CN100400164C - Method for preparing alumina supporter - Google Patents
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- CN100400164C CN100400164C CNB2004100507262A CN200410050726A CN100400164C CN 100400164 C CN100400164 C CN 100400164C CN B2004100507262 A CNB2004100507262 A CN B2004100507262A CN 200410050726 A CN200410050726 A CN 200410050726A CN 100400164 C CN100400164 C CN 100400164C
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Abstract
The present invention relates to a method for preparing an alumina carrier. The present invention has the following steps that acidic aluminum salt and basic aluminate are neutralized, and materials are neutralized for aging and then are filtered, washed, shaped, dried and baked so as to prepare the alumina carrier. In the preparation process, the present invention carries out ageing under the condition that the temperature and pH value are higher than the neutral temperature and the neutral pH value. The method of the present invention has no need of changing the preparation process of the existing alumina carrier, and only needs to adjust the technological conditions of the neutralization process and the ageing process, and thus, the preparation process is simple. The alumina carrier prepared by the method of the present invention has large hole diameter and suitable specific surface area, and can be used for hydrotreating catalysts for heavy oil and residual oil, especially for the hydrotreating catalyst for the residual oil.
Description
Technical field
The present invention relates to a kind of aluminium oxide or contain the preparation method of the alumina support of small amounts silicon.
Background technology
As everyone knows, catalyst carrier properties such as most probable aperture, surface area, average pore size play an important role to activity of such catalysts stability.Concerning heavy distillate especially residual oil, metal impurities (as Ni, V etc.) content height.If the aperture of catalyst carrier little (less than 15nm) just causes the aperture of catalyst little, cause heavy distillate especially the metal impurities in the residual oil be deposited near the catalyst aperture, the blocking catalyst aperture reduces catalyst activity reduction, stability.If the average pore size of catalyst carrier is excessive, then Zhi Bei catalyst strength is low, and abrasion are high.Therefore, heavy distillate especially the suitable average pore size of residual oil catalyst for demetalation carrier be that 15～30nm, most probable aperture are 15～25nm.In addition, it is big that pore volume is wanted, and because of pore volume is big, the metal of deposition is many, and the catalyst activity good stability generally requires the carrier specific surface to be not more than 200m
2G
-1
Physics expanding agents such as usefulness such as US4448896, US4102822 carbon black, starch enlarge the aperture of alumina support.But pore size distribution is not concentrated, and intensity is relatively poor.CN1209355A proposes a kind of macropore alumina supporter and preparation method thereof, be higher than under the condition of room temperature, the boehmite raw material is carried out peptization or slaking, material after the moulding is handled with the compound that contains ammonium ion, and the pore volume that makes the carrier hole diameter and be 10～20nm accounts for 70～85% of total pore volume.Its processing procedure is complicated.
CN94107295.9 discloses a kind of preparation method of catalyst carrier for hydrgenating.This carrier specific area is 250～500m
2G
-1, average pore size is 7～12nm.This preparing carriers method is: a) use the acid aluminium salt aqueous solution (as Al
2(SO
4)
3, AlCl
3) with the composite alkali aluminum saline solution (as NaAlO
2) neutralize, 30～85 ℃ of neutral temperatures, suitable is 40～80 ℃, the suitableeest is 50～70 ℃; In and pH be 6～10, suitable is 7～9.5, the suitableeest is 7.5～9; In and 0.25～4 hour time, suitable is 0.25～3 hour, the suitableeest is 1～2 hour.B) at 30～85 ℃, suitable is 40～80 ℃, and the suitableeest is that 50～70 ℃ of temperature and pH are 6～10, and suitable is 7～9.5, and the suitableeest is aging under 7.5～9 conditions, ageing time 0.25～8 hour, and suitable is 0.5～5 hour, the suitableeest is 1～3 hour.When c) needing at b) step before the adding aqueous silicate solution, make SiO
2Content is 0.1～5wt%, wears out again.D) washing.G) drying.H) roasting.The neutralization of said method is carried out under the same conditions with aging, and the catalyst carrier hole of preparation mainly concentrates in 7～12nm scope, and particularly the catalyst for hydrotreatment of residual oil carrier is not too suitable as heavy distillate.In addition, this process also needs to cause product yield to descend through repeatedly making beating.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method for preparing macropore alumina supporter simply, efficiently.
The preparation process of alumina support of the present invention comprises:
(1) with the acid aluminium salt aqueous solution and the alkali metal aluminate aqueous solution in preference temperature, pH value, neutralize under the time.
(2) neutralization finishes back feeding alkaline precipitating agent or basic aluminate aqueous solution adjusting slurry pH value, wears out in being higher than neutral temperature and being higher than He under the pH value condition.
(3) filtration, washing, drying, moulding, roasting get alumina support.
In (1) the acid aluminium salt aqueous solution in step, add silicate solutions, SiO when needing
2Content accounts for carrier 0.1～3.0wt%.Described silicate solutions is the suitableeest to be sodium silicate solution, its SiO
2Content 1～10g/100ml.The auxiliary agent that also can add if desired, other kind.
The described acid aluminium salt aqueous solution is meant AlCl
3, Al
2(SO
4)
3, Al (NO
3)
3, the suitableeest is Al
2(SO
4)
3, alkali metal aluminate refers to NaAlO
2Or KAlO
2Alkaline precipitating agent is meant NaOH, (NH
4)
2CO
3, NH
4OH.The suitableeest is NH
4OH, (NH
4)
2CO
3
Described neutral temperature scope is 50～80 ℃, and suitable is 55～75 ℃, and the suitableeest is 60～70 ℃.In described and pH value scope be that pH is 6.0～8.5, suitable is 6.5～8.0, the suitableeest is 7.0～8.0.In described and time range be 0.5～3.0 hour, suitable is 0.8～2.0 hour, the suitableeest is 0.8～1.5 hour.
Described aging temperature scope is 85～150 ℃, and suitable is 85～140 ℃, and the suitableeest is 90～120 ℃.Described aging pH value scope is that pH is 8.0～10.0, and suitable is 8.5～9.7, and the suitableeest is 9.0～9.6.Described ageing time scope is 0.1～2 hour, and suitable is 0.1～1 hour, and the suitableeest is 0.1～0.5 hour.Described washing is with distilled water or water purification washing aluminium hydroxide hydrogel.Wear out be higher than neutral temperature and in and carry out under the pH value condition, aging temperature generally is higher than 10～100 ℃ of neutral temperatures, preferred 20～80 ℃, during aging pH value generally is higher than with pH value 0.2～4.0, preferred 1.0～2.5.Generally speaking, the warm spot that boils of the material after the neutralization can reach 100～120 ℃, agingly with this understanding can adopt atmospheric operation, the operation of can wearing out in closed container under higher temperature.
Described drying condition is: drying is 3～10 hours under 50～140 ℃ of temperature; Described roasting condition was: 700～950 ℃ of following constant temperature 1～4 hour.
Zhi Bei alumina support has bigger aperture, suitable specific surface as stated above, and average pore size is 15～30nm, and the most probable aperture is 15～25nm; Surface area is 80～200m
2/ g is preferably 120～170m
2/ g.
Alumina support of the present invention or contain the small amounts silicon carrier can be used as carrier of hydrogenating catalyst, is specially adapted to nickel removal, vanadium is the carrier of main purpose Hydrodemetalation catalyst.
Find that through lot of experiments the material with neutralization under higher temperature and pH value wears out, and can obtain the bigger alumina support in aperture.Carrying alumina preparation of the present invention adopts and carry out burin-in process under higher temperature and pH value condition, the material that obtains can obtain the alumina support of larger aperture after moulding, roasting, process of the present invention is simple, only need to adjust operating condition, existing preparation process need be do not changed, both large-pore alumina carrier can be obtained.
The specific embodiment
Preparing the catalyst carrier detailed process by the present invention may further comprise the steps:
A) the preparation acid aluminium salt aqueous solution, Al
2O
3Concentration is 2～10g/100ml;
B) the preparation basic aluminate aqueous solution, Al
2O
3Concentration is 8～30g/00ml, or the preparation dilute ammonia solution, NH
3Content is 8～16g/100ml;
C) the acid aluminium salt aqueous solution and the basic aluminate aqueous solution join continuously simultaneously and stir in certain water gaging down, and neutral temperature is 50～80 ℃, and fitting is 55～75 ℃, and the suitableeest is 60～70 ℃; In and pH be 6.0～8.5, suitable 6.5～8.0, the suitableeest is 7.0～8.0; In and time range be 0.25～3 hour, suitable 0.5～2 hour, the suitableeest was 0.8～1.5 hour; In and slurries Al
2O
3Content 5～10wt%.
D) at 85～150 ℃, suitable 85～140 ℃, the suitableeest is 90～120 ℃; PH is 8.0～10.0, fits 8.5～9.5, and the suitableeest is 9.0～9.6; 0.1～2 hour time, suitable 0.1～1 hour, the suitableeest was to wear out under the condition in 0.1～0.5 hour.
In a), add aqueous silicate solution, its SiO when e) needing
2Content 1～10g/100ml.
F) filter, wash.
G) under 50～140 ℃ of temperature dry 2～10 hours.
H) moulding.
J) rise to 700～950 ℃ with 200～300 ℃ of/hour assorted temperature speed, preferred 800～900 ℃, constant temperature carried out roasting under the condition in 1～4 hour.
Large aperture of the present invention, suitable specific surface aluminium oxide or contain the preparation method of small amounts silicon carrier further specify with following example, but these examples can not limit the present invention.
Example 1
With the 2L sodium metaaluminate aqueous solution (Al
2O
3Concentration is 15g/100ml) and the aqueous solution (Al of 3L aluminum sulfate
2O
3Concentration is 4g/100ml) be respectively charged in the container of high level, connect down in the rustless steel container that flowmeter flows into belt stirrer that the 6L water purification is housed and heating jacket, be heated to 70 ℃.Under stirring state, two kinds of materials are added in the stainless cylinder of steel simultaneously by certain speed, keeping pH is 7.2, in and 1 hour.Neutralization is used NH after finishing
4OH adjusting slurry pH value is 9.6, in closed container slurry temperature is risen to 130 ℃, and is aging after 0.1 hour, isolated by filtration place mother liquor, washing.Under 140 ℃ of temperature dry 3 hours, moulding was carried out roasting under the condition in 4 hours rising to 800 ℃, constant temperature with 200 ℃ of/hour programming rates; Get sample 1.
Example 2
Prepare alumina support according to embodiment 1 described method, neutral temperature is 75 ℃, in and pH value be 8.0, in and the time be 0.5 hour, usefulness (NH
4)
2CO
3Regulating aging pH value is 9.5, and aging temperature is 90 ℃, and ageing time is 1 hour, gets sample 2.
Example 3
Prepare alumina support according to embodiment 1 described method, neutral temperature is 55 ℃, in and pH value be 6.5, in the time be 2 hours, be to use NaAlO
2Regulate aging pH value 9.0, aging temperature is 120 ℃, and ageing time is 0.5 hour, gets sample 3.
Example 4
Prepare alumina support according to embodiment 1 described method, be not both changes neutral temperature into 80 ℃, and aging temperature is 140 ℃, gets sample 4.
Example 5
With the 1L sodium metaaluminate aqueous solution (Al
2O
3Concentration is 24g/100ml) and the aqueous solution (Al of 1.5L aluminum sulfate
2O
3Concentration is 5g/100ml) be respectively charged in the container of high level, connect down in the stainless container that flowmeter flows into belt stirrer that the 3L water purification is housed and heating jacket, be heated to 50 ℃.Under stirring state, two kinds of materials are added in the stainless cylinder of steel simultaneously by certain speed, keeping pH is 7.0, in and 2 hours.Neutralization is used NH after finishing
4OH adjusting slurry pH value is 10.0, and slurry temperature is risen to 150 ℃, and is aging after 2 hours, isolated by filtration place mother liquor, washing then.Drying is 4 hours under 100 ℃ of temperature, and moulding was being carried out roasting under the condition in 3 hours with assorted 850 ℃ of 160 ℃ of/hour programming rates, constant temperature; Get sample 5.
Example 6
Prepare alumina support according to embodiment 1 described method, be not both with in and pH change 8.3 into, aging pH value is 9.5, baking temperature changes 50 ℃ into, the time is 10h, must sample 6.
Example 7
Prepare alumina support according to embodiment 1 described method, be not both with in and pH change 6.3 into, aging pH value is 8.9, must sample 7.
Example 8
Prepare alumina support according to embodiment 1 described method, be not both with in and the time change 3h into, sintering temperature changes 900 ℃ into, constant temperature time changes 2 hours into.Get sample 8.
Example 9
Prepare alumina support according to embodiment 1 described method, be not both with in and the time change 0.25h into, sintering temperature changes 930 ℃ into, constant temperature time changes 1 hour into.Get sample 9.
Example 10
Prepare alumina support according to embodiment 1 described method, institute's 200ml sodium silicate aqueous solution that is not both adds in the aluminum sulfate aqueous solution, gets sample 10.
Example 11
Prepare alumina support according to embodiment 1 described method, difference changes aging temperature into 85 ℃, and aging pH value changes into, gets sample 11.
Example 12
Prepare alumina support according to embodiment 1 described method, institute's 100ml sodium silicate aqueous solution that is not both adds in the aluminum sulfate aqueous solution, gets sample 12.
Comparative Examples 1
The preparation method who reveals catalyst carrier according to Chinese patent CN94107295.9 prepares catalyst carrier, gets sample 13.
Sample physico-chemical property data see Table 1.
By above result as can be seen, by the aluminium oxide of the inventive method preparation or the alumina support most probable aperture, average pore size that contain small amounts silicon all greater than the carrier of comparative example 1 preparation.Explanation can be satisfied the especially requirement of residuum hydrogenating and metal-eliminating catalyst of mink cell focus preferably by the aluminium oxide of the inventive method preparation or the alumina support that contains small amounts silicon.
Claims (11)
1. the preparation method of an alumina support, process comprises:
(1) with the acid aluminium salt aqueous solution and the alkali metal aluminate aqueous solution in preference temperature, pH value, neutralize under the time;
(2) neutralization finishes back feeding alkaline precipitating agent or basic aluminate aqueous solution adjusting slurry pH value, wears out in being higher than neutral temperature and being higher than He under the pH value condition; Aging temperature is higher than 10～100 ℃ of neutral temperatures, during aging pH value is higher than with pH value 0.2～4.0;
(3) filtration, washing, drying, moulding, roasting get alumina support.
2. in accordance with the method for claim 1, it is characterized in that the described aging temperature of step (2) is higher than 20～80 ℃ of neutral temperatures, during aging pH value is higher than with pH value 1.0～2.5.
3. in accordance with the method for claim 1, it is characterized in that adding silicate solutions, SiO in the acid aluminium salt aqueous solution of described step (1)
2Content accounts for carrier 0.1～3.0wt%, and described silicate solutions is a sodium silicate solution, its SiO
2Content 1～10g/100ml.
4. in accordance with the method for claim 1, it is characterized in that the described acid aluminium salt aqueous solution is meant AlCl
3, Al
2(SO
4)
3Or Al (NO
3)
3, alkali metal aluminate refers to NaAlO
2Or KAlO
2, alkaline precipitating agent is meant NaOH, (NH
4)
2CO
3Or NH
4OH.
5. in accordance with the method for claim 1, it is characterized in that described neutral temperature scope is 50～80 ℃, described in and pH value scope be 6.0～8.5, described in and time range be 0.5～3.0 hour.
6. in accordance with the method for claim 1, it is characterized in that described neutral temperature scope is 55～75 ℃, described in and pH value scope be 6.5～8.0, described in and time range be 0.8～2.0 hour.
7. in accordance with the method for claim 1, it is characterized in that described neutral temperature scope is 60～70 ℃, described in and pH value scope be 7.0～8.0, described in and time range be 0.8～1.5 hour.
8. in accordance with the method for claim 1, it is characterized in that described aging temperature scope is 85～150 ℃, described aging pH value scope is 8.0～10.0, and described ageing time scope is 0.1～2 hour.
9. in accordance with the method for claim 1, it is characterized in that described aging temperature scope is 85～140 ℃, described aging pH value scope is 8.5～9.7, and described ageing time scope is 0.1～1 hour.
10. in accordance with the method for claim 1, it is characterized in that described aging temperature scope is 90～120 ℃, described aging pH value scope 9.0～9.6, described ageing time scope is 0.1～0.5 hour.
11. in accordance with the method for claim 1, it is characterized in that described drying condition is: drying is 3～10 hours under 50～140 ℃ of temperature; Described roasting condition was: 700～950 ℃ of following constant temperature 1～4 hour.
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|---|---|---|---|
| CNB2004100507262A CN100400164C (en) | 2004-10-29 | 2004-10-29 | Method for preparing alumina supporter |
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|---|---|---|---|
| CNB2004100507262A CN100400164C (en) | 2004-10-29 | 2004-10-29 | Method for preparing alumina supporter |
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| CN100400164C true CN100400164C (en) | 2008-07-09 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100438971C (en) * | 2005-10-19 | 2008-12-03 | 中国石油化工股份有限公司 | A silicone modified aluminum hydroxide solid elastomer and preparation method thereof |
| CN101121120B (en) * | 2006-08-11 | 2010-09-01 | 中国石油化工股份有限公司 | Preparation method of aluminium oxide carrier with composite holes structure |
| CN102836747B (en) * | 2011-06-23 | 2014-04-16 | 中国石油化工股份有限公司 | Preparation method for alumina oxide carrier |
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| CN103801312B (en) * | 2012-11-08 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN103803615B (en) * | 2012-11-08 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of preparation method of alumina dry glue |
| CN103801346B (en) * | 2012-11-08 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method preparing hydrotreating catalyst |
| CN104549534B (en) * | 2013-10-23 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of alumina support and preparation method thereof |
| CN104671263B (en) * | 2013-11-26 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of boehmite |
| CN110935490B (en) * | 2018-09-25 | 2022-03-08 | 中国石油化工股份有限公司 | Copper-zinc catalyst and preparation method thereof |
| CN110935457B (en) * | 2018-09-25 | 2022-03-08 | 中国石油化工股份有限公司 | Preparation method of copper-zinc catalyst |
| CN112516993B (en) * | 2019-09-17 | 2023-01-10 | 中国石油化工股份有限公司 | Preparation method of alumina carrier |
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