CN104556164A - Macroporous alumina and preparation method thereof - Google Patents
Macroporous alumina and preparation method thereof Download PDFInfo
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- CN104556164A CN104556164A CN201310502495.3A CN201310502495A CN104556164A CN 104556164 A CN104556164 A CN 104556164A CN 201310502495 A CN201310502495 A CN 201310502495A CN 104556164 A CN104556164 A CN 104556164A
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Abstract
The invention discloses a preparation method of a macroporous alumina carrier. The method comprises the following steps: (1) preparing a solution containing grease and organic acid, an acidic aluminum solution and a basic aluminate solution, and respectively marking into a solution A, a solution B and a solution C; (2) combining the solution B and the solution C to perform gelation reaction, regulating pH to be 9.0 to 11.0, wherein the pH is preferably is 9.5 to 10.5; controlling the reaction temperature to be 60 to 95 DEG C, wherein the reaction temperature is preferably 75 to 85 DEG C; performing ageing, filtering, washing and drying after the gelation reaction, wherein the solution A is added before or during gelation; the solution A, the solution B and the solution C are preferably combined to perform the gelation reaction; (3) forming the material obtained in step (2), and then drying and roasting to obtain the macroporous alumina carrier, The macroporous alumina carrier prepared by the method has the advantages of being large in aperture, large in pore volume and high in strength.
Description
Technical field
The present invention relates to a kind of macroporous aluminium oxide and preparation method thereof, specifically relate to a kind of macropore alumina supporter for weight, residual hydrogenation and preparation method thereof, alumina support of especially HDM or hydrogenation protecting agent and preparation method thereof.
Background technology
Along with crude oil, heaviness and in poor quality and market are to the continuous increase of light-end products demand increasingly, and legislations of environmental protection increasingly stringent, residual oil weight-lightening technology just becomes one of important topic of world today's PETROLEUM PROCESSING industry.Due to containing macromolecular compounds such as a large amount of resin and asphalts in residual oil, so require that residual oil hydrocatalyst must have larger duct to ensure that these macromolecular compounds enter catalytic inner and participate in reaction.Prepare wide-aperture residual oil hydrocatalyst and depend primarily on carrier, especially adopt hydrogenation catalyst prepared by infusion process.Carrier wherein used mainly macroporous aluminium oxide, preparing macroporous aluminium oxide needs reaming just can meet the demands usually.
Aluminium oxide has a lot of type, as γ-Al
2o
3, η-Al
2o
3, θ-Al
2o
3, δ-Al
2o
3with α-Al
2o
3deng, wherein γ-Al
2o
3with η-Al
2o
3for conventional activated alumina.
Activated alumina has good specific area and pore structure, particularly γ-Al
2o
3owing to having the character that specific area is large, pore structure can be in harmonious proportion Heat stability is good, be therefore widely used as the catalyst carrier in oil refining, petrochemical industry and chemical fertilizer industry and drier, adsorbent etc.Preparation γ-Al
2o
3usual method be first produce boehmite, then roasting is at a certain temperature converted into γ-Al
2o
3.Boehmite industrially generally has three kinds of preparation methods: Alchlor process, aluminum sulfate method, carbonizatin method.General industry adopts the more of aluminum sulfate method and carbonizatin method.
CN1164563A discloses a kind of method that swing method prepares alumina support.The method is that acid solution and alkaline solution alternately add in reactor, makes pH value by acid to alkaline, then by after alkali to sour alternately change 2 ~ 7 times, fully reacts 10 ~ 120 minutes, then wash 3 ~ 6 times to remove sulfate radical or sodium ion with weak aqua ammonia.The aluminium oxide aperture of this swing method gained concentrates on 4 ~ 10nm, and aperture is too little, is not suitable for the carrier being used as the large aperture catalyst such as HDM.
CN1184078A discloses a kind of preparation method of alumina support.The method adopt and flow plastic generate aluminium hydroxide as crystal seed, then pH value swing method is utilized to obtain the aluminium oxide of pore distribution concentration, wherein by changing preparation condition, the pore volume that can obtain pore diameter range 20 ~ 60nm accounts for the aluminium oxide of total pore volume more than 70%.In the alumina support of the method gained, 20 ~ 60nm is concentrated in most of hole, and the ratio shared by macropore very little, is not suitable for the carrier being used as the large aperture catalyst such as HDM.
The precursor kneading of the physics expanding agents such as the carbon black such as US4448896, US4102822, starch and activated alumina or aluminium oxide expands the aperture of alumina support, the consumption of physics expanding agent is aluminium oxide more than 10wt %, said method adds physics expanding agent in aluminium oxide precursor, and the consumption of expanding agent is large, cause the pore size distribution disperse of aluminium oxide, intensity is poor.
US4,001,144 methods disclosing the pore size distribution of a kind of modified alumina catalyst precursor, the method comprises (1) by a kind of ammonium salt aqueous solution process aluminium oxide precursor, and described ammonium salt is selected from ammonium carbonate, carbonic hydroammonium or the mixture of the two; (2) at the temperature of about 100 ~ 160 DEG C, pressurized treatments is carried out 10 ~ 24 hours by with the aluminium oxide after described ammonium salt process; (3) aluminium oxide after about 100 ~ 200 DEG C of described pressurized treatments of drying about 1 ~ 24 hour, and in 500 ~ 700 DEG C of activation; (4) alumina support is reclaimed.The pore volume of the bore dia 4.5 ~ 30nm of this carrier at least accounts for 70% of cumulative volume.From properties of product, though the pore size distribution of this modified aluminas is improved, macropore ratio is still less.
CN98119912.7 discloses a kind of preparation method of alumina support, key step is contacted with a kind of precipitant solution by a kind of solution of aluminum contained compound, obtain the slurries of aluminium hydroxide, filter, wash the filter cake obtained, dry, shaping, wherein said contact, temperature 20 ~ 55 DEG C, is carried out under the condition of pH 6 ~ 9; Also have an Aging Step before filtration, describedly agingly to carry out in the medium containing carbanion and/or bicarbonate ion and ammonium ion, aging temperature 30 ~ 80 DEG C, ageing time at least 10 minutes; The method of washing is first with containing the solution washing of carbanion at least one times, then spends deionized water.The subject matter that the above-mentioned method preparing carrier exists is: (1) washing process is comparatively complicated, increases alumina producing operating cost.(2) although increase all to some extent with the aluminium oxide aperture of the method modification and pore volume, aperture is not almost had to be greater than the hole of 100nm.
CN98100800.3 discloses a kind of preparation method of aluminium oxide, key step is at the temperature of 10 ~ 300 DEG C, with containing ammonium ion and the slurry liquid contacts at least 30 minutes being selected from carbanion, the aqueous solution of bicarbonate ion and a kind of aluminium hydroxide and water, filter, and in the aluminium oxide of 500 ~ 700 DEG C of roastings.The subject matter that the above-mentioned method preparing carrier exists is as follows: it is pulled an oar with water after levigate by dried aluminium hydroxide that the aluminium hydroxide that (1) the method is used and water are pulled an oar again, or aluminum hydroxide precipitation through washing, filter after the wet cake that obtains and water pull an oar, and then with containing ammonium ion and the aqueous solution process being selected from carbanion, bicarbonate ion, process is comparatively complicated; (2) source of this patent to aluminium hydroxide used there is no special restriction, and needs reslurry, then with ammonium carbonate or ammonium bicarbonate aqueous solution process, the reaming of the aluminium carbonate salt pair aluminium oxide produced is limited.
CN101462074A discloses a kind of alumina support and preparation method thereof.This carrier adopts a small amount of starch/or carbon black to be crystal seed, prepares the slurries of aluminium hydroxide, then uses ammonium carbonate and/or carbonic hydroammonium adjust ph, finally obtain alumina support with the method for the first also rear swing of stream.The method can prepare the alumina support had compared with large pore volume and specific area, but preparation process is loaded down with trivial details, haves much room for improvement.
Summary of the invention
For the deficiencies in the prior art, the invention provides alumina support that a kind of aperture is large, pore volume is large, intensity is good and preparation method thereof.
A preparation method for macropore alumina supporter, comprises the steps:
(1) preparation is designated as solution A, solution B, solution C respectively containing fat and organic acid solution, acid aluminium salt solution, alkali aluminate soln;
(2) solution B, solution C stream carries out plastic reaction, pH value controls 9.0 ~ 11.0, and preferably 9.5 ~ 10.5, reaction temperature controls at 60 ~ 95 DEG C, preferably 75 ~ 85 DEG C, after plastic reaction terminates, through aging, filters, washing, dry; Wherein before plastic or in plastic process, add solution A, preferred solution A and solution B, solution C are together and stream carries out plastic reaction;
(3) material of step (2) gained is through shaping, then drying and roasting obtain macropore alumina supporter.
In the inventive method, described containing in fat and organic acid solution, acid is 1:1 ~ 10:1 with the mass ratio of ester, fat and organic acid add that gross weight is alumina dry basic weight amount 10.0% ~ 30.0%, be preferably 15.0% ~ 25.0%.Mass concentration containing fat and organic acid solution is 10% ~ 60%.Described ester can be selected from tert-butyl acetoacetate, butyl-acetoacetate, ethyl acetoacetate, methyl acetoacetate, acetoacetic acid allyl ester, one or more in isopropyl acetoacetate, is preferably ethyl acetoacetate, methyl acetoacetate.Organic acid can select acetic acid, succinic acid, formic acid, propionic acid, one or more in butyric acid, is preferably acetic acid, formic acid.
In the inventive method, described acid aluminium salt is AlC1
3, Al
2(SO
4)
3with Al (NO
3)
3in one or more, be preferably Al
2(SO
4)
3solution, the concentration of described acid aluminium salt solution is 2 ~ 10 g A1
2o
3/ 100ml.Described basic aluminate is NaAlO
2and/or KAlO
2, the concentration of described alkali aluminate soln is 8 ~ 30g A1
2o
3/ 100ml.
In the inventive method, can add one or more in silicate, borate and phosphate as required in the acid aluminium salt solution of step (2), its addition is with SiO
2, P
2o
5and/or B
2o
3meter accounts for 0.1 wt% ~ 5.0 wt% of carrying alumina body weight.Described silicate solutions is preferably sodium silicate solution, and borate solution is preferably dobell's solution, and phosphate solution is preferably ammonium phosphate solution.
In the inventive method, step (2) the plastic reaction time is 30 minutes ~ 90 minutes, is preferably 40 minutes ~ 60 minutes.Described aging condition is as follows: aging temperature is 60 ~ 95 DEG C, is preferably 75 ~ 85 DEG C.Ageing time is 0.5 ~ 5 hour, preferably 1.0 ~ 3.0 hours.Described drying condition is: drying 3 ~ 10 hours at 50 ~ 140 DEG C.
In the inventive method, the drying condition described in step (3) is: drying 3 ~ 10 hours at 50 ~ 140 DEG C; Described roasting condition is: roasting 2 ~ 10 hours at 600 ~ 800 DEG C.
Carrying alumina volume property prepared by the inventive method is as follows: specific surface is 100 ~ 170m
2/ g, pore volume 0. 60 ~ 1.50mL/g, preferred specific surface is 110 ~ 160m
2/ g, pore volume 0.90 ~ 1.45mL/g, most probable pore size 15 ~ 25nm, preferably 17 ~ 23nm, side pressure strength is 10 ~ 20N/mm; There is following pore size distribution: bore dia is that the pore volume in the hole being less than 6nm accounts for total pore volume less than 6%, preferably 4 below %, and the pore volume in the hole of bore dia 6 ~ 30nm accounts for 20% ~ 40% of total pore volume, preferably 25% ~ 35%; The pore volume in the hole of bore dia 30 ~ 100nm accounts for 40% ~ 80 % of total pore volume, is preferably 45% ~ 70%; The pore volume in the hole of 100 ~ 1000nm accounts for 1% ~ 15 % of total pore volume, and preferably 1% ~ 10%.
The invention has the advantages that the alumina support of preparation not only has larger aperture, pore volume, the pore size distribution of comparatively concentrating, can keep high strength again.The residual oil hydrocatalyst prepared with it can reduce the macromolecular compound diffusion restrictions in the catalyst such as the resin and asphalt in residual oil, improves the hydrogenation reaction activity and selectivity of catalyst.
In the present invention, adopt aluminum sulfate legal system for aluminium oxide, fat and organic acid is introduced in plastic process, growing up and nucleation process of effective adjustment alumina grain, inhibit the agglomeration of crystal grain, high-ratio surface can be prepared, aluminium oxide that large pore volume, pore-size distribution are concentrated, overcome in alumina preparation process, make the pore size distribution disperse of carrier and the poor shortcoming of intensity in the past owing to adding a large amount of starch and/or carbon black.
Alumina support of the present invention can be used as carrier of hydrogenating catalyst, is specially adapted to the carrier of catalyst for hydrotreatment of residual oil.
Detailed description of the invention
In wood invention, catalyst specific surface and pore structure adopt the test of low temperature liquid nitrogen absorption method.Catalyst strength is the side pressure strength that the ZQJ-II Intelligent testing machine for particle adopting Dalian device diagnostic device factory to produce measures.
The preparation method of alumina support of the present invention, further illustrates by following examples, but these embodiments can not limit the present invention.Wt% is mass fraction.
EXAMPLE l
By the 1L sodium metaaluminate aqueous solution (A1
2o
3concentration is 25g/100ml) and the aqueous solution (A1 of 2L aluminum sulfate
2o
3concentration is 3g/ 100ml) and association complex solution 200mL (wherein, containing ethyl acetoacetate 12 grams, acetic acid 60 grams) be respectively charged in the container of high level, lower even flowmeter flows into and is equipped with in the belt stirrer of 200mL water purification and the stainless steel reactor of heating jacket, the aqueous solution of the sodium metaaluminate aqueous solution and aluminum sulfate and the association complex aqueous solution stream adds reactor carries out plastic reaction, system temperature 80 DEG C, pH value controls 9.0.React after 45 minutes and stop.Temperature to be 80 DEG C and pH value be 9.0 times aging 1.5 hours.Filter, washing.At 140 DEG C of temperature dry 3 hours, shaping, then at 140 DEG C of temperature dry 3 hours, 800 DEG C of constant temperature calcinings 4 hours, obtain sample 1.
Embodiment 2
By the 1L sodium metaaluminate aqueous solution (A1
2o
3concentration is 20g/100ml) and the aqueous solution (A1 of 1.5L aluminum sulfate
2o
3concentration is 5g/ 100ml) and association complex solution 200mL (wherein, containing methyl acetoacetate 11 grams, acetic acid 44 grams) be respectively charged in the container of high level, lower even flowmeter flows into and is equipped with in the belt stirrer of 200mL water purification and the stainless steel reactor of heating jacket, the sodium metaaluminate aqueous solution and aluminum sulfate aqueous solution and the association complex aqueous solution stream adds reactor carries out plastic reaction, system temperature 85 DEG C, pH value controls 9.5.React after 45 minutes and stop.Temperature to be 85 DEG C and pH value be 9.0 times aging 2.0 hours.Filter, washing.At 130 DEG C of temperature dry 4 hours, shaping, then at 130 DEG C of temperature dry 4 hours, 780 DEG C of constant temperature calcinings 6 hours, obtain sample 2.
Embodiment 3
By the 1.5L sodium metaaluminate aqueous solution (A1
2o
3concentration is 20g/100ml), 2.0L aluminum sulfate aqueous solution (A1
2o
3concentration is 5g/100ml) and composite chelate agent solution 200mL is (wherein, containing butyl-acetoacetate 10 grams, 70 grams, formic acid) be respectively charged in the container of high level, the band flowmeter of 200mL water purification and the stainless steel reactor of agitator and heating jacket are equipped with in lower company, the aqueous solution of the sodium metaaluminate aqueous solution, aluminum sulfate and the association complex aqueous solution stream adds reactor carries out plastic reaction, system temperature 75 DEG C, pH value controls 10.0.React after 45 minutes and stop.Temperature to be 75 DEG C and pH value be 10.0 times aging 2.0 hours.Filter, washing.At 120 DEG C of temperature dry 5 hours, shaping, then at 120 DEG C of temperature dry 5 hours, 700 DEG C of constant temperature calcinings 8.0 hours, obtain sample 3.
Embodiment 4
By the 1.5L sodium metaaluminate aqueous solution (A1
2o
3concentration is 20g/100ml), the aqueous solution (A1 of 2.0L aluminum sulfate
2o
3concentration is 5g/ 100ml) and 200mL water purification (wherein containing association complex 60 grams, ethyl acetoacetate: 10 grams, formic acid: 50 grams), be respectively charged in the container of high level, the lower flowmeter that connects flows in the stainless steel reactor of belt stirrer and heating jacket, the aqueous solution of the sodium metaaluminate aqueous solution, aluminum sulfate and Gemini surface active agent solution stream adds reactor carries out plastic reaction, system temperature 85 DEG C, pH value controls 10.5.React after 45 minutes and stop.Temperature to be 85 DEG C and pH value be 10.5 times aging 2.0 hours.Filter, washing.At 110 DEG C of temperature dry 5 hours, shaping, then at 110 DEG C of temperature dry 5 hours, 750 DEG C of constant temperature calcinings 7.0 hours, obtain sample 4.
Comparative example 1
By the 1L sodium metaaluminate aqueous solution (A1
2o
3concentration is 25g/100ml) and the aqueous solution (A1 of 2L aluminum sulfate
2o
3concentration is 3g/100ml) be respectively charged in the container of high level, lower even flowmeter flows into and is equipped with in the belt stirrer of 200mL water purification (wherein containing acetic acid 72 grams) and the stainless steel reactor of heating jacket, the aqueous solution of the sodium metaaluminate aqueous solution and aluminum sulfate stream adds reactor carries out plastic reaction, system temperature 80 DEG C, pH value controls 9.0.React after 45 minutes and stop.Temperature to be 80 DEG C and pH value be 9.0 times aging 1.5 hours.Filter, washing.At 140 DEG C of temperature dry 3 hours, shaping, then at 140 DEG C of temperature dry 3 hours, 800 DEG C of constant temperature calcinings 4 hours, obtain sample 5.
The physical property data of embodiment and comparative example 1 ~ 5 gained sample is in table 1.
The physical property of table 1 alumina support
As can be seen from the above results, the carrier aperture prepared by the inventive method and pore volume are all greater than carrier prepared by comparative example, and carrier prepared by the inventive method still keeps higher side pressure strength.Illustrate that the alumina support prepared by the inventive method can meet the requirement of mink cell focus especially residuum hydrogenating and metal-eliminating or hydrogenation protecting agent carrier well.
Claims (14)
1. a preparation method for macropore alumina supporter, is characterized in that: comprise the steps:
(1) preparation is designated as solution A, solution B, solution C respectively containing fat and organic acid solution, acid aluminium salt solution, alkali aluminate soln;
(2) solution B, solution C stream carries out plastic reaction, pH value controls 9.0 ~ 11.0, and preferably 9.5 ~ 10.5, reaction temperature controls at 60 ~ 95 DEG C, preferably 75 ~ 85 DEG C, after plastic reaction terminates, through aging, filters, washing, dry; Wherein before plastic or in plastic process, add solution A, preferred solution A and solution B, solution C are together and stream carries out plastic reaction;
(3) material of step (2) gained is through shaping, then drying and roasting obtain macropore alumina supporter.
2. method according to claim 1, is characterized in that: in step (2), pH value controls 9.5 ~ 10.5, and reaction temperature controls at 75 ~ 85 DEG C.
3. method according to claim 1, is characterized in that: in step (2) solution A and solution B, solution C together also stream carry out plastic reaction.
4. method according to claim 1, it is characterized in that: described contains in fat and organic acid solution, acid is 1:1 ~ 10:1 with the mass ratio of ester, fat and organic acid add that gross weight is alumina dry basic weight amount 10.0% ~ 30.0%, the mass concentration containing fat and organic acid solution is 10% ~ 60%.
5. method according to claim 1, it is characterized in that: ester is selected from tert-butyl acetoacetate, butyl-acetoacetate, ethyl acetoacetate, methyl acetoacetate, acetoacetic acid allyl ester, one or more in isopropyl acetoacetate, acetic acid selected by organic acid, succinic acid, formic acid, propionic acid, one or more in butyric acid.
6. method according to claim 5, is characterized in that: fat is for being ethyl acetoacetate, and methyl acetoacetate, acid is acetic acid, formic acid.
7. method according to claim 1, is characterized in that: described acid aluminium salt is AlC1
3, Al
2(SO
4)
3with Al (NO
3)
3in one or more, the concentration of acid aluminium salt solution is 2 ~ 10 g A1
2o
3/ 100ml.
8. method according to claim 1, is characterized in that: described basic aluminate is NaAlO
2and/or KAlO
2, the concentration of alkali aluminate soln is 8 ~ 30g A1
2o
3/ 100ml.
9. method according to claim 1, is characterized in that: add one or more in silicate, borate and phosphate in the acid aluminium salt solution of step (2), its addition is with SiO
2, B
2o
3and/or P
2o
5meter accounts for 0.1 wt% ~ 5.0 wt% of carrying alumina body weight.
10. method according to claim 9, is characterized in that: described silicate solutions is sodium silicate solution, and borate solution is dobell's solution, and phosphate solution is ammonium phosphate solution.
11. methods according to claim 1, is characterized in that: step (2) the plastic reaction time is 30 minutes ~ 90 minutes, and aging temperature is 60 ~ 95 DEG C, ageing time is 0.5 ~ 5 hour, and drying condition is at 50 ~ 140 DEG C dry 3 ~ 10 hours.
12. methods according to claim 1, is characterized in that: the drying condition described in step (3) is: drying 3 ~ 10 hours at 50 ~ 140 DEG C; Described roasting condition is: roasting 2 ~ 10 hours at 600 ~ 800 DEG C.
Alumina support prepared by 13. claim 1-12 either method, is characterized in that: carrier specific surface is 100 ~ 170m
2/ g, pore volume 0. 60 ~ 1.50mL/g, pore volume 0.90 ~ 1.45mL/g, most probable pore size 15 ~ 25nm, side pressure strength is 10 ~ 20N/mm; There is following pore size distribution: bore dia is that the pore volume in the hole being less than 6nm accounts for total pore volume less than 6%, and the pore volume in the hole of bore dia 6 ~ 30nm accounts for 20% ~ 40% of total pore volume; The pore volume in the hole of bore dia 30 ~ 100nm accounts for 40% ~ 80 % of total pore volume; The pore volume in the hole of 100 ~ 1000nm accounts for 1% ~ 15 % of total pore volume.
14. carriers according to claim 13, is characterized in that: carrier specific surface is 110 ~ 160m
2/ g, pore volume 0.90 ~ 1.45mL/g, most probable pore size 17 ~ 23nm; There is following pore size distribution: bore dia is that the pore volume in the hole being less than 6nm accounts for total pore volume 4 below %, and the pore volume in the hole of bore dia 6 ~ 30nm accounts for 25% ~ 35% of total pore volume; The pore volume in the hole of bore dia 30 ~ 100nm accounts for 45% ~ 70% of total pore volume; The pore volume in the hole of 100 ~ 1000nm accounts for 1% ~ 10% of total pore volume.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046309A (en) * | 2018-08-13 | 2018-12-21 | 杭州电子科技大学 | A kind of macro-pore SiO for carbon-smoke combustion2One-pot synthesis method of environmental friendly material and products thereof |
| CN111686741A (en) * | 2019-03-12 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of copper-zinc catalyst |
| CN114057213A (en) * | 2020-07-27 | 2022-02-18 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina material |
| CN114436303A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Macroporous alumina and preparation method and application thereof |
| CN115448338A (en) * | 2021-05-21 | 2022-12-09 | 中国石油化工股份有限公司 | Macroporous spherical alumina and preparation method thereof |
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| CN102259033A (en) * | 2010-05-24 | 2011-11-30 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof |
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
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| CN102259033A (en) * | 2010-05-24 | 2011-11-30 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof |
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046309A (en) * | 2018-08-13 | 2018-12-21 | 杭州电子科技大学 | A kind of macro-pore SiO for carbon-smoke combustion2One-pot synthesis method of environmental friendly material and products thereof |
| CN109046309B (en) * | 2018-08-13 | 2021-08-10 | 杭州电子科技大学 | Macroporous SiO for soot combustion2One-pot synthesis method of material and product thereof |
| CN111686741A (en) * | 2019-03-12 | 2020-09-22 | 中国石油化工股份有限公司 | Preparation method of copper-zinc catalyst |
| CN114057213A (en) * | 2020-07-27 | 2022-02-18 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina material |
| CN114057213B (en) * | 2020-07-27 | 2023-07-28 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina material |
| CN114436303A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Macroporous alumina and preparation method and application thereof |
| CN114436303B (en) * | 2020-10-19 | 2023-07-28 | 中国石油化工股份有限公司 | Macroporous alumina and preparation method and application thereof |
| CN115448338A (en) * | 2021-05-21 | 2022-12-09 | 中国石油化工股份有限公司 | Macroporous spherical alumina and preparation method thereof |
| CN115448338B (en) * | 2021-05-21 | 2024-02-20 | 中国石油化工股份有限公司 | Macroporous spherical alumina and preparation method thereof |
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| CN104556164B (en) | 2016-03-30 |
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