CN1114290A - Process for preparing spheric aluminium oxide with low density and big pore volume - Google Patents
Process for preparing spheric aluminium oxide with low density and big pore volume Download PDFInfo
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- CN1114290A CN1114290A CN 94107313 CN94107313A CN1114290A CN 1114290 A CN1114290 A CN 1114290A CN 94107313 CN94107313 CN 94107313 CN 94107313 A CN94107313 A CN 94107313A CN 1114290 A CN1114290 A CN 1114290A
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Abstract
The process for preparing T-Al2O3 particles with 0.5-3.5 mm of diameter, 0.15-0.38 g/cm3 of packing density, 1.4-2.2 cm3/g of pore volume, 100-300 m2/g of specific surficial area and 5-50N/per particle of compressive strength, used as carrier of immobilized enzyme or catalyst, includes such steps as preparing crystal seed from aluminium salt and/or aluminate, parallel-flow neutralizing to obtain quasi-thin empholite seed crystal, filtering, washing in water, acidifying to obtain aluminium sol, oil-column shaping, quick drying, and roasting.
Description
The invention belongs to fixed enzyme vector, petrochemical catalyst and other support of the catalyst.Adopt the forming oil column method to prepare ball-aluminium oxide and see United States Patent (USP) 2620314 the earliest, adopt aqueous hydrochloric acid digestion metallic aluminium to make aluminium colloidal sol, colloidal sol is moulding in oil column, through pressure aging, washing, drying, roasting, water vapor reaming are handled and are obtained ball-aluminium oxide.The method of United States Patent (USP) 4399119 comprises under the high-temperature and high-pressure conditions, obtain the aluminium chlorohydroxide aqueous solution with hydrochloric acid digestion gibbsite, dissolve an amount of metallic aluminium to increase aluminium content in the colloidal sol, add ammoniacal liquor and form the aluminum chloride water-sol that contains ammonia chloride, with colloidal sol and mixed, through forming oil column at the dissociable jelling agent of temperature-rise period, aging, washing, drying, spherical I-Al2O3 is made in roasting.
The method of United States Patent (USP) 4390456 comprises with sodium metaaluminate-Tai-Ace S 150 makes raw material, neutralization, and washing obtains boehmite-pseudo-boehmite intermediate, spray-dried, peptization is made aluminium colloidal sol, adopts oil-ammonia post moulding, aging in the ammoniacal liquor, drying, spherical I-Al2O3 is made in roasting.
Chinese patent application 92109379.9 is to obtain pseudo-boehmite with aluminium salt or aluminate through neutralization, and the aluminium colloidal sol with acid treatment obtains adds jelling agent, through forming oil column, aging, drying, roasting prepares I-Al2O3, and this kind I-Al203 is particularly suitable for as the dehydrogenation of long-chain alkane catalyzer.
Adopt hydrochloric acid digestion metallic aluminium and/or gibbsite under the high-temperature pressurizing condition, to carry out, serious to equipment corrosion; Aging after the moulding, pressure aging, technology length consuming time such as washing; Oil--during the moulding of ammonia post, sol particles is by oily--is prone to sphericity during the ammonia interface poor, and the gelling solidification process of particle is inhomogeneous; The intensity that influences product is handled in the water vapor reaming.The technology that Chinese patent application 92109379.9 adopts has overcome other problems of the prior art, but still existence need be worn out the deficiency of washing step etc.
For solving the problem that above-mentioned prior art exists, seek that a kind of to have technological process simple, with short production cycle, quality product is the novel process of advantages of higher more, and the product I-Al2O3 of this technology is specially adapted to fixed enzyme vector simultaneously, also is applicable to bulky molecular catalysis catalyst for reaction and other support of the catalyst, the invention provides a kind of low density, large pore volume, intensity is moderate, the new preparation process of the ball-aluminium oxide of good sphericity.
Of the present inventionly thisly obtain hydrated alumina through neutralization by certain density aluminium salt and/or aluminate, add jelling agent after the filter cake acidification, through forming oil column, dry, roasting prepares the technology of ball-aluminium oxide, it is characterized in that, it is to adopt crystal seed method at first to prepare the pseudo-boehmite crystal seed of big crystal grain, promptly adopt the aqueous solution of certain density aluminium salt and/or aluminate, at 60-80 ℃, the pH value is under the condition of 7-9, earlier two kinds of mixing of materials is made the pseudo-boehmite crystal seed, also flows the hydrated alumina of neutralization generation based on pseudo-boehmite then, filter, washing, filter cake is through making beating, cool to after the acidifying below 15 ℃, add jelling agent, stir, aluminium colloidal sol is delivered to drying tower rapid drying immediately by behind 90-100 ℃ the forming oil column, and obtaining particle diameter through roasting then is 0.5-3.5mm, bulk density 0.15-0.38g/cm3, pore volume 1.4-2.2cm3/g, specific surface 100-300M2/g, the I-Al2O3 of crushing strength 5-50N/ grain.
In technology of the present invention, the raw material of preparation pseudo-boehmite crystal seed can be Al (NO3) 3, AlCl3, Al2 (SO4) 3, NaAlO2, or Al (NO3) is 3-NH4OH, Al (NO3) 3-NaOH, AlCl3-NH4OH, AlCl3-NaOH, Al (SO4) 3-NH4OH, Al2 (SO4) 3-NaOH, or NaAlO2-Al2 (So4) 3, NaAlO2-HNO3, or other similar raw materials.
In technology of the present invention, the ratio that is used for preparing the amount sum of the whole aluminum oxide that add in the amount of the amount of aluminum oxide of crystal seed pseudo-boehmite and crystal seed aluminum oxide and the N-process is 0.05-0.45.
Facts have proved, when all the ratio control of the amount of aluminum oxide was in the 0.05-0.45 scope in the amount of the aluminum oxide in the prepared crystal seed and the final neutralized reaction product, the prepared ball-aluminium oxide as fixed enzyme vector or other support of the catalyst had excellent more pore structure.
In technology of the present invention, aluminium colloidal sol can directly enter drying tower behind forming oil column, connect and adopt the rapid drying in drying tower of program control temperature-raising method, the span of control of drying temperature is 70-120 ℃, the speed of program control intensification can be regulated in the scope 5-30 ℃/time, and need not must be through overaging after the such moulding of prior art, and washing step just can enter drying program.
In technology of the present invention, the ball-aluminium oxide particle directly enters calcining process after rapid drying, and the temperature range of roasting control is 500-900 ℃.
Compared with prior art, advantage of the present invention and positively effect are as follows:
1. in the technology of the present invention, the preparation of aluminium colloidal sol with the hydrated alumina be raw material substituted metal aluminium in hydrochloric acid or aluminum chloride, equipment is not corroded, raw material is easy to get.
2. need not to wear out after the ball-aluminium oxide moulding, pressure aging, washing, operations such as water vapor reaming processing have been simplified technology, have shortened the production cycle, have improved production efficiency.
3. product I-Al2O3 particle applied range not only can be used as the support of the catalyst of chemical industry or other field, and is particularly suitable for the carrier as immobilized enzyme.
Be embodiments of the invention below, in order to without stint explanation the present invention.
Embodiment 1.
Prepare inclined to one side aluminium sodium solution: take by weighing 820g sheet NaOH, pour in the 1400ml water, be heated to 90 ℃, stir adding 800g alumina trihydrate down, the insulation of dissolving back is 4 hours fully.
The preparation alum liquor: take by weighing the 2500g industrial aluminum sulphate, pour in the 2000ml water, heated and stirred is to dissolving fully.
The sodium aluminate solution and the alum liquor that prepare concentration are respectively charged in two 5000ml tubualted bottles, take out 8% of total amount respectively, mix, reaction, control reaction temperature is 60-80 ℃, the pH value is 7-9, make crystal seed, stablized 20 minutes, after above-mentioned two kinds of solution are carried out cocurrent adding material, in and the time be 6 hours, the gained throw out is at every turn with 4000ml deionized water making beating washing, filter, 6 times repeatedly, it is pseudo-boehmite substantially that XRD detects precipitation
Embodiment 2.
The filter cake 180g that takes by weighing embodiment 1 places beaker, add 45g water, high-speed stirring 20 minutes adds 20%HNO36g, stirs 30 minutes, be warming up to 75 ℃, peptization 2.5 hours is cooled to 10 ℃, adds 35% vulkacit H solution 25ml, stir and it was uniformly dispersed in 10 minutes, make aluminium glue A.
The filter cake 150g that takes by weighing embodiment 1 places beaker, add 45g water, high-speed stirring 20 minutes adds 20%HNO3 7g, 200-400 order aluminum oxide powder 9g, stirred 30 minutes, and be warmed up to 75 ℃, peptization 2.5 hours, be cooled to 10 ℃, add 35% vulkacit H solution 25ml, stir and it was uniformly dispersed in 10 minutes, make aluminium glue B.
Embodiment 3.
The forming oil column device of " J " type of employing stainless steel, by the two table oil pumps control level height and the particulate residence time, be full of white oil in the post, adding thermal control oil temperature is about 98 ℃, any aluminium colloidal sol for preparing with embodiment 2 drips ball, the middle vulkacit H decomposes of aluminium colloidal sol makes particle sclerosis rapidly in oil, emits spheroidal particle with the end of post, a part is carried out rapid drying, drying temperature is 100-120 ℃, 5 hours time of drying, promptly obtains dry product A
1, B
1Another part (example as a comparison) enters that to proceed normal pressure in the aging tank aging, and temperature is 100-110 ℃, pressure aging, temperature is 135-145 ℃, pressure is 0.4MPa, and the particle that has worn out is dried in 100-120 ℃ of baking oven, and drying promptly obtained dry product A in 8 hours
2, B
2Example as a comparison.Two portions dry product changes over to and carries out roasting in the muffle furnace, and lowering the temperature naturally after 4 hours in 800 ℃ of constant temperature obtains spherical I-Al2O3.Its physical data is as follows:
Aluminium glue A aluminium glue B
The aging dry rapid drying of rapid drying is aging dry
A
1B
1A
2B
2Granularity mm 1.5-2.5 15-2.5 1.5-2.5 1.5-2.5 bulk density g/cm3 0.23 0.26 0.31 0.35 pore volume cm3/g 2.10 1.82 1.71 1.54 specific surface M2/g 220 179 163 144 crushing strength N/ grains 0.78 1.04 1.37 1.32
Embodiment 4.
Take by weighing the A of 10gr-Al2O3
1, the triethylene tetramine solution soaking with 5% stirred once in per 10 minutes, soak 2 hours after-filtration, improve triethylene tetramine concentration to 10% in the filtrate, soaked 2 hours, filter, filtrate can be used repeatedly, particle is poured in the 5% penta 3 aldehyde solution, slowly stirs down and soaks 3 hours, filters, show neutral with deionized water rinsing to filtrate, at this moment just finished the chemically modified of aluminum oxide.
Take by weighing A respectively
2, B
1, B
2Each 10g carries out chemically modified as stated above.
A after the modification
1, A
2, B
1, B
2Hang the extension enzyme test of carrying out glucose isomerase on the enzyme device, measuring its enzyme activity and be:
Sample A
1A
2B
1B
2
Hang enzyme activity (unit: gram) 5,538 4,726 4,315 3986
Embodiment 5.
The A for preparing the 500g chemically modified by the method for embodiment 4
1Make fixed glucose isomerase and carry out the test of glucose system high fructose syrup, the result is: the transformation period of fixed glucose isomerase is 49-54 days, and throughput is produced 8.9 tons of over dry sugar for the per kilogram immobilized enzyme.
Claims (5)
1. one kind obtains hydrated alumina by certain density aluminium salt and/or aluminate through neutralization, add jelling agent after the filter cake acidifying, through forming oil column, dry, roasting prepares the technology of ball-aluminium oxide, it is characterized in that, it is to adopt crystal seed method at first to prepare the pseudo-boehmite crystal seed of big crystal grain, promptly adopt the aqueous solution of aluminium salt and/or aluminate, at 60-80 ℃, the pH value is under the condition of 7-9, earlier two kinds of mixing of materials is made the pseudo-boehmite crystal seed, also flows the hydrated alumina of neutralization generation based on pseudo-boehmite then, filter, washing, filter cake is through making beating, cool to after the acidifying below 15 ℃, add jelling agent, stir, aluminium colloidal sol is delivered to drying tower rapid drying immediately by behind 90-100 ℃ the forming oil column, and obtaining particle diameter through roasting then is 0.5-3.5mm, bulk density 0.15-0.38g/cm3, pore volume 1.4-2.2cm3/g, specific surface 100-300M2/g, the I-Al2O3 of crushing strength 5-50N/ grain.
2. by the described technology of claim 1, it is characterized in that the raw material of preparation pseudo-boehmite crystal seed can be Al (NO3) 3, AlCl3, Al2 (SO4) 3, NaAlO2, or Al (NO3) is 3-NH4OH, Al (NO3) 3-NaOH, AlCl3-NH4OH, AlCl3-NaOH, Al2 (SO4) 3-NH4OH, Al2 (SO4) 3-NaOH, or NaAlO2-Al2 (SO4) 3, NaAlO2-HNO3.
3. by claim 1 and 2 described technologies, it is characterized in that the ratio that is used for preparing the amount sum of the whole aluminum oxide that add in the amount of the amount of aluminum oxide of crystal seed pseudo-boehmite and crystal seed aluminum oxide and the N-process is 0.05-0.45.
4. by the described technology of claim 1, it is characterized in that, described aluminium colloidal sol is through directly adopting the rapid drying in drying tower of program control temperature-raising method behind the forming oil column, the span of control of drying temperature is 70-120 ℃, and the speed of program control intensification can be regulated in the scope 5-30 ℃/time.
5. by the described technology of claim 1, it is characterized in that the particle after the rapid drying directly enters calcining process, the temperature range of roasting is 500-900 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN94107313A CN1048229C (en) | 1994-07-01 | 1994-07-01 | Process for preparing spheric aluminium oxide with low density and big pore volume |
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|---|---|---|---|
| CN94107313A CN1048229C (en) | 1994-07-01 | 1994-07-01 | Process for preparing spheric aluminium oxide with low density and big pore volume |
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| CN1114290A true CN1114290A (en) | 1996-01-03 |
| CN1048229C CN1048229C (en) | 2000-01-12 |
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| CN94107313A Expired - Fee Related CN1048229C (en) | 1994-07-01 | 1994-07-01 | Process for preparing spheric aluminium oxide with low density and big pore volume |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089031C (en) * | 1997-08-27 | 2002-08-14 | 中国石油化工集团公司 | Macroporous alumina supporter and preparation method therefor |
| CN1123379C (en) * | 2000-06-27 | 2003-10-08 | 中国科学院上海硅酸盐研究所 | Preparation of spherical alumina particle |
| CN1321895C (en) * | 2005-04-26 | 2007-06-20 | 北京化工大学 | Magnetic continuous separating refiner and its use during process of aluminium gum preparation |
| CN1332762C (en) * | 2004-07-29 | 2007-08-22 | 中国石油化工股份有限公司 | Method for preparing alumina supporter in structure of double peak holes |
| CN100363261C (en) * | 2006-06-22 | 2008-01-23 | 武汉理工大学 | Method for preparing pseudo-boehmite with large pore volume and high specific surface area |
| CN100400164C (en) * | 2004-10-29 | 2008-07-09 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN1944610B (en) * | 2006-10-24 | 2010-10-06 | 中国海洋石油总公司 | Process for preparing unsaturated oil hydrogenation catalyst |
| CN102219245A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Pseudoboehmite and aluminium oxide prepared from same |
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
| CN102795647A (en) * | 2011-05-26 | 2012-11-28 | 中国石油化工股份有限公司 | Macro-porous aluminum oxide and preparation method thereof |
| CN105502447A (en) * | 2014-10-16 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method of alumina pellets through hot oil column moulding |
| CN106795003A (en) * | 2014-08-08 | 2017-05-31 | 萨索尔功能化学品有限公司 | Precipitated alumina and preparation method |
| CN107837798A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of alumina globule carrier and preparation method thereof and catalytic reforming catalyst |
| CN110240187A (en) * | 2018-08-24 | 2019-09-17 | 广州凌玮科技股份有限公司 | A kind of easily distributed nm boehmite preparation method of inkjet printing adsorbing medium |
| CN116212841A (en) * | 2023-04-04 | 2023-06-06 | 福州大学 | Method for preparing alumina pellet carrier by oil column forming process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2449474A1 (en) * | 1979-02-26 | 1980-09-19 | Rhone Poulenc Ind | DOUBLE POROSITY ALUMINA BEADS, THEIR PREPARATION PROCESS AND THEIR APPLICATIONS AS CATALYST SUPPORTS |
| CN1030601C (en) * | 1992-08-17 | 1996-01-03 | 中国石油化工总公司 | Preparation method for carrier of low density, large void content and high intensity aluminium oxide |
-
1994
- 1994-07-01 CN CN94107313A patent/CN1048229C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089031C (en) * | 1997-08-27 | 2002-08-14 | 中国石油化工集团公司 | Macroporous alumina supporter and preparation method therefor |
| CN1123379C (en) * | 2000-06-27 | 2003-10-08 | 中国科学院上海硅酸盐研究所 | Preparation of spherical alumina particle |
| CN1332762C (en) * | 2004-07-29 | 2007-08-22 | 中国石油化工股份有限公司 | Method for preparing alumina supporter in structure of double peak holes |
| CN100400164C (en) * | 2004-10-29 | 2008-07-09 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN1321895C (en) * | 2005-04-26 | 2007-06-20 | 北京化工大学 | Magnetic continuous separating refiner and its use during process of aluminium gum preparation |
| CN100363261C (en) * | 2006-06-22 | 2008-01-23 | 武汉理工大学 | Method for preparing pseudo-boehmite with large pore volume and high specific surface area |
| CN1944610B (en) * | 2006-10-24 | 2010-10-06 | 中国海洋石油总公司 | Process for preparing unsaturated oil hydrogenation catalyst |
| CN102219245A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Pseudoboehmite and aluminium oxide prepared from same |
| CN102219245B (en) * | 2010-04-15 | 2013-06-05 | 中国石油化工股份有限公司 | Pseudoboehmite and aluminium oxide prepared from same |
| CN102795647B (en) * | 2011-05-26 | 2014-10-01 | 中国石油化工股份有限公司 | Macro-porous aluminum oxide and preparation method thereof |
| CN102795647A (en) * | 2011-05-26 | 2012-11-28 | 中国石油化工股份有限公司 | Macro-porous aluminum oxide and preparation method thereof |
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
| CN106795003A (en) * | 2014-08-08 | 2017-05-31 | 萨索尔功能化学品有限公司 | Precipitated alumina and preparation method |
| CN105502447A (en) * | 2014-10-16 | 2016-04-20 | 中国石油化工股份有限公司 | Preparation method of alumina pellets through hot oil column moulding |
| CN105502447B (en) * | 2014-10-16 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method that hot forming oil column prepares alumina globule |
| CN107837798A (en) * | 2016-09-21 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of alumina globule carrier and preparation method thereof and catalytic reforming catalyst |
| CN110240187A (en) * | 2018-08-24 | 2019-09-17 | 广州凌玮科技股份有限公司 | A kind of easily distributed nm boehmite preparation method of inkjet printing adsorbing medium |
| CN116212841A (en) * | 2023-04-04 | 2023-06-06 | 福州大学 | Method for preparing alumina pellet carrier by oil column forming process |
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| CN1048229C (en) | 2000-01-12 |
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