CN107303509B - A kind of preparation method of carbon containing macropore alumina supporter - Google Patents

A kind of preparation method of carbon containing macropore alumina supporter Download PDF

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CN107303509B
CN107303509B CN201610252529.1A CN201610252529A CN107303509B CN 107303509 B CN107303509 B CN 107303509B CN 201610252529 A CN201610252529 A CN 201610252529A CN 107303509 B CN107303509 B CN 107303509B
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alumina support
polyalcohol
acid
aqueous solution
alumina
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CN107303509A (en
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佟佳
吕振辉
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61Surface area
    • B01J35/615100-500 m2/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63Pore volume
    • B01J35/6350.5-1.0 ml/g
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64Pore diameter
    • B01J35/6472-50 nm
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66Pore distribution
    • B01J35/695Pore distribution polymodal

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a kind of preparation methods of carbon containing macropore alumina supporter, including following content: (1) being mixed with beating boehmite and deionized water, the mixed acid solution of appropriate organic acid and inorganic acid is added in Xiang Shangshu slurries, be heated to reflux processing;(2) appropriate urea is added and carries out hydro-thermal process, then washed, dry, treated boehmite obtains alumina support through molding, drying and roasting;(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;(4) alumina support after step (3) dipping is subjected to hydro-thermal charing process, then dries, obtains carbon containing macropore alumina supporter.The alumina support of this method preparation has large hole appearance and aperture, carbon content are radially in uneven distribution in carrier, which is suitable for the fields such as preparation weight, residuum hydrogenating and metal-eliminating catalyst.

Description

A kind of preparation method of carbon containing macropore alumina supporter
Technical field
The present invention relates to a kind of preparation methods of alumina support, relate in particular to a kind of with large hole appearance, aperture Carbon containing alumina support preparation method.
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.The pore structure of catalyst is determined that therefore, preparation has by the carrier for constituting catalyst Large hole is held and the carrier of larger bore dia is to prepare residual oil, especially prepare and add for the higher decompression residuum of tenor The key of hydrogen catalyst for demetalation.In addition, active metal component is easy and aluminium oxide after load active component in roasting process Carrier has an effect to form very strong M-O-Al key, causes active component to form Spinel and lose activity, or make activity 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 is proposed using carbon black as expanding agent.Expanding agent is uniformly mixed with boehmite dry glue powder, to Aqueous solution of nitric acid kneading 30 minutes that mass fraction is 4.3% are added in said mixture, it is 2.1% that mass fraction, which is then added, Ammonia spirit kneading 25 minutes, kneading uniformly after extruded moulding, carrier after molding, which is fired, is made final alumina support.Its The additional amount of middle carbon black powder is preferably greater than the 20% of activated alumina or its precursor weight.
CN102441436A discloses a kind of preparation method of alumina support.This method prepares the step of alumina support such as Under: (1) boehmite dry glue powder and extrusion aid be uniformly mixed, and is then added and has dissolved physics expanding agent and chemical enlargement agent Aqueous solution;(2) step (1) resulting material is uniformly mixed, the extruded moulding on banded extruder;(3) step (2) resulting material is dry Final alumina support is made in dry, roasting.
In conclusion usually using physics expanding agent and chemical enlargement during prior art preparation macropore alumina supporter Agent improves the aperture of carrier, and the addition of expanding agent can be such that alumina support macropore content increases really.But physics reaming is added Often the intensity of carrier is impacted when agent.In addition, between the alumina support and active component of prior art preparation mutually Effect remains to be further improved.
Summary of the invention
Aiming at the shortcomings of the prior art, the present invention provides a kind of preparation method of carbon containing macropore alumina supporter, this method The alumina support of preparation has large hole appearance and aperture, carbon content are radially in uneven distribution in carrier, which is suitable for Prepare the fields such as weight, residuum hydrogenating and metal-eliminating catalyst.
The preparation method of carbon containing macropore alumina supporter of the invention, including following content:
(1) boehmite and deionized water are mixed with beating, appropriate organic acid and inorganic acid is added in Xiang Shangshu slurries Mixed acid solution, control slurries pH value be 2-5, carry out being heated to reflux processing;(2) appropriate urea is added in Xiang Shangshu slurries Carry out hydro-thermal process, the slurries after hydro-thermal process are washed, dry, treated boehmite through molding, drying and roasting, Obtain alumina support;(3) prepare at least two various concentrations polyalcohol and/or monosaccharide aqueous solution, according to concentration by height to Low sequence sprays on the alumina support that step (2) obtains, so that the concentration of polyalcohol and/or monosaccharide is formed on carrier Ecto-entad is in gradient distribution from low to high;(4) alumina support after step (3) dipping is subjected to water in sealing container Hot charing process, is then dried, and obtains carbon containing macropore alumina supporter.
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 (2) 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 (2) 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 (2) is 100-120 DEG C, and drying time is 6-10 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 (4) 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, drying condition described in step (4) are as follows: drying temperature is 80-120 DEG C, drying time 2- 10 hours.
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:
NH4Al(OH)2CO3Gas is generated when roasting can play good reaming effect.Be added borate when borate with Double hydrolysis occur for aluminium salt, form boron-aluminium-oxygen composite oxide, compared with infusion process and kneading method introduce boron, more effectively The modulation pore structure and surface nature of carrier.
When the polyalcohol and/or monosaccharide aqueous solution of shaping carrier various concentration spray dipping, polyalcohol and/or monosaccharide Concentration, in distribution is incremented by, is carbonized by carrier surface to center by hydro-thermal, and gradient point is formed on carrier surface and duct inner wall The relatively thin internal carbon-coating of carbon-coating is thicker outside the carbon-coating of cloth, i.e. carrier.Since the presence of carbon-coating effectively prevents metal component and carries Strong interaction between body, the gradient distribution of carbon layers having thicknesses act between active metal and carrier and gradually weakening from outside to inside, I.e. catalyst activity is gradually increased from outside to inside, during hydrodemetallization, promotes the reaction inside catalyst duct, has Effect is avoided makes demetalization reaction acutely catalyst duct be caused to block and make to urge since outer surface active component activity is higher The phenomenon that agent inactivates, extends the service life of catalyst while improving catalyst activity.
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 carrier 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 be vacuum-treated 3 at 300 DEG C ~ 4 hours, finally product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test.Wherein surface area according to BET equation obtains, and pore-size distribution and pore volume are obtained according to BJH model.
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.Treated boehmite and 8g Sesbania powder is sufficiently mixed, and is added uniform dissolved with the aqueous solution kneading of 4g acetic acid in right amount in Xiang Shangshu material, is extruded into cylindrical bars.Molding Wet stock afterwards is 8 hours dry in 110 DEG C, 600 DEG C of roastings, 8 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 It is 3 hours dry at DEG C, oxidation carrier S1 is made, support 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.Alumina support is clover bar shaped, for the first time when spray dipping With the aqueous solution for the sorbierite that 30ml mass concentration is 30%, the sorb that second of spray is 10% with 50ml mass concentration when impregnating The aqueous solution of alcohol, the aqueous solution for the sorbierite that when third time spray dipping is 5% with 20ml mass concentration, temperature when charing process It is 200 DEG C, carbonization time is 8 hours, and alumina support S2 is made, and the property of carrier 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 alumina support S3 is made, and the property of carrier 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.Using spraying twice Leaching dipping, the aqueous solution for the arabite for being for the first time 40% with 50ml mass concentration when spray dipping, second of spray dipping When with 55ml mass concentration be 20% arabite aqueous solution, carbonization temperature be 250 DEG C, carbonization time be 6 hours, system Alumina support S4 is obtained, the property of carrier is shown in Table 1.
Embodiment 5
With embodiment 1, alumina support is bunge bedstraw herb bar shaped, xylitol change into the xylitol that mass ratio is 1:1:1:1, Ah Draw the mixing alcohol solution dipping of primary sugar alcohol, sorbierite and mannitol, temperature is 220 DEG C when charing process, and the processing time is 10 Hour, alumina support S5 is made, the property of carrier is shown in Table 1.
Comparative example 1
With embodiment 1, only the unmixed acid processing of boehmite and urea liquid seal hydro-thermal process, and oxidation is made The property of alumina supporter S6, carrier are shown in Table 1.
Comparative example 2
With embodiment 1, only not instead of repeatedly spray is not impregnated into alumina support xylitol, by same amount of xylose Alcohol is impregnated into alumina support in such a way that primary spray impregnates, and alumina support S7 is made, and the property of carrier is shown in Table 1.
Comparative example 3
With embodiment 1, only the unmixed acid processing of boehmite, is made alumina support S8, the property of carrier is shown in Table 1.
1 carrying alumina volume property of table
Pore size distribution refers to that the Kong Rong of certain diameter range inner hole in carrier accounts for the percentage of total pore volume.
Table 1 the result shows that, the carbon containing macropore alumina supporter prepared using the method for the present invention is same with larger aperture When have biggish Kong Rong, the pore size distribution of concentration, carbon content is radially in uneven distribution in alumina support.This method preparation Alumina support is suitable for weight, residuum hydrogenating and metal-eliminating field.
Embodiment 6
The present embodiment prepares Hydrodemetalation catalyst using aluminium oxide obtained by above-mentioned embodiment and comparative example as carrier.
Each 100 grams of alumina support prepared by embodiment 1-5 and comparative example 1-3 are weighed, 150mlMo-Ni-NH is added3 Solution (contains MoO312.0wt%, NiO3.0 wt%) dipping 2 hours, redundant solution is filtered off, 120 DEG C dry, then in 550 DEG C of temperature It is roasted 5 hours in lower nitrogen atmosphere, obtains Hydrodemetalation catalyst C1-C7.
Embodiment 7
The following examples illustrate by carrier of aluminium oxide of the present invention and comparative example aluminium oxide is prepared by carrier plus hydrogen is de- The catalytic performance of metallic catalyst.
Using feedstock oil listed by table 2 as raw material, the catalysis of catalyst C1-C7 is evaluated on 200 milliliters of hydrogenation reaction device Performance, catalyst are long 2 ~ 3 millimeters of item, and catalyst loading is 100 milliliters, and reaction temperature is 380 DEG C, hydrogen partial pressure 14MPa, Liquid hourly space velocity (LHSV) is 1.0 hours-1, hydrogen to oil volume ratio 1000, measurement generates the content of each impurity in oil, meter after reaction 300 hours Removal efficiency is calculated, evaluation result is shown in Table 3.
2 raw material oil nature of table
3 catalyst hydrogenation performance comparison of table
It can be seen from 3 data of table compared with comparing alumina support, the catalysis that is prepared using aluminium oxide of the present invention as carrier Agent hydrodemetallization activity with higher.

Claims (6)

1. a kind of preparation method of carbon containing macropore alumina supporter, it is characterised in that including following content: (1) by boehmite It is mixed with beating with deionized water, the mixed acid solution of organic acid and inorganic acid is added in Xiang Shangshu slurries, controls the pH value of slurries For 2-5, carry out being heated to reflux processing;(2) urea is added in Xiang Shangshu slurries and carries out hydro-thermal process, the slurries warp after hydro-thermal process Washing, dry, the boehmite that obtains that treated, treated boehmite is aoxidized through molding, drying and roasting Alumina supporter;(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 the alumina support that step (2) obtains, so that the concentration of polyalcohol and/or monosaccharide forms ecto-entad on carrier In gradient distribution from low to high;(4) alumina support after step (3) dipping is carried out at hydro-thermal charing in sealing container Reason, then dries, obtains carbon containing macropore alumina supporter;Organic acid described in step (1) is in acetic acid, oxalic acid or citric acid One or more mixing, the inorganic acid are the mixing of one or more of sulfuric acid, nitric acid or hydrochloric acid;In mixed acid solution The mass ratio of the material of organic acid and inorganic acid is 1:3-1:6, and the concentration of the mixed acid solution is calculated as 3-6mol/L with inorganic acid; Step (1) treatment temperature that is heated to reflux is 30-60 DEG C, and being heated to reflux the time is 1-5 hours;Hydro-thermal described in step (2) Processing is the heat treatment under the self-generated pressure of autoclave, and treatment temperature is 120-160 DEG C, and the processing time is 4-8 hours; Polyalcohol described in step (3) is one or more of xylitol, sorbierite, mannitol or arabite;The monosaccharide For one or more of glucose, ribose or fructose;The mass concentration of the polyalcohol and/or monosaccharide aqueous solution is 5%- 50%;Described in step (3) according to concentration from high to low spray sequence, adjacent polyalcohol twice and/or monosaccharide aqueous solution it is dense Degree difference is 5%-30%;Hydro-thermal charing process temperature described in step (4) is 180-250 DEG C, and hydrothermal conditions are 6-12 hours, Hydro-thermal process pressure is self-generated pressure.
2. according to the method for claim 1, it is characterised in that: amount of urea described in step (2) and boehmite Mass ratio is 1:5-1:10.
3. according to the method for claim 1, it is characterised in that: borate is added while urea is added in step (2), institute The borate stated is the mixing of one or more of metaborate, ortho-borate and multi-borate, and the additional amount of borate is with oxygen The mass ratio for changing boron meter and boehmite is 0.5:100-1.5:100.
4. according to the method for claim 1, it is characterised in that: the maceration extract dosage sprayed every time described in step (3) is The 10%-60% of alumina support saturated water adsorptive value, the total dosage of the maceration extract repeatedly sprayed are the saturated water adsorptive value of alumina support To ensure alumina support saturation dipping.
5. according to the method for claim 1, it is characterised in that: step (3) prepare 3 kinds of various concentrations polyalcohol and/or Monosaccharide aqueous solution is sprayed, and detailed process is as follows: being sprayed for the first time, the mass concentration of polyalcohol and/or monosaccharide aqueous solution is The dosage of 30%-50%, polyalcohol and/or monosaccharide aqueous solution is the 20%-30% of alumina support water absorption;It sprays for the second time, it is more The mass concentration of first alcohol and/or monosaccharide aqueous solution is 10%-30%, and the dosage of polyalcohol and/or monosaccharide aqueous solution is carrying alumina The 40%-60% of body water absorption;Third time sprays, and the mass concentration of polyalcohol and/or monosaccharide aqueous solution is 5%-10%, polyalcohol And/or the dosage of monosaccharide aqueous solution is the 10%-40% of alumina support water absorption.
6. 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.
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CN101066530A (en) * 2006-05-22 2007-11-07 林方 Hydrodemetalizing catalyst and its prepn
CN102861590A (en) * 2011-07-07 2013-01-09 中国石油化工股份有限公司 Hydrodemetallization catalyst and preparation method thereof
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