CN103055948B - Preparation method of macroporous alumina support - Google Patents
Preparation method of macroporous alumina support Download PDFInfo
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- CN103055948B CN103055948B CN201110322468.9A CN201110322468A CN103055948B CN 103055948 B CN103055948 B CN 103055948B CN 201110322468 A CN201110322468 A CN 201110322468A CN 103055948 B CN103055948 B CN 103055948B
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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 heavy-oil hydrogenation field.The diffusional resistance running in order to reduce macromolecular reaction, to hold more carbon deposit, metal deposit etc., catalyst should have larger aperture and pore volume.Because duct, large aperture can be played passage and hold sedimental effect, make 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, there is superior performance.The bore dia of aluminium oxide that is generally used for preparing hydrotreating catalyst is less, can not meet the needs of preparing 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.Conventional expanding method 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 be take carbon black as expanding agent, and it is become to plastic extruded moulding with boehmite kneading.In carrier roasting process, expanding agent, through oxidation, burning, is progressively overflowed with gaseous state thing, forms cavity in carrier, thereby forms macropore.But the method amount of carbon blacks used is larger, more than generally reaching 20wt%, the mechanical strength of gained carrier is lower, and pore size distribution is disperse comparatively.
It is that expanding agent is prepared macroporous aluminium oxide that EP 0237240 adopts carbon fiber, but has equally the large and low deficiency that waits of support strength of expanding agent consumption.
CN 1055877C by adding physics expanding agent if carbon black and chemical enlargement agent are as phosphide in boehmite dry glue powder, by kneading method moulding, the carrier finally obtaining can several bore dias be 10～20nm, but do not form double-pore structure, and the pore volume that has of the macropore that is greater than 100nm only accounts for 5% left and right of total pore volume, the support strength that method makes thus is simultaneously lower.Thereby when the required catalyst of reaction requires carrier have dual duct and will have higher mechanical strength, this kind of carrier has just been subject to certain limitation.
The common issue that said method faces also has, and carbon black used or NACF need to be prepared 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 of preparing through special process virtually to increase the preparation cost of macroporous aluminium oxide.
CN 1768947A discloses a kind of preparation method of macroporous aluminium oxide.It is expanding agent that the method be take crops stem shell powder, 10wt%～20wt% that addition is aluminium oxide.Although the cost of expanding agent used is comparatively cheap, but due to crops stem shell powder and aluminum oxide dry glue powder compatibility poor, while large usage quantity, in kneading and compacting process, stem shell powder disperses inhomogeneous in plastic, cause the large pore size distribution in 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 the 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, comprising:
(1) boehmite dry glue powder is evenly mixed with expanding agent, then add the triethanolamine aqueous solution, and kneading becomes plastic;
(2), by (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 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 a large number in rural area.As, in rural area, use and still take more widely in the native kitchen range that crops stem shell is fuel, can a large amount of lightweight ashes powder of deposition in 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 lightweight ashes powder that step (1) is described 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 that a kind of to intend thin water aluminum oxide dry glue powder can be also boehmite dry glue powder prepared by several distinct methods.In step (1), can also add as required required shaping assistant raw material, as the materials such as sesbania powder as extrusion aid.
The described moulding of step (2) can adopt conventional forming method, comprises extrusion, compressing tablet or balling-up etc.
The described dry run of step (2) is generally at 100～120 ℃ and is dried 1～4 hour, and preferably at room temperature dries in the shade 10～24 hours, is then warming up to 100～120 ℃, dry 1～4 hour.Described roasting process is roasting 1～6 hour at 600～850 ℃, and the heating rate of roasting process is preferably less than 10 ℃/h.
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 the pore volume that bore dia is greater than 100nm accounts for 20%～30% of total pore volume, and crushing strength is 110～140 N/mm.
In the inventive method, expanding agent consumption is few, 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 for crops stem shell, its wide material sources, can be to collect in a large number in 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, therefore better with boehmite dry glue powder compatibility, in kneading and compacting, can be distributed in formed body equably.Article shaped is in air during roasting, and expanding agent is carbonization gradually, 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, triethanolamine solution used is also alkaline matter simultaneously, make alumina precursor particle in kneading process, form reunion to a certain degree, therefore to be greater than the pore volume of 100nm larger in macroporous aluminium oxide of the present invention aperture, can account for 20%～30% of total pore volume.
The present invention, by heating up slowly at roasting process, progressively slowly forms macropore, therefore less on the mechanical strength impact of aluminium oxide.The inventive method is simple, 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 adopting is accessory substance or the waste material in 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 more concentrated pore size distribution of 10～20nm, also contain the higher macropore pore volume that is greater than 100nm, for the preparation of heavy, residual oil hydrocatalyst, be very beneficial for delaying the raising of inside diffusional resistance in weight, residual hydrogenation, thereby be conducive to keep hydrogenation catalyst apparent activity, the service cycle of extension fixture.
The specific embodiment
Below by embodiment to the inventive method detailed explanation in addition.
In the present invention, specific area, pore volume and pore size distribution are to adopt low temperature liquid nitrogen determination of adsorption method, and crushing strength is according to HG/T 2782-1996 standard, adopt QCY-602 type catalyst strength analyzer to measure.
Embodiment 1
100 grams of boehmite dry glue powders, lightweight ashes Powder Particle Size is 20 μ m, 5 grams of use amounts, 5 grams, sesbania powder, the triethanolamine solution 120ml that concentration is 2wt%.After fully kneading is plastic, be extruded into stripe shape.Under room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, with 5 ℃/h of speed, is warming up to 600 ℃, and at this temperature constant temperature 6 hours, the naturally cooling macropore alumina supporter that makes.
Embodiment 2
100 grams of boehmite dry glue powders, lightweight ashes Powder Particle Size is 20 μ m, 7 grams of use amounts, 5 grams, sesbania powder, the triethanolamine solution 120ml that concentration is 1.5wt%.After fully kneading is plastic, be extruded into stripe shape.Under room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, with 5 ℃/h of speed, is warming up to 650 ℃, and at this temperature constant temperature 6 hours, the naturally cooling macropore alumina supporter that makes.
Embodiment 3
100 grams of boehmite dry glue powders, lightweight ashes powder 40 μ m, 10 grams of use amounts, 5 grams, sesbania powder, the triethanolamine solution 125ml that concentration is 1wt%.After kneading is plastic, be extruded into stripe shape.Under room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, with 10 ℃/h of speed, is warming up to 700 ℃, and at this temperature constant temperature 5 hours, the naturally cooling macropore alumina supporter that makes.
Embodiment 4
100 grams of boehmite dry glue powders, lightweight ashes powder 60 μ m, 10 grams of use amounts, 5 grams, sesbania powder, the triethanolamine solution 120ml that concentration is 2wt%.After kneading is plastic, be extruded into stripe shape.Dried overnight under room temperature is dried 2 hours at 120 ℃.Drying sample is placed in to high temperature furnace, with 10 ℃/h of speed, is warming up to 800 ℃, and at this temperature constant temperature 6 hours, the naturally cooling macropore alumina supporter that makes.
Comparative example 1
With reference to the disclosed method of CN 1768947A, prepare formed alumina.100 grams of boehmite dry glue powders, 130 14 grams of object powdered rice hulls, 3 grams, sesbania powder, rare nitric acid 120ml that concentration is 3wt%.Mixture, after fully kneading is plastic, is extruded into stripe shape.Dried overnight under room temperature is dried 4 hours at 110 ℃.Drying sample is placed in to high temperature furnace, with 5 ℃/h of speed, is warming up to 600 ℃, and at this temperature constant temperature 6 hours, the naturally cooling moulding macropore alumina supporter that makes, its physico-chemical property is in Table 1.While using powdered rice hulls for expanding agent, due to rice husk and boehmite powder compatibility bad, be unfavorable for the dispersed of powdered rice hulls, so the reaming effect of powdered rice hulls can not well be brought into play, mechanical strength decreases, 10 ~ 20nm and be greater than the large pore size distribution of 100nm and reduce.
Comparative example 2
100 grams of boehmite dry glue powders, lightweight ashes Powder Particle Size is 20 μ m, 5 grams of use amounts, 5 grams, sesbania powder, rare nitric acid 190ml that concentration is 3wt%.After fully kneading is plastic, be extruded into stripe shape.Under room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, with 5 ℃/h of speed, is warming up to 600 ℃, and at this temperature constant temperature 6 hours, the naturally cooling moulding macropore alumina supporter that makes, its physico-chemical property is in Table 1.This example take lightweight ashes powder during as expanding agent, and owing to using nitric acid, first nitric acid react and be consumed part with alkaline ashes powder, therefore the extra nitric acid of needs.Dispersed step-down after ashes powder and 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 (4)
1. a preparation method for macropore alumina supporter, comprising:
(1) boehmite dry glue powder is evenly mixed with expanding agent, then add the triethanolamine aqueous solution, and kneading becomes plastic;
(2), by (1) prepared plastic moulding, dry and roasting obtains macropore alumina supporter; The heating rate of described roasting process is less than 10 ℃/h;
Described expanding agent is the lightweight ashes powder that the burning of crops stem shell generates, and the character of lightweight ashes powder is as follows: carbon content is not less than 80wt%, and granularity is 20～60 μ m; 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; The concentration of the described triethanolamine aqueous solution is 2wt%～10wt%.
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. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (2) is as follows: at 100～120 ℃, be dried 1～4 hour; Described roasting process is roasting 1～6 hour at 600～850 ℃.
4. 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 dry in the shade 10～24 hours, be then warming up to 100～120 ℃, dry 1～4 hour.
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| 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 |
| 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 |
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 |
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- 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 |
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