CN1030601C - Preparation method for carrier of low density, large void content and high intensity aluminium oxide - Google Patents

Preparation method for carrier of low density, large void content and high intensity aluminium oxide Download PDF

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Publication number
CN1030601C
CN1030601C CN 92109379 CN92109379A CN1030601C CN 1030601 C CN1030601 C CN 1030601C CN 92109379 CN92109379 CN 92109379 CN 92109379 A CN92109379 A CN 92109379A CN 1030601 C CN1030601 C CN 1030601C
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China
Prior art keywords
colloidal sol
aluminium colloidal
ranges
carrier
alumina
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Expired - Fee Related
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CN 92109379
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Chinese (zh)
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CN1068975A (en
Inventor
姜泰万
张兴国
谭克勤
杨祖润
薛秀男
陈永生
马群
李凯荣
付立郡
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Tianjin Chemical Inst., Ministry of Chemical Ind.
China Petrochemical Corp
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TIANJIN CHEMICAL ENGINEERING INST MINISTRY OF CHEMICAL INDUSTRY
China Petrochemical Corp
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Abstract

Pseudo-boehmite is prepared by neutralizing aluminum salt or aluminate, and is acidified to prepare aluminum colloidal sol, gelling agent is added, and gamma-Al2O3 is prepared after oil column forming, ageing, dryness and baking. The particle diameter ranges from 1.0 to 3.0mm, the specific surface area ranges from 120 to 280cm<2>/g., the bulk density ranges from 0.18 to 0.35 g/cm<3>, the hole capacity ranges from 1.5 to 2.0cm<3>/g, the hole diameter ranges from 300 to 600 angstroms, and the crushing strength ranges from 0.5 to 3.0 kgf/grain. The gamma-Al2O3 carrier is especially used as a dehydrogenation catalyst with long alkane chains.

Description

The preparation method of low density, large pore volume, high-strength alumina carrier
The present invention is a kind of low density, large pore volume, high-intensity spherical gamma-Al 2O 3The preparation method of carrier.
United States Patent (USP) 4390456 is that employing Tai-Ace S 150 sodium metaaluminate is made raw material, neutralization obtains boehmite-pseudo-boehmite intermediate, and spray-dried, peptization is made aluminium colloidal sol, carries out oil-ammonia post moulding, and spherical gamma-Al is made in aging in the ammoniacal liquor, dry, roasting 2O 3
γ-Al by this method preparation 2O 3Need operation many, and each operation required time is long, the γ-Al that obtains 2O 3Bulk density is higher (greater than 0.45g/cm 3, pore volume is less.
The pore volume of carrier is a mutual restriction between the parameters such as specific surface, bulk density, intensity.Our goal of the invention is the some shortcomings part that overcomes prior art, prepares to have to be suitable for the dehydrogenation of long-chain alkane catalyzer with γ-Al than low density, higher-strength, larger aperture 2O 3Carrier.This γ-Al 2O 3Carrier has following character: particle diameter is 1.0～3.0mm, and specific surface is 120～280m 2/ g, bulk density are 0.18～0.35g/cm 3, pore volume is 1.5～2.0cm 3/ g, crushing strength is the spherical gamma-Al of 0.5～3.0Kgf/ grain 2O 3
Concrete grammar of the present invention is as follows:
In the presence of the soluble carbon hydrochlorate, with aluminum sulfate aqueous solution and the aqueous sodium hydroxide solution or the sodium aluminate solution neutralization of certain proportioning, control reaction temperature is 60～90 ℃, pH value is 7～10, continuously stirring, in and the time be 2～5 hours, the throw out that obtains washes with water, filters.Add rare nitric acid in the filter cake, making beating evenly is heated to 90 ℃, adds 15～30% (weight) that are equivalent to alumina content in the aluminium colloidal sol, particle less than 200 purpose alumina powders.Stir, cool to below 15 ℃, add and be equivalent to Al 2O 330～50% vulkacit H jelling agent of amount continues to stir, and keeps aluminium colloidal sol below 15 ℃.Aluminium colloidal sol carries out forming oil column, places alumina desiccant in advance in the collector of oil column bottom, and it is in 95～110 ℃ the oil column that the aluminium colloidal sol of homogeneous splashes into temperature, and resulting bead under normal pressure aging 2～5 hours is separated oil, ball.Bead is dried under 100～120 ℃ of temperature, and then at 750～950 ℃ of roasting temperatures, obtaining particle diameter is 1.0～3.0mm, and specific surface is 120～280m 2/ g, bulk density are 0.18～0.35g/cm 3, pore volume is 1.5～2.0cm 3/ g, crushing strength is the spherical gamma-Al of 0.5～3.0kgf/ grain 2O 3
Compared with the prior art method of the present invention has reduced operations such as pressure aging, bead washing, hydro-thermal reaming processing, has shortened technical process, has also simplified operation.It is molten to have avoided high temperature to boil in the glue process, has alleviated the corrosion to equipment greatly, carrier yield height, and intensity also has raising.
In order to further specify method of the present invention, further specify method of the present invention below by embodiment, embodiment 1,2,3 and 4 is the γ-Al according to method preparation of the present invention 2O 3Carrier.Embodiment 7 and 8 is the γ-Al that use embodiment 1 and 2 respectively 2O 3The dehydrogenation of long-chain alkane catalyzer of preparing carriers with the test-results that approximate commercial production conditions is carried out, can find out that from the result they have good reaction activity, selectivity and well stable.Compare with embodiment 4, with the glue method of embodiment 5, owing to do not introduce carbanion, the product bulk density height (0.40g/cm that obtains 3), be not suitable for as the dehydrogenation of long-chain alkane catalyzer.
Embodiment 1
Preparation alkali lye: take by weighing the solid NaOH of 421 grams 95%, be dissolved in 1000 ml waters, the cooling back adds 92 gram NH 4HCO 3, stir and make it most of dissolving, continue to add water and make NH 4HCO 3All dissolving is diluted to 2000 milliliters.
Preparation alum liquor: the Al that takes by weighing 1249 grams 98% 2(SO 4) 2, 18H 2O is dissolved in 1000 milliliters of deionized waters, and heated and stirred is diluted to 2500 milliliters.
The alkali lye for preparing and alum liquor squeezed into two infusion pumps respectively carry out in one 5000 milliliters the beaker and flow neutralization reaction, control reaction temperature is 70～80 ℃, pH value is 7～9, stirring velocity is 480 rev/mins, in and the time be 5 hours, the throw out that obtains washes with water, suction filtration; Get 1/4th filter cakes 100～120 ℃ of dryings, 550 ℃ of roasting temperatures divide to sift out less than 200 purpose alumina powders and continue to employ.
System aluminium colloidal sol: take by weighing and be equivalent to 26 gram Al 2O 3Wet cake after the above-mentioned neutralization reaction of quantity places one 250 milliliters beaker, adds 55 milliliters of deionized waters, and making beating evenly back adds 20% (wt) HNO 313 milliliters of solution, continue making beating, be heated to 90 ℃, add 4 grams above-mentioned 550 ℃ of roasting temperatures obtain less than 200 purpose alumina powders, stir, stop heating, reduce the temperature to below 15 ℃, 20 milliliters of the vulkacit Hs of adding 35% (wt) stirred 10 minutes, keep aluminium colloidal sol below 15 ℃, use for moulding.
Forming oil column and aftertreatment: oil column is one high 1500 millimeters, and diameter is 60 millimeters a Glass tubing, and the bottom is that 2000 milliliters Glass Containers is as collector with a volume.Be full of white oil in the post, place 30～40 milliliters of alumina desiccants in the collector bottom in advance before the ball, heating reaches about 98 ℃ the oil column temperature, and the above-mentioned aluminium colloidal sol that has prepared can begin to drip a ball, and clock time dripped off above-mentioned aluminium colloidal sol in about 30 minutes.Holding temperature continued aging 4 hours.After the cooling oil and bead are separated, bead is placed in 100～120 ℃ the baking oven and dries, and dry 8 hours, changes over to and carries out roasting in the muffle furnace.Be warming up to 800 ℃ in 4 hours, 800 ℃ of following constant temperature 4 hours.Obtain spherical gamma-Al after the cooling 2O 3Product.The physical property measurement data are as follows:
Granularity 1.25～2.0mm
Bulk density 0.30g/cm 3
Pore volume 1.66cm 3/ g
Mean pore size 354
Crushing strength 1.0Kgf/ grain
Embodiment 2
Method similarly to Example 1 takes by weighing 462 and restrains 95% solid NaOH, is dissolved in the 1000ml water, adds 129.8 gram NH 4HCO 3, be mixed with 2000ml alkali lye.Adopt that the alum liquor identical with embodiment 1 neutralizes, glue, forming oil column, drying and roasting, obtain γ-Al 2O 3The rerum natura of product is as follows:
Granularity 1.25～2.0mm
Bulk density 0.32g/cm 3
Pore volume 1.69cm 3/ g
Mean pore size 338
Specific surface 172m 2/ g
Crushing strength 1.1Kgf/ grain
Embodiment 3
Press the same method of embodiment 1, take by weighing the beaker that the aluminum oxide wet cakes that are equivalent to 22 grams are put into 250ml, add the making beating of 120ml deionized water, drip 10% (wt) HNO 3Solution 32ml heats up and stirs, and adds 8 gram alumina powders under 85 ℃ of temperature, carries out glue, moulding, drying and roasting, obtains γ-Al 20 3The rerum natura of product is as follows:
Granularity 1.25～2.0mm
Bulk density 0.24g/cm 3
Pore volume 1.90cm 3/ g
Mean pore size 387
Specific surface 220m 2/ g
Crushing strength 1.0Kgf/ grain
Embodiment 4
Take by weighing 290 gram Na 2CO 3Be dissolved in the 1000ml deionized water, other takes by weighing the solid NaOH of 2100 grams 95%, is dissolved in the 2500ml water, is heated to 90 ℃, adds 2100 gram Al (OH) slowly 3, being warming up to 110 ℃ after the dissolving fully, constant temperature 3 hours is diluted to behind the naturally cooling in every liter of solution and contains Al 2O 3Be the sodium aluminate solution of 200 grams, alum liquor is with embodiment 1.
Method by embodiment 1 neutralizes, glue, forming oil column, drying and roasting, obtains γ-Al 2O 3The rerum natura of product is as follows:
Granularity 1.25～2.0mm
Bulk density 0.31g/cm 3
Pore volume 1.67cm 3/ g
Mean pore size 316
Specific surface 214m 2/ g
Crushing strength 1.0Kgf/ grain
Embodiment 5 (comparative example)
Take by weighing the solid NaOH of 2100 grams 95%, be dissolved in 2500 ml waters, be heated to 90 ℃, add 2100 gram Al (OH) slowly 3, being warming up to 110 ℃ after the dissolving fully, constant temperature 3 hours is diluted to behind the naturally cooling in every liter of solution and contains Al 2O 3Be the meta-aluminic acid solution of 200 grams.
Alum liquor and stream neutralization with above-mentioned sodium aluminate solution and the preparation of embodiment 1 method, temperature is 80-90 ℃, PH is about 9, the Tai-Ace S 150 flow is 1000 milliliters/hour, the sodium metaaluminate flow is 800 milliliters/hour, neutralization in 4 hours finishes, and carries out forming oil column, aging, dry, roasting then, obtains γ-Al 2O 3The physical index of product is:
Granularity 1.25～2.0mm
Bulk density 0.40g/cm 3
Pore volume 1.28cm 3/ g
Mean pore size 181
Specific surface 220m 2/ g
Crushing strength 1.2Kgf/ grain
Embodiment 6 (expanding test)
Press the processing condition of embodiment 1, on the expanding test device, prepare γ-Al 2O 3500 liters of preparation alum liquors, relative density is 1.28g/cm 3500 liters of NaOH solution, relative density are 1.20g/cm 3Also stream neutralization in one two cubic metres reactor, neutrality condition is identical with embodiment 1, and the gained throw out filters, washs with flame filter press, obtains 190 kilograms of filter cakes, get a part and carry out drying, 650 ℃ of following roastings, obtain less than 200 purpose alumina powders.Its specific surface is 310m 2/ g, pore volume are that 1.9ml/g, bulk density are 0.176ml/g.
Get the wet aluminium cake that is equivalent to 23.4 kilograms of aluminum oxide and make colloidal sol.On the expanding test device, carry out forming oil column and aftertreatment, the γ-AL that obtains 2O 3The physical index of product is as follows:
Granularity 1.25～2.0mm
Bulk density 0.31g/cm 3
Pore volume 1.62cm 3/ g
Mean pore size 341
Specific surface 155m 2/ g
Crushing strength 1.57Kgf/ grain
Embodiment 7
Spherical gamma-the AL that obtains by the method for embodiment 1 and 2 2O 3Carrier adopts pickling process to make two catalyst A and B respectively.On micro-reaction equipment, carry out the test of dehydrogenation of long-chain alkane performance, test conditions: pressure is 0.1～0.14MPa, temperature is 482 ℃, the mol ratio of hydrogen and hydrocarbon is 5.0～6.0, by the content of measuring monoolefine, diolefin in the products of dehydrogenation reactions, the increment of total non-n-alkane, the amount of split product calculates the transformation efficiency and the selectivity of two catalyzer, and its result is as follows:
React reaction in 8 hours 96 hours
Transformation efficiency % selectivity % transformation efficiency % selectivity %
Catalyst A 22.45 73.10 17.95 76.30
Catalyst B 23.00 73.80 16.80 80.20
Embodiment 8
Press the spherical gamma-Al of embodiment 1 method preparation 2O 3Carrier is made the catalyst A and the catalyzer C of different activities component concentration, has carried out 500 hours longevity test.Reaction conditions is near actual production process, and pressure is 0.14MPa, and reactor inlet temperature is 482 ℃, and the mol ratio of hydrogen and hydrocarbon is 6.0, and liquid hourly space velocity is that test result is as follows after 20 hours-1,500 hour:
Transformation efficiency % selectivity %
Catalyst A 14.86 81.58
Catalyzer C 12.97 84.34

Claims (1)

1. spherical gamma-Al who is suitable for doing carrier 2O 3, it has following character: particle diameter is 1.0～3.0mm, specific surface is 120～280m 2/ g, bulk density are 0.18～0.35Kg/cm 3, pore volume is 1.5～2.0cm 3/ g, crushing strength is 0.5～3.0Kgf/ grain; Its preparation method comprises the following steps: (1) in the presence of the soluble carbon hydrochlorate, and Tai-Ace S 150 and sodium hydroxide or sodium metaaluminate carry out neutralization reaction, and the add-on of carbonate is pressed carbonate/Al 2O 3Mol ratio is 0.1～0.8, and control reaction temperature is 60～90 ℃, and pH value is 7～10, and washing and filtering obtains wet cake; (2) wet cake makes aluminium colloidal sol with rare nitric acid peptization; (3) in aluminium colloidal sol, add less than 200 purpose γ-Al 2O 3Powder, add-on are to be equivalent to 15～30% of alumina content in the aluminium colloidal sol, and this alumina powder is to be obtained through washing, dry, roasting by the wet cake of step (1); (4) adding is equivalent to Al in the aluminium colloidal sol of mixing well 2O 330～50% vulkacit H jelling agent of amount is placed moulding in the oil column of alumina desiccant in advance in the collector bottom, and the place mat amount of alumina desiccant is 10～14% of an aluminium colloidal sol cumulative volume, and the oil temperature is 95～110 ℃ during moulding; (5) oily ball is separated, drying, roasting obtain spherical gamma-Al 2O 3Product.
CN 92109379 1992-08-17 1992-08-17 Preparation method for carrier of low density, large void content and high intensity aluminium oxide Expired - Fee Related CN1030601C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040845C (en) * 1993-07-16 1998-11-25 中国石油化工总公司 Preparation of micro-ball gamma aluminum oxide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040845C (en) * 1993-07-16 1998-11-25 中国石油化工总公司 Preparation of micro-ball gamma aluminum oxide

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