CN104556164B - A kind of macroporous aluminium oxide and preparation method thereof - Google Patents
A kind of macroporous aluminium oxide and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of macropore alumina supporter, comprises the steps: that (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, temperature of reaction 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.Alumina supporter prepared by the method has the advantages such as aperture is large, pore volume is large, intensity is good.
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 supporter of especially hydrodemetallation (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 refining of petroleum industry.Due to containing macromolecular cpds 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 cpds enter catalytic inner and participate in reaction.Prepare wide-aperture residual oil hydrocatalyst and depend primarily on carrier, especially adopt hydrogenation catalyst prepared by pickling process.Carrier wherein used mainly macroporous aluminium oxide, preparing macroporous aluminium oxide needs reaming just can meet the demands usually.
Aluminum 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 surface area and pore structure, particularly γ-Al
2o
3owing to having the character that specific surface area is large, pore structure can be in harmonious proportion Heat stability is good, be therefore widely used as the support of the catalyst in oil refining, petrochemical complex and chemical fertilizer industry and siccative, sorbent material etc.Preparation γ-Al
2o
3usual method be first produce pseudo-boehmite, then roasting is at a certain temperature converted into γ-Al
2o
3.Pseudo-boehmite industrially generally has three kinds of preparation methods: aluminium chloride process, Tai-Ace S 150 method, carborization.General industry adopts the more of Tai-Ace S 150 method and carborization.
CN1164563A discloses a kind of method that swing method prepares alumina supporter.The method is that acidic solution and basic 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 ammonia.The aluminum 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 wide aperture catalyzer such as hydrodemetallation (HDM).
CN1184078A discloses a kind of preparation method of alumina supporter.The method adopt and flow plastic generate aluminium hydroxide as crystal seed, then pH value swing method is utilized to obtain the aluminum oxide of pore distribution concentration, wherein by changing preparation condition, the pore volume that can obtain pore diameter range 20 ~ 60nm accounts for the aluminum oxide of total pore volume more than 70%.In the alumina supporter 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 wide aperture catalyzer such as hydrodemetallation (HDM).
The precursor kneading of the physics expanding agents such as the carbon black such as US4448896, US4102822, starch and activated alumina or aluminum oxide expands the aperture of alumina supporter, the consumption of physics expanding agent is more than aluminum oxide 10wt%, aforesaid method adds physics expanding agent in aluminum oxide precursor, and the consumption of expanding agent is large, cause the pore distribution disperse of aluminum oxide, intensity is poor.
US4,001,144 methods disclosing the pore distribution of a kind of modified alumina catalyst precursor, the method comprises (1) by a kind of ammonium salt aqueous solution process aluminum oxide precursor, and described ammonium salt is selected from volatile salt, bicarbonate of ammonia or the mixture of the two; (2) at the temperature of about 100 ~ 160 DEG C, pressure treatment is carried out 10 ~ 24 hours by with the aluminum oxide after described ammonium salt process; (3) aluminum oxide after about 100 ~ 200 DEG C of described pressure treatment of drying about 1 ~ 24 hour, and in 500 ~ 700 DEG C of activation; (4) alumina supporter is reclaimed.The pore volume of the bore dia 4.5 ~ 30nm of this carrier at least accounts for 70% of cumulative volume.From product performance, though the pore distribution of this modified aluminas is improved, macropore ratio is still less.
CN98119912.7 discloses a kind of preparation method of alumina supporter, 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 pH6 ~ 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, digestion time at least 10 minutes; The method of washing is first with containing the solution washing of carbanion at least one times, then uses deionized water wash.The subject matter that the above-mentioned method preparing carrier exists is: (1) washing process is comparatively complicated, increases alumina producing process cost.(2) although increase all to some extent with the aluminum 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 aluminum 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 aluminum 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 particular restriction, and needs reslurry, then with volatile salt or ammonium bicarbonate aqueous solution process, the reaming of the aluminium carbonate salt pair aluminum oxide produced is limited.
CN101462074A discloses a kind of alumina supporter 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 volatile salt and/or bicarbonate of ammonia adjust ph, finally obtain alumina supporter with the method for the first also rear swing of stream.This method can prepare the alumina supporter had compared with large pore volume and specific surface 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 supporter 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, temperature of reaction 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, methyl aceto acetate, methyl acetoacetate, acetoacetic acid allyl ester, one or more in ISOPROPYL ACETOACETATE, is preferably methyl aceto acetate, 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 ~ 10gA1
2o
3/ 100ml.Described basic aluminate is NaAlO
2and/or KAlO
2, the concentration of described alkali aluminate soln is 8 ~ 30gA1
2o
3/ 100ml.
In the inventive method, can add one or more in silicate, borate and phosphoric acid salt as required in the acid aluminium salt solution of step (2), its add-on is with SiO
2, P
2o
5and/or B
2o
3meter accounts for the 0.1wt% ~ 5.0wt% 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 times 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.Digestion time is 0.5 ~ 5 hour, preferably 1.0 ~ 3.0 hours.Described drying conditions is: drying 3 ~ 10 hours at 50 ~ 140 DEG C.
In the inventive method, the drying conditions 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; Have following pore distribution: bore dia is that the pore volume in the hole being less than 6nm accounts for total pore volume less than 6%, preferably less than 4%, the pore volume in the hole of bore dia 6 ~ 30nm accounts for 20% ~ 40% of total pore volume, and 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 supporter of preparation not only has larger aperture, pore volume, the pore distribution of comparatively concentrating, can keep high strength again.The residual oil hydrocatalyst prepared with it can reduce the macromolecular cpd diffusional limitation in the catalyst such as the resin and asphalt in residual oil, improves the hydrogenation reaction activity and selectivity of catalyzer.
In the present invention, adopt Tai-Ace S 150 legal system for aluminum 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, aluminum oxide that large pore volume, pore size distribution are concentrated, overcome in alumina preparation process, make the pore 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 supporter 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.
Embodiment
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 supporter of the present invention, further illustrates by following examples, but these embodiments can not limit the present invention.Wt% is massfraction.
EXAMPLE l
By the 1L sodium metaaluminate aqueous solution (A1
2o
3concentration is 25g/100ml) and the aqueous solution (A1 of 2L Tai-Ace S 150
2o
3concentration is 3g/100ml) and association complex solution 200mL (wherein, containing methyl aceto acetate 12 grams, acetic acid 60 grams) be respectively charged in the container of high level, lower even under meter 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 Tai-Ace S 150 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 Tai-Ace S 150
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 under meter 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 under meter 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, Tai-Ace S 150 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 Tai-Ace S 150
2o
3concentration is 5g/100ml) and 200mL water purification (wherein containing association complex 60 grams, methyl aceto acetate: 10 grams, formic acid: 50 grams), be respectively charged in the container of high level, the lower under meter that connects flows in the stainless steel reactor of belt stirrer and heating jacket, the aqueous solution of the sodium metaaluminate aqueous solution, Tai-Ace S 150 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 Tai-Ace S 150
2o
3concentration is 3g/100ml) be respectively charged in the container of high level, lower even under meter 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 Tai-Ace S 150 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 properties of table 1 alumina supporter
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 supporter 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 (13)
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 A and solution B, solution C are together and stream carries out plastic reaction, and pH value controls 9.0 ~ 11.0, and temperature of reaction controls at 60 ~ 95 DEG C, after plastic reaction terminates, through aging, filters, washing, dry;
(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 temperature of reaction controls at 75 ~ 85 DEG C.
3. 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%.
4. method according to claim 1, it is characterized in that: ester is selected from tert-butyl acetoacetate, butyl-acetoacetate, methyl aceto acetate, methyl acetoacetate, acetoacetic acid allyl ester, one or more in ISOPROPYL ACETOACETATE, organic acid is selected from acetic acid, succinic acid, formic acid, propionic acid, one or more in butyric acid.
5. method according to claim 4, is characterized in that: fat is methyl aceto acetate, methyl acetoacetate, and acid is acetic acid, formic acid.
6. 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 ~ 10gA1
2o
3/ 100ml.
7. 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 ~ 30gA1
2o
3/ 100ml.
8. method according to claim 1, is characterized in that: add one or more in silicate, borate and phosphoric acid salt in the acid aluminium salt solution of step (2), its add-on is with SiO
2, B
2o
3and/or P
2o
5meter accounts for the 0.1wt% ~ 5.0wt% of carrying alumina body weight.
9. method according to claim 8, 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.
10. method according to claim 1, is characterized in that: step (2) the plastic reaction times is 30 minutes ~ 90 minutes, and aging temperature is 60 ~ 95 DEG C, and digestion time is 0.5 ~ 5 hour, and drying conditions is at 50 ~ 140 DEG C dry 3 ~ 10 hours.
11. methods according to claim 1, is characterized in that: the drying conditions 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 supporter prepared by 12. claim 1-11 either method, is characterized in that: carrier specific surface is 100 ~ 170m
2/ g, pore volume 0.60 ~ 1.50mL/g, most probable pore size 15 ~ 25nm, side pressure strength is 10 ~ 20N/mm; There is following pore 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.
13. carriers according to claim 12, 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 distribution: bore dia is that the pore volume in the hole being less than 6nm accounts for total pore volume less than 4%, 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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| CN111686741B (en) * | 2019-03-12 | 2023-01-10 | 中国石油化工股份有限公司 | Preparation method of copper-zinc catalyst |
| 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 |
| 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 |
| 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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| 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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