CN108393091A - Liquefied coal coil hydrotreating catalyst and the preparation method and application thereof - Google Patents
Liquefied coal coil hydrotreating catalyst and the preparation method and application thereof Download PDFInfo
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- CN108393091A CN108393091A CN201611052918.6A CN201611052918A CN108393091A CN 108393091 A CN108393091 A CN 108393091A CN 201611052918 A CN201611052918 A CN 201611052918A CN 108393091 A CN108393091 A CN 108393091A
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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
- B01J23/76—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention discloses a kind of liquefied coal coil hydrotreating catalysts, the catalyst is using aluminium oxide as carrier, using group VIII metal and vib metals as active metal component, on the basis of the weight of catalyst, the content of aluminium oxide is 70%~84%, content of the group VIII metal in terms of oxide is 1wt%~9wt%, and content of the vib metals in terms of oxide is 15wt%~30wt%.The present invention also provides the preparation method and application of the catalyst.Using boiling bed process and catalyst of the present invention, liquefied coal coil can be used as hydrogen supply solvent naphtha after hydrotreating.
Description
Technical field
The present invention relates to a kind of hydrogenation catalysts and preparation method and application, and coal liquefaction is processed especially with ebullated bed
Oil is come the method that provides hydrogen supply solvent naphtha.
Background technology
DCL/Direct coal liquefaction is completed under high temperature, high pressure, it is so that protium is entered by means of hydrogen supply dissolvent and catalyst
The molecular structure of coal and its derivative, to convert coal into the advanced clean coal technology of liquid fuel or industrial chemicals.Coal by
Thermal decomposition and the unstable radical fragment generated carry out hydrocracking, and complicated macromolecule coal is made to be converted to H/C atoms
Relatively high low molecule liquid product（Liquefied coal coil）With a small amount of gaseous hydrocarbon.DCL/Direct coal liquefaction reaction solvent used comes from coal
Heavy distillate in itself product of direct liquefaction process, but its hydrogen content is low, condensed-nuclei aromatics content is high, aromatic carbon rate is high, hydrogen supply
Poor performance.To improve hydrogen supply capacity, heavy distillate is usually subjected to appropriate depth hydrotreating, is controlled in heavy distillate
Condensed-nuclei aromatics content is finally reached the target for improving its hydrogen supply capacity.At present industry generally believe when aromatic carbon rate 40~
It is strongest that solvent hydrogen supply capacity is recycled when 45mol%.
It will not be formed come hydrotreating liquefied coal coil since catalyst is in fluidized state in ebullated bed using ebullated bed
Bed pressure drop, while catalyst adds row online, ensure that reaction system activity maintains certain level, maintains stable product matter
Amount.For boiling-bed catalyst, abrasion resistance is very important an index, and the abrasion resistance of catalyst with it is former
The property of material is also closely bound up, therefore it is the key that solve the problems, such as this to develop the good catalysis material of caking property.
A kind of coal liquefied oil boiling bed hydrogenation techniques of CN200610027537.2, a kind of coal liquefactions of CN200610027539.1
At oil boiling bed hydrogenation catalyst carrier and preparation method thereof and a kind of coal liquefied oil boiling bed hydrogenations of CN200610027538.7
Catalyst and preparation method thereof is managed, a kind of preparation side of ebullated bed liquefied coal coil hydrotreating catalyst is proposed in these three patents
Method.At least one of hydrogenation catalyst catalyst contains fibrous auxiliary agent, and the content of fibrous auxiliary agent in the catalyst is
3wt%~10wt%, fibrous auxiliary agent are alumina fibre, aluminium oxide-silicon oxide fibre, carbon fiber, alkali-free glass fibre, boron
It is one or more in fiber, the length of 4~500 microns, 4~200 microns of preferred length, preferably 10~80 microns, directly
Diameter is 4~100 microns, 4~50 microns preferably a diameter of.It is to improve catalyst by the way that textile auxiliary agent is added in above-mentioned patent
Mechanical strength and abrasion resistance, but its cost is higher, and addition is larger.
CN201310638434.X discloses a kind of liquefied coal coil catalyst carrier for hydrgenating, catalyst and preparation method thereof,
It is in terms of 100% by the carrier gross weight, the carrier includes the carbon nanotube of 5-60wt%, the aluminium oxide of 32-90wt%, 0-
The silica of 8wt% and the titanium dioxide of 0-8wt%.The catalyst cost of material is higher, larger for catalyst amount
Ebullated bed process spends and increases, is unsuitable in commercial introduction application.
How to prepare that caking property is good, and cheap boehmite raw material is one of ebullated bed processing liquefied coal coil
Difficult point.Boehmite is industrially general, and there are three types of preparation methods：Alchlor process, aluminum sulfate method and carbonizatin method.Wherein preceding two
Kind method is liquid-liquid reactions, and carbonizatin method is gas liquid reaction, and reaction process is to fill liquid in a kettle, reaction kettle bottom
Portion is passed through gas and is reacted, and such range request gas breaking of crossing is uniform, micro-bubble, in favor of the progress of reaction, and is obtained
The uniform product of crystal grain, therefore it is higher to the Spreading requirements of gas, how to make gas formed uniformly, micro-bubble and liquid it is good
Good contact is the technical issues of current field is badly in need of solving.
CN201210409431.4 discloses a kind of method preparing alumina dry glue using carbonizatin method.This method be at
Suitable RPE types and/or PEP type nonionic surfactants are added during glue, nonionic surfactant both has reaming
Effect, and have the function of defoaming, make caused by Air Bubble Size it is suitable and uniform, solution is uniformly contacted with gas, is had
Hold conducive to generation large aperture, macropore, the aluminium oxide of reasonable pore distribution.This method is eliminated by way of chemical reagent is added
Bubble can not change the Air Bubble Size of air inlet, and to cannot efficiently utilize gas, and the cost of chemical reagent is higher, also can
Influence the cost of final products.
CN201110350784.7 discloses a kind of alumina support and preparation method thereof.The alumina support is to use carbon
Change method reacts preparation in circulation flow reactor, and reaction mass is placed in circulation flow reactor, then spurts into air and/or inertia
Gas and CO2Mixed gas, using circulation flow reactor internal flow orient it is well-regulated circulate, so that fluid is reached abundant
Mixing.The advantages of this method is conducive to gas-liquid mass transfer using circulation flow reactor, but the size of bubble is still by the shadow of jet size
It rings, and is still the few contact area of the more gases of liquid, to gas-liquid be made to efficiently use.
CN201210432682.4 discloses a kind of method that carbonizatin method prepares high silicon macropore contained amorphous silica-alumina dry glue.The party
When method reaches 1.0MPa using reaction pressure, the solubility of carbon dioxide will be than improving 10 times or more under normal pressure.With titanium dioxide
The raising of Carbon Solubility can be effectively reduced the pH value of reaction system, improve the environment of neutralization reaction, be conducive to improve without fixed
The quality of shape sial product arranges simultaneously because carbon dioxide is outer on a small quantity, substantially increases the utilization rate of carbon dioxide.This method is only
The dissolution rate for only improving carbon dioxide, does not propose the reaction effect of carbon dioxide gas and sodium metaaluminate liquid, and closed
Container is influenced by pressure control, and the flow velocity of carbon dioxide is restricted.
CN201110169570.X discloses a kind of reactor and method preparing aluminium hydroxide.The reactor uses self-priming
Agitator assembly, the component are mainly made of rotor and stator, and using curved flow channel type impeller after closing, rotor is fixed on to be stirred rotor
It mixes on axis, Air deflector is housed in stator.Compared with prior art, carburizing reagent is carried out using the reactor, due to stirring
In the process from sucking gas, undesirable gas compressor saves power and investment；Due to the self-priming stirring of rotor and leading for stator
To effect, the bubble size very little generated after making gas be distributed, gas effciency is enhanced about more than once.The process is intermittent anti-
It answers, does not ensure that the stability of every batch materials.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of liquefied coal coil hydrotreating catalyst and its preparation sides
Method is particularly suitable for the catalyst and preparation method thereof of ebullated bed coal liquefaction hydrotreating.Boehmite system in the present invention
Preparation Method realizes being carried out continuously for gas liquid reaction, and does not need aging, and the reaction time is short, and boehmite caking property is good,
With this raw material prepare liquefied coal coil hydrotreating catalyst wear-resisting property is good, Hydrogenation is good, especially suitable for ebullated bed plus
Hydrogen technique.
The present invention provides a kind of ebullated bed liquefied coal coil hydrotreating catalyst, using aluminium oxide as carrier, with group VIII
Metal and vib metals are active metal component, and on the basis of the weight of catalyst, the content of aluminium oxide is 70%~84%,
Content of the group VIII metal in terms of oxide is 1wt%~9wt%, content of the vib metals in terms of oxide for 15wt%~
30wt%；The property of the aluminium oxide is as follows：0.95~1.20mL/g of Kong Rongwei, specific surface area are 290~350m2/ g, most probable
Aperture is 12.5~14.0nm, and pore size distribution is as follows：The Kong Rong in the hole of bore dia ＜ 8nm accounts for the 12% of total pore volume hereinafter, preferably
10% hereinafter, the Kong Rong that bore dia is the hole of 8~15nm accounts for the 69%~83% of total pore volume, preferably 72%~82%, bore dia ＞
The Kong Rong in the hole of 15nm accounts for the 5%~19% of total pore volume, preferably 8%~18%.
In the ebullated bed liquefied coal coil hydrotreating catalyst of the present invention, group VIII metal is Ni and/or Co, Section VI B
Race's metal is W and/or Mo.
The physicochemical property of catalyst of the present invention is as follows：Specific surface area is 160 ~ 250m2/ g, Kong Rongwei 0.30 ~
0.60mL/g, aperture account for total pore volume 65% ~ 85%, preferably 70% ~ 85% in the hole of 6-15nm.
The present invention provides a kind of preparation method of ebullated bed liquefied coal coil hydrotreating catalyst, and the preparation method includes
Following content：
（1）Using basic aluminate and carbon dioxide gas as raw material, after reactor is reacted, boehmite is obtained,
The reactor includes reactor body, and rotatable impeller is arranged in the lower part in reactor body, and impeller 2 connects with rotary shaft 10
It connects, the driving device 10 that 10 other end of rotary shaft stretches out outside reactor body 1 connects, and semi open model impeller is equipped with above impeller
Cover, i.e. impeller chimney lower open, at least provided with three holes on impeller chimney, two of which hole respectively as carbon dioxide gas into
Material mouth and alkali aluminate soln feed inlet, another hole are exported as recycle stock, are provided with circulation pipe outside impeller chimney, are followed
Endless tube one end open is exported in impeller chimney as recycle stock, and the other end is opened on reactor bottom as recycle stock entrance,
It is provided with overflow port at the top of reactor body；
（2）By step（1）Obtained boehmite roasts 2~6 hours at 500~750 DEG C, obtains alumina support；
（3）Metal salt containing active metal component is configured to dipping solution, then loads to step（2）The carrying alumina of preparation
On body, ebullated bed liquefied coal coil hydrotreating catalyst is obtained after drying and roasting.
In preparation method of the present invention, step（1）Obtained boehmite, size distribution is as follows, with volume fraction：
Particle of the grain size less than 10 μm accounts for 10% hereinafter, the particle that grain size is 10~50 μm accounts for 76%~90%, and grain size is more than 50 μm of particle
14% is accounted for hereinafter, preferably grain size accounts for 9% hereinafter, the particle that grain size is 10~50 μm accounts for 82%~90% less than 10 μm of particle, grain
Particle of the diameter more than 50 μm accounts for 9% or less.
In preparation method of the present invention, step（1）The most probable grain size of obtained boehmite is 35~45 μm.
In preparation method of the present invention, step（2）The property of obtained aluminium oxide is as follows：0.95~1.20mL/g of Kong Rongwei,
Specific surface area is 290~350m2/ g, most probable pore size are 12.5~14.0 nm, and pore size distribution is as follows：The hole of bore dia ＜ 8nm
Kong Rong account for the 12% of total pore volume hereinafter, preferably 10% hereinafter, bore dia be 8~15nm hole Kong Rong account for total pore volume 69%~
The Kong Rong of 83%, preferably 72%~82%, the hole of bore dia ＞ 15nm accounts for the 5%~19% of total pore volume, preferably 8%~18%.
In preparation method of the present invention, step（1）In used reactor, the alkali aluminate soln feed inlet setting
It is 0.2~0.5MPa, a diameter of 10~30 μm of atomizer to have atomizer, atomizer pressure.
In preparation method of the present invention, step（1）Impeller chimney is hemispherical in used reactor, cover at the top of impeller and
Outside.Hole on impeller chimney can be uniformly arranged on impeller chimney.Three or more feed inlets can be arranged in hole on impeller chimney,
And be uniformly arranged on impeller chimney, so that carbon dioxide gas and alkali aluminate soln is uniformly sprayed onto on the impeller of rotation.
In preparation method of the present invention, step（1）In used reactor, auxiliary agent entrance can be provided on circulation pipe.
In preparation method of the present invention, step（1）In used reactor, overflow port is with a distance from reactor bottom and leaf
It is 1.5~2.5 to take turns the ratio of distances constant from reactor bottom：1.
In preparation method of the present invention, step（1）The preparation method of the boehmite specifically includes following process：Two
The carbon dioxide gas feed inlet and basic aluminate that carbon oxide gas and alkali aluminate soln are arranged from impeller chimney respectively
Solution feed mouth continuously sprays on high-speed rotating impeller, and the slurries for reacting generation are fallen by impeller surrounding in reactor, generates
Fraction slurries enter circulation pipe via cycle tube inlet, the outlet of recycle stock that recycle stock is arranged from impeller chimney sprays into high
On the impeller of speed rotation, the slurries for reacting generation are continuously discharged from the overflow port of reactor head, and the slurries of discharge are washed through filtering
It washs, it is dry, boehmite, wherein 10~30 DEG C of controlling reaction temperature are obtained, the residence time is 10~25min, is controlled from excessive
The pH value that slurries are discharged in head piece is 9~11, and the internal circulating load of slurries is 2 with the volume ratio of alkali aluminate soln inlet amount：1~5：
1.The drying condition is as follows：It is 3~6 hours dry at 110~130 DEG C.
In preparation method of the present invention, the computational methods of the residence time：The volume ÷ of residence time=reactor（Liquid
Phase raw material feed rate+generation serum recycle rate）.
In preparation method of the present invention, step（1）Described in basic aluminate be sodium metaaluminate and/or potassium metaaluminate, it is excellent
It is selected as sodium metaaluminate；A concentration of 15~55 gAl of alkali aluminate soln2O3/ L, preferably 20~35 gAl2O3/ L can be adopted
It is prepared with conventional preparation method.
In preparation method of the present invention, step（1）Described in carbon dioxide gas the mixing containing carbon dioxide may be used
Gas, wherein CO2Volume fraction be 30%~60%.In mixed gas, other than carbon dioxide, air, nitrogen can also be contained
Any one of gas, inert gas.
In preparation method of the present invention, step（3）Described in drying condition it is as follows：100 DEG C~150 DEG C of drying temperature is done
The dry time 2~for 24 hours；Step（3）Described in roasting condition be：400 DEG C~600 DEG C of calcination temperature, 2~8h of roasting time.
In preparation method of the present invention, step（1）It, can also be according to actual needs in the preparation process of the boehmite
Auxiliary agent, such as SiO is added2、P2O5、B2O3、TiO2One or more of predecessor, the predecessor is with the shape of water soluble inorganic substance
Formula is added, and can be added, can also be individually added into together with alkali aluminate soln.Auxiliary agent predecessor can be silicate, phosphorus
It is one or more in acid, boric acid, titanium sulfate, Titanium Nitrate.Promoter addition can be added according to catalyst requirement.
In preparation method of the present invention, step（3）Described in active metal component loaded using conventional method, that is, will
Metal salt containing active metal component is configured to dipping solution, then loads to carrier, through dry and roasting, obtains catalyst.
The dipping solution containing active metal component is Mo-Ni systems.Liquefied coal coil of the present invention refers to the life of DCL/Direct coal liquefaction
At oil, property is generally：Aromatic carbon rate is 0.5~0.65, and arene content is generally 50wt%~90wt%.
The catalyst is applied to coal liquefied oil boiling bed hydrogenation processing procedure the invention further relates to a kind of, application
Process conditions are：Reaction pressure is 10~20MPa, and temperature is 350~400 DEG C, and volume space velocity is 0.1~2.0h when liquid-1, hydrogen oil
Volume ratio is 100~1000.
The present invention uses specific reactor, makes alkali aluminate soln and carbon dioxide gas by high-speed rotating impeller
It is broken into fine drop, carbon dioxide gas is reacted on fine drop surface, and passes through the high speed rotation of impeller, impeller
Vacuum environment is formed between cover, and the fraction slurries of generation is made to enter circulation pipe through following by the recycle stock entrance of reactor bottom
Ring material outlet is sprayed onto on high-speed rotating impeller, while control loop inventory and suitable reaction condition, to make generation
Aluminum hydroxide grain it is tiny and uniform, the caking property of aluminium oxide is good, and the liquefied coal coil hydrotreating catalyst thus prepared is resistance to
Mill performance is good, Hydrogenation is good, and using boiling bed process and this patent catalyst, liquefied coal coil can be made after hydrotreating
For hydrogen supply solvent naphtha.
The method of the present invention preparation process is simple, realizes being carried out continuously for gas liquid reaction, and do not need aging, when reaction
Between it is short, alumina product property stablize.In addition, using basic aluminate and carbon dioxide as raw material, at low cost, raw material is easy to get,
Conducive to large-scale production.
Description of the drawings
Fig. 1 is the reactor used structural schematic diagram of the present invention.
Specific implementation mode
The reactor used structure of the present invention is shown in Fig. 1, and the reactor includes reactor body 1, in reactor body 1 under
Rotatable impeller 2 is arranged in portion, and impeller 2 is connect with rotary shaft 10, and 10 other end of rotary shaft stretches out the drive outside reactor body 1
Dynamic device 10 connects, and 2 top of impeller is equipped with semi open model impeller chimney 3, i.e. 3 lower open of impeller chimney, is at least arranged on impeller chimney 3
There are three hole, two of which hole 4 and 5 is another respectively as carbon dioxide gas feed inlet and alkali aluminate soln feed inlet
A hole 6 is exported as recycle stock, and circulation pipe 7 is provided with outside impeller chimney 3, and 7 one end open of circulation pipe is used as in impeller chimney and follows
Ring material outlet, the other end are opened on reactor bottom as recycle stock entrance, and reactor body top is provided with overflow port
8.Auxiliary agent entrance 9 can be provided on circulation pipe.
The preparation process of boehmite of the present invention is as follows：Carbon dioxide gas mixture and alkali aluminate soln respectively from
The carbon dioxide gas feed inlet 4 and alkali aluminate soln feed inlet 5 being arranged on impeller chimney continuously spray into high-speed rotating leaf
On wheel 2, reaction generates slurries and is fallen into reactor by 2 surrounding of impeller, the fraction slurries of generation via circulation pipe one end cycle
Material inlet enters circulation pipe 7, and the recycle stock outlet 6 that recycle stock is arranged from impeller chimney 3 sprays into high-speed rotating impeller 2
On, the slurries for reacting generation are continuously discharged from the overflow port 8 of reactor head, and the slurries of discharge are washed through filtering, dry, are obtained
To boehmite, wherein 10~30 DEG C of controlling reaction temperature, the residence time is 10~25min, and control is discharged from overflow port and starches
The pH value of liquid is 9~11, and internal circulating load and the alkali aluminate soln inlet amount volume ratio of slurries are 2：1~5：1.
The technical solution further illustrated the present invention by the following examples, but it is not limited to following embodiment.The present invention
In, granularity is measured using laser particle analyzer.In the present invention, Kong Rong, pore size distribution and specific surface area are inhaled using low temperature liquid nitrogen
What attached method measured.Three water contents are measured with X-ray diffractometer.
Embodiment 1
（1）The preparation of boehmite
Industrial level-one aluminium hydrate powder and an industrial sodium hydroxide is taken to be configured to a concentration of 360 gAl2O3The dense meta-aluminic acid of/L
Sodium solution, then it is diluted to a concentration of 25 gAl2O3The sodium aluminate solution of/L.By carbon dioxide gas mixture and diluted inclined aluminium
The feed inlet 4 and 5 that acid sodium solution is arranged from impeller chimney respectively continuously spray on high-speed rotating impeller 2, and reaction generates slurries
Fallen into reactor by 2 surrounding of impeller, the fraction slurries of generation enter circulation pipe 7 via recycle stock entrance, recycle stock from
The recycle stock outlet 6 being arranged on impeller chimney 3 sprays on high-speed rotating impeller 2, reacts the slurries of generation from reactor head
Overflow port 8 be continuously discharged, the slurries of discharge are washed through filtering, dry, obtain boehmite.Wherein CO in gaseous mixture2's
Volume fraction is 50%, remaining is air gas.Atomizer pressure is 0.5MPa, a diameter of 30 μm of atomizer, control reaction
20 DEG C, residence time 15min of temperature, it is 10 to control and the pH value of slurries is discharged from overflow port, the internal circulating load and meta-aluminic acid of slurries
Sodium solution inlet amount volume ratio is 3：1.Filtered sample is taken in reaction 1h and reaction 5h respectively, is 120 DEG C in drying temperature
It is 4 hours dry, obtain boehmite Al0-1 and Al0-5.
（2）Catalyst preparation
2.8g sesbania powders are added in the Al0-5 boehmite raw materials for taking 200g to prepare, and at ball forming, the sample after balling-up is passed through
It crosses 650 DEG C of roasting 5h and obtains the carrier Z-1 that granularity is 0.4~0.8mm.
Phosphoric acid 32.50g is weighed, distilled water 450mL is added, then sequentially adds molybdenum oxide 94.60g, basic nickel carbonate
Solution is settled to 500mL to after being completely dissolved, with distilled water, obtains solution L-1 by 40.46g, heating stirring.By carrier Z-1 with molten
Liquid L-1 solution saturation dipping obtains catalyst C-1 in 110 DEG C of dry 2h, 550 DEG C of roasting 5h.
Embodiment 2
For other conditions with embodiment 1, it is 20 μm, mixed gas CO only to change nozzle diameter2Volume fraction be 70%, remaining
For air gas.Overflow port slurry pH value is 10.5, negates sample when answering 1h, obtains boehmite Al0-2, carrier Z-2
With catalyst C-2.
Embodiment 3
（1）The preparation of boehmite
For other conditions with embodiment 1, it is 5 only to change the internal circulating load of slurries and sodium aluminate solution inlet amount volume ratio：1, together
When be added molar concentration be 1.02mol/L ammonium dihydrogen phosphate, negate sample when answering 1h, obtain boehmite Al0-3.
（2）The preparation of catalyst
2.8g sesbania powders and 25g ammonium hydroxide is added, at ball forming, after balling-up in the Al0-3 boehmite raw materials for taking 200g to prepare
Sample by 550 DEG C roasting 3h obtain granularity be 0.4~0.8mm carrier Z-3.
Phosphoric acid 37.49g is weighed, distilled water 450mL is added, then sequentially adds molybdenum oxide 135.77g, basic nickel carbonate
Solution is settled to 500mL to after being completely dissolved, with distilled water, obtains solution L-2 by 51.02g, heating stirring.By carrier Z-3 with molten
Liquid L-2 solution saturation dipping obtains catalyst C-3 in 110 DEG C of dry 4h, 500 DEG C of roasting 3h.
Embodiment 4
（1）The preparation of boehmite
Industrial level-one aluminium hydrate powder and an industrial sodium hydroxide is taken to be configured to a concentration of 360 gAl2O3The dense meta-aluminic acid of/L
Sodium solution, then it is diluted to a concentration of 50 gAl2O3The sodium aluminate solution of/L.By carbon dioxide gas mixture and diluted inclined aluminium
The feed inlet 4 and 5 that acid sodium solution is arranged from impeller chimney respectively continuously spray on high-speed rotating impeller 2, and reaction generates slurries
It is fallen into reactor by 2 surrounding of impeller, the fraction slurries of generation enter circulation pipe via the recycle stock entrance of circulation pipe one end
7, the recycle stock outlet 6 that recycle stock is arranged from impeller chimney 3 sprays on high-speed rotating impeller 2, reacts the slurries of generation
It being continuously discharged from the overflow port 8 of reactor head, the slurries of discharge are washed through filtering, dry, obtain boehmite, wherein
CO in gaseous mixture2Volume fraction be 60%, remaining is nitrogen gas.Atomizer pressure is 0.4MPa, and atomizer is a diameter of
15 μm, 15 DEG C, residence time 20min of controlling reaction temperature, it is 11 to control and the pH value of slurries is discharged from overflow port, and slurries follow
Circular rector is 4 with sodium aluminate solution inlet amount volume ratio：1.Sample when answering 1h is negated, is 110 in drying temperature after filtering
DEG C dry 6 hours, obtain boehmite Al0-4.
（2）The preparation of catalyst
2.8g Methyl cellulose speed is added, at ball forming, by the sample after balling-up in the Al0-4 boehmite raw materials for taking 200g to prepare
Product obtain the carrier Z-4 that granularity is 0.4~0.8mm by 500 DEG C of roasting 3h.
Carrier Z-4 is saturated with solution L-2 solution and is impregnated, catalyst C- is obtained in 110 DEG C of dry 4h, 480 DEG C of roasting 3h
4。
Comparative example 1
（1）It is prepared by boehmite
It is prepared according to method disclosed in CN201110350784.7.Take industrial level-one aluminium hydrate powder and an industrial sodium hydroxide
It is configured to a concentration of 365 gAl2O3The dense sodium aluminate solution of/L, then it is diluted to a concentration of 25 gAl2O3The sodium metaaluminate of/L is molten
Liquid takes 3L to be added in circulation flow reactor, and control gelling temperature is 20 DEG C.Organic expanding agent alkyl phenol and ethylene oxide is added
Condensation product (OP-10) and polyoxyethylene sorbitol acid anhydride list olein（T-80）, wherein OP-10 is 60 with T-80 weight ratios：40,
Organic expanding agent dosage accounts for the 0.6% of sodium metaaluminate weight, and for diesel oil as antifoaming agent, antifoaming agent dosage is organic expanding agent weight
0.5%.It is passed through air and CO2Mixed gas, flow 8mL/min, wherein CO2Volume fraction be 50%, utilize mixing
Gas Stirring stops plastic when pH value is down to 10.Slurries are washed with 40 DEG C of hot water to neutrality, and 120 DEG C of dryings 4 hours obtain
To boehmite F0-1.
（2）Catalyst preparation
2.8g sesbania powders are added in the F0-1 boehmite raw materials for taking 200g to prepare, and at ball forming, the sample after balling-up is passed through
650 DEG C of roasting 5h obtain the carrier F-1 that granularity is 0.4~0.8mm.
Carrier F-1 is saturated with solution L-1 solution and is impregnated, catalyst C- is obtained in 110 DEG C of dry 2h, 550 DEG C of roasting 5h
F-1。
Comparative example 2
The reactor that embodiment 1 uses is cancelled to the recycle stock outlet 6 being arranged on circulation pipe 7 and impeller chimney, detailed process
It is as follows：Industrial level-one aluminium hydrate powder and an industrial sodium hydroxide is taken to be configured to a concentration of 360 gAl2O3The dense meta-aluminic acid of/L
Sodium solution, then it is diluted to a concentration of 25 gAl2O3The sodium aluminate solution of/L.By carbon dioxide gas mixture and diluted inclined aluminium
The feed inlet 4 and 5 that acid sodium solution is arranged from impeller chimney respectively continuously spray on high-speed rotating impeller 2, and reaction generates slurries
It is fallen into reactor by 2 surrounding of impeller, the slurries for reacting generation are continuously discharged from the overflow port 8 of reactor head, the slurry of discharge
Liquid is washed through filtering, dry, obtains boehmite.Wherein CO in gaseous mixture2Volume fraction be 50%, liquid phase feeding mouth
Its nozzle exit pressure of atomizer is 0.5MPa, and nozzle diameter is 30 μm, 20 DEG C, residence time 15min of controlling reaction temperature, control
It is 10 to make and the pH value of slurries is discharged from overflow port.Sample when answering 1h is negated, is that 120 DEG C of dryings 4 are small in drying temperature after filtering
When, obtain boehmite F0-2.
（2）Catalyst preparation
2.8g sesbania powders are added in the F0-2 boehmite raw materials for taking 200g to prepare, and at ball forming, the sample after balling-up is passed through
650 DEG C of roasting 5h obtain the carrier F-2 that granularity is 0.4~0.8mm.
Carrier F-2 is saturated with solution L-1 solution and is impregnated, catalyst C- is obtained in 110 DEG C of dry 2h, 550 DEG C of roasting 5h
F-2。
Comparative example 3
Industrial level-one aluminium hydrate powder and an industrial sodium hydroxide is taken to be configured to a concentration of 360 gAl2O3The dense meta-aluminic acid of/L
Sodium solution, then it is diluted to a concentration of 25 gAl2O3The sodium aluminate solution of/L.By carbon dioxide gas mixture and diluted inclined aluminium
The feed inlet 4 and 5 that acid sodium solution is arranged from impeller chimney respectively continuously spray on high-speed rotating impeller 2, and reaction generates slurries
It is fallen into reactor by 2 surrounding of impeller, the fraction slurries of generation enter circulation pipe via the recycle stock entrance of circulation pipe one end
7, the recycle stock outlet 6 that recycle stock is arranged from impeller chimney 3 sprays on high-speed rotating impeller 2, reacts the slurries of generation
It is continuously discharged from the overflow port 8 of reactor head, the slurries of discharge are washed through filtering, dry, obtain boehmite.Wherein
CO in gaseous mixture2Volume fraction be 50%, the atomizer of liquid phase feeding mouth its nozzle exit pressure is 0.5MPa, and nozzle diameter is
30 μm, 20 DEG C, residence time 40min of controlling reaction temperature, it is 10 to control and the pH value of slurries is discharged from overflow port, and slurries follow
Circular rector is 3 with sodium aluminate solution inlet amount volume ratio：1.Sample when answering 1h is negated, is 120 DEG C in drying temperature after filtering
It is 4 hours dry, obtain boehmite F0-3.
（2）Catalyst preparation
2.8g sesbania powders are added in the F0-3 boehmite raw materials for taking 200g to prepare, and at ball forming, the sample after balling-up is passed through
650 DEG C of roasting 5h obtain the carrier F-3 that granularity is 0.4~0.8mm.
Carrier F-3 is saturated with solution L-1 solution and is impregnated, catalyst C- is obtained in 110 DEG C of dry 2h, 550 DEG C of roasting 5h
F-3。
Obtained boehmite property above is listed in table 1, the property of catalyst is listed in table 2..
The property of 1 boehmite of table
| Number | Al0-1-1 | Al0-1-5 | Al0-2 | Al0-3 | Al0-4 | F0-1 | F0-2 | F0-3 |
| Particle diameter distribution（Volume）, % | ||||||||
| <10μm | 8.1 | 7.8 | 6.6 | 7.6 | 9.0 | 25.3 | 20.1 | 10.5 |
| 10~50 μm | 82.9 | 83.3 | 86.9 | 83.7 | 84.8 | 53.6 | 60.4 | 73.9 |
| >50μm | 9.0 | 8.9 | 6.5 | 8.7 | 6.2 | 21.1 | 19.5 | 15.6 |
| Most probable grain size, μm | 41.1 | 40.9 | 42.6 | 38.7 | 37.3 | 30.5 | 32.4 | 31.7 |
| Three water contents, wt% | <1% | <1% | <1% | <1% | <1% | <1% | <1% | 5% |
The physico-chemical property of 2 catalyst of table
| Number | C-1 | C-2 | C-3 | C-4 | C-F-1 | C-F-2 | C-F-3 |
| Specific surface area, m2/g | 219 | 201 | 195 | 210 | 241 | 229 | 176 |
| Kong Rong, mL/g | 0.61 | 0.60 | 0.59 | 0.62 | 0.52 | 0.54 | 0.42 |
| Abrasion index, wt% | 0.58 | 0.61 | 0.55 | 0.50 | 1.24 | 1.03 | 3.18 |
| Catalyst forms, wt% | |||||||
| MoO3 | 14.21 | 14.32 | 19.34 | 19.28 | 14.35 | 14.41 | 14.19 |
| NiO | 3.41 | 3.38 | 3.89 | 3.91 | 3.47 | 3.51 | 3.43 |
| P | 1.26 | 1.19 | 1.37 | 1.34 | 1.21 | 1.32 | 1.25 |
The ebullated bed liquefied coal coil hydrogenation catalyst of preparation is loaded on 4L fluidized bed devices, activity rating, original used are carried out
Material oil nature and evaluation condition are shown in Table 3, and evaluation condition is shown in Table 4.
3 raw material oil nature of table and evaluation condition
| Project | Numerical value |
| Raw material oil nature | |
| Sulphur, wt% | 0.28 |
| Total aromatic hydrocarbons, % | 72.3 |
| Aromatic carbon rate, mol% | 64.02 |
| Process conditions | |
| Reaction temperature/DEG C | 360 |
| Reaction pressure/MPa | 12 |
| Air speed/h-1 | 1.5 |
| Hydrogen to oil volume ratio | 600：1 |
The evaluation result of 4 catalyst of table
| Number | C-1 | C-2 | C-3 | C-4 | C-F-1 | C-F-2 | C-F-3 |
| Generate oil nature | |||||||
| Sulphur, ng/ μ l | 14.4 | 13.8 | 6.3 | 5.6 | 35.6 | 31.2 | 32.1 |
| Total aromatic hydrocarbons, % | 64.3 | 62.5 | 58.9 | 57.4 | 66.1 | 65.4 | 66.4 |
| Aromatic carbon rate, mol% | 42.82 | 42.64 | 40.01 | 39.43 | 50.81 | 49.14 | 51.82 |
As can be seen from the table：It is concentrated using boehmite size distribution prepared by the method for the present invention, three water contents are few,
Product property is stablized, and the ebullated bed liquefied coal coil hydrotreating catalyst abrasion resistance thus prepared is good, and Hydrogenation is good, coal liquid
Carburetion after boiling bed hydrogenation is handled arene content reduce, aromatic hydrocarbons rate reduce, can as coal liquefaction unit hydrogen supply it is molten
Agent oil.
Claims (24)
1. a kind of ebullated bed liquefied coal coil hydrotreating catalyst, the catalyst is using aluminium oxide as carrier, with group VIII gold
Belong to and vib metals are active metal component, on the basis of the weight of catalyst, the content of aluminium oxide is 70%~84%, the
Content of the group VIII metal in terms of oxide is 1wt%~9wt%, content of the vib metals in terms of oxide for 15wt%~
30wt%；The property of the aluminium oxide is as follows：0.95~1.20mL/g of Kong Rongwei, specific surface area are 290~350m2/ g, most probable
Aperture is 12.5~14.0nm, and pore size distribution is as follows：The Kong Rong in the hole of bore dia ＜ 8nm accounts for the 12% of total pore volume hereinafter, preferably
10% hereinafter, the Kong Rong that bore dia is the hole of 8~15nm accounts for the 69%~83% of total pore volume, preferably 72%~82%, bore dia ＞
The Kong Rong in the hole of 15nm accounts for the 5%~19% of total pore volume, preferably 8%~18%.
2. ebullated bed liquefied coal coil hydrotreating catalyst described in accordance with the claim 1, it is characterised in that：Group VIII metal
For Ni and/or Co, vib metals are W and/or Mo.
3. ebullated bed liquefied coal coil hydrotreating catalyst described in accordance with the claim 1, it is characterised in that：The catalyst
For 160 ~ 250m20.30 ~ 0.60mL/g of/g, Kong Rongwei, aperture account for total pore volume 65% ~ 85% in the hole of 6-15nm, preferably 70% ~
85%。
4. the preparation side of the ebullated bed liquefied coal coil hydrotreating catalyst as described in any claim in claim 1-3
Method, it is characterised in that：The preparation method includes following content：
（1）Using basic aluminate and carbon dioxide gas as raw material, after reactor is reacted, boehmite is obtained,
The reactor includes reactor body, and rotatable impeller is arranged in the lower part in reactor body, and impeller 2 connects with rotary shaft 10
It connects, the driving device 10 that 10 other end of rotary shaft stretches out outside reactor body 1 connects, and semi open model impeller is equipped with above impeller
Cover, i.e. impeller chimney lower open, at least provided with three holes on impeller chimney, two of which hole respectively as carbon dioxide gas into
Material mouth and alkali aluminate soln feed inlet, another hole are exported as recycle stock, are provided with circulation pipe outside impeller chimney, are followed
Endless tube one end open is exported in impeller chimney as recycle stock, and the other end is opened on reactor bottom as recycle stock entrance,
It is provided with overflow port at the top of reactor body；
（2）By step（1）Obtained boehmite roasts 2~6 hours at 500~750 DEG C, obtains alumina support；
（3）Metal salt containing active metal component is configured to dipping solution, then loads to step（2）The carrying alumina of preparation
On body, ebullated bed liquefied coal coil hydrotreating catalyst is obtained after drying and roasting.
5. preparation method according to claim 4, it is characterised in that：Step（1）Obtained boehmite, granularity point
Cloth is as follows, with volume fraction：Grain size less than 10 μm of particle account for 10% hereinafter, the particle that grain size is 10~50 μm account for 76%~
90%, particle of the grain size more than 50 μm accounts for 14% hereinafter, preferably particle of the grain size less than 10 μm accounts for 9% hereinafter, grain size is 10~50
μm particle account for 82%~90%, particle of the grain size more than 50 μm accounts for 9% or less.
6. preparation method according to claim 4, it is characterised in that：Step（1）The most probable of obtained boehmite
Grain size is 35~45 μm.
7. preparation method according to claim 4, it is characterised in that：Step（2）The property of obtained aluminium oxide is as follows：Hole
It is 0.95~1.20mL/g to hold, and specific surface area is 290~350m2/ g, most probable pore size are 12.5~14.0 nm, and pore size distribution is such as
Under：The Kong Rong in the hole of bore dia ＜ 8nm accounts for the 12% of total pore volume hereinafter, preferably 10% hereinafter, bore dia is the hole of 8~15nm
Kong Rong accounts for the 69%~83% of total pore volume, preferably 72%~82%, the Kong Rong in the hole of bore dia ＞ 15nm account for total pore volume 5%~
19%, preferably 8%~18%.
8. preparation method according to claim 4, it is characterised in that：Step（1）In used reactor, the alkalinity
Aluminate solution feed inlet is provided with atomizer, and atomizer pressure is 0.2~0.5MPa, atomizer a diameter of 10~30
μm。
9. preparation method according to claim 4, it is characterised in that：Step（1）Impeller chimney is in used reactor
Hemispherical covers on impeller top and outside.
10. preparation method according to claim 4, it is characterised in that：Hole on the impeller chimney is uniformly arranged on impeller
On cover.
11. preparation method according to claim 4, it is characterised in that：Step（1）In used reactor, circulation pipe
On be provided with auxiliary agent entrance.
12. preparation method according to claim 4, it is characterised in that：Step（1）In used reactor, overflow port
With a distance from reactor bottom and ratio of distances constant of the impeller from reactor bottom is 1.5~2.5：1.
13. preparation method according to claim 4, it is characterised in that：Step（1）The preparation side of the boehmite
Method specifically includes following process：The carbon dioxide that carbon dioxide gas and alkali aluminate soln are arranged from impeller chimney respectively
Gas feed mouth and alkali aluminate soln feed inlet continuously spray on high-speed rotating impeller, react the slurries of generation by impeller
Surrounding is fallen into reactor, and the fraction slurries of generation enter circulation pipe via cycle tube inlet, and recycle stock is set from impeller chimney
The recycle stock outlet set sprays on high-speed rotating impeller, and the slurries for reacting generation are continuously arranged from the overflow port of reactor head
Go out, the slurries of discharge are washed through filtering, dry, obtain boehmite.
14. preparation method according to claim 13, it is characterised in that：In the preparation process of the boehmite, instead
It is 10~25min to answer 10~30 DEG C of temperature, residence time, and it is 9~11 to control and the pH value of slurries is discharged from overflow port, and slurries follow
The volume ratio of circular rector and alkali aluminate soln inlet amount is 2：1~5：1.
15. preparation method according to claim 13, it is characterised in that：The drying condition is as follows：110~130
DEG C dry 3~6 hours.
16. preparation method according to claim 4, it is characterised in that：Step（1）Described in basic aluminate be inclined aluminium
Sour sodium and/or potassium metaaluminate, preferably sodium metaaluminate；A concentration of 15~55 gAl of alkali aluminate soln2O3/ L, preferably
20~35 gAl2O3/L。
17. preparation method according to claim 4, it is characterised in that：Step（1）Described in carbon dioxide gas using containing
There are the mixed gas of carbon dioxide, wherein CO2Volume fraction be 30%~60%.
18. preparation method according to claim 17, it is characterised in that：In the carbon dioxide gas mixture, in addition to two
Outside carbonoxide, contain any one of air, nitrogen, inert gas.
19. preparation method according to claim 4, it is characterised in that：Step（3）Described in drying condition it is as follows：It is dry
100 DEG C~150 DEG C of dry temperature, drying time 2~for 24 hours；Step（3）Described in roasting condition be：400 DEG C of calcination temperature~
600 DEG C, 2~8h of roasting time.
20. preparation method according to claim 4, it is characterised in that：Step（1）The preparation of the boehmite
Auxiliary agent, such as SiO are added in journey2、P2O5、B2O3、TiO2One or more of predecessor, the predecessor is with water soluble inorganic substance
Form be added, be added together with alkali aluminate soln, or be individually added into.
21. preparation method according to claim 20, it is characterised in that：The auxiliary agent predecessor is silicate, phosphoric acid, boron
It is one or more in acid, titanium sulfate, Titanium Nitrate.
22. the catalyst in a kind of claim 1-3 described in any claim is applied to coal liquefied oil boiling bed hydrogenation processing.
23. according to the application described in claim 22, it is characterised in that：The liquefied coal coil refers to the generation oil of DCL/Direct coal liquefaction,
Its property is：Aromatic carbon rate is 0.5~0.65, and arene content is 50wt%~90wt%.
24. according to the application described in claim 22, it is characterised in that：The boiling bed process condition is：Reaction pressure is 10
~20MPa, temperature are 350~400 DEG C, and volume space velocity is 0.1~2.0h when liquid-1, hydrogen to oil volume ratio is 100~1000.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085935A (en) * | 2006-06-07 | 2007-12-12 | 神华煤制油研究中心有限公司 | Coal liquefied oil boiling bed hydrogenation catalyst carrier and preparation method thereof |
| CN101433842A (en) * | 2008-09-27 | 2009-05-20 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| WO2015189195A1 (en) * | 2014-06-13 | 2015-12-17 | IFP Energies Nouvelles | Mesoporous residuum hydroconversion catalyst and method for preparing same |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085935A (en) * | 2006-06-07 | 2007-12-12 | 神华煤制油研究中心有限公司 | Coal liquefied oil boiling bed hydrogenation catalyst carrier and preparation method thereof |
| CN101433842A (en) * | 2008-09-27 | 2009-05-20 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| WO2015189195A1 (en) * | 2014-06-13 | 2015-12-17 | IFP Energies Nouvelles | Mesoporous residuum hydroconversion catalyst and method for preparing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116060023A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN116060023B (en) * | 2021-10-29 | 2024-07-02 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method thereof |
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