CN105126899B - A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application - Google Patents
A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application, it is characterised in that the component of its hydrogenation catalyst includes Y type molecular sieve carrier and the VIB and/or VIII transition metal in supported on carriers；Its Y type molecular sieve carrier is using bauxite and diatomite as Material synthesis；Y type molecular sieve be carrier loaded VIB and/or VIII transition metal based on metal oxide, load capacity is the wt% of 0.1 wt% ~ 15.Inferior heavy oil hydrogenation catalyst obtained by the present invention not only has hydrogenating function, but also has cracking function, therefore has higher catalytic activity and relatively low coking yield in inferior heavy oil hydro-upgrading.In addition, it is natural mineral raw wide material sources used in the present invention, cheap, so that the preparation cost of catalyst and the running cost of hydrogenation process substantially reduce.
Description
Technical field
A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application, are related to day
Right mineral are the inferior heavy oil that Y type molecular sieve prepared by raw material is the transition metal active component composition of carrier and load thereon
Floating bed hydrogenation solid powder th-1 catalyst and preparation method thereof.
Background technology
In recent years, the heaviness of oil supply is more and more obvious, and environmental regulation is increasingly strict, and this is to refinery products
Higher quality requirement is proposed, there is an urgent need to develop inferior heavy oil (to refer to the decompression residuum of conventional crude, density is more than 0.934
Kg/L crude oil or kin coal tar) lighting and deep processing technique.Suspension bed hydrogenation process is by the thin of high dispersive
Beaded catalyst or additive, by reactor, are a kind of investment and the relatively low poor quality of operating cost together with feedstock oil and hydrogen
Heavy oil deep working method, have adaptability to raw material is strong (to be specially adapted to handle that metal and impurity content are higher, use fixed bed hydrogenation
The uneconomic inferior heavy oil of device processing), the features such as technique is simple, conversion ratio and demetallization per are high, light oil yield is high.Therefore,
Common concern both domestic and external is caused using floating bed hydrogenation technical finesse inferior heavy oil, as suspension bed hydrogenation process technology core
The catalyst of the heart just turns into the focus of floating bed hydrogenation technical research exploitation.
Catalyst for floating bed hydrogenation technology mainly has solid particle catalyst, loaded catalyst and decentralized to urge
Agent (including water-soluble and oil-soluble catalyst).Wherein, loaded catalyst is made up of carrier and active component, catalyst
Catalytic performance depends on the property of the intrinsic catalysis characteristics and carrier itself of active component, and such catalyst splits in distillate hydrogenation
Had a wide range of applications in the petroleum refining processes such as change, mild hydrocracking, hydrofinishing, hydrotreating.Loaded catalyst
Have the advantages that preparation method is simple, pattern is easily controllable, suppression Jiao's property is good, recoverable, by reasonable selection carrier, to carrying
Body, which is modified the means such as pretreatment, can improve the suppression Jiao ability and dispersiveness of catalyst to a certain extent.
CN101433865A discloses a kind of inferior heavy oil catalyst carrier for hydrgenating and preparation method thereof, described carrier bag
Aluminum oxide and modified kaolin are included, wherein modified kaolin accounts for 1 ~ 80 wt% of vehicle weight, and the pore volume of carrier is 0.5 ~ 1.5
cm3/ g, specific surface area are 140 ~ 300 m2/ g, the average pore diameter of modified kaolin is 4 ~ 12 nm.However, above-mentioned carrier is soaked
When stain active component and conduct inferior heavy oil hydrogenation catalyst, the hydrogenation activity of catalyst is low, it is impossible to the drip in inferior heavy oil
The heavy components such as blue or green matter and colloid carry out effective hydro-conversion, and inferior heavy oil conversion ratio is low.
CN1086534A discloses a kind of heavy-oil hydrogenation denitrification catalyst, and the catalyst is characterized in carrier extruded moulding
During add low sodium Ludox to increase the pore volume of carrier, while make pore size distribution become more to concentrate, and add carrier
Acid amount.SiO on carrier2Content is 14 ~ 19 wt%, and pore volume is 0.55 ~ 0.65 cm3/ g, average pore size are smaller.Although the patent adds
Enter low sodium Ludox, improve support acidity, but aperture is still smaller, is not suitable for adding for inferior heavy oil bigger molecule reactant
Hydrogen process.
CN1448468A discloses a kind of mink cell focus and inferior heavy oil hydrogenation conversion catalyst and preparation method thereof, described
Catalyst uses a kind of silicon-containing alumina as support material, and the preparation process of silicon-containing alumina uses to be added less during plastic
Silicon is measured, the silicon of surplus is added after plastic or in ageing process, the aluminum oxide can be made with the same of more strong acid center
When there is relatively comparatively ideal pore structure, but the surface nature of catalyst for preparing of this method and pore structure still need to be changed
Enter.
CN101543783A discloses a kind of hydrocracking catalyst for suspension bed and its preparation method and application, and described urges
Agent includes the transition metal of carrier and load thereon, and its carrier is the catalytic cracking spent catalyst that particle diameter is less than 150 μm,
One or more of the transition metal in VIB and group VIII metal.This method, which is made full use of in catalytic cracking spent catalyst, divides
The acidity and cracking capability of son sieve (Y types and ZSM-5 types), add the cracking probability of the macromolecule hydrocarbons such as colloid, asphalitine；This
Outside, itself is containing transition metal such as Ni, V and Fe in catalyst carrier, and to hydrogenation activity and suppressing green coke has certain promotion to make
With.But due in catalytic cracking spent catalyst most of framework of molecular sieve structure caved in, cause to be reported in the patent
Bottoms conversion it is still relatively low (<72%), and coking yield it is still higher (>13%), not up to ideal effect.
Although loaded catalyst has many advantages, such as, the loaded catalyst prepared using commonsense method is in poor quality
Still suffered from during processing of heavy oil dispersiveness is low, conversion ratio is low, easy coking, short life the shortcomings of, and prepare polymolecularity and urge
The novel method for synthesizing of agent also by cost, process conditions restriction and be difficult to industrialize.Therefore, if catalyst can reduced
Cost, raising service efficiency etc. make a breakthrough, then loaded catalyst is expected to obtain industry in inferior heavy oil manufacture field
Using.
The content of the invention
The purpose of the present invention is aiming at insufficient existing for above-mentioned prior art, there is provided one kind can effectively solve hydrogenation activity
It is low, coking yield is high, effective hydro-conversion can not be carried out to heavy components such as the asphalitine in inferior heavy oil and colloids, and cost compared with
The inferior heavy oil suspension bed hydrogenation catalyst and its preparation and application that are carried on molecular sieve of high problem.
The purpose of the present invention is achieved through the following technical solutions.
A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve, it is characterised in that the group of its hydrogenation catalyst
Part includes Y type molecular sieve carrier and the VIB and/or VIII transition metal in supported on carriers.
A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, it is characterised in that its Y type point
Son sieve carrier is using bauxite and diatomite as Material synthesis.
A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, it is characterised in that in Y types point
Son sieve is carrier loaded VIB and/or VIII transition metal based on metal oxide, and load capacity is the wt% of 0.1 wt% ~ 15.
A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, it is characterised in that its transition gold
Category active component is the one or more in molybdenum, nickel, cobalt, tungsten and iron.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
Include in the step of its preparation process：
(1) bauxite powder and diatomite material are activated respectively；
(2) bauxite powder and diatomite material after activating mix with sodium hydroxide, directed agents and deionized water, enter
Row aging, then crystallization under hydrothermal conditions, solid product obtain point of inferior heavy oil suspension bed hydrogenation catalyst after ammonium exchanges
Son sieve carrier；
(3) molecular sieve carrier of obtained inferior heavy oil suspension bed hydrogenation catalyst is used and contains VIB and/or VIII
After metal front liquid solution carries out incipient impregnation；Again through drying, roasting, inferior heavy oil suspension bed hydrogenation catalyst is obtained.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
Activated in its bauxite powder using sub-molten salt medium, diatomite uses process of thermal activation.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
In the sub-molten salt medium of bauxite powder activation process be NaOH-H2O, it is in mass ratio by bauxite powder and sub-molten salt medium
1:0.2 ~ 2 is well mixed, 100 ~ 400oAt a temperature of C, soak time is 0.5 ~ 4 h.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
In its diatomaceous activation process be 500 ~ 1000 by diatomiteoAt a temperature of C, 1 ~ 10 h is calcined.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
The molar ratio that bauxite powder and diatomite material after its activation mix with sodium hydroxide, directed agents and deionized water
For (2.0 ~ 14.4) Na2O: (5~12)SiO2: (0.8~1.2)Al2O3: (180~250)H2O, the constitutive molar ratio of directed agents are
(16~18)Na2O: (16~18)SiO2: (0.8~1.2)Al2O3: (310~340)H2O, directing agent solution addition are compound body
It is the 9% ~ 16% of gross mass.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
In step (3) aging temperature be 50 ~ 70 oC, crystallization temperature are 95 ~ 110oC。
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
In step (3) sintering temperature be 500 ~ 800 oC, roasting time are 2 ~ 8 h.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
In described VIB and/or group VIII metal presoma be ammonium molybdate, nickel nitrate, cobalt nitrate, metatungstic acid, nickel sulfate, ferric sulfate
With the one or more in/ferric nitrate.
A kind of preparation method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
In the transition metal total amount of the molecular sieve carrier load in inferior heavy oil suspension bed hydrogenation catalyst, based on metal oxide, account for
The % of 0.1 % of final catalyst quality ~ 15.
A kind of application method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
It is used for the inferior heavy oil hydrogenation process of slurry bed system or suspension bed in its catalyst, operating procedure includes：
(1) described the inferior heavy oil suspension bed hydrogenation catalyst, sublimed sulfur and the inferior heavy oil that are carried on molecular sieve are mixed
Close, based on transition metal oxide, catalyst amount is 100 ~ 2000 ppm, and sublimed sulfur dosage is 100 ~ 2000 ppm；
(2) in presence of hydrogen by catalyst vulcanization, curing temperature is 200 ~ 400oC, cure time are 0.2 ~ 2 h；
(3) it is warming up to reaction temperature and carries out hydrocracking reaction, reaction temperature is 350 ~ 450oC, reaction pressure be 5 ~
20 MPa, reaction time are 0.5 ~ 4 h.
A kind of application method of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, its feature exist
It is less than 0.074mm in the granularity of described bauxite powder（- 200 mesh）, with Fe in its bauxite powder2O3The ferriferous oxide weight of meter
Content is less than 20%.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：
(1) present invention is directly used as synthesis of molecular sieve using rich reserves, cheap natural bauxite and diatomite
Raw material, and its sub-molten salt activating process process is simple, easy to operate, can effectively reduce the preparation cost of molecular sieve, has good
Prospects for commercial application；
(2) inferior heavy oil hydrogenation catalyst of the present invention, the Y type molecules prepared using the natural minerals as raw material
Sieve is used as carrier, impregnated transition metal active constituent, so that inferior heavy oil hydrogenation catalyst of the present invention not only has
There is hydrogenating function, but also there is cracking function, can making the macromoleculars such as colloid, asphalitine, more cracking is that small molecule is free
Base, under the conditions of existing for transition metal active component, these small molecule free radicals hydrogenation turns into stable small molecule hydro carbons, and
It is not condensation coking；
(3) present invention uses molecular sieve as carrier, in addition to excellent acidity, also with larger ratio surface
Product, can improve the decentralization of active metal, be advantageous to the raising of catalytic efficiency；In addition, the Fe itself contained in natural minerals
Impurity can also be used as activated centre, have certain facilitation to hydrogenation activity and suppression green coke.Therefore, the catalyst is bad
There is higher catalytic activity and relatively low coking yield in reduced fuel oil hydro-upgrading.
The method of the present invention, the use of its Y type molecular sieve carrier is using bauxite and diatomite as Material synthesis, due to using
Natural mineral raw, it is wide material sources, cheap, so that the running cost of the preparation cost of catalyst and hydrogenation process is significantly
Reduce.Resulting inferior heavy oil hydrogenation catalyst not only has hydrogenating function, but also has cracking function, therefore in poor quality
There is higher catalytic activity and relatively low coking yield in heavy-oil hydrogenation modification.
Embodiment
A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention, the specific behaviour of its preparation process
It is as follows to make step：
(1) natural bauxite powder is well mixed with sub-molten salt medium, is placed in baking oven and activates, after crushing, it is stand-by；
It is stand-by after natural diatomaceous earth mineral are placed in into Muffle kiln roasting；
(2) after the activation mineral obtained in step (1) being mixed into aging with sodium hydroxide, directed agents and deionized water
Crystallization under hydrothermal condition, solid product produce the carrier of described inferior heavy oil suspension bed hydrogenation catalyst after ammonium exchanges；
(3) incipient impregnation is carried out to carrier with containing VIB and/or group VIII metal precursor solution, dried, roasting
Described inferior heavy oil suspension bed hydrogenation catalyst is produced afterwards；
In step (1), described sub-molten salt medium is NaOH-H2O, the quality of described bauxite and sub-molten salt medium
Than for 1:0.2 ~ 2, described bauxite sub-molten salt activation temperature is 100 ~ 400oC, soak time are 0.5 ~ 4 h, described silicon
Diatomaceous earth heat activation temperature is 500 ~ 1000oC, soak time are 1 ~ 10 h；
In step (2), described molar ratio is (2.0 ~ 14.4) Na2O: (5~12)SiO2: (0.8~1.2)
Al2O3: (180~250)H2O；Directed agents can synthesize according to a conventional method, the preparation method as described by according to CN103043679A
Synthesis, the constitutive molar ratio of directed agents is (16 ~ 18) Na2O: (16~18)SiO2: (0.8~1.2)Al2O3: (310~340)
H2O, directing agent solution addition are the 9 ~ 16% of synthetic system gross mass；Described aging temperature is 50 ~ 65 oC, crystallization temperature
For 95 ~ 110oC。
In step (3), described VIB and/or group VIII metal presoma are ammonium molybdate, nickel nitrate, cobalt nitrate, inclined tungsten
One or more in acid, nickel sulfate, ferric sulfate and ferric nitrate；The transition metal total amount of the load, based on metal oxide,
Account for 0.1 ~ 15 wt% of final catalyst quality；Described sintering temperature is 500 ~ 800 oC, roasting time are 2 ~ 8 h.
The application method and catalytic of a kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve of the present invention
It can evaluate, comprise the following steps：
(1) above-mentioned catalyst, sublimed sulfur and inferior heavy oil are mixed, based on transition metal oxide, catalyst amount is
100 ~ 2000 ppm, sublimed sulfur dosage are 100 ~ 2000 ppm；
(2) in presence of hydrogen by catalyst vulcanization, curing temperature is 200 ~ 400oC, cure time are 0.2 ~ 2 h；
(3) it is warming up to reaction temperature and carries out hydrocracking reaction, reaction temperature is 350 ~ 450oC, reaction pressure be 5 ~
20 MPa, reaction time are 0.5 ~ 4 h.
The implementation process of the present invention and caused beneficial effect are described in detail below by way of specific embodiment, it is intended to which help is read
Person more fully understand the present invention essence and feature, not as to this case can practical range restriction.The explanation catalysis of embodiment 1 ~ 5
The preparation method of agent carrier and catalyst, embodiment 6 ~ 10 illustrate what catalyst was applied during inferior heavy oil floating bed hydrogenation
Effect.
Diatomite, bauxite used in each embodiment are commercially available prod.Diatomaceous main component is：SiO2's
Content is 93.20 wt%, Al2O3Content be 3.31 wt%, Fe2O3Content be 1.50 wt%；The main component of bauxite
For：SiO2Content be 9.72 wt%, Al2O3Content be 68.85 wt%, Fe2O3Content be 18.62 wt%.
Relative crystallinity described in each embodiment obtains according to ASTM D 3906-03 criterion calculations, its calculating side
Method is that (Catalyst Factory, Nankai Univ is produced, and 100%) X that its crystallinity is defined as is penetrated with synthesis of molecular sieve sample and standard sample
2 θ angles are 15.7 in line diffraction (XRD) spectrogramo、18.7o、20.4o、23.7o、27.1o、30.8o、31.5oWith 34.2oEight of place
The ratio of characteristic peak peak area sum, is expressed as a percentage；Described specific surface area is to pass through N2Adsorption-desorption experiment measures
's.
The analysis project of evaluation experimental catalytic performance is mainly the simulation distillation of fluid product, gas composition analysis, toluene
Insoluble matter measures.Referred to using cut oil yield, inferior heavy oil conversion ratio and coking yield as the primary evaluation of catalyst catalytic performance
Mark, computational methods are as follows：
Inferior heavy oil conversion ratio=524oC following components quality (containing gas)/raw material oil quality × 100%；
Cut oil yield=524oBelow C liquid components quality/raw material oil quality × 100%；
Coking yield=toluene insoluble amount of substance/raw material oil quality × 100%；
Liquid yield=product liquid quality/raw material oil quality × 100%；
Gas recovery ratio=(feedstock oil addition-solid, product liquid total amount)/raw material oil quality × 100%.
Embodiment 1
The activation of mineral：20.00 g diatomite powders are weighed in 700oC is calcined 6 h, standby；It is natural to weigh 50.00 g
Bauxitic ore original powder and the NaOH-H that 60.00 g concentration are 80%2O sub-molten salt solution is well mixed, and is placed in 350oDried in C baking ovens
It is standby after dry, crushing.
The preparation of directing agent solution：Take 16.32 g sodium hydroxides to be dissolved in 22.80 g water, be cooled to room temperature, it is standby；
Take 16.00 g aluminum sulfate to be dissolved in 22.80 g water, the aluminum sulfate solution of preparation is added solution I is obtained in sodium hydroxide solution, will
51.16 g sodium metasilicate are dissolved in 60.00 g water, add 43.20 g Ludox (SiO2Content is 24.96%) 2 h of quick stirring,
Then solution I is added under stirring condition, 30 after being well mixedoC stirs the h of aging 4, stands 48 h at room temperature, is made and leads
To agent solution.
The preparation of carrier：Weigh the g of diatomite powder 10.00 after above-mentioned roasting, add 4.58 g sodium hydroxides, 3.64
The above-mentioned treated bauxite powder of g, 7.52 g directed agents, 57.00 g deionized waters, 60o, will after the h of C mixing aging 12
The mixture is moved into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is warming up to 100oThe static h of crystallization 24 of C；Crystallization knot
Shu Hou, cool down, be filtered to remove mother liquor, solid product is scrubbed, after drying, obtains NaY molecular sieve；With 1 mol/L ammonium chloride
Solution carries out ion exchange to NaY molecular sieve, obtains catalyst carrier HY molecular sieves, and its relative crystallinity is 85%, specific surface area
For 610 m2/g。
The preparation of catalyst：Weigh 20.00 g catalyst carriers obtained above and be impregnated in and lived containing 1.00 g
Property metal Mo is (with Mo2O3Meter) (NH4)6Mo7O24·4H2In the O aqueous solution, impregnated on the carrier using equi-volume impregnating
The active metal Mo, after through drying, 650oC is calcined 6 h, produces described inferior heavy oil hydrogenation catalyst A.
Embodiment 2
The preparation of directing agent solution is the same as embodiment 1.
The activation of mineral：20.00 g diatomite powders are weighed in 600oC is calcined 8 h, standby；It is natural to weigh 50.00 g
Bauxitic ore original powder and the NaOH-H that 100.00 g concentration are 75%2O sub-molten salt solution is well mixed, and is placed in 250oIn C baking ovens
It is standby after drying, crushing.
The preparation of carrier：The g of diatomite powder 7.00 after above-mentioned roasting is weighed, adds 0.80 g sodium hydroxides, 6.13 g
Above-mentioned treated bauxite powder, 8.80 g directed agents, 59.50 g deionized waters, 50o, will after the h of C mixing aging 18
The mixture is moved into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is warming up to 95oThe static h of crystallization 18 of C；Crystallization terminates
Afterwards, cool down, be filtered to remove mother liquor, solid product is scrubbed, after drying, obtains NaY molecular sieve；Ammonium chloride with 1 mol/L is molten
Liquid carries out ion exchange to NaY molecular sieve, obtains catalyst carrier HY molecular sieves, and its relative crystallinity is 90%, and specific surface area is
646 m2/g。
The preparation of catalyst：Weigh 20.00 g catalyst carriers obtained above and be impregnated in and lived containing 0.20 g
Property metal Mo is (with Mo2O3Meter) (NH4)6Mo7O24·4H2O and 0.20 g active metals Ni (in terms of NiO) Ni (NO3)2·
6H2In O mixed aqueous solution, impregnate the active metal Mo and Ni on the carrier using equi-volume impregnating, after pass through
Drying, 500oC is calcined 4 h, produces described inferior heavy oil hydrogenation catalyst B.
Embodiment 3
The preparation of directing agent solution is the same as embodiment 1.
The activation of mineral：20.00 g diatomite powders are weighed in 800oC is calcined 4 h, standby；It is natural to weigh 50.00 g
Bauxitic ore original powder and the NaOH-H that 25.00 g concentration are 80%2O sub-molten salt solution is well mixed, and is placed in 150oDried in C baking ovens
It is standby after dry, crushing.
The preparation of carrier：The g of diatomite powder 7.00 after above-mentioned roasting is weighed, adds 6.00 g sodium hydroxides, 2.38 g
Above-mentioned treated bauxite powder, 10.50 g directed agents, 59.50 g deionized waters, 55o, will after the h of C mixing aging 24
The mixture is moved into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is warming up to 98oThe static h of crystallization 12 of C；Crystallization terminates
Afterwards, cool down, be filtered to remove mother liquor, solid product is scrubbed, after drying, obtains NaY molecular sieve；Ammonium chloride with 1 mol/L is molten
Liquid carries out ion exchange to NaY molecular sieve, obtains catalyst carrier HY molecular sieves, and its relative crystallinity is 88%, and specific surface area is
635 m2/g。
The preparation of catalyst：Weigh 20.00 g catalyst carriers obtained above and be impregnated in and lived containing 2.00 g
Property metal Mo is (with Mo2O3Meter) (NH4)6Mo7O24·4H2In the O aqueous solution, impregnated on the carrier using equi-volume impregnating
The active metal Mo, after through drying, 700oC is calcined 2 h, produces described inferior heavy oil hydrogenation catalyst C.
Embodiment 4
The preparation of directing agent solution is the same as embodiment 1.
The activation of mineral：20.00 g diatomite powders are weighed in 1000oC is calcined 2 h, standby；It is natural to weigh 50.00 g
Bauxitic ore original powder and the NaOH-H that 75.00 g concentration are 85%2O sub-molten salt solution is well mixed, and is placed in 300oDried in C baking ovens
It is standby after dry, crushing.
The preparation of carrier：Weigh the g of diatomite powder 10.50 after above-mentioned roasting, add 2.55 g sodium hydroxides, 3.48
The above-mentioned treated bauxite powder of g, 6.90 g directed agents, 60.00 g deionized waters, 65o, will after the h of C mixing aging 12
The mixture is moved into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is warming up to 105oThe static h of crystallization 16 of C；Crystallization knot
Shu Hou, cool down, be filtered to remove mother liquor, solid product is scrubbed, after drying, obtains NaY molecular sieve；With 1 mol/L ammonium chloride
Solution carries out ion exchange to NaY molecular sieve, obtains catalyst carrier HY molecular sieves, and its relative crystallinity is 92%, specific surface area
For 662 m2/g。
The preparation of catalyst：Weigh 20.00 g catalyst carriers obtained above and be impregnated in and lived containing 1.60 g
Property metal Co is (with Co2O3Meter) Co (NO3)2·6H2In the O aqueous solution, institute is impregnated on the carrier using equi-volume impregnating
State active metal Co, after through drying, 600oC is calcined 5 h, produces described inferior heavy oil hydrogenation catalyst D.
Embodiment 5
The preparation of directing agent solution is the same as embodiment 1.
The activation of mineral：20.00 g diatomite powders are weighed in 900oC is calcined 5 h, standby；It is natural to weigh 50.00 g
Bauxitic ore original powder and the NaOH-H that 75.00 g concentration are 80%2O sub-molten salt solution is well mixed, and is placed in 300oDried in C baking ovens
It is standby after dry, crushing.
The preparation of carrier：Weigh the g of diatomite powder 10.50 after above-mentioned roasting, add 0.60 g sodium hydroxides, 4.40
The above-mentioned treated bauxite powder of g, 7.60 g directed agents, 60.00 g deionized waters, 70o, will after the h of C mixing aging 18
The mixture is moved into the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, is warming up to 108oThe static h of crystallization 12 of C；Crystallization knot
Shu Hou, cool down, be filtered to remove mother liquor, solid product is scrubbed, after drying, obtains NaY molecular sieve；With 1 mol/L ammonium chloride
Solution carries out ion exchange to NaY molecular sieve, obtains catalyst carrier HY molecular sieves, and its relative crystallinity is 82%, specific surface area
For 598 m2/g。
The preparation of catalyst：Weigh 20.00 g catalyst carriers obtained above and be impregnated in and lived containing 1.60 g
Property metal Co is (with Co2O3Meter) Co (NO3)2·6H2In the O aqueous solution, institute is impregnated on the carrier using equi-volume impregnating
State active metal Co, after through drying, 600oC is calcined 5 h, produces described inferior heavy oil hydrogenation catalyst E.
Embodiment 6 ~ 10
In order to prove application effect of the catalyst of the present invention in the reaction of inferior heavy oil floating bed hydrogenation, the present invention is set
Experimental example has been put to test the floating bed hydrogenation catalytic performance of catalyst.Experimental procedure is specific as follows：
With decompression residuum (Fujian joint petrochemical industry provides) for reaction raw materials, add into the autoclave that volume is 0.3 L
Enter 60.00 g decompression residuum, the gained catalyst of 100 ~ 2000 ppm above-described embodiments 1 ~ 5 and 100 ~ 2000 ppm sublimed sulfurs, room
Under temperature, first air in kettle is sufficiently displaced from hydrogen, 200 ~ 400oThe h of vulcanizing treatment 0.2 ~ 2 is carried out under C, is pressurized to 5 afterwards
~20 MPa；Reaction temperature is 350 ~ 450oC, reaction time are 0.5 ~ 4 h, and specific reaction condition is as shown in table 1.Reaction terminates
Afterwards, treat that temperature is down to room temperature, the liquid oil of taking-up is weighed, and inferior heavy oil conversion ratio, boiling point are calculated 524 according to formulaoBelow C cuts oil yield, the evaluation index of liquid yield, gas recovery ratio as experimental result, experiment gained active testing result
It is shown in Table 2.
The active testing condition of 1 different suspension bed hydrogenation catalysts of table
The active testing result of 2 different suspension bed hydrogenation catalysts of table
The inferior heavy oil that inferior heavy oil suspension bed hydrogenation catalyst of the present invention is can be seen that by the data of table 2 converts
For rate in 84.5 more than wt%, distillate yield is higher than 76.5 wt%, and liquid yield is that light oil constituents yield reaches 89.0 wt%,
And coking yield is below 0.9 wt%.It can draw catalyst of the present invention in inferior heavy oil hydro-upgrading by above-mentioned analysis
With higher catalytic activity and relatively low coking yield.
Claims (11)
- A kind of 1. inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve, it is characterised in that the component of its hydrogenation catalyst VIB and/or VIII transition metal including Y type molecular sieve carrier and in supported on carriers, transition metal active component be molybdenum, One or more in nickel, cobalt, tungsten, for transition metal based on metal oxide, load capacity is 0.1 ~ 15 wt%, and Y type molecular sieve carries Body is using bauxite and diatomite as Material synthesis.
- A kind of 2. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 1 Method, it is characterised in that include the step of its preparation process：(1) bauxite powder and diatomite material are activated respectively；(2) bauxite powder and diatomite material after activating mix with sodium hydroxide, directed agents and deionized water, carry out old Change, then crystallization under hydrothermal conditions, solid product obtain the molecular sieve of inferior heavy oil suspension bed hydrogenation catalyst after ammonium exchanges Carrier；(3) molecular sieve carrier of obtained inferior heavy oil suspension bed hydrogenation catalyst is used and contains VIB and/or group VIII metal After precursor solution carries out incipient impregnation；Again through drying, roasting, inferior heavy oil suspension bed hydrogenation catalyst is obtained.
- A kind of 3. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 2 Method, it is characterised in that its bauxite powder is activated using sub-molten salt medium, and diatomite uses process of thermal activation.
- A kind of 4. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 2 Method, it is characterised in that the sub-molten salt medium of bauxite powder activation process is NaOH-H2O, bauxite powder and sub-molten salt are situated between Matter is 1 in mass ratio:0.2 ~ 2 is well mixed, 100 ~ 400oAt a temperature of C, soak time is 0.5 ~ 4 h.
- A kind of 5. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 2 Method, it is characterised in that its diatomaceous activation process is 500 ~ 1000 by diatomiteoAt a temperature of C, 1 ~ 10 h is calcined.
- A kind of 6. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 2 Method, it is characterised in that its bauxite powder and diatomite material after activating mixes with sodium hydroxide, directed agents and deionized water Molar ratio be (2.0 ~ 14.4) Na2O: (5~12)SiO2: (0.8~1.2)Al2O3: (180~250)H2O, directed agents Constitutive molar ratio is (16 ~ 18) Na2O: (16~18)SiO2: (0.8~1.2)Al2O3: (310~340)H2O, directing agent solution add Dosage is the 9% ~ 16% of synthetic system gross mass.
- A kind of 7. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 2 Method, it is characterised in that the aging temperature of step (2) is 50 ~ 70oC, crystallization temperature are 95 ~ 110oC。
- A kind of 8. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 2 Method, it is characterised in that the sintering temperature of step (3) is 500 ~ 800oC, roasting time are 2 ~ 8 h.
- A kind of 9. preparation side of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 2 Method, it is characterised in that described VIB and/or group VIII metal presoma are ammonium molybdate, nickel nitrate, cobalt nitrate, metatungstic acid, sulfuric acid One or more in nickel.
- A kind of 10. user of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 1 Method, it is characterised in that its catalyst is used for the inferior heavy oil hydrogenation process of suspension bed, and operating procedure includes：(1) by described the inferior heavy oil suspension bed hydrogenation catalyst catalyst, sublimed sulfur and the inferior heavy oil that are carried on molecular sieve Mixing, based on transition metal oxide, catalyst amount is 100 ~ 2000 ppm, and sublimed sulfur dosage is 100 ~ 2000 ppm；(2) in presence of hydrogen by catalyst vulcanization, curing temperature is 200 ~ 400oC, cure time are 0.2 ~ 2 h；(3) it is warming up to reaction temperature and carries out hydrocracking reaction, reaction temperature is 350 ~ 450oC, reaction pressure are 5 ~ 20 MPa, reaction time are 0.5 ~ 4 h.
- A kind of 11. user of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve according to claim 10 Method, it is characterised in that the granularity of described bauxite is less than 0.074mm, with Fe in its bauxite powder2O3The weight of the ferriferous oxide of meter Measure content and be less than 20%.
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| CN106423142A (en) * | 2016-09-20 | 2017-02-22 | 福州大学化肥催化剂国家工程研究中心 | Catalyst for suspension bed hydrocracking of inferior heavy oil and preparation method thereof |
| CN110465306B (en) * | 2019-08-02 | 2022-04-12 | 中海油天津化工研究设计院有限公司 | Preparation method of efficient bulk phase hydrogenation catalyst |
| CN111468097B (en) * | 2020-03-24 | 2023-03-03 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
| CN111420670B (en) * | 2020-05-11 | 2023-08-04 | 太原理工大学 | Hydrogenation catalyst and preparation method and application thereof |
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| CN1667093A (en) * | 2005-02-22 | 2005-09-14 | 大连理工大学 | High performance hydrocracking catalyst and process for preparing same |
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