CN103055948A - Preparation method of macroporous alumina support - Google Patents
Preparation method of macroporous alumina support Download PDFInfo
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- CN103055948A CN103055948A CN2011103224689A CN201110322468A CN103055948A CN 103055948 A CN103055948 A CN 103055948A CN 2011103224689 A CN2011103224689 A CN 2011103224689A CN 201110322468 A CN201110322468 A CN 201110322468A CN 103055948 A CN103055948 A CN 103055948A
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Abstract
The invention discloses a preparation method of a macroporous alumina support. The method is characterized by taking light ash generated through combustion of crop stems and husks as a pore-enlarging agent, simultaneously adding a triethanolamine water solution and adopting a kneading method to prepare the macroporous alumina support. The method has the beneficial effects that the pore-enlarging agent is small in dosage, wide in source and low in cost, so the preparation cost of the alumina support can be effectively reduced; and the prepared macroporous alumina has the characteristics of double pore distribution, more concentrated pore distribution and higher mechanical strength, is used for preparing heavy/residual oil hydrogenation catalysts and is very favorable for delaying the increase of diffusion resistance in heavy/residual oil hydrogenation, thus being favorable for maintaining the apparent activities of the hydrogenation catalysts and lengthening the running period of the device.
Description
Technical field
The present invention relates to a kind of preparation method of macropore alumina supporter, especially for the preparation method of the macropore alumina supporter of heavy oil, residuum hydrogenating and metal-eliminating catalyst.
Background technology
Macroporous aluminium oxide is that the hydrogenation catalyst of carrier is widely used in the heavy-oil hydrogenation field.The diffusional resistance that runs in order to reduce macromolecular reaction, in order to hold more carbon deposit, metal deposit etc., catalyst should have larger aperture and pore volume.Because the duct, large aperture can be played passage and be held sedimental effect, makes the catalyst inner surface obtain more efficiently utilization, activity and the stability of catalyst are improved.Therefore, adopt large small-bore and catalyst that carrier that the Based on Dual-Aperture deposited distributes is made, have superior performance.The bore dia of aluminium oxide that is generally used for preparing hydrotreating catalyst is less, can not satisfy the needs of preparation heavy oil, residuum hydrogenating and metal-eliminating or heavy oil hydrodesulfurization catalyst.Therefore must in preparation process, adopt the way of reaming to obtain macropore.Expanding method commonly used is to add various types of expanding agents in intending the forming processes such as thin water aluminum oxide dry glue powder kneading, extrusion.
US 4448896 becomes plastic and extruded moulding with it with the boehmite kneading take carbon black as expanding agent.In the carrier roasting process, expanding agent is progressively overflowed with the gaseous state thing through oxidation, burning, forms the cavity in carrier, thereby consists of macropore.But the used amount of carbon blacks of the method is larger, generally reaches more than the 20wt%, and the mechanical strength of gained carrier is lower, and pore size distribution is disperse comparatively.
It is that expanding agent prepares macroporous aluminium oxide that EP 0237240 adopts carbon fiber, but exists equally the expanding agent consumption to reach greatly the low deficiency that waits of support strength.
CN 1055877C is by adding physics expanding agent such as carbon black and chemical enlargement agent such as phosphide in the boehmite dry glue powder, by the kneading method moulding, the carrier that finally obtains can several bore dias be 10～20nm, but do not form double-pore structure, and only accounting for about 5% of total pore volume greater than the pore volume that the macropore of 100nm has, the support strength that makes of method is lower thus simultaneously.Thereby when the required catalyst of reaction required carrier to have dual duct and will higher mechanical strength be arranged, this kind carrier just had been subject to certain limitation.
The common issue with that said method faces also has, and used carbon black or NACF need to prepare by special technique.Such as, the source of carbon powder mainly contains channel black, high wear-resistant carbon black and acetylene method carbon charcoal.Use this expanding agent through the special process preparation virtually to increase the preparation cost of macroporous aluminium oxide.
CN 1768947A discloses a kind of preparation method of macroporous aluminium oxide.The method is take crops stem shell powder as expanding agent, and addition is the 10wt%～20wt% of aluminium oxide.Although the cost of used expanding agent is comparatively cheap, but because crops stem shell powder and aluminum oxide dry glue powder compatibility are relatively poor, the while large usage quantity, stem shell powder disperses inhomogeneous in plastic in the kneading and compacting process, cause the large pore size distribution in the carrier also inhomogeneous, affect the mechanical strength of macroporous aluminium oxide.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method with macropore alumina supporter that diplopore distributes, pore size distribution is concentrated, mechanical strength is high.
The preparation method of macropore alumina supporter of the present invention comprises:
(1) the boehmite dry glue powder is evenly mixed with expanding agent, then add the triethanolamine aqueous solution, and kneading becomes plastic;
(2) with (1) prepared plastic moulding, dry and roasting obtains macropore alumina supporter;
Described expanding agent is the lightweight ashes powder that the burning of crops stem shell generates, and addition is the 3wt%～12wt% of boehmite dry glue powder weight, is preferably 5wt%～10wt%; The consumption of described triethanolamine is the 0.1wt%～2.5wt% of boehmite dry glue powder weight.
In the step (1), the concentration of the described triethanolamine aqueous solution is 2wt%～10wt%.
The described expanding agent of step (1) is the lightweight ashes powder that crops stem shell generates in burning, and its wide material sources can be collected in the rural area in a large number.As, in the rural area is used still more widely with the native kitchen range of crops stem shell as fuel, can a large amount of lightweight ashes powder of deposition in the smoke evacuation combustion flue.These lightweight ashes mealiness matter and carbon black have certain similarity, but itself have certain alkalescence, and source and cost are far below the cost of carbon black of industrial special preparation.The character of the described lightweight ashes of step (1) powder is as follows, and carbon content is not less than 80wt%, and granularity is 20～60 μ m.
The described boehmite dry glue powder of step (1) can be a kind of boehmite dry glue powder that thin water aluminum oxide dry glue powder also can be several distinct methods preparations of intending.In step (1), can also add as required required shaping assistant raw material, such as the materials such as sesbania powder as extrusion aid.
The described moulding of step (2) can be adopted conventional forming method, comprises extrusion, compressing tablet or balling-up etc.
The described dry run of step (2) is generally at 100～120 ℃ and descends dry 1～4 hour, and preferably at room temperature dries in the shade 10～24 hours, then is warming up to 100～120 ℃, dry 1～4 hour.Described roasting process is that the heating rate of roasting process was preferably less than 10 ℃/hour 600～850 ℃ of lower roastings 1～6 hour.
The character of the macropore alumina supporter of the inventive method gained is as follows: pore volume is 0.6～1.2ml/g, and specific area is 140～220m
2/ g, bore dia accounts for 50%～70% of total pore volume at the pore volume of 10～20nm, and bore dia accounts for 20%～30% of total pore volume greater than the pore volume of 100nm, and crushing strength is 110～140 N/mm.
In the inventive method, the expanding agent consumption is few, and is with low cost, and wide material sources can effectively reduce the preparation cost of alumina support.
The lightweight ashes powder that the expanding agent that the present invention uses generates in burning as crops stem shell, its wide material sources can be to collect in a large number in the rural area.Described lightweight ashes powder has higher carbon content, is light soluble organic matter at a certain temperature.And the particle surface of this lightweight ashes powder contains abundant nitrogen oxygen hydrophilic radical, and is therefore better with boehmite dry glue powder compatibility, can be distributed in the formed body equably in kneading and compacting.During roasting, expanding agent is carbonization gradually in air for article shaped, produces gaseous matter, and the generation of these gases and effusion cause the generation of macropore.The lightweight ashes powder expanding agent itself that the present invention adopts has certain alkalescence, used triethanolamine solution also is alkaline matter simultaneously, make the alumina precursor particle in kneading process, form to a certain degree reunion, therefore macroporous aluminium oxide of the present invention aperture is larger greater than the pore volume of 100nm, can account for 20%～30% of total pore volume.
The present invention progressively slowly forms macropore by heating up slowly at roasting process, and is therefore less on the mechanical strength impact of aluminium oxide.The inventive method is simple, the expanding agent particle in kneading process easily and other mixing of materials even, therefore, the pore size distribution of prepared alumina support is quite concentrated.In addition, the expanding agent that adopts is accessory substance or the waste material in the Processing Farm Produce, and wide material sources are cheap, can effectively reduce the preparation cost of carrier.
Alumina support of the present invention is except having the concentrated pore size distribution of 10～20nm, also contain the higher macropore pore volume greater than 100nm, for the preparation of heavy, residual oil hydrocatalyst, be very beneficial for delaying the raising of inside diffusional resistance in weight, the residual hydrogenation, thereby be conducive to keep the hydrogenation catalyst apparent activity, the service cycle of extension fixture.
The specific embodiment
Below by embodiment in addition detailed explanation of the inventive method.
Specific area, pore volume and pore size distribution are to adopt the low temperature liquid nitrogen determination of adsorption method among the present invention, and crushing strength is according to HG/T 2782-1996 standard, adopt QCY-602 type catalyst strength analyzer to measure.
Embodiment 1
Boehmite dry glue powder 100 grams, lightweight ashes Powder Particle Size is 20 μ m, use amount 5 grams, sesbania powder 5 grams, concentration is the triethanolamine solution 120ml of 2wt%.After fully kneading is plastic, be extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 110 ℃ under the room temperature.Drying sample is placed high temperature furnace, is warming up to 600 ℃ with 5 ℃/speed at one hour rating, and under this temperature constant temperature 6 hours, cooling makes macropore alumina supporter naturally.
Embodiment 2
Boehmite dry glue powder 100 grams, lightweight ashes Powder Particle Size is 20 μ m, use amount 7 grams, sesbania powder 5 grams, concentration is the triethanolamine solution 120ml of 1.5wt%.After fully kneading is plastic, be extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 110 ℃ under the room temperature.Drying sample is placed high temperature furnace, is warming up to 650 ℃ with 5 ℃/speed at one hour rating, and under this temperature constant temperature 6 hours, cooling makes macropore alumina supporter naturally.
Embodiment 3
Boehmite dry glue powder 100 grams, lightweight ashes powder 40 μ m, use amount 10 grams, sesbania powder 5 grams, concentration is the triethanolamine solution 125ml of 1wt%.After kneading is plastic, be extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 110 ℃ under the room temperature.Drying sample is placed high temperature furnace, is warming up to 700 ℃ with 10 ℃/speed at one hour rating, and under this temperature constant temperature 5 hours, cooling makes macropore alumina supporter naturally.
Embodiment 4
Boehmite dry glue powder 100 grams, lightweight ashes powder 60 μ m, use amount 10 grams, sesbania powder 5 grams, concentration is the triethanolamine solution 120ml of 2wt%.After kneading is plastic, be extruded into stripe shape.Dried overnight under the room temperature was in 120 ℃ of lower oven dry 2 hours.Drying sample is placed high temperature furnace, is warming up to 800 ℃ with 10 ℃/speed at one hour rating, and under this temperature constant temperature 6 hours, cooling makes macropore alumina supporter naturally.
Comparative example 1
Prepare formed alumina with reference to the disclosed method of CN 1768947A.Boehmite dry glue powder 100 grams, 130 purpose powdered rice hulls, 14 grams, sesbania powder 3 grams, concentration is rare nitric acid 120ml of 3wt%.Mixture after fully kneading is plastic, is extruded into stripe shape.Dried overnight under the room temperature was in 110 ℃ of lower oven dry 4 hours.Drying sample is placed high temperature furnace, is warming up to 600 ℃ with 5 ℃/speed at one hour rating, and under this temperature constant temperature 6 hours, cooling makes the moulding macropore alumina supporter naturally, its physico-chemical property sees Table 1.When using powdered rice hulls as expanding agent, because rice husk and boehmite powder compatibility are bad, be unfavorable for the Uniform Dispersion of powdered rice hulls, so the reaming effect of powdered rice hulls can not be brought into play well, mechanical strength decreases, and 10 ~ 20nm reaches greater than the large pore size distribution of 100nm and reduces.
Comparative example 2
Boehmite dry glue powder 100 grams, lightweight ashes Powder Particle Size is 20 μ m, use amount 5 grams, sesbania powder 5 grams, concentration is rare nitric acid 190ml of 3wt%.After fully kneading is plastic, be extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 110 ℃ under the room temperature.Drying sample is placed high temperature furnace, is warming up to 600 ℃ with 5 ℃/speed at one hour rating, and under this temperature constant temperature 6 hours, cooling makes the moulding macropore alumina supporter naturally, its physico-chemical property sees Table 1.This example is take lightweight ashes powder during as expanding agent, owing to using nitric acid, nitric acid at first is consumed part with the ashes powder reaction of alkalescence, therefore needs extra nitric acid.Dispersed step-down after ashes powder and the nitric acid effect causes the micropore of product to increase simultaneously, and large pore size distribution reduces.
?
The physico-chemical property of table 1 macropore alumina supporter
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Pore volume, ml/g | 0.64 | 0.90 | 0.98 | 1.14 | 0.54 | 0.67 |
| Specific surface, m 2/g | 210 | 175 | 182 | 141 | 167 | 221 |
| Crushing strength, N/mm | 135 | 125 | 122 | 114 | 105 | 117 |
| Pore size distribution, % | ? | ? | ? | ? | ? | ? |
| <10nm | 11 | 9 | 7 | 12 | 20 | 43 |
| 10～20nm | 68 | 52 | 55 | 65 | 49 | 44 |
| >100nm | 20 | 27 | 22 | 28 | 9 | 7 |
Claims (7)
1. the preparation method of a macropore alumina supporter comprises:
(1) the boehmite dry glue powder is evenly mixed with expanding agent, then add the triethanolamine aqueous solution, and kneading becomes plastic;
(2) with (1) prepared plastic moulding, dry and roasting obtains macropore alumina supporter;
Described expanding agent is the lightweight ashes powder that the burning of crops stem shell generates, and addition is the 3wt%～12wt% of boehmite dry glue powder weight; The consumption of described triethanolamine is the 0.1wt%～2.5wt% of boehmite dry glue powder weight.
2. the addition that in accordance with the method for claim 1, it is characterized in that described expanding agent is the 5wt%～10wt% of boehmite dry glue powder weight.
3. the concentration that in accordance with the method for claim 1, it is characterized in that the described triethanolamine aqueous solution is 2wt%～10wt%.
4. in accordance with the method for claim 1, it is characterized in that the character of the described lightweight ashes of step (1) powder is as follows: carbon content is not less than 80wt%, and granularity is 20～60 μ m.
5. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (2) is as follows: lower dry 1～4 hour at 100～120 ℃; Described roasting process is 600～850 ℃ of lower roastings 1～6 hour.
6. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (2) is as follows: at room temperature dried in the shade 10～24 hours, and then be warming up to 100～120 ℃, dry 1～4 hour.
7. in accordance with the method for claim 1, it is characterized in that the heating rate of the described roasting process of step (2) is less than 10 ℃/hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107456979A (en) * | 2017-09-18 | 2017-12-12 | 北京欧奏普尔环保设备有限公司 | macroporous catalyst preparation method |
| CN114149072A (en) * | 2021-12-28 | 2022-03-08 | 华夏碧水环保科技有限公司 | A kind of preparation method and filler system of water treatment filler that can be loaded with microorganisms |
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| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| EP0237240A2 (en) * | 1986-02-28 | 1987-09-16 | Nippon Oil Co. Ltd. | Process for the production of hydrogenating catalysts |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN1768947A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | A kind of preparation method of macroporous alumina carrier |
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2011
- 2011-10-21 CN CN201110322468.9A patent/CN103055948B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| EP0237240A2 (en) * | 1986-02-28 | 1987-09-16 | Nippon Oil Co. Ltd. | Process for the production of hydrogenating catalysts |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN1768947A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | A kind of preparation method of macroporous alumina carrier |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107456979A (en) * | 2017-09-18 | 2017-12-12 | 北京欧奏普尔环保设备有限公司 | macroporous catalyst preparation method |
| CN114149072A (en) * | 2021-12-28 | 2022-03-08 | 华夏碧水环保科技有限公司 | A kind of preparation method and filler system of water treatment filler that can be loaded with microorganisms |
| CN114149072B (en) * | 2021-12-28 | 2023-10-13 | 华夏碧水环保科技股份有限公司 | Preparation method and filling system of water treatment filler capable of loading microorganisms |
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