CN1218713A - Ball-aluminium oxide containing lithium - Google Patents
Ball-aluminium oxide containing lithium Download PDFInfo
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- CN1218713A CN1218713A CN 97121809 CN97121809A CN1218713A CN 1218713 A CN1218713 A CN 1218713A CN 97121809 CN97121809 CN 97121809 CN 97121809 A CN97121809 A CN 97121809A CN 1218713 A CN1218713 A CN 1218713A
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Abstract
The ball aluminium oxide is produced with alpha-gibbsite powder, which is first produced into x-Al2O3 through fast dewatering at 400-800 deg.C for 0.05-0.5 sec, rolling to form ball, curing, hydration, drying and roasting at 450-500 deg.C. The x-Al2O3 is further produced into the ball aluminium oxide through treatment of water or ammonia water under saturated vapor pressure and at 120-220 deg.C, drying, soaking in the solution of lithium compound, drying and roasting at 600-700 deg.C. The ball aluminium oxide may be also produced by soaking x-Al2O3 directly in lithium compound solution and roasting after drying at 600-970 deg.C in the air. It has the features of large pores, low specific surface area and low acidity, and is suitable for use as carrier of catalyst for selective hydrogenation or hydramination of fatty alcohol.
Description
The present invention is a kind of activated alumina, specifically, is a kind of spherical activated alumina that contains lithium.
Activated alumina is commonly used does catalyst carrier, also other purposes can be arranged, as adsorbent, dehydrating agent etc.Its preparation method is a lot, and the character of aluminium oxide can exist than big-difference because of preparation method's difference.
USP 3,222, and the technology of preparing of 129 pairs of activated aluminas is described to some extent, its process is with aluminum hydroxide particles partial roasting in stove, grinds into required particle size then, subsequently with water mixing balling-up and gel, particle after the gel heats at low temperatures, then calcination activation.For example: gibbsite is subdivided into particle less than 100 μ m, heating is to change the gibbsite structure under being no more than 500 ℃, crystallization water is volatilized during this, to such an extent as to the dehydration material of part is ground particle and is become minimum, 1～2 μ m just, the particle after the grinding mixes the formation gelatinised granule with water, then at low temperatures, for example 100 ℃, heat and carried out slaking (curing) in several hours, under the temperature that is higher than 700 (371 ℃), heat a period of time then.The improvements of this patent are with gibbsite that with fuel-air Mixture by burning zone, the temperature of flame reaches 3000～3500 °F (1667～1944 ℃) during burning, chilling then, and the chilling temperature is 1/4 or 1/6 of a flame temperature.With conventional mode moulding, granulation, aging, hydration, 650-700 calcination activation makes activated alumina then.
USP 4,419, and 275 also disclose a kind of preparation method of aluminium oxide, and this method mainly is that the water content of boehmite in the control amorphous hydroted alumina slurries is 1.20～1.50mol/mol Al
2O
3, then with the dehydration of this slurries, make the shape of pre-sizing, drying, and in water vapour calcination activation, make aluminium oxide.With this aluminium oxide is carrier, and carried metal hydrogenation activity component can make the Hydrobon catalyst better desulphurizing activated and life-span.
DE2,826,095th, with gibbsite, fast dewatering obtains amorphous Al (OH) under 350～600 ℃, 0.05～0.5 second condition
3Catabolite, with catabolite hydration 0.5～10 hour under 20～100 ℃, the condition of pH value 5～12, become water-soluble basic aluminium salt with acid treatment more then.This aluminium salt is obtained activated alumina with conventional method moulding, drying, roasting.Conditioned disjunction treatment conditions when wherein controlling the catabolite hydration can change the pore structure of final product alumina granules within the specific limits.The aluminium oxide specific area that obtains is 200～400 meters
2/ gram, total pore volume is 0.45～0.9 centimetre
3/ gram.This method has been owing to increased acid treatment step, makes Al
2O
3Preparation process become comparatively loaded down with trivial details.
DE3301143A1 has introduced a kind of preparation method of Li-Al bead.This method is to make Al (OH) earlier
3Glueballs, other materials on the flush away glueballs are containing the Li ion solution with the Al glueballs, as exchanging in the LiOH solution, the Li ion are entered in the glueballs, use NH
4The remaining Li ion of OH solution flush away, the glueballs that the Li ion processing is crossed is put into the isopropyl alcohol immersion except that anhydrating and NH again
4OH, wherein soak time is very important, should be 20 minutes at least, otherwise the time is not enough, and sphere will be damaged when dry, and the surface clumps together.Bead drying after isopropyl alcohol soaks and 1200～1300 ℃ high-temperature roasting make the Li-Al bead.The Al/Li atomic ratio is 1: 1 in the gained Li-Al bead.This bead is mainly used in the nuclear fission reactor or is used to examine the poly-guard shield of handing over reactor.
It is cheap and easy to get to the purpose of this invention is to provide a kind of raw material, and the source is abundant, and preparation technology simply has the ball-aluminium oxide that contains lithium of macropore, low specific surface, low acidic character.
The lithium ball-aluminium oxide that contains provided by the invention, its lithium content are 0.1～2.0 heavy %, are preferably 0.3～1.0 heavy %.The specific surface of this ball-aluminium oxide is 40～140 meters
2/ gram, pore volume is 0.2～0.5 a milliliter/gram, the total acid content of mobile adsorption capacity heat method [seeing " CHARACTERISATION OF HITERO-GENEOVSCATALYST BY MODIFIED FLOW MICRO-CALORIMETRY " Themechimca Acta for details, 165 (1990) 171-182] mensuration of sample introduction is less than 6.0 * 10 in batches
-5MM/milligram.Its preparation method generates the variant aluminium oxide for being raw material with α-gibbsite powder through the high temperature fast dewatering, again this variant aluminium oxide roller forming, health, hydration, low-temperature bake is made x-Al
2O
3, again with x-Al
2O
3Carry out hydrothermal treatment consists or ammoniacal liquor heat treatment, use roasting behind this crystalline aluminum oxide of lithium compound solution impregnation after the drying again, make the ball-aluminium oxide that contains lithium.Above-mentioned preparation process also can directly be used lithium compound solution impregnation x-Al
2O
3, high-temperature roasting makes the ball-aluminium oxide that contains lithium in dry air then.
Specifically, the preparation process that contains the lithium ball-aluminium oxide provided by the invention is:
(1) α-gibbsite powder fast dewatering in 400～800 ℃, 0.05～0.5 second is obtained fast shedding,
(2) with fast shedding roller forming, health, hydration, drying, 450-500 ℃ of roasting gets x-Al
2O
3,
(3) gained x-Al
2O
3With water or ammoniacal liquor that 120-220 ℃, saturated vapor are depressed handle, after the drying, with lithium compound solution impregnation, drying, 600-750 ℃ roasting 4-6 hour.
Described step (3) also can be replaced by step (4):
(4) directly use lithium compound solution impregnation x-Al
2O
3, roasting is 4～6 hours in dry, 600～970 ℃ of dry air.
Fast shedding roller forming is operating as fast shedding is placed on the rotating disk of comminutor in the described step (2), rolls while spraying water, and adjusts rotating speed and angle, to meet the requirements of particle diameter.Wherein the consumption of water is 15～40% times of fast shedding weight.Particle needs health at room temperature 12～24 hours after the spin, be hydration 5～8 hours under 5.0～10.0 the condition at 60～100 ℃, pH value then, the volume of hydration institute water was not advisable to have the aluminium hydroxide bead, was preferably 1.2～3.5 times of aluminium hydroxide bead volume.The gained ball was 80～120 ℃ of dryings 4～8 hours after the hydration, and roasting generated x-Al in 4～6 hours in 450～500 ℃ of flow of dried air
2O
3
X-Al in the described step (3)
2O
3, heat-treat with water or ammoniacal liquor that 120～220 ℃, saturated vapor are depressed, the volume ratio of water or ammoniacal liquor and Al2O3 ball is 1.2～3.5 during heat treatment, the processing time is 2～60 hours.Wherein the concentration of ammoniacal liquor is 1.0～5.0 heavy %.Al after hydro-thermal or the ammoniacal liquor heat treatment
2O
3Ball in 80～120 ℃ of flow of dried air dry 4～8 hours, the lithium compound solution with scheduled volume carries out saturated dipping then.The lithium compound consumption should make Al
2O
3In lithium content reach 0.1～2.0 heavy %, be preferably 0.3～1.0 heavy %.Dipping back bead was 80～120 ℃ of dryings 4～8 hours, and roasting is 4～6 hours in 600～750 ℃ of flow of dried air.
The same step of drying condition (3) in the described step (4), sintering temperature is 600～970 ℃, is preferably 900～970 ℃.
The preferred lithium hydroxide of described lithium compound, lithium nitrate or lithium chloride, highly preferred is lithium nitrate.
The lithium ball-aluminium oxide that contains provided by the invention can be used as catalyst carrier, is particularly suitable as the carrier of selective hydrogenation catalyst for pyrolysis gasoline, also is suitable for the carrier by the synthetic tertiary amine catalyst of fatty alcohol.
Provided by the invention to contain lithium ball-aluminium oxide preparation technology simple, and easy operating, raw material are α-gibbsite that Bayer process is produced, and the source is abundant, cheap, and the lithium ball-aluminium oxide that contains that makes has macropore, low specific surface, low acid characteristics.With this aluminium oxide is the selective hydrocatalyst of making after the carrier to load metal hydrogenation activity component, its activity, and it is the similar hydrogenation catalyst of carrier that selectivity all is better than with simple aluminium oxide with stability.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
The preparation of this example water heat treating process contains the lithium ball-aluminium oxide.
In the container with 1000 gram α-gibbsite powder (Shandong Aluminum Plant adopts Bayer process production, and solid content is the heavy % of 60-65), the 2 liters of vibrations of packing into, and make it fast by 700 ℃ of high-temperature regions, the time of staying is 0.5 second.Then fast shedding is put into rolling limit, small-sized comminutor limit water spray, the control injection flow rate is 300 grams, and it is 2～4 millimeters that the angle of adjustment comminutor and rotating speed make the spin particle diameter.Collect the gained ball and place sealing bag, health is 24 hours under the room temperature, puts into 90 ℃, pH value and be 7 water hydration 8 hours, and with wet bulb in 120 ℃ of flow of dried air dry 8 hours, roasting was 4 hours in 450 ℃ of dry air, obtains x-Al then
2O
3, its X-ray diffraction spectrogram as shown in Figure 1.
With 100 gram x-Al
2O
3Put into airtight autoclave pressure with 250 gram deionized waters, be warming up to 160 ℃ and handled 4 hours, 120 ℃ of dryings 8 hours, with lithium hydroxide solution dipping 1 hour, lithium content was 0.7 weight % to the consumption of lithium hydroxide in the aluminium oxide in order to make then.Dipping back was 120 ℃ of dryings 8 hours, and roasting is 4 hours in 720 ℃ of flow of dried air, must contain the spherical Al of lithium
2O
3A-3.Its physical and chemical performance sees Table 1.Intensity adopts ZQJ intelligence granule strength testing machine to measure in the table 1, and the heap ratio adopts the graduated cylinder method to measure, and total acid content adopts sample introduction flow method mensuration in batches.
Example 2
This example also contains the lithium ball-aluminium oxide for the preparation of water heat treating process.
Get the x-Al of 100 gram examples, 1 preparation
2O
3Put into airtight autoclave pressure with 250 gram deionized waters, be warming up to 200 ℃ and handled 4 hours, 120 ℃ of dryings 8 hours, 55 ml solns that are made into 7.2 gram lithium nitrates flooded 1 hour then, 120 ℃ of dryings 8 hours, roasting is 4 hours in 720 ℃ of flow of dried air, lithium content be the spherical Al of 0.7 heavy %
2O
3A-4.Its physical and chemical performance sees Table 1.
Example 3
This example contains the lithium ball-aluminium oxide with the preparation of ammoniacal liquor heat treating process.
Get the x-Al that 50 gram examples 1 make
2O
3(concentration is 2.1 heavy % with 250 milliliters of ammoniacal liquor, proportion is 0.99) put into closed container, handled 6 hours 120 ℃ of dryings 8 hours down at 195 ℃, flooded 1 hour with lithium hydroxide solution then, lithium content is 0.5 heavy % to the consumption of lithium hydroxide in the aluminium oxide in order to make in this solution.Dipping back wet bulb was 120 ℃ of dryings 8 hours, and roasting is 4 hours in 720 ℃ of flow of dried air, must contain lithium ball-aluminium oxide A-7.Physical and chemical performance sees Table 1.
Example 4～6
Following example lithium compound solution direct impregnation x-Al
2O
3Preparation contains the lithium ball-aluminium oxide.
X-Al with 1 preparation of 50 gram examples
2O
3, put into by a certain amount of LiOHH
2Dipping is 6 hours in 50 ml solns of O preparation, 120 ℃ of dryings 4 hours, and roasting is 4 hours in 900 ℃ of flow of dried air.Must contain lithium ball-aluminium oxide A-5, A-8, A-9, wherein the physicochemical property of A-5 sees Table 1.LiOHH during preparation
2Lithium content and surface acidity see Table 2 in the consumption of O and the gained aluminium oxide.The surface acidity assay method is an infrared spectrum pyridine adsorption method.By table 2 data as can be known in the aluminium oxide lithium content little to its acid influence.
Comparative example 1
With the hydration of example 1 preparation, dried aluminium hydroxide 100 grams, without low-temperature bake with soak the lithium step, roasting is 4 hours in 900 ℃ of flow of dried air, makes ratio aluminum oxide B, and its physical and chemical performance sees Table 1.
Comparative example 2
By the method preparation contrast ball-aluminium oxide C for preparing ball-aluminium oxide B, different is that sintering temperature is 720 ℃, and its physical and chemical performance sees Table 1.
Example 7
This example is the preparing carriers selective hydrocatalyst with ball-aluminium oxide provided by the invention.
A-5, A-7 alumina balls with 50 grams are carrier respectively, the Ni (NO of each personal 29.2 gram
3)
26H
2The 27 ml solns dipping of O preparation 12 hours, 120 ℃ of dryings, 450 ℃ of roastings make selective hydrocatalyst E, F.Metal component content and physical and chemical performance see Table 3 in E, the F catalyst.
Example 8
The explanation of this example is the reactivity worth of the selective hydrocatalyst of preparing carriers with aluminium oxide provided by the invention.
On 270 milliliters of middle-scale devices, using catalyst E respectively is 14.0～29.5 gram I/100 grams with comparative catalyst D (D is industrial similar hydrogenation catalyst) to diene value, the bromine valency is that the drippolene of 62.5 gram Br/100 grams carries out hydrogenation reaction, reaction pressure is 2.7MPa, hydrogen/oil volume ratio is 180: 1, and the feedstock oil air speed is 8.0 hours
-1, wherein metal component content and the physical and chemical performance of catalyst D see Table 3, and reaction result sees Table 4.
By table 4 data is that activity, selectivity and the stability of the catalyst E of preparing carriers all is better than comparative catalyst D by aluminium oxide provided by the invention as can be known.
Example 9
This example is that aluminium oxide provided by the invention is the activity stability experiment of the hydrogenation catalyst of preparing carriers.
On 5 milliliters of micro-reactors, respectively catalyst F and contrast medium D are carried out the hydrogenation activity stability experiment.Testing raw materials used oil is that volume ratio is 1: 1 styrene and a cyclohexane.Live at the beginning of during evaluation the stage with recover the stage condition and be: 75 ℃ of temperature, pressure 1.5MPa, hydrogen/oil volume is than 720: 1, weight space velocity 33 hours
-1Evaluation result sees Table 5, and the activity of catalyst F and stability all are better than contrast medium D as shown in Table 5.
Example 10
This example is a preparing carriers aminating reaction catalyst with aluminium oxide provided by the invention.
Get 100 gram A-4 aluminium oxide, with the saturated dipping of 50 milliliters of maceration extracts of copper nitrate, nickel nitrate and chromic nitrate preparation 6 hours, 120 ℃ of dryings 8 hours, 450 ℃ of roastings 4 hours make aminating reaction catalyst G, and its composition sees Table 6.The consumption of Cu, Ni, Cr nitrate is to make the content of Cu in the aluminium oxide, Ni, Cr be respectively 12.5 heavy %, 1.2 heavy %, 1.0 heavy % during dipping.
Comparative example 3
Get 100 gram SB aluminium oxide (Chang Ling oil plant catalyst subsidiary factory), prepare aminating reaction catalyst H by the method for example 9, its composition sees Table 6.
Example 10
The explanation of this example is the aminating reaction catalyst of preparing carriers and comparative catalyst's reactivity worth with aluminium oxide provided by the invention.
Being reaction raw materials with lauryl alcohol and dimethylamine on 100 milliliters of devices, is catalyst with G, H respectively, carries out the reaction of synthesization of dimethyl lauryl amine in the presence of hydrogen.Dimethylamine is 5 with the volume ratio of alcohol during charging, and hydrogen is 20 with the volume ratio of alcohol, reaction condition and the results are shown in Table 7.It is that the aminating reaction catalyst of preparing carriers has higher tertiary amine selectivity that table 7 data show with aluminium oxide provided by the invention.
Table 1
Table 2
| Example | The alumina balls numbering | LiOHH during preparation 2The consumption of O, gram | Lithium content in the aluminium oxide, heavy % | Alumina surface acidity, absorbance/gram per centimeter 2 | |
| ????200℃ | ????350℃ | ||||
| ????4 | ????A-5 | ????2.1 | ????0.7 | ????10.7 | ????5.9 |
| ????5 | ????A-8 | ????0.9 | ????0.3 | ????9.1 | ????5.9 |
| ????6 | ????A-9 | ????6.0 | ????2.0 | ????10.8 | ????6.3 |
Table 3
Table 4
Table 5
| The catalyst numbering | ????F | ????D | |
| Bearer number | ????A-7 | ????- | |
| Initial activity stage conversion ratio, % | 2 hours | ????79.3 | ????77.4 |
| 3 hours | ????78.6 | ????77.1 | |
| 4 hours | ????76.9 | ????75.8 | |
| Recovery stage conversion ratio, % | 2 hours | ????36.8 | ????37.0 |
| 3 hours | ????36.1 | ????35.0 | |
| 4 hours | ????35.5 | ????34.5 | |
Table 6
Table 7
*Tertiary amine refers to the dimethyl lauryl amine
Claims (8)
1. ball-aluminium oxide that contains lithium, its lithium content are 0.1～2.0 heavy %, and specific area is 40～140 meters
2/ gram, pore volume are 0.2～0.5 milliliter/gram, and total acid content is less than 6.0 * 10
-5MM/milligram is characterized in that the preparation process of this aluminium oxide is:
(1) α-gibbsite powder fast dewatering in 400～800 ℃, 0.05～0.5 second is obtained fast shedding,
(2) with fast shedding roller forming, health, hydration, drying, 450-500 ℃ of roasting gets x-Al
2O
3,
(3) with gained x-Al
2O
3After water of depressing with 120-220 ℃, saturated vapor or WITH AMMONIA TREATMENT, the drying, with lithium compound solution impregnation, drying, 600-750 ℃ roasting 4-6 hour.
2. according to the described aluminium oxide of claim 1, it is characterized in that step (3) can be replaced by step (4):
(4) directly use lithium compound solution impregnation x-Al
2O
3, drying, and in 600-970 ℃ of dry air roasting 4-6 hour.
3. according to the described aluminium oxide of claim 1, the content that it is characterized in that lithium in this carrier is 0.3～1.0 heavy %.
4. according to claim 1 or 2 described aluminium oxide, it is characterized in that the temperature of hydration in the step (2) is 60-100 ℃, pH value is 5-10, and the time is 5-8 hour.
5. according to the described aluminium oxide of claim 1, the concentration that it is characterized in that ammoniacal liquor in the step (3) is 1.0～5.0 heavy %.
6. according to the described aluminium oxide of claim 2, it is characterized in that sintering temperature is 900-970 ℃.
7. according to claim 1 or 2 described aluminium oxide, it is characterized in that the lithium compound described in step (3) or (4) is lithium hydroxide, lithium nitrate, lithium chloride.
8. according to the described aluminium oxide of claim 7, it is characterized in that described lithium compound is a lithium nitrate.
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|---|---|---|---|
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|---|---|---|---|
| CN97121809A CN1088396C (en) | 1997-11-28 | 1997-11-28 | Ball-aluminium oxide containing lithium |
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| CN1088396C CN1088396C (en) | 2002-07-31 |
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| CN102309995A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for lithium-containing alumina carrier |
| CN103480427A (en) * | 2012-06-11 | 2014-01-01 | 中国石油化工股份有限公司 | Lithium containing hydrated alumina forming material and its application, eggshell type catalyst and its preparation method and application and method for preparing vinyl carboxylates |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031398A (en) * | 1987-06-15 | 1989-03-01 | 东北工学院 | The preparation method of aluminium otide containing lighium |
| IN171590B (en) * | 1987-07-31 | 1992-11-21 | Eniricerche Spa |
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- 1997-11-28 CN CN97121809A patent/CN1088396C/en not_active Expired - Lifetime
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| CN103480427A (en) * | 2012-06-11 | 2014-01-01 | 中国石油化工股份有限公司 | Lithium containing hydrated alumina forming material and its application, eggshell type catalyst and its preparation method and application and method for preparing vinyl carboxylates |
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| CN103480249B (en) * | 2012-06-11 | 2015-10-28 | 中国石油化工股份有限公司 | Hydrated alumina forming matter and preparation method and aluminium oxide article shaped and catalyst and preparation method and application and hydrotreating method |
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| WO2022037483A1 (en) * | 2020-08-17 | 2022-02-24 | 中国石油天然气股份有限公司 | Alumina, preparation method therefor, composite alumina catalyst and use thereof in claus reaction process |
| CN114146699A (en) * | 2020-08-17 | 2022-03-08 | 中国石油天然气股份有限公司 | Catalyst for organic sulfur hydrolysis and preparation method thereof |
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|---|---|
| CN1088396C (en) | 2002-07-31 |
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