CN106732606B - A kind of kerosene co grinding method ferrum-based catalyst - Google Patents
A kind of kerosene co grinding method ferrum-based catalyst Download PDFInfo
- Publication number
- CN106732606B CN106732606B CN201611225343.3A CN201611225343A CN106732606B CN 106732606 B CN106732606 B CN 106732606B CN 201611225343 A CN201611225343 A CN 201611225343A CN 106732606 B CN106732606 B CN 106732606B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- kerosene
- grinding method
- feooh
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01J23/75—Cobalt
-
- 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
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of kerosene co grinding method ferrum-based catalysts, the catalyst uses nanoscale alpha-feooh for main active component, a small amount of secondary active element Ni, Co are adulterated, and increases the dispersion degree of FeOOH by the way that a small amount of Al, Zn element is added, improves the overall activity of catalyst.Meanwhile using the active carbon of bigger serface as carrier, further dispersed catalyst active component makes it show high catalytic activity in the reaction of kerosene co grinding method, and extends its service life in the reaction of kerosene co grinding method.In the Coal liquefaction using catalytic cracked oil pulp as solvent, catalyst components collective effect of the present invention, show good catalytic performance, and the coke precursor generated in metal impurities and reaction process in raw material can be adsorbed, it effectively prevent generating coking and blocking on reactor wall and inner member.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to it is a kind of using catalytic cracked oil pulp as solvent, catalytic activity it is high,
The kerosene co grinding method ferrum-based catalyst of service life length.
Background technique
Low-carbon, green, cleaning, high-efficient development have become new round international economy growth point and focus of the competition, and core is
Establish high energy efficiency, the development model of low emission.Discharge, comprehensive utilization of resources, Coal Clean of the coal liquefaction technology in carbon dioxide
Use aspects have advantage, therefore, develop the key areas that coal liquefaction technology is the following Development of Coal Chemical Industry under low coal price,
Wherein direct coal liquefaction technology is the main aspect of contemporary coal liquefaction technology.
Direct coal liquefaction technology is by coal dust and liquefaction solvent (heavy poor oil, the self-produced solvent naphtha of coal liquefaction, polycyclic aromatic hydrocarbon
Deng) it is converted into light-end products at high temperature under high pressure, wherein catalyst is one of key factor of direct coal liquefaction technology, is enhancing
One impetus of direct coal liquefaction technology competitiveness.
At present both at home and abroad in terms of heavy poor oil lighting and DCL/Direct coal liquefaction, catalyst research is catalyzed mainly for three classes
Agent system is the oil-soluble catalyst that the metallic elements such as Ni, Co, Mo and W are active component respectively；Zinc chloride, stannic chloride etc. are weak
Water-soluble catalyst based on Lewis acid；And Fe base throw-away-type catalyst.Since technological conditions for direct coal liquefaction determines it
Catalyst disposably passes through with reactant in core reaction device, and catalyst enters reaction residues and is expelled directly out device.Therefore
In view of the emission treatment of the economic benefit and subsequent residue of catalyst cost and overall technology, industrialized at present in the technology
The catalyst of application is based on Fe base throw-away-type catalyst.
As the continuous popularization and application, the research and development of iron-based throw-away-type catalyst of domestic and international coal liquefaction technology are more and more wider
It is general, to study based on catalyst for coal liquefaction of the active component for FeOOH.Patent CN1579623A and CN1778871A are published
A kind of to reoxidize to obtain the nanometer γ-FeOOH catalyst being carried on coal particle by aqueous slkali and ferrous reactant salt, this is urged
Agent has good activity.Patent CN104096563A, which has published one kind and participates in structure, helps Si, CN104437492A public
The FeOOH catalyst for coal liquefaction that exploitation table one kind participates in structural promoter Al and Si, and is carried on coal dust or do not load, the catalysis
The use of agent further enhances the activity of FeOOH class catalyst for coal liquefaction.Patent CN104888797A has published one kind
Second active component such as Ni, Co, Mo, W and the catalyst of structural promoter Al, Si or Zr are mixed into FeOOH.It is above-mentioned each special
Benefit is furtherd investigate in terms of the high degree of dispersion of catalyst activity and FeOOH, and has obtained corresponding achievement.And it is anti-in coal liquefaction
During answering, catalyst contactant in such reaction includes machinery entrained by the reactant and product, reactant of macromolecular
Coking material, the heavy metal substance etc. that impurity, reversible reaction generate, contact of the catalyst with these substances easilys lead to catalyst
Inactivation reduces the service life of catalyst in the reactor.Therefore the FeOOH catalyst of support type, on the one hand due to the presence of carrier
Dispersibility of the active component FeOOH in carrier surface and reaction system is improved, is improved between catalyst and reactant
Contact probability improves catalyst activity；On the other hand by the protection of carrier, reduce catalyst activity component FeOOH's
Deactivation rate extends the catalytic life of catalyst activity component, improves the conversion number in catalyst units activity site, increases
Strong catalyst activity.And coal dust as carrier when, one side coal dust belongs to reactant in Coal liquefaction system, with anti-
The progress answered, catalyst carrier participate in reaction and convert, and catalyst activity component is caused phenomena such as falling off, reuniting occur；It is another
Aspect coal dust specific surface area is too small, and the effect in entire reaction system in terms of guard catalyst active component is very limited.
(Energy and Fuels, 1998,12 (5): 1020-1030 such as researcher Rahimi；Fuel
Processing Technology, 2001,69 (3): 191-203) by studying the carbon material of different specific surface areas to pitch heat
The influence of coking process is reacted, the fullerene cigarette ash of discovery more bigger serface has effectively adsorbed in the coking generated in reaction
Between phase, so that the coke induction period of polycondensation reaction generation is significantly extended, when specific surface area is from 152m2/ g increases to 208m2/g
When, coking reaction coke induction period extends 10 minutes or so, and provides physics place for coke deposits, to prevent this kind of anti-
It should be in the coking carbon deposit on reactor.Therefore, big point can preferably on the one hand be extended as carrier compared with the carbon material of Large ratio surface
The coke induction period of polycondensation reaction occurs between son, and coke precursor and mechanical admixture in energy adsorption reaction system, protects
Protect catalyst activity component；On the other hand, can effectively adsorption reaction object molecule, promotion reactant divide compared with the carbon material of Large ratio surface
The contact probability of son and active catalyst sites improves catalyst activity.In patent CN104923231A with alpha-feooh be activity
Component, using bigger serface carbon material as carrier, which has excellent activity in Coal liquefaction, and is catalyzed
Agent usage amount is substantially reduced than original industrializeding catalyst.But the activity of active component alpha-feooh is still limited in the catalyst,
And alpha-feooh crystal grain is relatively regular, and dispersibility is poor.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome above-mentioned existing coal liquefaction technology there are the shortcomings that, one kind is provided
Using catalytic cracked oil pulp as solvent, the kerosene co grinding method ferrum-based catalyst that catalytic activity is high, the service life is long.
Solving technical solution used by above-mentioned technical problem is: the first active component of the catalyst is alpha-feooh, the
Two active components are one or both of Ni, Co element, and one or both of structural promoter Al, Zn element, carrier is
Active carbon, wherein being 1wt%~15wt% with Fe metering load capacity, the load capacity refers to the ratio between Fe mass and carrier quality,
And be in terms of 100% by the integral molar quantity of metallic element, Fe element account for the 80%~98%, second active component account for 1%~10%, knot
Structure auxiliary agent accounts for 1%~10%.
It is preferably 5wt%~10wt% with Fe metering load capacity in above-mentioned catalyst.
In above-mentioned catalyst, further preferably by the integral molar quantity of metallic element it is in terms of 100% that Fe element accounts for 85%~
95%, the second active component accounts for 3%~8%, structural promoter and accounts for 2%~7%.
In above-mentioned catalyst, be more preferably in terms of 100% by the integral molar quantity of metallic element Fe element accounts for 88%~92%,
Second active component accounts for 4%~6%, structural promoter and accounts for 4%~6%.
In above-mentioned catalyst, alpha-feooh is strip, a length of 30~300nm, and width is 10~100nm, and preferably its is a length of
50~150nm, width are 20~50nm.
In above-mentioned catalyst, the specific surface area of the active carbon is 200~2000m2/ g, the preferably specific surface area of active carbon
For 400~1000m2/g。
Kerosene co grinding method ferrum-based catalyst of the present invention the preparation method comprises the following steps: according to above-mentioned catalyst form, by ferrous sulfate,
Nickel sulfate and/or cobaltous sulfate, aluminum sulfate and/or zinc sulfate are added in distilled water and are configured to sulfate liquor, then to the sulphur
Active carbon and uniform stirring are added in acid salt solution, is passed through air or oxygen, and ammonium hydroxide is added, the pH of reaction solution is kept to exist
It between 6.0~8.0, is reacted at 20~50 DEG C 0.5~4 hour, discharges, filters after reaction, is dry, obtaining kerosene and be total to liquid
Change ferrum-based catalyst.
Compared with prior art, the invention has the following advantages:
1, the present invention uses nanoscale alpha-feooh for main active component, adulterates a small amount of secondary active element Ni, Co,
So that catalyst activity further enhances, and improves the dispersibility of FeOOH by the way that a small amount of Al, Zn element is added, catalysis is improved
The overall activity of agent, using the active carbon of bigger serface as carrier, the guard catalyst active group in the reaction of kerosene co grinding method
Point, it improves the activity of entire catalyst and extends service life of the catalyst in the reaction of kerosene co grinding method.
2, catalyst of the present invention collective effect in Coal liquefaction has good activity, and catalyst usage amount is few, is
0.3wt%~3wt% of reaction raw materials.Meanwhile coke precursor is adsorbed and trapped to the phase, in raw material to monolithic catalyst after the reaction
Metal impurities, and adsorption reaction during generate coke precursor, prevent on reactor wall and inner member generate knot
Burnt carbon distribution effectively prevent generating coking and blocking on reactor wall and inner member.
3, catalyst preparation conditions of the present invention are mild, and catalyst is easily stored and transports, and catalyst particle size is with carrier grain
Diameter range is adjustable, and the partial size of nano level active component and the activity of catalyst are unaffected.
Detailed description of the invention
Fig. 1 is catalyst n i-Al- in catalyst Co-Al-Zn-FeOOH/ active carbon and embodiment 2 in embodiment 1
The X-ray diffraction spectrogram of FeOOH/ active carbon.
Fig. 2 is the stereoscan photograph of catalyst Co-Al-Zn-FeOOH/ active carbon in embodiment 1.
Fig. 3 is the enlarged drawing of Fig. 2.
Fig. 4 is the stereoscan photograph of catalyst n i-Al-FeOOH/ active carbon in embodiment 2.
Fig. 5 is the enlarged drawing of Fig. 4.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
According to being 5wt% with Fe metering load capacity, the molar ratio of Fe, Co, Al, Zn element is 90:5:2.5:2.5, will
24.8223g (0.0893mol) green vitriol, 1.3946g (0.0050mol) Cobalt monosulfate heptahydrate, 0.8331g
(0.00125mol) Patent alum, 0.7175g (0.0025mol) Zinc vitriol are added in 500mL distilled water, match
Sulfate liquor is made, it is 600 () m that 100g specific surface area is then added into the sulfate liquor2The active carbon of/g, and be passed through
Flow is 1m3The air of/h, while the ammonia spirit of 1mol/L is added, keep the pH of reaction solution between 6.0~7.0,38
It is reacted 1.5 hours at DEG C, discharging, suction filtration and the drying in 100 DEG C of thermostatic drying chamber after having reacted obtain loading with Fe metering
Amount is the Co-Al-Zn-FeOOH/ activated-carbon catalyst of 5wt%.
It can be seen from Fig. 1 that gained catalyst occurs at 18 °, 21 °, 26 °, 33 °, 35 °, 37 °, 40 °, 41 °, 53 °, 59 ° etc.
, there is the characteristic diffraction peak of active carbon at 21 °, 26.5 °, does not observe doping in apparent alpha-feooh characteristic diffraction peak
The response characteristic diffraction maximum of element.By Fig. 2 and 3 as it can be seen that strip alpha-feooh particle is carrier surface is more dispersed, distribution is equal
One, the length of alpha-feooh is about 100nm, wide about 30nm.
Embodiment 2
According to being 5wt% with Fe metering load capacity, the molar ratio of Fe, Ni, Al element is 90:5:5, by 248.2232g
(0.8929mol) green vitriol, 13.0381g (0.0496mol) six hydration nickel sulfate, 16.5275g (0.0248mol)
Patent alum is added in 5L distilled water, is configured to sulfate liquor, and 1000g then is added into the sulfate liquor
Specific surface area is 600m2The active carbon of/g, and being passed through flow is 1.5m3The air of/h, while it is 25% that mass fraction, which is added,
Industrial ammonia keeps the pH of reaction solution between 6.0~7.0, reacts 2 hours at 35 DEG C, reacted after discharging, filter and
It is dry in 110 DEG C of thermostatic drying chamber, obtain measuring load capacity with Fe as the Ni-Al-FeOOH/ activated-carbon catalyst of 5wt%.
It can be seen from Fig. 1 that gained catalyst occurs at 18 °, 21 °, 26 °, 33 °, 35 °, 37 °, 40 °, 41 °, 53 °, 59 ° etc.
, there is the characteristic diffraction peak of active carbon at 21 °, 26.5 °, does not observe doping in apparent alpha-feooh characteristic diffraction peak
The response characteristic diffraction maximum of element.By Figure 4 and 5 as it can be seen that strip alpha-feooh particle is carrier surface is more dispersed, distribution is equal
One, the length of alpha-feooh is about 100nm, wide about 30nm.
Embodiment 3
According to being 5wt% with Fe metering load capacity, the molar ratio of Fe, Ni, Al, Zn element is 90:5:2.5:2.5, will
24.8223g (0.0893mol) green vitriol, 1.3142g (0.0050mol) six hydration nickel sulfate, 0.8331g
(0.00125mol) Patent alum, 0.7175g (0.0025mol) Zinc vitriol are added in 500mL distilled water,
It is configured to sulfate liquor, it is 600m that 100g specific surface area is then added into the sulfate liquor2The active carbon of/g, and lead to
Inbound traffics are 1m3The air of/h, while the ammonia spirit of 1mol/L is added, keep the pH of reaction solution between 6.0~7.0,
It is reacted 1.5 hours at 38 DEG C, discharging, suction filtration and the drying in 110 DEG C of thermostatic drying chamber after having reacted obtain measuring with Fe negative
Carrying capacity is the Ni-Al-Zn-FeOOH/ activated-carbon catalyst of 5wt%.
Embodiment 4
According to being 5wt% with Fe metering load capacity, the molar ratio of Fe, Co, Ni, Al, Zn element is 90:2.5:2.5:2.5:
2.5, by 24.8223g (0.0893mol) green vitriol, 0.7029g (0.0025mol) Cobalt monosulfate heptahydrate,
0.6571g (0.0025mol) six hydration nickel sulfate, 0.8331g (0.00125mol) Patent alum, 0.7175g
(0.0025mol) Zinc vitriol is added in 500mL distilled water, is configured to sulfate liquor, then molten to the sulfate
It is 600m that 100g specific surface area is added in liquid2The active carbon of/g, and being passed through flow is 1m3The air of/h, while 1mol/L is added
Ammonia spirit, keep the pH of reaction solution between 6.0~7.0, reacted 1.5 hours at 38 DEG C, reacted after discharging, filter
And it is dry in 110 DEG C of thermostatic drying chamber, obtain the Co-Ni-Al-Zn-FeOOH/ activity for measuring load capacity with Fe as 5wt%
Pd/carbon catalyst.
In order to prove beneficial effects of the present invention, catalyst that inventor obtains Examples 1 to 4, existing method preparation
γ-FeOOH/ coal catalyst, alpha-feooh/carbon carrier catalyst (CN104923231A) and red mud catalyst be respectively applied to
In the reaction of kerosene co grinding method, wherein in γ-FeOOH/ coal catalyst and alpha-feooh/carbon carrier catalyst Fe element load capacity
For 5wt%, catalyst crystallization time is 1.5 hours；Fe in red mud catalyst2O3Content is 48.5wt%.With cycle oil
Slurry and bituminous coal (ash content) are used as raw material, reaction condition: reaction temperature is 455 DEG C；Reaction initial hydrogen pressure is 9MPa；Catalyst
Additional amount is 1wt% (reaction raw materials)；Coal additional amount is 20wt%；Vulcanizing agent is sulphur powder；Reaction time is 1 hour.Reaction knot
Fruit is as shown in table 1.
Table 1
Seen from table 1, catalyst of the present invention is used to be catalyzed and react by the kerosene co grinding method of solvent of catalytic cracked oil pulp, nothing
By conversion ratio, the asphalitine conversion ratio for being coal, still < 525 DEG C oil yield, is urged relative to red mud catalyst and γ-FeOOH/ coal
Agent is significantly increased；Compared with alpha-feooh/carbon carrier catalyst, catalyst of the present invention shows higher catalytic activity, tool
There is more preferably industrial application value.
In order to further prove beneficial effects of the present invention, the catalyst that embodiment 2 obtains is applied to by inventor
In the floating bed hydrocracking pilot-plant of 150kg/d, the catalytic performance of reaction evaluating catalyst is refined altogether by kerosene, with catalysis
Cracking slurry oil and bituminous coal (ash content) are used as raw material.Reaction condition are as follows: 460 DEG C of reaction temperature；Reaction pressure 22MPa；Catalyst adds
Enter amount 1wt% (reaction raw materials)；Coal additional amount 40wt% and 45wt%；Vulcanizing agent is sulphur powder；Air speed is 0.5kg/Lh.Reaction
It the results are shown in Table 2.
Table 2
| Test number | 1 | 2 |
| Coal additional amount/wt% | 40 | 45 |
| Temperature/DEG C | 459.8 | 460.1 |
| Catalyst usage amount (total raw material)/wt% | 1.00 | 1.00 |
| Coal conversion ratio/wt% | 83.13 | 82.34 |
| > 525 DEG C of residue fraction (being free of solid) conversion ratios/wt% | 85.95 | 86.37 |
| Asphalitine conversion ratio/wt% | 83.62 | 83.51 |
| C1-C4Yield/wt% | 9.63 | 10.09 |
| C5 +Yield/wt% | 0.42 | 1.07 |
| H2S (content in recycle hydrogen)/vol% | 0.31 | 0.38 |
| Green coke or/and unconverted coal/wt% | 6.25 | 7.36 |
| < 525 DEG C of oil yields (contain C5 +, to butt coal) and/wt% | 78.18 | 74.18 |
Claims (8)
1. a kind of kerosene co grinding method ferrum-based catalyst, it is characterised in that: the first active component of the catalyst is alpha-feooh, the
Two active components are one or both of Ni, Co element, and structural promoter is Al and Zn element, and carrier is active carbon, wherein with
It is the wt% of 1 wt%~15 that Fe, which measures load capacity, and the load capacity refers to the ratio between Fe mass and carrier quality, and with metallic element
Integral molar quantity is 100% meter, and Fe element, which accounts for the 80%~98%, second active component and accounts for 1%~10%, structural promoter, accounts for 1%~10%.
2. kerosene co grinding method ferrum-based catalyst according to claim 1, it is characterised in that: the catalyst is negative with Fe metering
Carrying capacity is the wt% of 5 wt%~10.
3. kerosene co grinding method ferrum-based catalyst according to claim 2, it is characterised in that: with the integral molar quantity of metallic element
For 100% meter, Fe element, which accounts for the 85%~95%, second active component and accounts for 3%~8%, structural promoter, accounts for 2%~7%.
4. kerosene co grinding method ferrum-based catalyst according to claim 2, it is characterised in that: with the integral molar quantity of metallic element
For 100% meter, Fe element, which accounts for the 88%~92%, second active component and accounts for 4%~6%, structural promoter, accounts for 4%~6%.
5. kerosene co grinding method ferrum-based catalyst described in any one according to claim 1~4, it is characterised in that: the α-
FeOOH is strip, a length of 30~300 nm, and width is 10~100 nm.
6. kerosene co grinding method ferrum-based catalyst described in any one according to claim 1~4, it is characterised in that: the α-
FeOOH is strip, a length of 50~150 nm, and width is 20~50 nm.
7. kerosene co grinding method ferrum-based catalyst described in any one according to claim 1~4, it is characterised in that: the work
Property charcoal specific surface area be 200~2000 m2/g。
8. kerosene co grinding method ferrum-based catalyst described in any one according to claim 1~4, it is characterised in that: the work
Property charcoal specific surface area be 400~1000 m2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611225343.3A CN106732606B (en) | 2016-12-27 | 2016-12-27 | A kind of kerosene co grinding method ferrum-based catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611225343.3A CN106732606B (en) | 2016-12-27 | 2016-12-27 | A kind of kerosene co grinding method ferrum-based catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106732606A CN106732606A (en) | 2017-05-31 |
| CN106732606B true CN106732606B (en) | 2019-10-15 |
Family
ID=58921567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611225343.3A Active CN106732606B (en) | 2016-12-27 | 2016-12-27 | A kind of kerosene co grinding method ferrum-based catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106732606B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906081B (en) * | 2018-06-25 | 2021-02-19 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of multifunctional suspension bed catalyst |
| CN109926052B (en) * | 2019-03-14 | 2021-08-17 | 李大鹏 | Supported patina-based multi-metal hydroxide catalyst and preparation method thereof |
| CN109926057B (en) * | 2019-03-14 | 2021-11-02 | 李大鹏 | Fe (III) -based catalyst and preparation method and application thereof |
| CN110743526A (en) * | 2019-11-07 | 2020-02-04 | 陕西师范大学 | Resource utilization process for kerosene co-refining residue |
| CN111349460A (en) * | 2020-03-17 | 2020-06-30 | 中国神华煤制油化工有限公司 | Low freezing point diesel oil and its preparation method and device |
| CN112156785B (en) * | 2020-10-16 | 2023-03-31 | 中国神华煤制油化工有限公司 | Direct coal liquefaction catalyst, preparation method thereof and direct coal liquefaction method |
| CN115007148A (en) * | 2022-04-18 | 2022-09-06 | 陕西延长石油（集团）有限责任公司 | Supported alpha-FeOOH catalyst with regenerated wooden waste activated carbon as carrier and preparation method and application thereof |
| CN115770574B (en) * | 2022-11-14 | 2024-07-12 | 陕西延长石油（集团）有限责任公司 | Carbon-supported catalyst and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4508381B2 (en) * | 1999-08-25 | 2010-07-21 | メタウォーター株式会社 | Iron oxide catalyst for decomposition of organic waste, method for producing the same, and method for treating organic waste |
| JP2001164263A (en) * | 1999-12-08 | 2001-06-19 | Kobe Steel Ltd | Method for liquefying coal |
| CN104888797A (en) * | 2015-06-10 | 2015-09-09 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| CN104923231B (en) * | 2015-06-29 | 2017-11-21 | 陕西延长石油（集团）有限责任公司 | A kind of catalyst for coal liquefaction and its preparation method and application |
| CN105013505A (en) * | 2015-07-22 | 2015-11-04 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
-
2016
- 2016-12-27 CN CN201611225343.3A patent/CN106732606B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106732606A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106732606B (en) | A kind of kerosene co grinding method ferrum-based catalyst | |
| Ghiyasiyan-Arani et al. | Enhanced photodegradation of dye in waste water using iron vanadate nanocomposite; ultrasound-assisted preparation and characterization | |
| Ma et al. | Evolution of nanoscale amorphous, crystalline and phase-segregated PtNiP nanoparticles and their electrocatalytic effect on methanol oxidation reaction | |
| Wang et al. | Energy band engineering of hydroxyethyl group grafted on the edge of 3D g-C3N4 nanotubes for enhanced photocatalytic H2 production | |
| CN104923231B (en) | A kind of catalyst for coal liquefaction and its preparation method and application | |
| CN1274415C (en) | Method for preparing high dispersion iron-base catalyst for coal direct liquefication | |
| CN105013505A (en) | Iron-based catalyst and preparation method thereof | |
| Shi et al. | In-situ growth of NiS co-catalyst on MnS/Mn0. 3Cd0. 7S heterojunction for boosting photocatalytic hydrogen evolution under visible light irradiation | |
| Wang et al. | Ultralow-temperature synthesis of small Ag-doped carbon nitride for nitrogen photofixation | |
| CN102560216A (en) | Preparation method of dense coated composite powder and super coarse and extra coarse grained cemented carbide | |
| Hou et al. | Co-MOF induced “blossom branch like” MoS2@ Co9S8/C nanofibers as a bifunctional catalyst for HER and OER | |
| Liu et al. | Multiphase phosphide cocatalyst for boosting efficient photocatalytic H2 production and enhancing the stability | |
| Zhao et al. | Synergistic effects of cocatalyst and homojunction/heterojunction with boosted photocatalytic H2 evolution over Zn0. 5Cd0. 5S/NDs | |
| Sun et al. | Modulating charge transport behavior across the interface via g-C3N4 surface discrete modified BiOI and Bi2MoO6 for efficient photodegradation of glyphosate | |
| CN1182026C (en) | Process for preparing Fe-series catalyst used to synthesize nano carbon tubes | |
| İzgi̇ et al. | Green and active hydrogen production from hydrolysis of ammonia borane by using caffeine carbon quantum dot-supported ruthenium catalyst in methanol solvent by hydrothermal treatment | |
| Yang et al. | Loading density modulation of Zn0. 5Cd0. 5S nanoparticles on ZnS (en) 0.5 nanosheets with effective hole transfer channels towards highly efficient hydrogen evolution | |
| Saka | Facile oxygen doped heterojunction structured hybrid particles with γ-aluminium oxide dispersed over graphitic carbon nitride for dehydrogenation of sodium borohydride in methanol: Catalytic properties and mechanism | |
| Chen et al. | Noble-metal-free pn heterojunction of iron (III) hydroxide and graphitic carbon nitride for hydrogen evolution reaction | |
| Wei et al. | Visible-light-enhanced hydrogen evolution from catalytic hydrolysis of ammonia borane using Ru nanoparticles supported on CdS-modified graphitic carbon nitride | |
| CN111686735A (en) | Hydrogenation co-refining catalyst for preparing high-dispersion briquette/heavy oil by modifying carrier coal | |
| Keshipour et al. | Palladium, and platinum nanoparticles supported on chitosan aerogel as a photocatalyst of formic acid degradation | |
| CN114669300B (en) | Coal liquefaction catalyst and preparation method and application thereof | |
| Wang et al. | Enhanced photocatalytic hydrogen evolution by combining water soluble graphene with cobalt salts | |
| Cai et al. | High temperature shock synthesis of superfine Ru nanoparticles anchored on TiO2@ nitrogen-doped carbon for pH-universal hydrogen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |