CN107303491B - The preparation method of Hydrodemetalation catalyst - Google Patents
The preparation method of Hydrodemetalation catalyst Download PDFInfo
- Publication number
- CN107303491B CN107303491B CN201610252535.7A CN201610252535A CN107303491B CN 107303491 B CN107303491 B CN 107303491B CN 201610252535 A CN201610252535 A CN 201610252535A CN 107303491 B CN107303491 B CN 107303491B
- Authority
- CN
- China
- Prior art keywords
- acid
- hours
- hydro
- polyalcohol
- thermal
- 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
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of Hydrodemetalation catalyst, including following content: (1) being mixed with beating boehmite and deionized water, the mixed acid solution of organic acid and inorganic acid is added in Xiang Shangshu slurries, carries out being heated to reflux processing；Urea is added into above-mentioned slurries and carries out hydro-thermal process；(2) the boehmite dry glue powder obtained with the aqueous solution impregnation steps (1) containing polyalcohol and/or glucide carries out hydro-thermal charing process；(3) polyalcohol and/or monosaccharide aqueous solution for preparing at least two various concentrations, spray on the alumina support that step (2) obtains according to the sequence of concentration from high to low, and the alumina support after dipping carries out hydro-thermal charing process；(4) hydrogenation active component is loaded to and product is made on carrier.The Hydrodemetalation catalyst of this method preparation has suitable pore structure, and active component and carrier effect is moderate, metal removal activity and activity stability with higher in weight, residual hydrogenation reaction.
Description
Technical field
The present invention relates to a kind of preparation methods of Hydrodemetalation catalyst.
Background technique
Currently, in the production process of mink cell focus hydrodemetallization, since feedstock oil contains a certain amount of vanadium, sulphur, arsenic, nickel
Equal impurity, easily form deposition, so that the duct of blocking catalyst, causes catalyst activity to decline rapidly, or even inactivation, influence
Industrial application.Hold with large hole and the catalyst of larger bore dia holds metal and appearance coke formation is strong, catalyst can be slowed down
The operation cycle for inactivating, making catalyst extends.After load active component in roasting process, active metal component is easy and oxidation
Alumina supporter has an effect to form very strong M-O-Al key, causes active component to form Spinel and lose activity, or make to live
Property component can not complete cure to reducing catalyst activity.
CN1160602A disclose a kind of macropore alumina supporter for being suitable as Hydrodemetalation catalyst carrier and its
Preparation method.The preparation method of the macropore alumina supporter includes that boehmite dry glue powder is mixed with water or aqueous solution,
It is kneaded into plastic, obtained plastic is extruded into bar on banded extruder, drying simultaneously roasts to obtain product, its main feature is that,
It is additionally added carbon black powder in above process as physics expanding agent and chemical action can occur with boehmite or aluminium oxide
The chemical enlargement agent of phosphorous, silicon or boron compound.Wherein carbon black powder dosage is 3-10 weight %(on the basis of the weight of aluminium oxide).
Alumina support obtained can be used for preparing mink cell focus especially residuum hydrogenating and metal-eliminating and/or Hydrobon catalyst.
US4448896 discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, proposes using carbon black as expansion
Hole agent.Expanding agent is uniformly mixed with boehmite dry glue powder, the nitre that mass fraction is 4.3% is added into said mixture
Aqueous acid kneading 30 minutes, it was ammonia spirit kneading 25 minutes of 2.1% that mass fraction, which is then added, kneading uniformly after extrusion
Molding, carrier after molding, which is fired, is made final alumina support.Wherein the additional amount of carbon black powder is preferably greater than active oxygen
Change aluminium or the 20% of its precursor weight.
CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, and the catalyst is with VIII race
And/or VI B race metallic element be active component, be supported on a kind of large-pore alumina carrier.The residuum hydrogenating and metal-eliminating is urged
The preparation method of agent is to joined the carbon black powder that granular size is 30 microns as physics in boehmite kneading process
Expanding agent and the chemical enlargement agent that the phosphorous of chemical action, silicon or boron compound can occur with boehmite or aluminium oxide, are mixed
Object kneading is closed into plastic, extruded moulding, dry, the obtained carrier of roasting, then is loaded to spraying impregnation method for active component
On carrier, through drying, obtained catalyst is roasted.
In conclusion usually making during prior art preparation macropore alumina supporter and/or Hydrodemetalation catalyst
The aperture of carrier is improved with physics expanding agent and chemical enlargement agent, the addition of expanding agent can be such that alumina support macropore contains really
Amount increases.But it, need to be by kneadings such as boehmite dry glue powder, extrusion aid, peptizing agents at plastic in alumina support forming process
Body, then extruded moulding, collapses since the presence of the larger pressure of extrusion process can make the macropore of alumina powder itself that part occur
It collapses, so that the hole appearance of final carrier and macropore content be made to substantially reduce.In addition, the interaction of active component and carrier need into
One step improves.
Summary of the invention
Aiming at the shortcomings of the prior art, the present invention provides a kind of preparation method of Hydrodemetalation catalyst, party's legal system
Standby Hydrodemetalation catalyst has suitable pore structure, and active component and carrier acts on moderate, the hydrodemetallisation catalyst
Agent hydrodemetallization activity with higher and activity stability.
The preparation method of Hydrodemetalation catalyst of the invention, including following content:
(1) boehmite and deionized water are mixed with beating, the mixed of organic acid and inorganic acid is added in Xiang Shangshu slurries
Acid solution is closed, the pH value for controlling slurries is 2-5, carries out being heated to reflux processing；Urea is added into above-mentioned slurries to carry out at hydro-thermal
It manages, the slurries after hydro-thermal process are washed, dry；
(2) the boehmite dry glue powder obtained with the aqueous solution impregnation steps (1) containing polyalcohol and/or glucide,
Material after dipping carries out hydro-thermal charing process, treated material forming, dry, roasting；
(3) polyalcohol and/or monosaccharide aqueous solution for preparing at least two various concentrations, according to the sequence of concentration from high to low
It sprays on step (2) alumina support, so that it is in by low that the concentration of polyalcohol and/or monosaccharide forms ecto-entad on carrier
To high gradient distribution, the alumina support after dipping carries out hydro-thermal charing process in sealing container, is dried to be made and contains
Oxidation of coal alumina supporter；
(4) hydrogenation active component maceration extract impregnation steps (3) carrier is used, hydrodemetallization is made through drying, roasting in material
Catalyst.
In the method for the present invention, it is mixed with beating process described in step (1) and is carried out using conventional method in that art, intends thin water aluminium
Stone and the mass ratio of deionized water are preferably 1:3-1:10.The organic acid be one of acetic acid, oxalic acid or citric acid or
Several mixing, the inorganic acid are the mixing of one or more of sulfuric acid, nitric acid or hydrochloric acid；Organic acid in mixed acid solution
The mass ratio of the material with inorganic acid is 1:3-1:6, and the concentration of the mixed acid solution is calculated as 3-6mol/L with inorganic acid.It is described to add
Hot reflow treatment temperature is 30-60 DEG C, and being heated to reflux the time is 1-5 hours.
In the method for the present invention, the mass ratio of amount of urea described in step (1) and boehmite is 1:5-1:10.Adding
Preferably while borate is added while entering urea, the borate can be metaborate, ortho-borate and multi-borate
One or more of mixing, the additional amount of borate is 0.5:100-1.5 with the mass ratio of boehmite in terms of boron oxide:
100。
In the method for the present invention, hydro-thermal process described in step (1) is the heat treatment under the self-generated pressure of autoclave,
Treatment temperature is 120-160 DEG C, and the processing time is 4-8 hours.
In the method for the present invention, drying temperature described in step (1) is 100-120 DEG C, and drying time is 6-10 hours.
In the method for the present invention, polyalcohol described in step (2) is in xylitol, sorbierite, mannitol or arabite
It is one or more of；The carbohydrate is the mixing of one or more of glucose, ribose or fructose etc.；Containing polyalcohol and/or sugar
The mass concentration of the aqueous solution of substance is 20%-40%.The dosage of aqueous solution containing polyalcohol and/or glucide is thin for that will intend
Diaspore dry glue powder is totally submerged；Dip time is 3-5 hours.
In the method for the present invention, hydro-thermal charing process described in step (2) is the heat treatment carried out in sealing device, preferably
Autoclave can be dynamic response kettle or static reaction kettle, preferably static reaction kettle；The hydro-thermal charing process temperature
It is 120-160 DEG C, the processing time is 8-16 hours.
In the method for the present invention, molding, drying and roasting described in step (2) can be carried out using conventional method in that art.
In forming process, it can according to need and one of conventional shaping assistant, such as peptizing agent, extrusion aid etc. or a variety of is added.
The peptizing agent is one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., and the extrusion aid, which refers to, to be conducive to squeeze
One or more of molded substance, such as sesbania powder, carbon black, graphite powder, citric acid, the total material of dosage Zhan of extrusion aid
1wt%~10wt% of butt.The drying condition are as follows: 60-130 DEG C of drying temperature, drying time is 1-10 hours.Described
500-750 DEG C of maturing temperature of roasting roasts 2-10 hours.
In the method for the present invention, polyalcohol described in step (3) includes xylitol, sorbierite, mannitol or arabite etc.
One or more of；The monosaccharide includes one or more of glucose, ribose or fructose etc..
In the method for the present invention, the mass concentration of polyalcohol described in step (3) and/or monosaccharide aqueous solution is 5%-50%.
In the method for the present invention, described in step (3) according to concentration from high to low spray sequence, adjacent polyalcohol twice
And/or the concentration difference of monosaccharide aqueous solution is 5%-30%, preferably 10%-20%；It is preferred that prepare 2-4 kind various concentration polyalcohol and/
Or monosaccharide aqueous solution.
In the method for the present invention, the maceration extract dosage sprayed every time described in step (3) is alumina support saturated water adsorptive value
10%-60%, preferably 20%-30%, the total dosage of the maceration extract repeatedly sprayed be alumina support saturated water adsorptive value to ensure oxygen
Change alumina supporter saturation dipping.
In the method for the present invention, the preferred polyalcohol for preparing 3 kinds of various concentrations of step (3) and/or monosaccharide aqueous solution are sprayed
Leaching, detailed process is as follows: spray for the first time, the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 30%-50%, polyalcohol and/
Or the dosage of monosaccharide aqueous solution is the 20%-30% of alumina support water absorption；It sprays for the second time, polyalcohol and/or monosaccharide are water-soluble
The mass concentration of liquid is 10%-30%, and the dosage of polyalcohol and/or monosaccharide aqueous solution is the 40%-60% of alumina support water absorption；
Third time sprays, and the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 5%-10%, the use of polyalcohol and/or monosaccharide aqueous solution
Amount is the 10%-40% of alumina support water absorption.
In the method for the present invention, alumina support described in step (3) is graininess, can be spherical, bar shaped (including cylinder
Shape, trilobal, quatrefoil etc.) or piece shape, preferably bar shaped or spherical shape, more preferably bar shaped.It can also in the alumina support
One or more of auxiliary elements such as Si, Ti, Zr, B or F to be added as needed.
In the method for the present invention, hydro-thermal charing process temperature described in step (3) be 180-250 DEG C, preferably 200-230 DEG C,
Hydrothermal conditions are 6-12 hours, and preferably 8-10 hours, hydro-thermal process pressure was self-generated pressure, under this hydro-thermal carbonization condition
It can guarantee that polyalcohol and/or monosaccharide carbonize completely.Wherein, self-generated pressure is related with treatment temperature, when temperature is 100 DEG C, pressure
Force value (gauge pressure) general 0.1MPa, at 150 DEG C, pressure value is generally 0.43MPa, and at 250 DEG C, pressure value is generally 1.95MPa.
In the method for the present invention, hydrogenation active component maceration extract described in step (4) is to form to calculate according to final catalyst
It prepares.In hydrogenation active component maceration extract, vib metals content is calculated as 7-15g/100ml, group VIII metal with oxide
Content is calculated as 0.8-3g/100ml with oxide, can use volume impregnation, incipient impregnation or spray impregnating mode, leaching
The stain time is 1-5 hours.
In the method for the present invention, drying condition described in step (4) is 6-10 hours dry at 80-120 DEG C；The roasting
Condition is to roast 3-6 hours in nitrogen atmosphere at 400-600 DEG C.
Can there are the unformed phase hydrated alumina in part, this partially hydrated alumina pore in boehmite preparation process
Appearance, aperture are lower, will affect final carrying alumina body opening appearance and macropore content.
The method of the present invention is first handled boehmite with mixed acid solution, since mixed acid and boehmite are made
With more moderate, it can not only overcome and dissolve amorphous phase hydrated alumina halfway deficiency when organic acid is used alone, but also can be with
It avoids damaging boehmite duct when inorganic acid is used alone, by nothing while guaranteeing boehmite pore structure
Setting phase hydrated alumina dissolution is removed.Dissolved aluminium salt is retained in slurries, then urea and sealing water are added into slurries
When heat treatment, urea is decomposed into NH under high temperature environment3And CO2, NH3And CO2NH is generated in the presence of water vapour4 +With
HCO3 -Ion, NH4 +And HCO3 -Ion at high temperature under high pressure, regrows boehmite crystal grain and crystallization, makes to intend thin
Diaspore crystal grain is grown up, and the accumulation mode of crystal grain is changed, and improves the content of macropore, while the Al dissolved3+Following reaction occurs:
Al3++NH3.H2O Al(OH)3+NH4 +, Al (OH)3+ NH4 ++HCO3 -NH4Al(OH)2CO3, NH4Al(OH)2CO3It is generated when roasting
Gas can play good reaming effect.Double hydrolysis, the oxidation of formation occur for borate and aluminium salt when borate is added
Boron precipitating load is in oxidation aluminium surface, the surface nature of modulation carrier while improving carrier aperture.Boehmite dry glue powder
Through hydro-thermal charing process, the carbons substance of formation is filled in the intercrystalline duct of boehmite, when extruded moulding, due to carbon
The presence of particle can play good supporting role, effectively prevent the collapsing of boehmite macropore, improve carrier
Hole hold and macropore content, carbon particle removed in subsequent roasting process.The polyalcohol of shaping carrier various concentration and/or
When monosaccharide aqueous solution spray dipping, the concentration of polyalcohol and/or monosaccharide, in distribution is incremented by, passes through hydro-thermal by carrier surface to center
Charing forms the carbon-coating of gradient distribution on carrier surface and duct inner wall.Due to carbon-coating there are modulation metal component with
Strong interaction between carrier promotes the reaction inside catalyst duct, extends while improving catalyst activity
The service life of catalyst.
Specific embodiment
The effect and effect of the method for the present invention are further illustrated below with reference to embodiment, but are not limited to following implementation
Example.
Using N2Physics suction-desorption characterization embodiment and comparative example catalyst pore structure, concrete operations are as follows: using
ASAP-2420 type N2Physics is inhaled-is desorbed instrument and characterizes to catalyst sample pore structure.Take a small amount of sample vacuum at 300 DEG C
Product is finally placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test by processing 3 ~ 4 hours.Wherein surface
Product is obtained according to BET equation, and pore-size distribution and pore volume are obtained according to BJH model.
It is as follows using XRF characterization embodiment and comparative example catalyst component, concrete operations: to use RIGAKU company, Japan
ZSX-100e type Xray fluorescence spectrometer, performance indicator: X-ray tube Be window thickness: 30 μm；Power: 4kW；Output voltage: 20-
60kV；Export electric current: 2-150mA；2 0.0001 ° of the angle θ reproducibilities；2 0.0002 ° of the angle θ accuracys.
Using carbon content in EPMA measurement alumina support, concrete operations are as follows: using Japan Electronics JXA-8230 electronics
Probe is measured, and the acceleration voltage that when measurement selects is 15KV, and probe current is 8 × 10-8A, beam spot size are 3 μm.Respectively
It measures at alumina support cross-section center and with distance at alumina support kernel of section as at 1/4R, 1/2R, 3/4R and R
Carbon content, wherein R is that alumina support cross-section center is (substantive at a distance from line segment between any point in the outer most edge of cross section
On be cross section radius), then by division calculation, obtain the ratio between each content.
Embodiment 1
Weigh 200g boehmite dry glue powder (production of Wenzhou essence crystal alumina Co., Ltd) set in a round bottom flask, to
600 grams of deionized water mashing are added in flask, it is 3mol/L, acetic acid mole that appropriate nitric acid molar concentration, which is added, in Xiang Shangshu slurries
Concentration is the mixed acid solution of 1mol/L, and the pH value for controlling slurries is 3 and is heated to reflux 3 hours in 40 DEG C.Above-mentioned slurries are turned
Enter in autoclave, 20 grams of urea are added into mixed material and are heat-treated 6 hours after sealing autoclave in 140 DEG C.It is cooled to
Mixed serum is filtered after room temperature, is washed, 120 DEG C of dryings, 8 hours obtained boehmites.
It weighs above-mentioned boehmite 200g to be placed in a beaker, the xylose that 400mL mass concentration is 25% is added into beaker
Alcohol solution impregnates 4 hours.For material after dipping through filtering, filter cake, which is transferred in autoclave, carries out charing process, processing temperature
Degree is 140 DEG C, and the processing time is 10 hours.Treated, and dry materials are sufficiently mixed with 4g sesbania powder, are added in Xiang Shangshu material
Entering uniform dissolved with the aqueous solution kneading of 5g acetic acid in right amount, is extruded into cylindrical bars, wet stock after molding is 8 hours dry in 110 DEG C,
600 DEG C of roastings, 4 hours obtained alumina supports.
It weighs 100 grams of alumina support of above-mentioned γ phase cylinder bar shaped to be put into spray rolling pot, under rotary state, with atomization
The xylose alcohol solution 25ml that carrier spray impregnating effect concentration of the mode into rolling pot is 40%；It then is 20% with mass concentration
Xylose alcohol solution 40ml continue spray oxide impregnation alumina supporter；The xylose alcohol solution for being finally 10% with mass concentration
40ml continues to spray oxide impregnation alumina supporter.Dipping terminates for alumina support to be transferred in autoclave and autoclave is placed in baking oven
In under 180 DEG C, self-generated pressure charing process 9 hours, cooled to room temperature.Alumina support after hydro-thermal process is in 120
Carbon containing alumina support is made within dry 3 hours at DEG C.
It weighs 100 grams of above-mentioned alumina support to be placed in a beaker, contains MoO with 150 milliliters310 grams, NiO1.2 grams of molybdenum-
Nickel-phosphor active metal maceration extract oxide impregnation alumina supporter 5 hours, filters redundant solution, and the material after dipping dries 6 in 120 DEG C
Hour, then roasted 5 hours in nitrogen atmosphere at 500 DEG C, catalyst C1 is made, the property of the catalyst is shown in Table 1.
Embodiment 2
With embodiment 1, only the additional amount of deionized water is 1400 grams.Mixed acid is dissolved with 4 mol sulfuric acid and 1mol grass
The mixed acid of acid, the pH value for controlling slurries is 2, and the temperature being heated to reflux is 30 DEG C, is flowed back 5 hours.The additional amount of urea is 30
Gram, hydro-thermal process temperature is 120 DEG C, hydro-thermal process 8 hours.With the mass ratio that mass concentration is 40% be 1:1 sorbierite with it is sweet
The mixed aqueous solution for revealing alcohol impregnates boehmite 3 hours.Charing process temperature is 130 DEG C, is handled the time 14 hours.Aluminium oxide
Carrier is clover bar shaped, the aqueous solution for the sorbierite that first time spray is 30% with 30ml mass concentration when impregnating, second of spray
The aqueous solution for the sorbierite for being 10% with 50ml mass concentration when drenching dipping, third time sprays when impregnating is with 20ml mass concentration
The aqueous solution of 5% sorbierite, temperature is 200 DEG C when charing process, and carbonization time is 8 hours, and catalyst C2, the catalysis is made
The property of agent is shown in Table 1.
Embodiment 3
With embodiment 1, only the additional amount of deionized water is 2000 grams.Mixed acid is dissolved with 6mol/L sulfuric acid and 1mol/L
The mixed acid of citric acid, the pH value for controlling slurries is 5, and being heated to reflux temperature is 60 DEG C, return time 1 hour.Urea additional amount
It is 40 grams, 160 DEG C of hydro-thermal process temperature, hydrothermal conditions are 4 hours.The Portugal for being 1:1 with the mass ratio that mass concentration is 30%
The mixed aqueous solution of grape sugar and ribose impregnates boehmite 5 hours.Charing process temperature is 120 DEG C, and the charing process time is
16 hours.It is impregnated using four sprays, the aqueous solution for the mannitol for being for the first time 50% with 20ml mass concentration when spray dipping,
The aqueous solution for the sorbierite for being 30% with 40ml mass concentration when spraying dipping for the second time, third time spray when impregnating with 20ml matter
Measure concentration be 20% sorbierite aqueous solution, the 4th time spray dipping when with 20ml mass concentration be 10% sorbierite it is water-soluble
Liquid.Temperature is 240 DEG C when charing process, and carbonization time is 12 hours, and catalyst C3 is made, and the property of the catalyst is shown in Table 1.
Embodiment 4
With embodiment 1,3.0 grams of sodium tetraborates are added into mixed material while urea is only added.Use mass concentration
The mixed aqueous solution for the arabite and fructose that mass ratio for 20% is 1:1 impregnates boehmite 4 hours.Charing process
Temperature is 150 DEG C, and the charing process time is 12 hours.Using spray dipping twice, with 50ml mass when spray impregnates for the first time
The aqueous solution for the arabite that concentration is 40%, the arabite that second of spray is 20% with 55ml mass concentration when impregnating
Aqueous solution, carbonization temperature is 250 DEG C, and carbonization time is 6 hours, catalyst C4 is made, the property of the catalyst is shown in Table 1.
Embodiment 5
With embodiment 1, only impregnated boehmite 5 hours with the sorbitol aqueous solution that mass concentration is 35%.At charing
Managing temperature is 160 DEG C, and the charing process time is 8 hours.Alumina support is bunge bedstraw herb bar shaped, and it is 1 that xylitol, which changes mass ratio into:
The xylitol of 1:1:1, arabite, sorbierite and mannitol mixing alcohol solution dipping, temperature is 220 when charing process
DEG C, the processing time is 10 hours, and catalyst C5 is made, and the property of the catalyst is shown in Table 1.
Comparative example 1
With embodiment 1, only boehmite is not impregnated with xylitol and hydro-thermal process, but by the xylitol of phase homogenous quantities
It is added in carrier in a manner of kneading in carrier molding, comparative example catalyst C6 is made, the property of catalyst is shown in Table 1.
Comparative example 2
With embodiment 1, only the unmixed acid processing of boehmite and urea liquid seal hydro-thermal process, and comparison is made
Example catalyst C7, the property of catalyst are shown in Table 1.
Comparative example 3
With example 1, only not instead of repeatedly spray is not impregnated into alumina support xylitol, by same amount of xylitol
It is impregnated into alumina support in a manner of primary spray dipping, comparative example catalyst C8 is made, the property of catalyst is shown in Table 1.
1 catalyst property of table.
Pore size distribution refers to that the Kong Rong of certain diameter range inner hole in catalyst accounts for the percentage of total pore volume.
Table 1 the result shows that, using the method for the present invention prepare carbon containing Hydrodemetalation catalyst, have convenient hole
Structure, carbon content is in catalyst radial direction distribution gradient.The carbon containing Hydrodemetalation catalyst of this method preparation is suitable for weight, slag
Oily hydrodemetallization field.
Embodiment 6
The following examples illustrate the catalyst of the method for the present invention preparation and the catalytic performance of comparative example catalyst.
Using feedstock oil listed by table 2 as raw material, the catalytic performance of C1-C8 is evaluated on 200 milliliters of hydrogenation reaction device, is urged
Agent is long 2 ~ 3 millimeters of item, and catalyst loading is 100 milliliters, and reaction temperature is 375 DEG C, hydrogen partial pressure 13MPa, liquid space-time
Speed is 1.0 hours-1, hydrogen to oil volume ratio 1000, measurement generates the content of each impurity in oil after reaction 200 hours, calculates metal
Opposite removal efficiency, evaluation result are shown in Table 3.
2 raw material oil nature of table.
| Project | Content |
| S, wt% | 4.21 |
| N, wt% | 0.34 |
| Ni, μ g/g | 19.8 |
| V, μ g/g | 81.6 |
| CCR, wt% | 18 |
3 catalyst hydrogenation performance comparison of table.
| C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | |
| Metal phase is to removal efficiency | 0.98 | 1.0 | 0.95 | 1.05 | 0.96 | 0.78 | 0.72 | 0.84 |
It can be seen from 3 data of table compared with comparative example, the method for the present invention preparation Hydrodemetalation catalyst have compared with
High hydrodemetallization activity.
Activity rating is carried out to catalyst obtained by above-described embodiment and comparative example, the temperature rise for running 5000h is shown in Table 4.
4 reaction temperature lift-off value of table
| Catalyst number | Reaction temperature lift-off value after reaction 5000 hours, DEG C |
| C1 | 17 |
| C2 | 16 |
| C3 | 18 |
| C4 | 16 |
| C5 | 19 |
| C6 | 25 |
| C7 | 26 |
| C8 | 23 |
Find out from the result of table 4, after reaction 5000 hours, using Hydrodemetalation catalyst provided by the invention, in order to
High demetallization per is kept, required reaction temperature increase rate is far smaller than comparative catalyst, this explanation is provided by the invention to add hydrogen
Catalyst for demetalation activity stability with higher.
Claims (6)
1. a kind of preparation method of Hydrodemetalation catalyst, it is characterised in that including following content: (1) by boehmite with
Deionized water is mixed with beating, and the mixed acid solution of organic acid and inorganic acid is added in Xiang Shangshu slurries, and the pH value for controlling slurries is
2-5 carries out being heated to reflux processing；Urea is added into above-mentioned slurries and carries out hydro-thermal process, the slurries after hydro-thermal process are washed,
It is dry；(2) the boehmite dry glue powder obtained with the aqueous solution impregnation steps (1) containing polyalcohol and/or glucide, dipping
Material afterwards carries out hydro-thermal charing process, treated material forming, dry, roasting；(3) at least two various concentrations are prepared
Polyalcohol and/or monosaccharide aqueous solution spray on step (2) alumina support according to the sequence of concentration from high to low, so that more
It is in gradient distribution from low to high that the concentration of first alcohol and/or monosaccharide forms ecto-entad on carrier, the carrying alumina after dipping
Body carries out hydro-thermal charing process in sealing container, and carbon containing alumina support is made in drying process；(4) it is soaked with hydrogenation active component
Hydrodemetalation catalyst is made through drying, roasting in stain liquid impregnation steps (3) carrier, material；Organic acid described in step (1)
For the mixing of one or more of acetic acid, oxalic acid or citric acid, the inorganic acid be one of sulfuric acid, nitric acid or hydrochloric acid or
Several mixing；The mass ratio of the material of organic acid and inorganic acid in mixed acid solution be 1:3-1:6, the mixed acid solution it is dense
Degree is calculated as 3-6mol/L with inorganic acid；The treatment temperature that is heated to reflux is 30-60 DEG C, and being heated to reflux the time is 1-5 hours；Step
Suddenly the mass ratio of amount of urea and boehmite described in (1) is 1:5-1:10；Polyalcohol described in step (2) is xylose
One or more of alcohol, sorbierite, mannitol or arabite；The carbohydrate is one in glucose, ribose or fructose
Kind or several mixing；The mass concentration of aqueous solution containing polyalcohol and/or glucide is 20%-40%；Containing polyalcohol and/or sugar
The dosage of the aqueous solution of substance is to be totally submerged boehmite dry glue powder；Dip time is 3-5 hours；Step (2) institute
The hydro-thermal charing process stated is the heat treatment carried out in sealing device；The hydro-thermal charing process temperature is 120-160 DEG C,
Handling the time is 8-16 hours；Polyalcohol described in step (3) is one in xylitol, sorbierite, mannitol or arabite
Kind is several；The monosaccharide is one or more of glucose, ribose or fructose；The polyalcohol and/or monosaccharide water
The mass concentration of solution is 5%-50%；Described in step (3) according to concentration from high to low spray sequence, adjacent polyalcohol twice
And/or the concentration difference of monosaccharide aqueous solution is 5%-30%；Hydro-thermal charing process temperature described in step (3) is 180-250 DEG C, hydro-thermal
Handling the time is 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
2. according to the method for claim 1, it is characterised in that: boric acid is added in step (1) simultaneously while urea is added
Salt, the borate are the mixing of one or more of metaborate, ortho-borate and multi-borate, the additional amount of borate
It with the mass ratio of boehmite is 0.5:100-1.5:100 in terms of boron oxide.
3. according to the method for claim 1, it is characterised in that: hydro-thermal process described in step (1) is in autoclave
Self-generated pressure under heat treatment, treatment temperature be 120-160 DEG C, processing the time be 4-8 hours.
4. according to the method for claim 1, it is characterised in that: drying temperature described in step (1) is 100-120 DEG C, is done
The dry time is 6-10 hours.
5. according to the method for claim 1, it is characterised in that: alumina support described in step (3) is graininess；It is described
Alumina support in one or more of Si, Ti, Zr, B or F auxiliary element is added.
6. according to the method for claim 1, it is characterised in that: drying condition described in step (4) is at 80-120 DEG C
It is 6-10 hours dry；The roasting condition is to roast 3-6 hours in nitrogen atmosphere at 400-600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610252535.7A CN107303491B (en) | 2016-04-21 | 2016-04-21 | The preparation method of Hydrodemetalation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610252535.7A CN107303491B (en) | 2016-04-21 | 2016-04-21 | The preparation method of Hydrodemetalation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107303491A CN107303491A (en) | 2017-10-31 |
| CN107303491B true CN107303491B (en) | 2019-08-06 |
Family
ID=60152930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610252535.7A Active CN107303491B (en) | 2016-04-21 | 2016-04-21 | The preparation method of Hydrodemetalation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107303491B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111822012B (en) * | 2019-04-17 | 2022-06-07 | 中国石油化工股份有限公司 | Alumina carrier, hydrodemetallization catalyst and preparation method thereof |
| CN116116404B (en) * | 2023-04-19 | 2023-08-01 | 浙江工业大学 | Method for preparing hydrogenation catalyst by hydrothermal method and application of catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3812374B2 (en) * | 2001-07-02 | 2006-08-23 | 住友金属鉱山株式会社 | Heavy hydrocarbon oil hydrodemetallation catalyst |
-
2016
- 2016-04-21 CN CN201610252535.7A patent/CN107303491B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549328A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing residual oil hydro-demetallization catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107303491A (en) | 2017-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107303490B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN107303485B (en) | A kind of preparation method of modified aluminium oxide supports | |
| CN107303484B (en) | A kind of preparation method and hydrotreating catalyst of siliceous macropore alumina supporter | |
| CN103785400B (en) | A kind of preparation method of high activity residuum hydrogenating and metal-eliminating catalyst | |
| CN106140187B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN105709711B (en) | A kind of preparation method of alumina support | |
| CN106140182B (en) | A kind of preparation method of heavy oil hydrogenating treatment catalyst | |
| CN106140181B (en) | A kind of preparation method of siliceous Hydrodemetalation catalyst | |
| CN103785401B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
| CN102861615B (en) | Preparation method of macroporous alumina carrier | |
| CN105582951B (en) | A kind of preparation method of alkaline including earth metal Hydrodemetalation catalyst | |
| CN109420483A (en) | One kind alumina supporter containing char combustion and preparation method thereof | |
| CN104549328A (en) | Method for preparing residual oil hydro-demetallization catalyst | |
| CN107304062B (en) | A kind of preparation method of alumina support | |
| CN107303491B (en) | The preparation method of Hydrodemetalation catalyst | |
| CN107303492B (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN103785396A (en) | Preparation method of hydrodemetalization catalyst for heavy oil | |
| CN105709765B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
| CN107303509B (en) | A kind of preparation method of carbon containing macropore alumina supporter | |
| CN102861588B (en) | Residual oil hydrogenation demetalization catalyst and preparation method thereof | |
| CN106140122A (en) | A kind of preparation method of boracic Hydrodemetalation catalyst | |
| CN109277108A (en) | Siliceous Hydrodemetalation catalyst and its preparation method and application | |
| CN107303510B (en) | A kind of preparation method of carbon containing alumina support | |
| CN106140183B (en) | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium | |
| CN105618072A (en) | Method for preparing hydrodemetalization catalyst |
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 |