CN107303491A - The preparation method of Hydrodemetalation catalyst - Google Patents
The preparation method of Hydrodemetalation catalyst Download PDFInfo
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- CN107303491A CN107303491A CN201610252535.7A CN201610252535A CN107303491A CN 107303491 A CN107303491 A CN 107303491A CN 201610252535 A CN201610252535 A CN 201610252535A CN 107303491 A CN107303491 A CN 107303491A
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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
- 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
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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Abstract
The invention discloses a kind of preparation method of Hydrodemetalation catalyst, including following content：（1）Boehmite is mixed into mashing with deionized water, the mixed acid solution of organic acid and inorganic acid is added into above-mentioned slurries, progress is heated to reflux processing；Urea is added into above-mentioned slurries and carries out hydro-thermal process；（2）With the aqueous solution impregnation steps containing polyalcohol and/or glucide（1）Obtained boehmite dry glue powder, carries out hydro-thermal charing process；（3）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed according to the order of concentration from high to low in step（2）On obtained alumina support, the alumina support after dipping carries out hydro-thermal charing process；（4）Hydrogenation active component is loaded to product is made on carrier.Hydrodemetalation catalyst prepared by this method has suitable pore structure, and active component and carrier effect is moderate, has higher metal removal activity and activity stability in weight, residual hydrogenation reaction.
Description
Technical field
The present invention relates to a kind of preparation method of Hydrodemetalation catalyst.
Background technology
At present, in the production process of mink cell focus HDM, because feedstock oil contains a certain amount of vanadium, sulphur, arsenic, nickel
Deng impurity, deposition is easily formed, so that the duct of blocking catalyst, causes catalyst activity to decline rapidly, in addition inactivation, influence
Commercial Application.Catalyst with larger pore volume and larger bore dia holds metal and holds coke formation by force, can slow down catalyst
The service cycle for inactivating, making catalyst extends.After load active component in roasting process, active metal component easily with oxidation
Alumina supporter has an effect to form very strong M-O-Al keys, causes active component formation Spinel and loses activity, or makes work
Property component can not complete cure so as 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 boehmite dry glue powder to be mixed with water or the aqueous solution,
Plastic is kneaded into, obtained plastic is extruded into bar on banded extruder, dries and is calcined and obtain product, is characterized in,
Carbon powder is additionally added in above process as physics expanding agent and can occur chemical action with boehmite or aluminum oxide
The chemical enlargement agent of phosphorous, silicon or boron compound.Wherein carbon powder consumption is 3-10 weights %（On the basis of the weight of aluminum oxide）.
Obtained alumina support can be used for preparing mink cell focus particularly residuum hydrogenating and metal-eliminating and/or Hydrobon catalyst.
US4448896 discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, proposes to be used as expansion using carbon black
Hole agent.Expanding agent is well 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 is 2.1% ammonia spirit kneading 25 minutes, extrusion after kneading is uniform then to add mass fraction
Shaping, the fired obtained final alumina support of carrier after shaping.The addition of wherein carbon 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 races 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 that in boehmite kneading process, it is 30 microns of carbon powder as physics to add granular size
Expanding agent and chemical enlargement agent that can be with boehmite or aluminum oxide generation the phosphorous of chemical action, silicon or boron compound, are mixed
Compound kneading is dried, roasting is made carrier, then is loaded to active component with spraying impregnation method into plastic, extruded moulding
On carrier, catalyst is made through drying, roasting.
In summary, prior art generally makes during preparing 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 contain alumina support macropore really
Amount increase.But, need to be by kneadings such as boehmite dry glue powder, extrusion aid, peptizing agents into plastic in alumina support forming process
Body, then extruded moulding, collapses because the presence of the larger pressure of extrusion process can make the macropore of alumina powder itself occur part
Collapse, so that the pore volume and macropore content of final carrier are substantially reduced.In addition, the interaction of active component and carrier need into
One step improves.
The content of the invention
For existing technical deficiency, 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 has higher HDM active and activity stability.
The preparation method of the Hydrodemetalation catalyst of the present invention, including following content：
（1）Boehmite is mixed into mashing with deionized water, the mixed acid of organic acid and inorganic acid is added into above-mentioned slurries
Solution, the pH value for controlling slurries is 2-5, and progress is heated to reflux processing；Urea is added into above-mentioned slurries and carries out hydro-thermal process, water
Slurries after heat treatment are scrubbed, dry；
（2）With the aqueous solution impregnation steps containing polyalcohol and/or glucide（1）Obtained boehmite dry glue powder, dipping
Material afterwards carries out hydro-thermal charing process, and the material forming after processing is dried, is calcined；
（3）The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed according to the order of concentration from high to low
In step（2）On alumina support so that the concentration of polyalcohol and/or monose forms ecto-entad in from low to high on carrier
Gradient distribution, the alumina support after dipping carries out hydro-thermal charing process in sealing container, and carbon containing oxygen is made in drying process
Change alumina supporter；
（4）With hydrogenation active component maceration extract impregnation steps（3）Hydrodemetallisation catalyst is made through drying, roasting in carrier, material
Agent.
In the inventive method, step（1）Described mixing pulping process is carried out using this area conventional method, intends thin water aluminium
Stone and the mass ratio of deionized water are preferably 1:3-1:10.Described organic acid be acetic acid, oxalic acid or citric acid in one kind or
Several mixing, described inorganic acid is one or more of mixing in sulfuric acid, nitric acid or hydrochloric acid；Organic acid in mixed acid solution
Amount ratio with the material of inorganic acid is 1:3-1:6, 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, is heated to reflux the time for 1-5 hours.
In the inventive method, step（1）Described amount of urea and the mass ratio of boehmite are 1:5-1:10.Adding
Preferably while adding borate, described borate can be metaborate, ortho-borate and multi-borate while entering urea
In one or more of mixing, the addition of borate counts the mass ratio with boehmite as 0.5 using boron oxide:100-1.5:
100。
In the inventive method, step（1）Described hydro-thermal process is the heat treatment under the self-generated pressure of autoclave,
Treatment temperature is 120-160 DEG C, and processing time is 4-8 hours.
In the inventive method, step（1）Described drying temperature is 100-120 DEG C, and drying time is 6-10 hours.
In the inventive method, step（2）Described polyalcohol is in xylitol, sorbierite, mannitol or arabite
It is one or more of；Described carbohydrate is one or more of mixing in glucose, ribose or fructose etc.；Containing polyalcohol and/or sugar
The mass concentration of the aqueous solution of class material is 20%-40%.The consumption of the aqueous solution containing polyalcohol and/or glucide is that will intend thin
Diaspore dry glue powder is totally submerged；Dip time is 3-5 hours.
In the inventive method, step（2）Described hydro-thermal charing process is the heat treatment carried out in sealing device, preferably
Autoclave, can be dynamic response kettle or static reaction kettle, preferably static reaction kettle；Described hydro-thermal charing process temperature
For 120-160 DEG C, processing time is 8-16 hours.
In the inventive method, step（2）Described being molded, dry and be calcined can be carried out using this area conventional method.
In forming process, the one or more that can be added as needed in conventional shaping assistant, such as peptizing agent, extrusion aid etc..
Described peptizing agent is one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., and described extrusion aid refers to be conducive to squeezing
One or more in molded material, such as sesbania powder, carbon black, graphite powder, citric acid, the consumption of extrusion aid accounts for total material
1wt%~10wt% of butt.Described drying condition is：60-130 DEG C of drying temperature, drying time is 1-10 hours.Described
500-750 DEG C of sintering temperature is calcined, is calcined 2-10 hours.
In the inventive method, step（3）Described polyalcohol includes xylitol, sorbierite, mannitol or arabite etc.
In one or more；Described monose includes the one or more in glucose, ribose or fructose etc..
In the inventive method, step（3）Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5%-50%.
In the inventive method, step（3）It is described according to concentration from high to low spray order, adjacent polyalcohol twice
And/or the concentration difference of the monose aqueous solution is 5%-30%, preferably 10%-20%；It is preferred that prepare 2-4 kind various concentrations polyalcohol and/
Or the monose aqueous solution.
In the inventive method, step（3）The described maceration extract consumption sprayed every time is alumina support saturated water adsorptive value
10%-60%, preferably 20%-30%, the total consumption of maceration extract repeatedly sprayed for alumina support saturated water adsorptive value to ensure oxygen
Change alumina supporter saturation dipping.
In the inventive method, step（3）It is preferred that the polyalcohol and/or the monose aqueous solution of preparing 3 kinds of various concentrations are sprayed
Leaching, detailed process is as follows：Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, polyalcohol and/
Or the 20%-30% that the consumption of the monose aqueous solution is alumina support water absorption；Spray for the second time, polyalcohol and/or monose are water-soluble
The mass concentration of liquid is 10%-30%, and the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of alumina support water absorption；
Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, polyalcohol and/or the monose aqueous solution use
Measure as the 10%-40% of alumina support water absorption.
In the inventive method, step（3）Described alumina support is graininess, can be spherical, bar shaped（Including cylinder
Shape, trilobal, quatrefoil etc.）Or piece shape, preferably bar shaped or spherical, more preferably bar shaped.Also may be used in described alumina support
To add the one or more in the auxiliary elements such as Si, Ti, Zr, B or F as needed.
In the inventive method, step（3）Described hydro-thermal charing process temperature 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 ensure that polyalcohol and/or monose are carbonized completely.Wherein, self-generated pressure is relevant 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 inventive method, step（4）Described hydrogenation active component maceration extract is to constitute to calculate according to final catalyst
Prepare.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 inventive method, step（4）Described drying condition is to be dried 6-10 hours at 80-120 DEG C；The roasting
Condition is to be calcined 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 relatively low, can influence final alumina support pore volume and macropore content.
The inventive method is first handled boehmite with mixed acid solution, due to mixed acid and boehmite work
With more moderate, the halfway deficiency of amorphous phase hydrated alumina is dissolved when can both overcome exclusive use organic acid, again can be with
Avoid damaging boehmite duct when inorganic acid is used alone, by nothing while boehmite pore structure is ensured
The hydrated alumina dissolving of setting phase is removed.Aluminium salt after dissolving is retained in slurries, then is added urea into slurries and sealed water
During heat treatment, urea is decomposed into NH in high temperature environments3And CO2, NH3And CO2NH is generated in the presence of water vapour4 +With
HCO3 -Ion, NH4 +And HCO3 -Ion at high temperature under high pressure, makes boehmite crystal grain regrow and crystallization, makes plan thin
Diaspore crystal grain is grown up, and is changed the accumulation mode of crystal grain, is improved the content of macropore, while the Al of dissolving3+Occurs following reaction：
Al3++NH3.H2O Al(OH)3+NH4 +, Al (OH)3+ NH4 ++HCO3 -NH4Al(OH)2CO3, NH4Al(OH)2CO3Produced during roasting
Gas can play good reaming effect.With aluminium salt double hydrolysis, the oxidation of formation occur for borate when adding borate
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 material of formation is filled in the intercrystalline duct of boehmite, during extruded moulding, due to carbon
The presence of particle, can play good supporting role, be effectively prevented caving in for boehmite macropore, improve carrier
Pore volume and macropore content, carbon particle removes in follow-up roasting process.The polyalcohol of shaping carrier various concentrations and/or
During monose aqueous solution spray dipping, the concentration of polyalcohol and/or monose, in incremental distribution, passes through hydro-thermal by carrier surface to center
Charing, forms the carbon-coating of gradient distribution on carrier surface and duct inwall.Due to carbon-coating presence modulation metal component with
Strong interaction between carrier, promotes the reaction inside catalyst duct, is extended while catalyst activity is improved
The service life of catalyst.
Embodiment
The effect and effect of the inventive method are further illustrated with reference to embodiment, but is not limited to following implementation
Example.
Using N2Physics suction-desorption characterizes embodiment and comparative example catalyst pore structure, and concrete operations are as follows：Using
ASAP-2420 types N2Physics is inhaled-is desorbed instrument and catalyst sample pore structure is characterized.Take a small amount of sample vacuum at 300 DEG C
Processing 3 ~ 4 hours, is finally placed in liquid nitrogen cryogenics by product（-200℃）Under the conditions of carry out nitrogen suction-desorption test.Wherein surface
Product is obtained according to BET equations, and pore-size distribution and pore volume are obtained according to BJH models.
Embodiment and comparative example catalyst component are characterized using XRF, concrete operations are as follows：Using Japanese RIGAKU companies
ZSX-100e type Xray fluorescence spectrometers, performance indications：X-ray tube Be window thickness：30μm；Power：4kW；Output voltage：20-
60kV；Output current：2-150mA；2 0.0001 ° of θ angles repeatabilities；2 0.0002 ° of θ angles accuracys.
Carbon content in alumina support is determined using EPMA, concrete operations are as follows：Using JEOL's JXA-8230 electronics
Probe is measured, and the accelerating potential selected during measure is 15KV, and probe current is 8 × 10-8A, beam spot size is 3 μm.Respectively
Measure 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 are the distance of line segment between any point in alumina support cross-section center and cross section outer most edge（Essence
On be cross section radius）, then by division calculation, obtain the ratio between each content.
Embodiment 1
Weigh 200g boehmite dry glue powders（The production of Wenzhou essence crystal alumina Co., Ltd）It is placed in round-bottomed flask, to flask
It is middle to add 600 grams of deionized water mashing, appropriate nitric acid molar concentration is added into above-mentioned slurries for 3mol/L, acetic acid molar concentration
For 1mol/L mixed acid solution, the pH value for controlling slurries is 3 and is heated to reflux 3 hours in 40 DEG C.Above-mentioned slurries are transferred to height
Press in kettle, 20 grams of urea are added into mixed material and are heat-treated autoclave sealing 6 hours after 140 DEG C.It is cooled to room temperature
Mixed serum is filtered afterwards, washed, 120 DEG C of dryings, 8 hours obtained boehmites.
Weigh above-mentioned boehmite 200g to be placed in beaker, the xylose that 400mL mass concentrations are 25% is added into beaker
Alcohol solution impregnates 4 hours.Material after dipping is through filtering, and filter cake, which is transferred in autoclave, carries out charing process, processing temperature
Spend for 140 DEG C, processing time is 10 hours.Dry materials after processing are sufficiently mixed with 4g sesbania powders, are added into above-mentioned material
Enter the appropriate aqueous solution kneading dissolved with 5g acetic acid uniform, be extruded into cylindrical bars, the wet stock after shaping is dried 8 hours in 110 DEG C,
600 DEG C of roastings, 4 hours obtained alumina supports.
Weigh above-mentioned 100 grams of γ phases cylinder bar shaped alumina support to be put into spray rolling pot, under rotary state, to be atomized
Carrier of the mode into rolling pot sprays the xylose alcohol solution 25ml that impregnating effect concentration is 40%；Then it is 20% with mass concentration
Xylose alcohol solution 40ml continue spray oxide impregnation alumina supporter；Finally with the xylose alcohol solution that mass concentration is 10%
40ml continues to spray oxide impregnation alumina supporter.Dipping terminates alumina support being transferred in autoclave and autoclave is placed in into baking oven
In in charing process 9 hours under 180 DEG C, self-generated pressure, naturally cool to room temperature.Alumina support after hydro-thermal process is in 120
Dried at DEG C 3 hours and carbon containing alumina support is made.
Weigh above-mentioned 100 grams of alumina support to be placed in beaker, contain MoO with 150 milliliters310 grams, NiO1.2 grams of molybdenum-
Nickel-phosphor active metal maceration extract oxide impregnation alumina supporter 5 hours, filters the material after redundant solution, dipping and dries 6 in 120 DEG C
Hour, then be calcined 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
Be the same as Example 1, simply the addition of deionized water is 1400 grams.Mixed acid is dissolved with 4 mol sulfuric acid and 1mol oxalic acid
Mixed 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 addition of urea is 30 grams, water
Heat treatment temperature is 120 DEG C, hydro-thermal process 8 hours.The mass ratio for being 40% with mass concentration is 1:1 sorbierite and mannitol
Mixed aqueous solution dipping boehmite 3 hours.Charing process temperature is 130 DEG C, 14 hours processing times.Alumina support
For clover bar shaped, with the aqueous solution of the 30ml mass concentrations for 30% sorbierite when spray impregnates for the first time, second of spray leaching
It is for the third time 5% with 20ml mass concentrations during spray dipping with the aqueous solution of the 50ml mass concentrations for 10% sorbierite during stain
The aqueous solution of sorbierite, temperature is 200 DEG C during charing process, and carbonization time is 8 hours, and catalyst C2 is made, the catalyst
Property is shown in Table 1.
Embodiment 3
Be the same as Example 1, simply the addition of deionized water is 2000 grams.Mixed acid is dissolved with 6mol/L sulfuric acid and 1mol/L lemons
The mixed acid of acid, the pH value for controlling slurries is 5, and it is 60 DEG C, return time 1 hour to be heated to reflux temperature.Urea addition is 40
Gram, 160 DEG C of hydro-thermal process temperature, hydrothermal conditions are 4 hours.The mass ratio for being 30% with mass concentration is 1:1 glucose
Boehmite is impregnated with the mixed aqueous solution of ribose 5 hours.Charing process temperature is 120 DEG C, and the charing process time is 16 small
When.Impregnated using four sprays, for the first time with the aqueous solution of the 20ml mass concentrations for 50% mannitol, second during spray dipping
It is dense with 20ml mass during third time spray dipping with the aqueous solution of the 40ml mass concentrations for 30% sorbierite during secondary spray dipping
The aqueous solution of the sorbierite for 20% is spent, with the aqueous solution of the 20ml mass concentrations for 10% sorbierite during the 4th spray dipping.
Temperature is 240 DEG C during 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
Be the same as Example 1,3.0 grams of sodium tetraborates are added into mixed material while simply adding urea.It is 20% with mass concentration
Mass ratio be 1:1 arabite and the mixed aqueous solution of fructose impregnate boehmite 4 hours.Charing process temperature is
150 DEG C, the charing process time is 12 hours.Using spray dipping twice, it is with 50ml mass concentrations during spray dipping for the first time
The aqueous solution of 40% arabite, is for the second time the water-soluble of 20% arabite with 55ml mass concentrations during spray dipping
Liquid, carbonization temperature is 250 DEG C, and carbonization time is 6 hours, and catalyst C4 is made, and the property of the catalyst is shown in Table 1.
Embodiment 5
Be the same as Example 1, simply impregnates boehmite 5 hours with mass concentration for 35% sorbitol aqueous solution.Charing process temperature
Spend for 160 DEG C, 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,:1:1:
1 xylitol, arabite, the mixing alcohol solution dipping of sorbierite and mannitol, temperature is 220 DEG C during charing process,
Processing time is 10 hours, and catalyst C5 is made, and the property of the catalyst is shown in Table 1.
Comparative example 1
Be the same as Example 1, simply boehmite is not impregnated with xylitol and hydro-thermal process, but the xylitol of phase homogenous quantities is being carried
It is added to when body formed in the way of kneading in carrier, comparative example catalyst C6 is made, the property of catalyst is shown in Table 1.
Comparative example 2
Be the same as Example 1, the simply unmixed acid treatment of boehmite and urea liquid sealing hydro-thermal process, obtained comparative example urges
Agent C7, the property of catalyst is shown in Table 1.
Comparative example 3
With example 1, simply xylitol is not that multiple spray is impregnated into alumina support, but by same amount of xylitol with one
The mode of secondary spray dipping is impregnated into alumina support, comparative example catalyst C8 is made, the property of catalyst is shown in Table 1.
The catalyst property of table 1.
The pore volume that pore size distribution refers to the diameter range endoporus of certain in catalyst accounts for the percentage of total pore volume.
The result of table 1 shows, the carbon containing Hydrodemetalation catalyst prepared using the inventive method, with convenient hole
Structure, carbon content is in catalyst radial direction distribution gradient.Carbon containing Hydrodemetalation catalyst prepared by this method is applied to weight, slag
Oily HDM field.
Embodiment 6
The following examples illustrate the catalytic performance of catalyst and comparative example catalyst prepared by the inventive method.
Using feedstock oil listed by table 2 as raw material, C1-C8 catalytic performance is evaluated on 200 milliliters of hydrogenation reaction device, is urged
Agent is long 2 ~ 3 millimeters bar, and catalyst loading amount is 100 milliliters, and reaction temperature is 375 DEG C, and hydrogen dividing potential drop is 13MPa, liquid space-time
Speed is 1.0 hours-1, hydrogen to oil volume ratio is 1000, and reaction determines the content of each impurity in generation oil after 200 hours, calculate metal
With respect to removal efficiency, evaluation result is shown in Table 3.
The raw material oil nature of table 2.
| 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 |
The catalyst hydrogenation performance comparison of table 3.
| 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 the data of table 3 compared with comparative example, the inventive method prepare Hydrodemetalation catalyst have compared with
High HDM activity.
Activity rating is carried out to the catalyst obtained by above-described embodiment and comparative example, operation 5000h temperature rise is shown in Table 4.
The reaction temperature lift-off value of table 4
| Catalyst is numbered | Reaction temperature lift-off value after reacting 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 reacting 5000 hours, the Hydrodemetalation catalyst provided using the present invention, in order to keep
High demetallization per, required reaction temperature increase rate is far smaller than comparative catalyst, the de- gold of hydrogenation that this explanation present invention is provided
Metal catalyst has higher activity stability.
Claims (13)
1. a kind of preparation method of Hydrodemetalation catalyst, it is characterised in that including following content：（1）By boehmite with
Deionized water mixing mashing, the mixed acid solution of organic acid and inorganic acid is added into above-mentioned slurries, the pH value for controlling slurries is
2-5, progress is heated to reflux processing；Urea is added into above-mentioned slurries and carries out hydro-thermal process, the slurries after hydro-thermal process are scrubbed,
Dry；（2）With the aqueous solution impregnation steps containing polyalcohol and/or glucide（1）Obtained boehmite dry glue powder, dipping
Material afterwards carries out hydro-thermal charing process, and the material forming after processing is dried, is calcined；（3）Prepare at least two various concentrations
Polyalcohol and/or the monose aqueous solution, are sprayed in step according to the order of concentration from high to low（2）On alumina support so that many
The concentration of first alcohol and/or monose forms ecto-entad on carrier and is distributed in gradient from low to high, 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）Soaked with hydrogenation active component
Stain liquid impregnation steps（3）Hydrodemetalation catalyst is made through drying, roasting in carrier, material.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）Described organic acid is acetic acid, oxalic acid or lemon
One or more of mixing in acid, described inorganic acid is one or more of mixing in sulfuric acid, nitric acid or hydrochloric acid；Mixed acid is molten
The amount ratio of the material of organic acid and inorganic acid in liquid is 1:3-1:6, the concentration of the mixed acid solution is calculated as 3- with inorganic acid
6mol/L；The treatment temperature that is heated to reflux is heated to reflux the time for 1-5 hours for 30-60 DEG C.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described amount of urea and boehmite
Mass ratio is 1:5-1:10.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）Boric acid is added while urea is added simultaneously
Salt, described borate is one or more of mixing in metaborate, ortho-borate and multi-borate, the addition of borate
Mass ratio with boehmite is counted as 0.5 using boron oxide:100-1.5:100.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Described hydro-thermal process is in autoclave
Self-generated pressure under heat treatment, treatment temperature be 120-160 DEG C, processing time be 4-8 hours.
6. in accordance with the method for claim 1, it is characterised in that：Step（1）Described drying temperature is 100-120 DEG C, is done
The dry time is 6-10 hours.
7. in accordance with the method for claim 1, it is characterised in that：Step（2）Described polyalcohol be xylitol, sorbierite,
One or more in mannitol or arabite；Described carbohydrate is the one or more in glucose, ribose or fructose etc.
Mixing；The mass concentration of the aqueous solution containing polyalcohol and/or glucide is 20%-40%；Containing polyalcohol and/or glucide
The consumption of the aqueous solution is to be totally submerged boehmite dry glue powder；Dip time is 3-5 hours.
8. in accordance with the method for claim 1, it is characterised in that：Step（2）Described hydro-thermal charing process is in sealing dress
Put the heat treatment of interior progress；Described hydro-thermal charing process temperature is 120-160 DEG C, and processing time is 8-16 hours.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described polyalcohol be xylitol, sorbierite,
One or more in mannitol or arabite；Described monose is the one or more in glucose, ribose or fructose etc.；
Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5%-50%.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）Described the spraying from high to low according to concentration
Sequentially, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5%-30%.
11. in accordance with the method for claim 1, it is characterised in that：Step（3）Described alumina support is graininess；Institute
The one or more added in the alumina support stated in Si, Ti, Zr, B or F auxiliary element.
12. in accordance with the method for claim 1, it is characterised in that：Step（3）Described hydro-thermal charing process temperature is 180-
250 DEG C, hydrothermal conditions are 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
13. in accordance with the method for claim 1, it is characterised in that：Step（4）Described drying condition is at 80-120 DEG C
Dry 6-10 hours；The roasting condition is to be calcined 3-6 hours in nitrogen atmosphere at 400-600 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111822012A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Alumina carrier, hydrodemetallization catalyst and preparation method thereof |
| CN116116404A (en) * | 2023-04-19 | 2023-05-16 | 浙江工业大学 | Method for preparing hydrogenation catalyst by hydrothermal method and application of catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003010682A (en) * | 2001-07-02 | 2003-01-14 | Sumitomo Metal Mining Co Ltd | Hydro-demetallizing catalyst of heavy hydrocarbon oil |
| 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 |
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2016
- 2016-04-21 CN CN201610252535.7A patent/CN107303491B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003010682A (en) * | 2001-07-02 | 2003-01-14 | Sumitomo Metal Mining Co Ltd | Hydro-demetallizing catalyst of heavy hydrocarbon oil |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111822012A (en) * | 2019-04-17 | 2020-10-27 | 中国石油化工股份有限公司 | Alumina carrier, hydrodemetallization catalyst and preparation method thereof |
| 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 |
| CN116116404A (en) * | 2023-04-19 | 2023-05-16 | 浙江工业大学 | Method for preparing hydrogenation catalyst by hydrothermal method and application of catalyst |
| 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 |
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