CN1068975A - The preparation method of low-density, large pore volume, high-strength alumina carrier - Google Patents

The preparation method of low-density, large pore volume, high-strength alumina carrier Download PDF

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CN1068975A
CN1068975A CN 92109379 CN92109379A CN1068975A CN 1068975 A CN1068975 A CN 1068975A CN 92109379 CN92109379 CN 92109379 CN 92109379 A CN92109379 A CN 92109379A CN 1068975 A CN1068975 A CN 1068975A
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colloidal sol
alumina
aluminium
aluminium colloidal
oil column
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CN1030601C (en
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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

Aluminium salt or aluminate obtain boehmite through neutralization, and the aluminium colloidal sol with acid treatment obtains adds gelling agent, and through forming oil column, aging, dry, roasting prepares γ-Al 2O 3, its particle diameter is 1.0～3.0mm, 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, aperture 300～600A, crushing strength is 0.5～3.0kgf/ grain, this γ-Al 2O 3Carrier is particularly suitable for as the dehydrogenation of long-chain alkane catalyst.

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.
The alumina sol of preparation alumina support is pressed aluminium source difference, and can be divided into two lines: one is to prepare aluminium colloidal sol with metallic aluminium, generally is to be dissolved in the hydrochloric acid with highly purified metallic aluminium, perhaps at AlCl 3Aluminium colloidal sol is made in digestion in the solution.Another is to prepare aluminium colloidal sol from hydrated alumina, generally is [as Al(NO by aluminium salt or aluminate 3) 3, AlCl 3, Al 2(SO 4) 3, or KAlO 2, NaAlO 2] use nertralizer [as NH 4OH, KOH, NaOH, Na 2CO 3Or HNO 3, HCl, Al 2(SO 4) 3Deng] neutralizing obtains hydrated alumina, makes aluminium colloidal sol through peptization.Other also can prepare hydrated alumina from the aluminium alcoholates hydrolysis.
Aluminium colloidal sol is through further forming processes, and steps such as aging, drying, roasting obtain the finished product aluminium oxide at last.
United States Patent (USP) 2620314 is to adopt hydrochloric acid-metallic aluminium to make aluminium colloidal sol, obtains spherical gamma-Al through forming oil column, pressure aging, washing, drying, roasting, hydrothermal treatment consists reaming 2O 3
United States Patent (USP) 4390456 is that employing aluminum sulfate-sodium metaaluminate is made raw material, neutralization obtains boehmite-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
CN87101513A, be under 60～80 ℃, to neutralize, obtain aluminium chloride, colloidal sol moulding in oil-ammonia post with alchlor and ammoniacal liquor, through aging, washing, drying, roasting, hydrothermal treatment consists, the water vapour reaming is handled and is obtained spherical gamma-Al under 600～800 ℃ of conditions then 2O 3
These prior arts part that all comes with some shortcomings, for example, their required operations are many, and each operation required time is long; It is that raw material is serious to equipment corrosion that prior art adopts alchlor, hydrochloric acid; CN87101513 adopts oil-ammonia post moulding, and bead causes sphericity poor during by oil-ammonia interface, and the bead hardening process relies on ammonia progressively to permeate in spheroid, need wash after aging, and the water vapour reaming is handled, and influences the intensity of product.γ-the Al of United States Patent (USP) 4390456 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, has prepared than low-density, and eurypyloue, and the alumina support of high strength and suitable specific surface is arranged simultaneously.This carrier is particularly suitable for dehydrogenation of long-chain alkane catalyst usefulness, because the big (C of the molecular proportion of long chain alkane 10～C 13), so require that bigger aperture is arranged, to satisfy the requirement of catalyst regeneration needs higher-strength in addition.
Concrete grammar of the present invention is as follows:
In the presence of the soluble carbon hydrochlorate, with aluminum sulfate aqueous solution and the sodium hydrate aqueous solution or the sodium aluminate solution neutralization of certain proportioning, the control reaction temperature is 60～90 ℃, pH value is 7～10, continuous stirring, in and the time be 2～5 hours, the sediment that obtains washes with water, filters.Add rare nitric acid in the filter cake, making beating evenly is heated to 90 ℃, adds the 15～30%(weight that is equivalent to alumina content in the aluminium colloidal sol), particle is less than 200 purpose alumina powders.Stir, cool to below 15 ℃, add and be equivalent to Al 2O 330～50% hexa gelling 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 gatherer 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 technological 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 catalyst of preparing carriers with the result of the test 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 catalyst.
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 aluminum sulfate solution: the Al that takes by weighing 1249 grams 98% 2(SO 4) 3, 18H 2O is dissolved in 1000 milliliters of deionized waters, adds thermal agitation, is diluted to 2500 milliliters.
The alkali lye for preparing and aluminum sulfate solution squeezed into two infusion pumps respectively carry out in one 5000 milliliters the beaker and flow neutralization reaction, the control reaction temperature is 70～80 ℃, and pH value is 7～9, and mixing speed is 480 rev/mins, in and the time be 5 hours, the sediment that obtains washes with water, suction filtration; Get 1/4th filter cake 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 ℃, add 35%(wt) 20 milliliters of hexas, stirred 10 minutes, keep aluminium colloidal sol below 15 ℃, use for moulding.
Forming oil column and post processing: oil column is one high 1500 millimeters, and diameter is 60 millimeters a glass tube, and the bottom is that 2000 milliliters glass container is as gatherer with a volume.Be full of white oil in the post, place 30～40 milliliters of alumina desiccants in the gatherer 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 γ-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
Average pore size 354
Figure 921093799_IMG2
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 aluminum sulfate solution 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
Average pore size 338
Figure 921093799_IMG3
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 aluminium 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 2O 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
Average 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 in every liter of solution after cooling off naturally and contains Al 2O 3Be the sodium aluminate solution of 200 grams, aluminum sulfate solution 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
Average pore size 316
Figure 921093799_IMG5
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 in every liter of solution after cooling off naturally and contains Al 2O 3It is the sodium aluminate solution of 200 grams.
Aluminum sulfate solution and stream neutralization with above-mentioned sodium aluminate solution and the preparation of example 1 method, temperature is 80～90 ℃, PH is about 9, the aluminum sulfate 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
Average pore size 181
Specific surface 220m 2/ g
Crushing strength 1.2kgf/ grain
Embodiment 6(expanding test)
Press the process conditions of example 1, on the expanding test device, prepare γ-Al 2O 3500 liters of preparation aluminum sulfate solutions, relative density is 1.28g/cm 3; 500 liters of NaOH solution, relative density are 1.20g/cm 3; Also stream neutralization in one two cubic metres reactor, neutrality condition is identical with embodiment 1, and the gained sediment 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 aluminium oxide and make aluminium colloidal sol.On the expanding test device, carry out forming oil column and post processing, 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
Average pore size 341
Figure 921093799_IMG7
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 infusion process to make two catalyst A and B respectively.On micro-reaction equipment, carry out the test of dehydrogenation of long-chain alkane performance, experimental condition: 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 pyrolysis product calculates the conversion ratio and the selectivity of two catalyst, and its result is as follows:
React reaction in 8 hours 96 hours
Conversion ratio % selectivity % conversion ratio % 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 catalyst C of different activities constituent content, has carried out 500 hours life test.Reaction condition 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 (LHSV) is 20 hours -1, test result is as follows after 500 hours:
Conversion ratio % selectivity %
Catalyst A 14.86 81.58
Catalyst C 12.97 84.34

Claims (6)

1, aluminium salt or aluminate obtain boehmite through neutralization, wash with water after acid treatment obtains aluminium colloidal sol, add gelling agent and prepare ball-aluminium oxide through forming oil column, aging, dry, roasting, the neutralization reaction that it is characterized in that aluminum sulfate and NaOH or sodium metaaluminate is to carry out in the presence of auxiliary nertralizer carbanion; Carry out obtaining aluminium colloidal sol after the acid treatment with nitric acid, add alumina powder and mix well; When adopting forming oil column, add the hexa gelling agent, forming process is to carry out in the oil column of gatherer bottom elder generation placement alumina desiccant, and continues aging; To obtain particle diameter be 1.0～3.0mm for drying, roasting then, 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 3Carrier, this γ-Al 2O 3Carrier is particularly suitable for as the dehydrogenation of long-chain alkane catalyst.
2, auxiliary nertralizer carbanion according to claim 1 can be the soluble carbon hydrochlorate, as carbonic hydroammonium, and sodium acid carbonate, sodium carbonate etc.
3, the addition according to claim 1 and 2 described auxiliary nertralizer carbonate is: the mol ratio of carbonate/aluminium oxide is 0.1～1.0.
4, alumina powder according to claim 1 can be the boehmite sediment that aluminum sulfate and NaOH or sodium metaaluminate neutralization obtain, through washing, filter, dry, at 450～1000 ℃, more preferably divide behind 500～700 ℃ of roasting temperatures sift out less than 200 purpose alumina powders.
5, the addition according to claim 1 and 4 described alumina powders is 15～30%(weight of alumina content in the aluminium colloidal sol).
6, the aluminium colloidal sol of adding gelling agent according to claim 1 is to carry out moulding in the oil column of gatherer bottom elder generation placement alumina desiccant, and the place mat amount of alumina desiccant is 10～30% of an aluminium colloidal sol cumulative volume; The oil temperature is 95～110 ℃ during moulding, and holding temperature continued aging 2～5 hours behind the chou bundle.
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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CN1043312C (en) * 1993-06-24 1999-05-12 中国石油化工总公司 Method for producing alumina carrier
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