CN104549540A - Preparation method of macroporous amorphous silica-alumina carrier - Google Patents

Preparation method of macroporous amorphous silica-alumina carrier Download PDF

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CN104549540A
CN104549540A CN201310499346.6A CN201310499346A CN104549540A CN 104549540 A CN104549540 A CN 104549540A CN 201310499346 A CN201310499346 A CN 201310499346A CN 104549540 A CN104549540 A CN 104549540A
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ultrasonic
frequency
alumina
solution
preparation
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CN104549540B (en
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范丹丹
杜艳泽
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a preparation method of a macroporous amorphous silica-alumina carrier. The preparation method comprises the following steps: firstly, mixing acid aluminum salt solution and sodium aluminate solution, so as to prepare aluminum sol, secondly, adding sodium silicate solution to the aluminum sol obtained in the first step, thirdly, performing ageing treatment on the material obtained in the second step, fourthly, filtering and washing the material obtained in the third step, fifthly, drying the material obtained in the fourth step, ensuring that the drying temperature is 100 to 150 DEG C and the drying time is 2 hours, and then roasting the material, so as to obtain a macroporous amorphous silica-alumina material. The method can prepare high-quality amorphous silica-alumina with uniformly distributed silicon and aluminum, high silicon dioxide content and large pore volume and specific surface area, meanwhile adopts inorganic salt with low cost as a raw material, is free of a pore adjusting agent, and can also reduce the preparation cost of the macroporous amorphous silica-alumina.

Description

A kind of preparation method of macropore amorphous silicon alumina supporter
Technical field
The present invention relates to a kind of macropore amorphous aluminum silicide and preparation method thereof, especially as the macropore amorphous aluminum silicide and preparation method thereof of one of carrier of hydrogenating catalyst producing intermediate oil.
Background technology
Research shows, the oxide carrier with irregular pore structure is particularly suited for hydrotreatment application.Amorphous aluminum silicide obtains large quantifier elimination because of its distinctive acidity, using it as carrier, is conducive to the dispersion of carried metal.As carrier, the distinguishing feature of amorphous aluminum silicide compared with molecular sieve has amorphous structure and larger aperture.This also make amorphous aluminum silicide petroleum refining raw material increasingly deterioration today, there is more wide application prospect.In preparation, amorphous aluminum silicide is synthesized by sol method under the existence of pore regulator with organometallic precursor usually.
Make raw material with organic metal, cost is higher, and environmental pollution is heavier.Pore regulator, as the use of TPAOH, although be beneficial to concentrating of pore-size distribution, must increase preparation process, numerousization subsequent operation.Have at present and much adopt cheap inorganic salts to be raw material, without the report preparing amorphous aluminum silicide under pore regulator condition.
" Microporous and Mesoporous Materials " the 96th volume P197-204 " Synthesis and Properties of mesoporous silica-alumina with narrow pore size distribution obtained without use of pore-regulating agents " reports and does not a kind ofly use pore regulator and with simple inorganic salts for the method for mesoporous amorphous sial prepared by raw material, be specially: solution of sodium metasilicate through mixes the silica dioxide gel generated and mixes with vigorous stirring with aluminum nitrate solution with nitric acid.Add concentrated ammonia liquor and pH is adjusted to 7, continue stirring 4 hours, during this period, temperature is increased continuously to 60 DEG C.Mixture, through distilled water diluting, leaves standstill 16 hours, the hydrosol is precipitated.Removing supernatant, the hydrosol through filtered on buchner funnel, under room temperature dry 3 days.Dry glue hot water surname extraction 8 hours, product at 120 DEG C dry 6 hours, and roasting 6 hours in 500 DEG C of air stream.Be not difficult to find out from preparation process, the manufacturing cycle of this method is long, and wherein room temperature normal pressure Aging Step needs 3 days.In addition, the method use niffy concentrated ammonia liquor, not only operating environment of pollution, also can be detrimental to health.
CN 101239328A discloses a kind of using sodium aluminate and sodium metasilicate as aluminium, silicon source, the method for preparing amorphous silicon alumnium using carbonization.CO 2here not only as reaction raw materials, also possess disturbance, stirring simultaneously, make the effect of the full and uniform mixing of reactant.But, CO 2notorious greenhouse gases, if CO 2dosage controls inaccurate, the excessive CO added 2directly enter environment without recycling, then can aggravate greenhouse gases and pollute.
CN 101491774A discloses a kind of first with inorganic silicon-aluminum source co-precipitation plastic, then adds the organic-silicon-modified method preparing amorphous aluminum silicide.Coprecipitation method has self drawback, precipitates and settling velocity is close in order to make sial simultaneously, then need to be controlled deposition condition, and optimum condition when this condition is not generally one-component precipitation.
Yao Nan proposes the method that " ultrasonic sol-gal process " prepares mesoporous amorphous sial in Chinese Academy of Sciences Ph.D. Dissertation " the non-template agent Synthesis and characterization research of mesopore nano catalytic material ".Can be raw material at ambient temperature with inorganic aluminate through precipitation, dispergation process by the method, dispergation process is prepared under the effect of ultrasonic disperse be needed under the high temperature conditions just getable Alumina gel originally.Under the prerequisite not using template and other additive, by to the control of sol particles with homogeneous size distribution, these sol particleses are reunited together with being deposited in regularly in gel process, thus has successfully prepared the alumina material of middle pore distribution concentration.Although this section of paper make use of hyperacoustic cavitation or peptizaiton, prepare quality good mesopore amorphous silicon aluminium product, but ultrasonic wave Main Function used is realize the homogenising of solution and the stabilisation of colloidal sol to a certain extent, be difficult to the meticulousr control realizing silica-alumina supports particulate and pore structure.Also need to add ammonium nitrate in this preparation process ageing process, to prevent the contraction of sial skeleton in dry run and to cave in.
Summary of the invention
For the deficiencies in the prior art, the present invention adopts the method preparation of heavy silicon after first heavy aluminium, dual-frequency ultrasonic wave is adopted in ageing process, the mode of pressurization is adopted in dry run, can not only prepare Distribution of silicon and aluminium even, dioxide-containing silica is high, pore volume and the large high-quality amorphous aluminum silicide of specific area, adopt cheap inorganic salts to make raw material simultaneously, do not add and adjust hole agent, the preparation cost of amorphous aluminum silicide can also be reduced.
The preparation method of a kind of macropore amorphous silicon of the present invention alumina supporter, comprises following content:
(1) acid aluminium salt solution and sodium aluminate solution are mixed with Alumina gel;
(2) in the Alumina gel of step (1) gained, sodium silicate solution is added;
(3) burin-in process is carried out to the material of step (2), first ageing process adopts dual-frequency ultrasonic wave aging, frequency is respectively 20 ~ 50kHz and 30 ~ 100kHz, preferably 25 ~ 45kHz, 35 ~ 80kHz, two frequency-splittings control at 1 ~ 50kHz, preferably 5 ~ 35kHz, and ultrasonic radiation time controling is at 10 ~ 60min, preferably 10 ~ 15min, at room temperature continues aging after ultrasonic aging end;
(4) step (3) gained material is carried out filtering, washing;
(5) step (4) gained material is carried out drying, baking temperature is 100 ~ 150 DEG C, 1 ~ 20 hour drying time, then namely obtains macropore amorphous silicon aluminum through roasting.
The inventive method, the acid aluminium salt solution described in step (1) comprises AlCl 3, Al (NO 3) 3, Al 2(SO 4) 3one or more in solution.
The inventive method, adds sodium silicate solution process and stirring or carrying out under ultrasonic effect, and in the scope of regulation system pH value to 4.0 ~ 9.5, temperature controls at 20 ~ 80 DEG C in step (2);
The inventive method, in step (3), aging can simultaneously the carrying out of dual-frequency ultrasonic wave also can be hocketed.Ultrasonic power counts 0.01 ~ 20W/mL by the acid aluminium salt liquor capacity in step (1), preferably 0.05 ~ 10W/mL.During ultrasonic radiation, temperature controls at 20 ~ 80 DEG C, preferably 40 ~ 60 DEG C.Continuing ageing time under room temperature is 30 ~ 300min.
The inventive method, the filtration in step (4), washing adopt conventional method to carry out.Dry run in step (5) can be carried out under an increased pressure, and controlling dry gauge pressure is 0.05 ~ 0.2MPa.High-pressure drying serves further reaming effect.Described roasting roasting 0.5 ~ 10 hour at 300 ~ 750 DEG C.
The inventive method adds sodium metaaluminate and prepares silicon-aluminum sol in Alumina gel; Dual-frequency ultrasonic wave is adopted in colloidal sol ageing process; In dry run, adopt high-pressure drying, the two synergy can effectively suppress and avoid the framework shrinkage of silicon-aluminum sol in dry, roasting process and cave in, and affects amorphous silicon alumina supporter.Relative to the preparation process using the ultrasonic and conventional drying methods of single-frequency, prepared amorphous silicon aluminum has larger aperture and larger specific area, and pore size distribution is comparatively concentrated.Preparation method described in this patent have cheaper starting materials be easy to get, without the need to add pore regulator, preparation process simple, be easy to the features such as operation, good product quality.This material is particularly suited for the carrier as load type metal catalyst in catalytic hydrogenation application.
The present invention introduces dual-frequency ultrasonic wave in the process preparing the dry glue of sial.Ultrasonic wave causes sol particle or micelle fast movement, and caking can be avoided to cause sol particle or micelle size to increase; By controlling dual-frequency ultrasonic wave frequency and energy level, the sol particle being greater than and being less than aimed dia can be made to produce resonance, cause movement velocity too fast and pulverize or dissolve, obtain the sial colloid that particle diameter distribution is comparatively single, pore size distribution is comparatively concentrated, realized the object of precise controlling pore structure and character by the adjustment of preparation method.
In addition, under hyperacoustic effect, also can prevent or reduce between particle or micelle producing agglomeration, reduce the generation of abnormal large-volume particulate, thus effectively control the generation of super big hole.
Detailed description of the invention
A kind of detailed process of amorphous aluminum silicide of the present invention is as follows:
(1) AlCl 3the preparation of solution: general aluminium oxide and hydrochloric acid are reacted at 90 ~ 120 DEG C, uses active carbon deferrization, make Fe/Al by weight 2o 3value is less than 0.005%, obtained smart AlCl 3solution, then dilute, concentration is 10 ~ 60g Al 2o 3/ L can as working solution during plastic.
(2) NaAlO is configured respectively 2solution and sodium silicate solution, respectively with Al 2o 3meter is containing 5 ~ 80g Al 2o 3/ L, with SiO 2meter is containing 5 ~ 120g SiO 2/ L.
(3) plastic process: by AlCl 3solution and NaAlO 2solution joins in plastic cans with certain flow velocity simultaneously, and stirs, and gelling temperature controls, at 20 ~ 80 DEG C, preferably to control at 50 ~ 70 DEG C.After forming Alumina gel, at 25kHz, 2W/mL(with AlCl 3liquor capacity meter) under hyperacoustic effect, add the sodium silicate solution prepared, and adjust ph is in 4.0 ~ 9.5 scopes, temperature controls at 20 ~ 80 DEG C, and gelation time control is at 30 ~ 60min.
(4) ageing process: adopt dual-frequency ultrasonic wave, frequency is respectively 20 ~ 50kHz and 30 ~ 100kHz, preferably 25 ~ 45kHz and 35 ~ 80kHz, and two frequency-splittings control at 1 ~ 50kHz, preferably 5 ~ 35kHz, and ultrasonic power presses AlCl 3liquor capacity counts 0.01 ~ 20W/mL, preferably 0.05 ~ 10W/mL.Ultrasonic radiation time controling is at 10 ~ 60min, and preferably 10 ~ 15min, during ultrasonic radiation, temperature controls at 20 ~ 80 DEG C, preferably 40 ~ 60 DEG C.Then, at room temperature aging 30 ~ 300min is left standstill.
(5) filter, wash: filtered by aging slurries, be separated mother liquor, the filter cake obtained spends deionized water, and during washing, control temperature is between 60 ~ 80 DEG C, and wash time is 20 ~ 50min, and washing times is 3 ~ 5 times.
(6) dry: namely the filtration cakes torrefaction after washing is obtained the dry glue of sial, and baking temperature is 100 ~ 150 DEG C, preferably 120 DEG C, dry 1 ~ 20 hour, dryly preferably to carry out having under suitable pressure, dry gauge pressure is 0.05 ~ 0.2MPa, preferred 0.1MPa.
comparative example 1
Prepare contained amorphous silica-alumina dry glue (SiO 2: Al 2o 3mass ratio is 50:50) 2L is contained Al 2o 3the AlCl of 30g/L 3solution and 1.5L are containing Al 2o 3the NaAlO of 120g/L 2solution also flows plastic, and reaction temperature is 60 DEG C.After plastic, add prepare containing SiO 2the Na of 20g/L 2siO 3solution, control ph is 8.0, and temperature controls at 50 DEG C, reaction contact time 45min.At temperature 60 C, carry out aging under pH 9.0 condition, ageing time is 2 hours, and ageing process adopts single-frequency ultrasonic wave, and frequency is 80kHz, and power is 2W/mL.Filter product, be then the deionized water washing of 1: 20 by solid-to-liquid ratio, wash temperature 60 DEG C, washs 3 times, about 10min at every turn.Gained filter cake at 120 DEG C dry 3 hours.
embodiment 1
Under the plastic process of comparative example 1 is in ultrasonic environment, controlling ultrasonic instrument (double frequency constant-temperaturenumerical-control numerical-control ultrasonic device is selected in this test) frequency is 30kHz and 60kHz, and ultrasonic power presses AlCl 3liquor capacity is counted and is respectively 2W/mL and 5W/mL, and two kinds of frequencies replace radiation, and each radiation 60s forms a transformation period, altogether radiation 12min, and radiative process temperature control is at 60 DEG C.Then, in left at room temperature aging 2 hours.Other is with comparative example 1.
embodiment 2
Under the dry run of embodiment 1 is in pressurized conditions, gauge pressure 0.1MPa, the other the same as in Example 1.
embodiment 3
The while that ageing process adopting, dual-frequency ultrasonic wave is aging, and ultrasonic frequency is respectively 50kHz and 100kHz, and ultrasonic power presses AlCl 3liquor capacity is counted and is respectively 6W/mL and 12W/mL, and ultrasonic radiation time controling, at 120S, is total to radiation 30min, during ultrasonic radiation, temperature controls at 75 DEG C, ultrasonic aging after at room temperature leave standstill aging 60min, controlled pressure 0.2MPa time dry, all the other are with comparative example 1.
embodiment 4
Prepare contained amorphous silica-alumina dry glue (SiO 2: Al 2o 3mass ratio is 30:70) other is with example 2.
Example 1 ~ 4 prepare the dry glue of sial 400 DEG C of roastings after 3 hours product property in table 1
Table 1

Claims (11)

1. a preparation method for macropore amorphous silicon alumina supporter, is characterized in that comprising following content:
(1) acid aluminium salt solution and sodium aluminate solution are mixed with Alumina gel;
(2) in the Alumina gel of step (1) gained, sodium silicate solution is added;
(3) burin-in process is carried out to the material of step (2), first ageing process adopts dual-frequency ultrasonic wave aging, frequency is respectively 20 ~ 50kHz and 30 ~ 100kHz, two frequency-splittings control at 1 ~ 50kHz, ultrasonic radiation time controling, at 10 ~ 60min, at room temperature continues aging after ultrasonic aging end;
(4) step (3) gained material is carried out filtering, washing;
(5) step (4) gained material is carried out drying, baking temperature is 100 ~ 150 DEG C, 1 ~ 20 hour drying time, then namely obtains macropore amorphous silicon aluminum through roasting.
2. method according to claim 1, is characterized in that: the microwave frequency adopted in step (2) is respectively 25 ~ 45kHz, 35 ~ 80kHz, and two frequency-splittings control at 5 ~ 35kHz, and ultrasonic radiation time controling is at 10 ~ 15min.
3. method according to claim 1, is characterized in that: the acid aluminium salt solution described in step (1) comprises AlCl 3, Al (NO 3) 3, Al 2(SO 4) 3one or more in solution.
4. method according to claim 1, is characterized in that: add sodium silicate solution process in step (2) and stirring or carrying out under ultrasonic effect, and in the scope of regulation system pH value to 4.0 ~ 9.5, temperature controls at 20 ~ 80 DEG C;
Method according to claim 1, is characterized in that: in step (3), the ultrasonic wave of the different frequency of the aging employing of dual-frequency ultrasonic wave carries out simultaneously or hockets.
5. method according to claim 1, is characterized in that: in step (3), ultrasonic power counts 0.01 ~ 20W/mL by the acid aluminium salt liquor capacity in step (1).
6. the method according to claim 1 or 6, is characterized in that: ultrasonic power counts 0.05 ~ 10W/mL by the acid aluminium salt liquor capacity in step (1).
7. method according to claim 1, is characterized in that: in step (3), during ultrasonic radiation, temperature controls at 20 ~ 80 DEG C.
8. the method according to claim 1 or 8, is characterized in that: during ultrasonic radiation, temperature controls at 40 ~ 60 DEG C.
9. method according to claim 1, is characterized in that: continuing ageing time under room temperature in step (3) is 30 ~ 300min.
10. method according to claim 1, is characterized in that: the dry run in step (5) is carried out under an increased pressure, and controlling dry gauge pressure is 0.05 ~ 0.2MPa.
11. methods according to claim 1, is characterized in that: the roasting 0.5 ~ 10 hour at 300 ~ 750 DEG C of the roasting in step (5).
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CN106085546A (en) * 2016-06-08 2016-11-09 上海理工大学 One carries out method for removing sodium to high sodium raw coal
CN108283890A (en) * 2018-04-01 2018-07-17 中鸿纳米纤维技术丹阳有限公司 Mixing component in a kind of aeroge aging equipment
CN108325416A (en) * 2018-04-01 2018-07-27 中鸿纳米纤维技术丹阳有限公司 A kind of aeroge aging equipment
CN109888288A (en) * 2019-01-29 2019-06-14 无锡凯帕德瑞科技有限公司 The preparation method of anode sizing agent
CN114471642A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Phosphorus and boron-containing hydrodesilicification catalyst, preparation method thereof and hydrodesilicification method
CN115445596A (en) * 2022-09-21 2022-12-09 郑州大学 Method for preparing copper-based amorphous denitration catalyst by purifying red mud

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106085546A (en) * 2016-06-08 2016-11-09 上海理工大学 One carries out method for removing sodium to high sodium raw coal
CN108283890A (en) * 2018-04-01 2018-07-17 中鸿纳米纤维技术丹阳有限公司 Mixing component in a kind of aeroge aging equipment
CN108325416A (en) * 2018-04-01 2018-07-27 中鸿纳米纤维技术丹阳有限公司 A kind of aeroge aging equipment
CN109888288A (en) * 2019-01-29 2019-06-14 无锡凯帕德瑞科技有限公司 The preparation method of anode sizing agent
CN109888288B (en) * 2019-01-29 2021-10-08 无锡凯帕德瑞科技有限公司 Preparation method of positive electrode slurry
CN114471642A (en) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 Phosphorus and boron-containing hydrodesilicification catalyst, preparation method thereof and hydrodesilicification method
CN114471642B (en) * 2020-10-27 2023-07-14 中国石油化工股份有限公司 Hydrodesilicification catalyst containing phosphorus and boron, preparation method thereof and hydrodesilicification method
CN115445596A (en) * 2022-09-21 2022-12-09 郑州大学 Method for preparing copper-based amorphous denitration catalyst by purifying red mud
CN115445596B (en) * 2022-09-21 2023-09-22 郑州大学 Method for preparing copper-based amorphous denitration catalyst by red mud purification

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