CN1597092A - Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method - Google Patents
Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method Download PDFInfo
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Abstract
A catalyst carrier with pseudo-boehmite structure is prepared from silicon oxide and aluminium oxide through calcining. It has higher catalytic cracking activity and high N value (0.2-1).
Description
Technical field
The invention relates to a kind of silica-alumina and preparation method thereof, more specifically say so about a kind of silica-alumina and preparation method thereof with structure of similar to thin diaspore.
Background technology
With respect to molecular sieve, certain acid catalysis activity can be got well and have to the activated back of silica-alumina specific surface height, anti-agglutinatting property with divergence hole distribution, and Chang Zuowei carrier and active component are used to prepare various dissimilar catalyst.In the existing method, silica-alumina is often by alkali silicate with contain aluminium salt glue or substep become the method for glue to prepare altogether.Silica-alumina by these method preparations mostly is amorphous silicon oxide-aluminium oxide.For amorphous silicon oxide-aluminium oxide, ubiquitous problem is the poor operability of constant product quality and moulding.For example, in actual applications, silica-alumina adopts oil ammonia column to drip ball forming method usually and makes carrier, and its yield rate and production efficiency are low.
USP 5045519 discloses a kind of preparation method of the catalyst carrier based on alumina silicate.This method is in aqueous medium a kind of aluminum contained compound to be mixed with silicic acid, and dry then and roasting obtains product.Its used aluminum contained compound is by C
2-C
20 +The aluminum alkoxide hydrolysis obtains, and simultaneously or will join in the aluminum contained compound through the positive silicic acid of ion-exchange process purifying subsequently, comprising one the 90-235 ℃ of process that mixture is heat-treated.The x-ray analysis result shows to have before the silica-alumina roasting by this method preparation and intend thin water constructed of aluminium.This easy moulding of silica-alumina with structure of similar to thin diaspore is even when silica content during up to 40 weight %, still can pass through the moulding of extruded moulding mode.But, be raw material owing to adopt aluminum alkoxide and positive silicic acid, this method preparation cost height.In addition, its preparation is carried out under the condition that is bordering on neutrality, is unfavorable for that the reaction of silica and aluminium oxide generates the acid site.
Aluminium in alumina silicate or the silica-alumina mainly contain two kinds of four-coordination and hexa-coordinates different have a form.Adopt solid-state nuclear magnetic resonance to characterize, four-coordination aluminium and hexa-coordinate aluminium exist
27Characteristic peak occurs on the Al NMR spectrogram, wherein, the peak of 5 ± 0.1-0.2ppm chemical shift place belongs to the aluminium of hexa-coordinate, and the peak of 60 ± 0.1-0.2ppm chemical shift place belongs to the aluminium of four-coordination.Acid site number in alumina silicate or the silica-alumina is by the wherein content decision of contained four-coordination aluminium.Be that four-coordination aluminium content is big more, the acid site number is many more.The shortcoming of the silica-alumina with structure of similar to thin diaspore that existing method provides is that four-coordination aluminium content is low.
Summary of the invention
The objective of the invention is at the low shortcoming of four-coordination aluminium content in the existing silica-alumina with structure of similar to thin diaspore, provide a kind of new four-coordination aluminium content higher have silica-alumina of structure of similar to thin diaspore and preparation method thereof.
Silica-alumina with structure of similar to thin diaspore provided by the invention contains the silica of 5-60 weight % after its roasting, the aluminium oxide of 40-95 weight %, and its N value is 0.2-1; Described N=P1/P2, P1 are the solid of described silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of described silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
Preparation method with silica-alumina of structure of similar to thin diaspore provided by the invention comprises the mixed liquor of a kind of boehmite of preparation and water, introduce a kind of solution of silicon-containing compound, aging and drying afterwards, described aging condition: the pH value be 7.5-11, temperature be carry out under the 75-120 ℃ of condition, the time is 6-24 hour, the condition of described drying: temperature is that 80-300 ℃, time are 2-24 hour, and it is 5-60 weight % that the introducing amount of the solution of silicon-containing compound makes the content of silica in the final silica-alumina.
Compare with existing silica-alumina with structure of similar to thin diaspore, the N value height with silica-alumina of structure of similar to thin diaspore provided by the invention has higher catalytic cracking activity behind high-temperature activation.
For example, be that the N value of the silica-alumina with structure of similar to thin diaspore of 39 weight % is 0.78 by a kind of silica content provided by the invention, it in 600 ℃ of activation 4 hours, is used n-C afterwards
14For raw material is estimated on the pulse micro-inverse device, its cracking activity is 11%; And existing N value with silica-alumina of structure of similar to thin diaspore only is 0.12, and it in 600 ℃ of activation 4 hours, is used n-C afterwards
14For raw material is estimated on the pulse micro-inverse device, its cracking activity only is 5%.
Description of drawings
Fig. 1 for the silica-alumina with structure of similar to thin diaspore provided by the invention, existingly have the silica-alumina of structure of similar to thin diaspore and an x-ray diffraction spectra of boehmite.
The specific embodiment
According to the silica-alumina with structure of similar to thin diaspore provided by the invention, preferably contain the silica of 10-45 weight % after its roasting, the aluminium oxide of 55-90 weight %.The N value is preferably 0.2-0.8.
Several x-ray diffraction spectra with silica-alumina of structure of similar to thin diaspore provided by the invention is seen a, b, c, d, the e among Fig. 1.As a comparison, provided a kind of x-ray diffraction spectra (Fig. 1 f) of silica-alumina and a kind of x-ray diffraction spectra (Fig. 1 g) of boehmite of having now among Fig. 1 simultaneously with structure of similar to thin diaspore.
According to method provided by the invention, the method for the mixed liquor of a kind of boehmite of wherein said preparation and water is the conventional method for preparing boehmite.For example, can be the solution of at least a aluminum contained compound is mixed, becomes glue with the solution of a kind of alkali or acid and to wear out, described aging condition: pH is 7-8.5, temperature is that 30-75 ℃, time are 5-120 minute.
Described aluminum contained compound is selected from one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate, alchlor, aluminum alkoxide, the alkyl aluminum, is preferably in aluminum sulfate, sodium metaaluminate, aluminum nitrate, the alchlor one or more.
Described alkali be hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, the potassium hydroxide; Preferred salt is selected from one or more in carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, the potash.
Described acid is Bronsted acid or is acid oxide that in aqueous medium preferred Bronsted acid is selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid; Preferred oxide is a carbon dioxide.
According to method provided by the invention, the introducing of the solution of described silicon-containing compound is that the solution with silicon-containing compound mixes with the mixed liquor of water with prepared boehmite, for example, can be under agitation the solution of silicon-containing compound to be joined in the mixed liquor of boehmite and water, also can be to contain in the mixed liquor and stream adding reaction vessel of solution with boehmite and water of silicon-containing compound, the consumption of the solution of silicon-containing compound makes the silica that contains 5-60 weight % in final silica one aluminium oxide, is preferably 10-45 weight %.
Described silicon-containing compound can be any water-soluble silicon-containing compound and the silicon-containing compound that can hydrolysis in aqueous medium forms silicon gel, colloidal sol.For example, one or more in the compounds such as waterglass, the hydrosol and esters of silicon acis.
Described aging condition is preferred: the pH value is that 8-10, temperature 80-98 ℃, time are 12-24 hour.
Described drying is conventional drying, preferred condition: temperature is that 100-150 ℃, time are 4-20 hour,
According to method provided by the invention, an embodiment preferred may further comprise the steps:
(1) a kind of solution that contains aluminium salt and a kind of aqueous slkali or acid solution and stream are joined be carried out to the glue reaction in the reaction vessel, reaction condition: the pH value is 6.5-8.5, and temperature is 30-75 ℃;
(2) product that step (1) is generated is at pH7-8.5, and temperature 30-75 ℃ was worn out 5-120 minute down;
(3) under agitation, a kind of solution of silicon-containing compound is joined in the product that step (2) obtains;
(4) at pH8-10,80-98 ℃ of product 12-24 hour of descending aging step (3) to obtain;
(5) product that wash, filtration step (4) obtains;
(6) product that obtains of drying steps (5) obtains product provided by the invention.
Have after silica-alumina with structure of similar to thin diaspore provided by the invention is activated conventional silica-alumina specific surface, pore volume, can several apertures, its specific surface is a 250-500 rice
2/ gram is preferably 300-420 rice
2/ gram, pore volume is 0.4-2 milliliter/gram, is preferably 0.5-1.5 milliliter/gram, can several apertures be the 4-20 nanometer, is preferably the 5-15 nanometer.Therefore, the silica-alumina with structure of similar to thin diaspore provided by the invention can be used as the matrix of various adsorbents, catalyst carrier and catalyst and/or the precursor use of binding agent.Be particularly suitable for the carrier precursor of catalyst such as hydrotreatment, hydrocracking, catalytic cracking, isomerization, alkylation, disproportionation.As a kind of matrix precursor, it can also with combination of components such as molecular sieve, clay, also can make the catalyst of various desired properties with the combination of molecular sieve and/or metal component.
The following examples are with the present invention is further illustrated.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Example 1-5 explanation silica-alumina with structure of similar to thin diaspore provided by the invention and preparation method thereof.
Example 1
Take by weighing 515 gram alchlors (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum trichloride solution a1 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b1 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 220 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 1000 ml soln c1 with deionized water; Get 75 gram NaOH, be dissolved into 150 ml soln d1 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 40 ℃, and stream adds solution a1 and b1, it is 7 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, aging condition: pH is 7, temperature is 45 ℃, ageing time is 30 minutes, behind aging the end, under agitation adds solution c1 and d1 successively.This moment, the pH of reaction system was 8.9, and temperature is 50 ℃, was warming up to 85 ℃ and constant temperature and filtered after 23 hours.Filter cake spends deionised water 5 times, filter after each washing, the filter cake after the last washing 110 ℃ dry 20 hours down, promptly obtain silica-alumina M-1 provided by the invention.The x-ray diffraction spectra of M-1 is seen Fig. 1 a, the content of silica, aluminium oxide, N value and specific surface, can several holes, pore volume sees Table 1.
The X-ray diffracting spectrum is measured on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44KV, 40mA, sweep speed is 2 °/minute (down together).
Silica, alumina content adopt x-ray fluorescence spectrometry.Before the mensuration, sample is at first in 600 ℃ of roastings 2 hours (down together).
Specific surface, can several apertures, pore volume adopts B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.Before the mensuration, sample is at first in 600 ℃ of roastings 2 hours (down together).
27The chemical shift at each peak and each peak area are that reference is measured with saturated aluminum sulfate aqueous solution on Varian UnityInova 300 M type nuclear magnetic resonance spectrometers in the Al NMR spectrogram.And according to formula N=P1/P2 calculating N value, P1 is the solid of silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of silica-alumina
27Chemical shift is the peak area (down together) at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
Example 2
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a2 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b2 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 60 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 240 ml soln c2 with deionized water; Get 75 gram NaOH, be dissolved into 150 ml soln d2 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 50 ℃, and stream adds solution a2 and b2, it is 8 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 7.6, temperature is 60 ℃, ageing time is 30 minutes, behind aging the end, under agitation adds solution c2 and d2 successively.This moment, the pH of reaction system was 8.5, and temperature is 65 ℃, was warming up to 90 ℃ and constant temperature and filtered after 13 hours.Filter cake spends deionised water 5 times, filter after each washing, the filter cake after the last washing 150 ℃ dry 6 hours down, promptly obtain silica-alumina M-2 of the present invention.The x-ray diffraction spectra of M-2 is seen Fig. 1 b, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Example 3
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a3 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b3 with deionized water; The modulus of getting technical grade is 3.26, SiO
2160 milliliters of the water glass solutions of content 280 grams per liters (Chang Ling refinery product) are diluted to 500 ml soln c3 with deionized water; Get 35 gram NaOH, be dissolved into 150 ml soln d3 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 40 ℃, and stream adds solution a3 and b3, it is 8 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 8, temperature is 45 ℃, ageing time is 60 minutes, behind aging the end, under agitation adds solution c3 and d3 successively.This moment, the pH of reaction system was 8.2, and temperature is 50 ℃, was warming up to 95 ℃ and constant temperature and filtered after 20 hours.Filter cake spends deionised water 4 times, filter after each washing, the filter cake after the last washing 120 ℃ dry 15 hours down, promptly obtain silica-alumina M-3 of the present invention.The x-ray diffraction spectra of M-3 is seen Fig. 1 c, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Example 4
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a4 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b4 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 220 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 1000 ml soln c4 with deionized water; Get 120 gram NaOH, be dissolved into 150 ml soln d4 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 40 ℃, and stream adds solution a4 and b4, it is 7.3 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 7.6, temperature is 40 ℃, ageing time is 15 minutes, behind aging the end, under agitation adds solution c4 and d4 successively.This moment, the pH of reaction system was 9.7, and temperature is 35 ℃, was warming up to 98 ℃ and constant temperature and filtered after 18 hours.Filter cake spends deionised water 6 times, filter after each washing, the filter cake after the last washing 120 ℃ dry 15 hours down, promptly obtain silica-alumina M-4 of the present invention.The x-ray diffraction spectra of M-4 is seen Fig. 1 d, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Example 5
Get 1.6 liters of (Al of industrial sulphuric acid aluminum solutions a5
2O
3Concentration is about 98 grams per liters, free acid content 1.5 grams per liters).500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b5 with deionized water.Get the modulus 3.26 of technical grade, SiO
2Content is 220 milliliters of the water glass solutions of 280 grams per liters, is diluted to 1000 milliliters with deionized water, obtains solution c5.Get 50 gram NaOH, be dissolved into 150 ml soln d5 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 60 ℃, and stream adds solution a5 and b5, it is 7.5 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 7, temperature is 70 ℃, ageing time is 15 minutes, behind aging the end, under agitation adds solution c5 and d5 successively.This moment, the pH of reaction system was 8.5, and temperature is 70 ℃, was warming up to 98 ℃ and constant temperature and filtered after 16 hours.Filter cake spends deionised water 5 times, filter after each washing, the filter cake after the last washing 120 ℃ dry 15 hours down, promptly obtain silica-alumina M-5 of the present invention.The x-ray diffraction spectra of M-5 is seen Fig. 1 e, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Comparative Examples 1
Directly get silica-alumina commodity Siral40 that Condea company has structure of similar to thin diaspore as reference.The x-ray diffraction spectra of this product is seen Fig. 1 f; The content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Fig. 1 g is the x-ray diffraction spectra of boehmite (SB powder, German Condea company product).
Table 1
| Example | Numbering | ????SiO 2????％ | ????Al 2O 3????％ | The N value | Pore structure character | ||
| Specific surface m 2·g -1 | Can a few aperture | Pore volume cm 3·g -1 | |||||
| ????1 | ????M-1 | ????41 | ????59 | ??0.27 | ????390 | ????110 | ????0.98 |
| ????2 | ????M-2 | ????15 | ????85 | ??0.21 | ????320 | ????58 | ????0.63 |
| ????3 | ????M-3 | ????29 | ????71 | ??0.23 | ????350 | ????60 | ????0.66 |
| ????4 | ????M-4 | ????39 | ????61 | ??0.78 | ????342 | ????100 | ????1.07 |
| ????5 | ????M-5 | ????43 | ????57 | ??0.41 | ????417 | ????95 | ????0.96 |
| Comparative Examples 1 | ??Siral40 | ????40 | ????60 | ??0.12 | ????437 | ????75 | ????0.89 |
The result that table 1 provides can show, by the N value of the silica-alumina with structure of similar to thin diaspore provided by the invention apparently higher than existing silica-alumina with structure of similar to thin diaspore.
Example 6-10
This example explanation is provided by the invention to have the silica-alumina of the structure of similar to thin diaspore pure hydrocarbon cracking performance after activated.
With M-1, M-2, M-3, M-4, M-5 respectively 600 ℃ of following roastings 4 hours.Afterwards, as raw material, on the pulse micro-inverse device, estimate with n-C14, catalyst loading amount 0.1 gram, 480 ℃ of reaction temperatures, sample size is 0.3 microlitre.Nitrogen is done carrier gas, and flow velocity is 30 ml/min, fid detector.As cracking activity, the results are shown in Table 2 with the conversion ratio of n-C14.
Comparative Examples 2
Catalytic cracking performance after this Comparative Examples explanation Siral40 is activated.
Evaluation method the results are shown in Table 2 with example 6.
Table 2
| Example | Silica-alumina | ??n-C 14Cracking activity/% |
| ????6 | ????M-1 | ????7.0 |
| ????7 | ????M-2 | ????6.0 |
| ????8 | ????M-3 | ????6.5 |
| ????9 | ????M-4 | ????11.0 |
| ????10 | ????M-5 | ????8.5 |
| Comparative Examples 2 | ????Siral40 | ????5.0 |
The result that table 2 provides can show, compares with existing silica-alumina with structure of similar to thin diaspore, and after the silica-alumina with structure of similar to thin diaspore provided by the invention was activated, its cracking activity obviously improved.
Example 11-12
This example explanation is provided by the invention to have the silica-alumina of the structure of similar to thin diaspore catalytic cracking performance after activated.
In this example, the evaluation of catalyst is carried out according to the method that RIPP 92-90 provides.M-1, M-3 are activated 4 hours down at 600 ℃ respectively, be broken into 20-40 purpose particle afterwards, feedstock oil is grand celebration VGO, catalyst 5 grams of in fixed bed reactors, packing into, and 500 ℃ of reaction temperatures, oil inlet quantity 1.7 grams, the oil-feed time is 70 seconds, conversion ratio sees Table 3.
Comparative Examples 3
Catalytic cracking performance after this Comparative Examples explanation Siral40 is activated.
Evaluation method the results are shown in Table 3 with example 11.
Example 13-14
This example illustrates that silica-alumina provided by the invention is through the catalytic cracking performance of 800 ℃ of steam treatment after 4 hours.
In this example, the evaluation of the evaluate catalysts of catalyst is carried out according to the method that RIPP 92-90 provides.Be specially, M-1, M-3 respectively 800 ℃ of following hydrothermal treatment consists 4 hours, are become catalyst breakage 20-40 purpose particle afterwards, catalyst 5 grams of in reactor, packing into, 500 ℃ of reaction temperatures, oil inlet quantity 1.7 grams, the results are shown in Table in 3 70 seconds oil-feed time.
Comparative Examples 4
This Comparative Examples explanation Siral40 is through through the catalytic cracking performance of 800 ℃ of steam treatment after 4 hours.
Evaluation method the results are shown in Table 3 with example 13.
Table 3
| Example | ????11 | ????12 | Comparative Examples 3 | ????13 | ????14 | Comparative Examples 4 |
| Silica-alumina | ????M-1 | ????M-3 | ????Siral40 | ????M-1 | ????M-3 | ????Siral40 |
| Activation temperature/℃ | ????600 | ????600 | ????600 | ????800 | ????800 | ????800 |
| Conversion ratio/% | ????77 | ????80 | ????70 | ????75 | ????77 | ????68 |
The result that table 3 provides shows, compares with existing silica-alumina with structure of similar to thin diaspore, and is not only active high after the silica-alumina with structure of similar to thin diaspore provided by the invention is activated, has good hydrothermal stability simultaneously.
Claims (14)
1, the silica-alumina that has structure of similar to thin diaspore contains the silica of 5-60 weight % after its roasting, the aluminium oxide of 40-95 weight % is characterized in that, the N value of described silica-alumina is 0.2-1; Described N=P1/P2, P1 are the solid of described silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of described silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
2, silica-alumina according to claim 1 is characterized in that, contains the silica of 10-45 weight % after its roasting, the aluminium oxide of 55-90 weight %.
3, silica-alumina according to claim 1 is characterized in that, described N value is 0.2-0.8.
4, the preparation method of the described silica-alumina of claim 1, this method comprises the mixed liquor of a kind of boehmite of preparation and water, introduce a kind of solution of silicon-containing compound, aging and drying afterwards, it is characterized in that, described aging condition: the pH value is that 7.5-11, temperature are that 75-120 ℃, time are 6-24 hour, the condition of described drying: temperature is that 80-300 ℃, time are 2-24 hour, and it is 5-60 weight % that the introducing amount of the solution of silicon-containing compound makes the content of silica in the final silica-alumina.
5, method according to claim 4 is characterized in that, described aging condition: the pH value is that 8-10, temperature are that 80-98 ℃, time are 12-24 hour, and the condition of described drying: temperature is 100-150 ℃, and the time is 4-20 hour.
6, method according to claim 4, it is characterized in that, described boehmite and the preparation of the mixed liquor of water are that the solution with at least a aluminum contained compound mixes, becomes glue with the solution of a kind of alkali or acid and wears out, wherein Lao Hua condition: pH is 7-8.5, and temperature is that 30-75 ℃, time are 5-120 minute.
7, method according to claim 6 is characterized in that, described aluminum contained compound is selected from one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate, alchlor, aluminum alkoxide, the alkyl aluminum.
8, method according to claim 7 is characterized in that, described aluminum contained compound is selected from one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate, the alchlor.
9, method according to claim 6 is characterized in that, described alkali be hydroxide or in aqueous medium hydrolysis make the aqueous solution be alkalescence salt.
10, method according to claim 9 is characterized in that, described hydroxide is selected from one or more in ammoniacal liquor, NaOH, the potassium hydroxide; Described salt is selected from one or more in carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, the potash.
11, method according to claim 6 is characterized in that, described acid is Bronsted acid or is acid oxide in aqueous medium.
12, method according to claim 11 is characterized in that, described Bronsted acid is selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid; Described oxide is a carbon dioxide.
13, method according to claim 4 is characterized in that, described silicon-containing compound be any water-soluble silicon-containing compound or in aqueous medium hydrolysis can form the silicon-containing compound of silicon gel or colloidal sol.
14, method according to claim 13 is characterized in that, described silicon-containing compound is selected from one or more in waterglass, Ludox and the esters of silicon acis.
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| CN1915485B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Alumina containing additive |
| CN1915486B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Hydrated alumina with structure of similar to thin diaspore of containing additive |
| CN102160996A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Composition of boehmite and silicon-containing compound and silicon oxide-alumina prepared from same |
| CN102139217B (en) * | 2010-02-03 | 2013-04-24 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN109053418A (en) * | 2018-07-31 | 2018-12-21 | 菏泽华立新材料有限公司 | A kind of the organic acid processing method and its device of aluminium isopropoxide dead catalyst |
-
2003
- 2003-09-17 CN CN 03157163 patent/CN1267187C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915485B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Alumina containing additive |
| CN1915486B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Hydrated alumina with structure of similar to thin diaspore of containing additive |
| CN102139217B (en) * | 2010-02-03 | 2013-04-24 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN102160996A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Composition of boehmite and silicon-containing compound and silicon oxide-alumina prepared from same |
| CN102160996B (en) * | 2010-02-24 | 2013-06-26 | 中国石油化工股份有限公司 | Composition of boehmite and silicon-containing compound and silicon oxide-alumina prepared from same |
| CN109053418A (en) * | 2018-07-31 | 2018-12-21 | 菏泽华立新材料有限公司 | A kind of the organic acid processing method and its device of aluminium isopropoxide dead catalyst |
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| CN1267187C (en) | 2006-08-02 |
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