CN101121120B - Preparation method of aluminium oxide carrier with composite holes structure - Google Patents
Preparation method of aluminium oxide carrier with composite holes structure Download PDFInfo
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- CN101121120B CN101121120B CN200610029963XA CN200610029963A CN101121120B CN 101121120 B CN101121120 B CN 101121120B CN 200610029963X A CN200610029963X A CN 200610029963XA CN 200610029963 A CN200610029963 A CN 200610029963A CN 101121120 B CN101121120 B CN 101121120B
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Abstract
The present invention relates to a composite-pore structural alumina carrier and the preparation method. The present invention mainly solves the technical problem that the prior art is hard to obtain a macroporous alumina carrier with different distributions of pores, which are larger than 20nm and the preparation method. The present invention solves the problem well by a technical proposal whichadopting the alumina carrier that a specific surface area of which is 40 square meters per gram to 160 square meters per gram; a total pore volume is 0.3 milliliters per gram to 1.2 milliliters per gram; the pore volume that a pore diameter of which is less than 30nm is 5 percent to 60 percent of the total pore volume; the pore volume that the pore diameter of which is between 30nm to 60nm is 20 percent to 75 percent of the total pore volume; the pore volume that the pore diameter of which is more than 60nm is 20 percent to 60 percent of the total pore volume as a composite carrier. In a technical proposal, the preparation method of the composite carrier is that firstly the alumina A is mixed with the alumina B to be shaped and is dried for 1 to 24 hours under 50 DEG C to 100 DEG C and then is calcined for 1 to 10 hours under 800 DEG C to 1150 DEG C to obtain the composite carrier. The carrier can be used for the industrial production of pyrolysis gasoline hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of alumina support and preparation method thereof with composite pore structural.More particularly relate to be used to comprise alumina support that pyrolysis gasoline hydrogenation reacts and the hydrogenation catalyst of hydrotreatment reacts and preparation method thereof.
Background technology
In the hydrocarbon process, alumina support is because of having bigger serface, high stability and being used widely.And in such as the hydrogenation reaction of full-cut fraction pyrolysis gasoline with the olefin impurity in the removal gasoline, because of wherein being rich in C
5, C
9 +(carbon nine and more than) unsaturated component, the diene height, easily polymerization, colloid (high molecular polymer that unsaturated component polymerization reaction take place such as alkadienes and styrene generates) height, heavy ends are many, coke powder content height, stability is poor, and, causing the raw material free water content higher because formation azeotropic mixture or commercial plant lack effective water-oil separating means, poisonous substances such as heavy metal easily are enriched in drippolene C
9 +In (carbon nine and more than) hydrocarbon-fraction and characteristics such as the hydrogenation thermal discharge is big, cause the quick decline and the inactivation of catalyst activity easily, the outlet diene is higher, and the diolefin hydrogenation rate is on the low side.Have and hold metal and hold the carbon ability strong than the catalyst of large pore volume and larger aperture, anti-colloid and free water can slow down the inactivation of catalyst, and prolonged the service cycle of catalyst.The pore structure of catalyst is by the carrier decision that constitutes catalyst, therefore, preparation has than large pore volume and aperture, can guarantee again that simultaneously carrier that catalyst has a good low temperature active is the key that preparation selective hydrocatalyst, especially preparation are used to contain the full-cut fraction pyrolysis gasoline hydrogenation catalyst of high colloid, high free water.
At one-tenth glue, the washing process of preparation boehmite or in the boehmite forming process, introduce expanding agent, be that prior art for preparing has than large pore volume with than the normal method that adopts of macropore diameter carrier.
CN1714937A discloses a kind of preparation method of large pore volume formed alumina carrier, and this method is mixed the nitrogen-containing compound beyond a kind of aluminium carbonate ammonium and a kind of deacidification, moulding and in 350～650 ℃ of roastings 1～8 hour.This method gained carrier specific area is 200～350 meters
2/ gram, mean pore sizes is 25～35 nanometers.
CN1689703A discloses a kind of preparation method with alumina support of double-hole, this method is mixed a kind of hydrated alumina with a kind of deacidification nitrogen-containing compound and a kind of halide in addition, moulding and in 600～850 ℃ of roastings 1～10 hour, the pore volume that gained carrier hole is distributed as bore dia 10～20 nanometers accounts for 35～80% of total pore volume, the pore volume of bore dia 500～1200 nanometers accounts for 15～60% of total pore volume, bore dia＜10 nanometers, 20～＜500 nanometers and the pore volume sum of 1200 nanometers accounts for 5～40% of total pore volume, the acid amount is 0.05～0.2 mM/gram.
CN1647857A discloses a kind of preparation method of macropore alumina supporter, and this method adopts a kind of degree of crystallinity less than 70% boehmite and a kind of organic expanding agent mixed atomizing drying, moulding and in 600～1100 ℃ of roastings 0.5～4 hour.This method gained carrier pore volume is 0.9～1.3 a milliliter/gram, and the aperture accounts for 7～25% of total pore volume greater than the hole of 100 nanometers.
CN1600430A discloses a kind of preparation method of macropore alumina supporter, this method with a kind of hydrated alumina mix with a kind of expanding agent, moulding and in 600～850 ℃ of roastings 1～10 hour, the gained carrier can several apertures be 14～20 nanometers, pore volume is 0.6～1.2 a milliliter/gram, and specific area is 150～200 meters
2/ gram, the acid amount is 0.05～0.2 mM/gram.
As seen, though adopt expanding agent can prepare part large pore volume carrier, be difficult to produce the above macropore of 20 nanometers, and these macropores are particularly important to the raw material of high colloid and high free water content.Have, the less DeGrain of expanding agent consumption will exert an influence to performances such as carrier mechanical strengths if consumption increases again.
Summary of the invention
One of technical problem to be solved by this invention is to have the problem that is difficult to obtain the macropore alumina supporter of different pore size distributions more than 20 nanometers in the prior art, and a kind of new alumina support with composite pore structural is provided.Two of technical problem to be solved by this invention is the problems that do not relate to the preparation method of the macropore alumina supporter of different pore size distributions more than 20 nanometers in the prior art, and a kind of preparation method of the alumina support with composite pore structural newly is provided.The alumina support that makes with this method has multiple pore size distribution, have bigger can several apertures etc. advantage.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of alumina support with composite pore structural, carrier specific area are 40～160 meters
2/ gram, total pore volume is 0.3～1.2 a milliliter/gram, and the pore volume of bore dia＜30 nanometers accounts for 5～60% of total pore volume, and the pore volume of bore dia 30～60 nanometers accounts for 20～75% of total pore volume, and the pore volume of bore dia＞60 nanometers accounts for 20～60% of total pore volume.
In the technique scheme, the preferable range with alumina support of composite pore structural is: the carrier specific area is 50～150 meters
2/ gram, total pore volume are 0.4～1.0 milliliter/gram, the pore volume of bore dia＜30 nanometers account for total pore volume 5～55%, the pore volume of bore dia 30～60 nanometers accounts for 20～72% of total pore volume, the pore volume of bore dia＞60 nanometers accounts for 20～30% of total pore volume.The aluminium oxide preferred version is the mixture that is selected from least a aluminium oxide A among hibbsite, boehmite, boehmite or the amorphous hydroted alumina and is selected from aluminium oxide B at least a in γ, η, δ, θ, κ or the alpha-phase aluminum oxide, wherein, the weight ratio of aluminium oxide A and aluminium oxide B is 1: 0.1～1.Aluminium oxide A preferred version is to be selected from least a among hibbsite or the boehmite, and aluminium oxide B preferred version is to be selected from least a in δ, θ or the alpha-phase aluminum oxide, and the weight ratio preferable range of aluminium oxide A and aluminium oxide B is 1: 0.2～1.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method with alumina support of composite pore structural, earlier aluminium oxide A and aluminium oxide B are mixed in required ratio, add entry, peptizing agent, after extrusion, moulding again 50～100 ℃ dry 1～24 hour down, roasting 1～10 hour under 800～1150 ℃ of conditions then.
In the technique scheme, the sintering temperature preferable range is 900～1100 ℃, and the roasting time preferable range is 2～8 hours; The peptizing agent preferred version is to be selected from least a in colloidal sol, polyvinyl alcohol, the acid, is 0.5～10% in its consumption of alumina weight.
According to method provided by the invention, described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.For example during extrusion, described mixture can be mixed with water in alumina weight 50～200%, and add peptizing agent, extrusion molding then in alumina weight 0.5～10%.
Among the present invention owing to adopt the technical scheme in required ratio mixing, extrusion, moulding with aluminium oxide A and aluminium oxide B, make the alumina support that makes with composite pore structural had bigger can several apertures, be rich in abundant mesoporously, the pore volume of its median pore diameter 30～60 nanometers accounts for 20～75% of total pore volume.Catalyst by preparing carriers provided by the invention can be used for hydrogenation reaction and hydrotreatment, in particular for full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) selective hydrogenation process of drippolene.Catalyst by preparing carriers provided by the invention is being used for full cut (C
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) during the drippolene selective hydrogenation, have the hydrogenation activity height, and have good anti-high colloid and Nai Gao free water performance.Than 80: 1, the green oil air speed was 3.8 hours in 40 ℃ of inlet temperatures, reaction pressure 2.65Mpa, hydrogen/oil volume
-1Under the condition, be that 150 milligrams/100 gram oil, free water content are the full cut (C of 1000ppm to gum level
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene carries out selective hydrogenation reaction, and its outlet diene mean value is 0.0 gram iodine/100 gram oil, and the diolefin hydrogenation rate is 100%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.But these embodiment in no case are construed as limiting scope of the present invention.
The specific embodiment
Agents useful for same among the embodiment except that specifying, is AR.
Embodiment 1～3 explanation alumina support provided by the invention and preparation method thereof.Wherein the specific area of used boehmite is 274.32 meters
2/ gram, pore volume are 0.70 milliliter/gram, and average pore size is 10.21 nanometers.
[embodiment 1]
Take by weighing boehmite 300 grams, 30 gram δ aluminium oxide, 9 gram sesbania powder, 18 gram poly-vinyl alcohol solutions (mass concentration is 5%), 4.0 gram nitric acid mixes, and is extruded into the clover of 2.5 millimeters of φ, wet bar through 100 ℃ of dryings after 2 hours in 900 ℃ of roastings 8 hours, obtain carrier Z1.Adopt mercury injection method measure the specific surface of Z1, pore volume, can several apertures and pore size distribution, the results are shown in Table 1.
[embodiment 2]
Take by weighing boehmite 300 grams, 150 gram alpha-aluminium oxides, 12 gram sesbania powder, 30 gram poly-vinyl alcohol solutions (mass concentration is 5%), 6.0 gram acetic acid mixes, and is extruded into the clover of 2.5 millimeters of φ, wet bar through 50 ℃ of dryings after 24 hours in 1000 ℃ of roastings 4 hours, obtain carrier Z2.Adopt mercury injection method measure the specific surface of Z2, pore volume, can several apertures and pore size distribution, the results are shown in Table 1.
[embodiment 3]
Take by weighing boehmite 200 grams, 200 gram θ aluminium oxide, 12 gram sesbania powder, 25 gram poly-vinyl alcohol solutions (mass concentration is 5%), 4.0 gram nitric acid, 34 gram aluminium colloidal sols mix, and are extruded into the clover of 2.5 millimeters of φ, wet bar through 80 ℃ of dryings after 6 hours in 1100 ℃ of roastings 2 hours, obtain carrier Z3.Adopt mercury injection method measure the specific surface of Z3, pore volume, can several apertures and pore size distribution, the results are shown in Table 1.
[comparative example 1]
Take by weighing boehmite 300 gram, 9 gram sesbania powder, 45 gram graphite mix, and are extruded into the clover of 2.5 millimeters of φ, wet bar through 120 ℃ of dryings after 4 hours in 1050 ℃ of roastings 4 hours, obtain carrier D1.Adopt mercury injection method measure the specific surface of D1, pore volume, can several apertures and pore size distribution, the results are shown in Table 1.
Table 1
Embodiment 4～6 explanation the results are shown in Table 2 by the catalyst of preparing carriers provided by the invention one-stage hydrogenation performance to the full-cut fraction pyrolysis gasoline of high colloid, high free water content.
[embodiment 4]
Get carrier 60 grams of embodiment 1 preparation, with carrier at excessive PdCl
2Flood in the maceration extract, be colourless, drain to maceration extract, drying, roasting makes the catalyst based Cl of Pd, and making final Pd content is 0.3% of alumina catalyst support weight.
[embodiment 5]
Get carrier 60 grams of embodiment 2 preparation, with the same catalyst based C2 of immersion process for preparing Pd of embodiment 4, making final Pd content is 0.3% of alumina catalyst support weight.
[embodiment 6]
Get carrier 60 grams of embodiment 3 preparation, with the same catalyst based C3 of immersion process for preparing Pd of embodiment 4, making final Pd content is 0.3% of alumina catalyst support weight.
[comparative example 2]
Get carrier 60 grams of comparative example 1 preparation, with the same catalyst based CD1 of immersion process for preparing Pd of embodiment 4, making final Pd content is 0.3% of alumina catalyst support weight.
Full cut (C with gum level 150 milligrams/100 gram oil, free water content 1000ppm
5Hydrocarbon～do is 204 ℃ a hydrocarbon compound cut) drippolene is raw material, its percentage by weight consists of C
5Hydrocarbon 15～16%, C
6～C
8Hydrocarbon 63～67%, C
9 +Hydrocarbon 17.7～18.5%, diene value 27.12.Estimate on 100 milliliters of small-sized insulation fix bed reactors respectively with above-mentioned catalyst C1, the C2 that obtains, C3, CD1, wherein reaction condition is 40 ℃ of temperature, pressure 2.65MPa, green oil air speed 3.8 hours
-1, hydrogen/oil volume ratio is 80: 1, its evaluation result sees Table 2.
Table 2
| Embodiment | The catalyst numbering | Outlet diene value (gram iodine/100 gram oil) | Diolefin hydrogenation rate % |
| 4 | C1 | 0.25 | 99.0 |
| 5 | C2 | 0.1 | 99.6 |
| 6 | C3 | 0.0 | 100.0 |
| Comparative example 2 | CD1 | 3.4 | 86.4 |
Can see that by table 2 result the one-stage hydrogenation performance that the catalyst that the invention provides preparing carriers adapts to the full-cut fraction pyrolysis gasoline of high colloid, high free water content obviously is better than the catalyst of existing macropore alumina supporter preparation.
Claims (4)
1. preparation method with alumina support of composite pore structural, comprise aluminium oxide moulding and roasting, it is characterized in that before moulding and roasting, earlier aluminium oxide A and aluminium oxide B are mixed in required ratio, add entry and peptizing agent, after extrusion, moulding again 50～100 ℃ dry 1～24 hour down, roasting 1～10 hour under 800～1150 ℃ of conditions then, carrier; Wherein, aluminium oxide A is at least a for being selected among hibbsite, boehmite, boehmite or the amorphous hydroted alumina, aluminium oxide B is at least a for being selected from γ, η, δ, θ, κ or the alpha-phase aluminum oxide, and wherein the weight ratio of aluminium oxide A and aluminium oxide B is 1: 0.1～1; The carrier specific area that makes is 40～160 meters
2/ gram, total pore volume is 0.3～1.2 a milliliter/gram, and the pore volume of bore dia＜30 nanometers accounts for 5～60% of total pore volume, and the pore volume of bore dia 30～60 nanometers accounts for 20～75% of total pore volume, and the pore volume of bore dia＞60 nanometers accounts for 20～60% of total pore volume.
2. the alumina support with composite pore structural according to claim 1, it is characterized in that aluminium oxide A is selected from least a among hibbsite or the boehmite, aluminium oxide B is selected from least a in δ, θ or the alpha-phase aluminum oxide, and the weight ratio of aluminium oxide A and aluminium oxide B is 1: 0.2～1.
3. according to the described preparation method with alumina support of composite pore structural of claim 1, it is characterized in that described sintering temperature is 900～1100 ℃, roasting time is 2～8 hours.
4. the preparation method with alumina support of composite pore structural according to claim 1 is characterized in that the carrier specific area that makes is 50～150 meters
2/ gram, total pore volume are 0.4～1.0 milliliter/gram, the pore volume of bore dia＜30 nanometers account for total pore volume 5～55%, the pore volume of bore dia 30～60 nanometers accounts for 20～72% of total pore volume, the pore volume of bore dia＞60 nanometers accounts for 20～30% of total pore volume.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610029963XA CN101121120B (en) | 2006-08-11 | 2006-08-11 | Preparation method of aluminium oxide carrier with composite holes structure |
| KR1020097004763A KR101402093B1 (en) | 2006-08-11 | 2007-08-02 | Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline |
| US12/377,157 US8110527B2 (en) | 2006-08-11 | 2007-08-02 | Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline |
| PCT/CN2007/002321 WO2008019581A1 (en) | 2006-08-11 | 2007-08-02 | Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline |
| TW096129009A TW200906487A (en) | 2006-08-11 | 2007-08-07 | Alumina having a complex pore structure, and catalyst and process for selective hydrogenation of cracking gasoline |
| DE102007037785.3A DE102007037785B4 (en) | 2006-08-11 | 2007-08-07 | Process for the selective hydrogenation of pyrolysis gasoline |
| FR0757026A FR2904783B1 (en) | 2006-08-11 | 2007-08-10 | MULTIPOREUS STRUCTURE ALUMINA, CATALYST AND SELECTIVE HYDROGENATION PROCESS OF PYROLYTIC ESSENCE |
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| CN200610029963XA CN101121120B (en) | 2006-08-11 | 2006-08-11 | Preparation method of aluminium oxide carrier with composite holes structure |
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| CN101121120B true CN101121120B (en) | 2010-09-01 |
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| CN109126754B (en) * | 2018-09-03 | 2021-08-03 | 中国石油天然气股份有限公司 | Alumina carrier with trimodal pore structure as well as preparation method and application thereof |
| CN109539713B (en) * | 2018-10-30 | 2020-11-10 | 北京科荣达航空科技股份有限公司 | Pressure equalizing device of aviation spare part drying cabinet |
| CN111482203B (en) * | 2019-01-25 | 2023-04-11 | 上海杰标能源科技有限公司 | Method for molding hollow spherical carrier |
| CN111744483B (en) * | 2019-03-28 | 2021-09-07 | 中国石油化工股份有限公司 | Aluminum oxide, preparation method and application thereof |
| CN114433189A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Aromatization catalyst and preparation method and application thereof |
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