81g and 10g semicoke are mixed into solution, stir evenly.Solution is set
In drying box, 100 DEG C of dryings are for 24 hours.Further progress at dried carrier under nitrogen protection 400 DEG C is baked, the time
In 1h.
Embodiment 3: using active carbocoal as the nanometer binary metal-base catalytic cracking of tar catalyst of carrier in the present embodiment
It is to be completed by following step:
Step 1: 2.3g ferric nitrate is added in the beaker of 100mL deionized water, through electromagnetic agitation by 1.58g nickel nitrate
With ultrasonic disperse it is each after form uniform and stable solution, under stiring by 5g acrylamide and 1gN, N- methylene bisacrylamide phthalein
Amine is added in beaker, and configured solution is put into thermostat water bath, and 0.05g persulfuric acid is added and presses, and is made uniform and stable solidifying
Glue.Gel is dried to obtain xerogel at 90 DEG C of vacuum oven, and xerogel is placed in the Noah's ark of tube furnace, in the guarantor of nitrogen
It is heated to 500 DEG C under shield with the heating rate of 8 DEG C/min to be calcined, constant temperature 30min obtains mixed powder after calcining；
Step 2: the hydrochloric acid solution soaking and washing of 10g semicoke 1mol/L, deionized water is washed till pH value neutrality, then sets
In drying box, dried for 24 hours at 110 DEG C；
Step 3: mixed powder and step 2 treated semicoke that step 1 is obtained are added in 100mL deionized water,
It stirs evenly；
Step 4: being subsequently placed in drying box, drying for 24 hours, is protected in the nitrogen that bulk purity is 99.98% at 110 DEG C
Processing 2h is baked under shield, at 500 DEG C, carrier gas protection decline warms to room temperature；Complete.
Comparative example 3: by nickel nitrate 1.58g, ferric nitrate 2.3g and 10g semicoke are mixed into solution, stir evenly.Solution is set
In drying box, 110 DEG C of dryings are for 24 hours.Further progress at dried carrier under nitrogen protection 500 DEG C is baked, the time
In 2h.
Embodiment 4: using active carbocoal as the nanometer binary metal-base catalytic cracking of tar catalyst of carrier in the present embodiment
It is to be completed by following step:
Step 1: 1.41g magnesium nitrate is added in the beaker of 100mL deionized water by 1.58g nickel nitrate, stirred through electromagnetism
Each rear uniform and stable solution of formation of ultrasonic disperse is mixed and stirred, under stiring by 5g acrylamide and 1gN, N- methylene bisacrylamide
Phthalein amine is added in beaker, and configured solution is put into thermostat water bath, and 0.05g persulfuric acid is added and presses, is made uniform and stable
Gel.Gel is dried to obtain xerogel at 90 DEG C of vacuum oven, xerogel is placed in the Noah's ark of tube furnace, in nitrogen
It is heated to 500 DEG C under protection with the heating rate of 8 DEG C/min to be calcined, constant temperature 30min obtains mixed powder after calcining
Body；
Step 2: the hydrochloric acid solution soaking and washing of 10g semicoke 1mol/L, deionized water is washed till pH value neutrality, then sets
In drying box, dried for 24 hours at 110 DEG C；
Step 3: mixed powder and step 2 treated semicoke that step 1 is obtained are added in 100mL deionized water,
It stirs evenly；
Step 4: being subsequently placed in drying box, drying for 24 hours, is protected in the nitrogen that bulk purity is 99.98% at 110 DEG C
Processing 2h is baked under shield, at 500 DEG C, carrier gas protection decline warms to room temperature；Complete.
Comparative example 4: by nickel nitrate 1.58g, magnesium nitrate 1.41g and 10g semicoke are mixed into solution, stir evenly.By solution
It is placed in drying box, 110 DEG C of dryings are for 24 hours.Further progress at dried carrier under nitrogen protection 500 DEG C is baked, when
Between in 2h.
Embodiment 1-4 and comparative example 1-4 catalysis prepare toluene, the result is shown in Figure 1, as shown in Figure 1, using the method for the present invention
It prepares metal-powder and carries out the catalyst that infusion process is prepared again, the size of nanoparticle becomes smaller, metallic dispersion degree
It is higher, reduce reunion and the blocking in duct, the conversion ratio of toluene is significantly improved.
Claims (10)
1. a kind of using active carbocoal as the nanometer binary metal-base catalytic cracking of tar catalyst of carrier, it is characterised in that described to urge
Agent be using nickel salt and one of molysite and magnesium salts and semicoke as made of raw material, specifically first by nickel salt and molysite,
Or nickel salt and magnesium salts are prepared into a nanometer mixed metal powder, are mixed together with the semicoke after pickling processes with deionized water, do
Made of being baked after dry.
2. catalyst according to claim 1, it is characterised in that the mass ratio of nickel salt, molysite and semicoke is in raw material
(1.58~3.15): (2.3~4.6): 10；The mass ratio of nickel salt, magnesium salts and semicoke is (1.58~3.15) in raw material: (1.41
~3.5): 10.
3. catalyst according to claim 1, it is characterised in that the nickel salt is nickel nitrate, and the molysite is ferric nitrate,
The magnesium salts is magnesium nitrate.
4. the preparation method of catalyst as described in claim 1,2 or 3, it is characterised in that the preparation method is by following steps
Suddenly it completes:
It is mixed Step 1: nickel salt and molysite or nickel salt and magnesium salts are prepared into nanometer using high-molecular gel method as presoma
Metal-powder；
Step 2: semicoke hydrochloric acid solution soaking and washing, deionized water is washed till pH value neutrality, then dries；
Step 3: mixed powder and step 2 treated semicoke that step 1 is obtained are added in deionized water, stir evenly；
Step 4: then drying, under carrier gas protection, baking processing, carrier gas protection decline is warmed to room temperature；Complete.
5. preparation method according to claim 4, it is characterised in that calcination temperature is 400 DEG C -500 DEG C in step 1, the time
For 30min.
6. preparation method according to claim 4, it is characterised in that in step 2 semicoke be by pine sawdust, stalk, rice husk with
And one of semicoke or in which several mixing made of sewage sludge biomass pyrolysis.
7. preparation method according to claim 4, it is characterised in that semicoke partial size is 40-60 mesh in step 2.
8. preparation method according to claim 4, it is characterised in that dried for 24 hours at 100 DEG C -110 DEG C in step 2；Step 4
In at 100 DEG C -110 DEG C it is dry for 24 hours.
9. preparation method according to claim 4, it is characterised in that the carrier gas in step 4 is 99.9% or more bulk purity
Nitrogen or argon gas.
10. preparation method according to claim 4, it is characterised in that stoving temperature is 400 DEG C -600 DEG C in step 4, roasting
Time is 0.5h-2h.
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| CN110102310A (en) * | 2019-05-15 | 2019-08-09 | 太原理工大学 | The method for preparing tar lightening catalyst based on spent FCC catalyst |
| CN110540857A (en) * | 2019-08-05 | 2019-12-06 | 北京联谊华海能源科技有限公司 | Method for preparing chemical raw material and liquid fuel from biomass |
| CN111250092A (en) * | 2020-03-06 | 2020-06-09 | 中国矿业大学 | Preparation method and application of biomass honeycomb-shaped semicoke-loaded nickel-iron nanoparticle catalyst |
| CN112536037A (en) * | 2020-12-31 | 2021-03-23 | 淮阴工学院 | Preparation method of biomass charcoal-loaded nickel-copper nano alloy catalyst and application of catalyst in catalytic cracking of tar |
| CN115672334A (en) * | 2022-10-27 | 2023-02-03 | 华北理工大学 | Binary metal gasification ash-based catalyst and preparation method and application thereof |
| CN116550391A (en) * | 2023-04-19 | 2023-08-08 | 山东科技大学 | Preparation method of pennisetum hydridum porous carbon-based catalyst for organic matter solid pyrolysis |
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| CN111250092A (en) * | 2020-03-06 | 2020-06-09 | 中国矿业大学 | Preparation method and application of biomass honeycomb-shaped semicoke-loaded nickel-iron nanoparticle catalyst |
| CN112536037A (en) * | 2020-12-31 | 2021-03-23 | 淮阴工学院 | Preparation method of biomass charcoal-loaded nickel-copper nano alloy catalyst and application of catalyst in catalytic cracking of tar |
| CN115672334A (en) * | 2022-10-27 | 2023-02-03 | 华北理工大学 | Binary metal gasification ash-based catalyst and preparation method and application thereof |
| CN116550391A (en) * | 2023-04-19 | 2023-08-08 | 山东科技大学 | Preparation method of pennisetum hydridum porous carbon-based catalyst for organic matter solid pyrolysis |
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