CN104549540B - A kind of preparation method of macropore amorphous silicon alumina supporter - Google Patents
A kind of preparation method of macropore amorphous silicon alumina supporter Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of macropore amorphous silicon alumina supporter, including following content：（1）Acid aluminium salt solution is mixed with Alumina gel with sodium aluminate solution；（2）To step（1）Sodium silicate solution is added in the Alumina gel of gained；（3）To step（2）Material carry out burin-in process；（4）By step（3）Resulting material is filtered, washed；（5）By step（4）Resulting material is dried, and drying temperature is 100~150 DEG C, 1~20 hour drying time, then fired to produce macropore amorphous silicon aluminum.This method can not only prepare Distribution of silicon and aluminium uniformly, and dioxide-containing silica is high, pore volume and the big high-quality amorphous silica-alumina of specific surface area, while making raw material using cheap inorganic salts, being not added with adjusting hole agent, can also reduce the preparation cost of amorphous silica-alumina.
Description
Technical field
The present invention relates to a kind of macropore amorphous silica-alumina and preparation method thereof, especially as adding for production intermediate oil
Macropore amorphous silica-alumina of one of hydrogen processing catalyst carrier and preparation method thereof.
Background technology
Research shows that the oxide carrier with irregular pore structure is particularly suited for hydrotreating application.Amorphous silica-alumina
Because its distinctive acidity has obtained substantial amounts of research, using it as carrier, be conducive to the scattered of carried metal.It is used as carrier, nothing
Distinguishing feature of the amorphous silicon-alumina compared with molecular sieve is with amorphous structure and larger aperture.This also causes amorphous silica-alumina
Today deteriorated increasingly in petroleum refining raw material, with broader practice prospect.In terms of preparation, amorphous silica-alumina generally with
Organometallic precursor is synthesized in the presence of pore regulator by sol method.
Raw material is made with organic metal, cost is higher, and environmental pollution is heavier.Pore regulator, such as TPAOH
Use, although beneficial to the concentration of pore-size distribution, but necessarily increase preparation process, numerousization subsequent operation.Many uses existing at present
Cheap inorganic salts are raw material, without the report that amorphous silica-alumina is prepared under the conditions of pore regulator.
《Microporous and Mesoporous Materials》P197-204 " the Synthesis and of volume 96
Properties of mesoporous silica-alumina with narrow pore size distribution
Obtained without use of pore-regulating agents " report one kind without using pore regulator and with letter
The method that single inorganic salts prepare mesoporous amorphous sial for raw material, be specially：Solution of sodium metasilicate through mixes the two of generation with nitric acid
Silica gel is mixed with vigorous stirring with aluminum nitrate solution.Add concentrated ammonia liquor and pH is adjusted to 7, continue stirring 4 hours, herein
Period, temperature is increased continuously to 60 DEG C.Mixture stands 16 hours, precipitates the hydrosol through distilled water diluting.Remove supernatant
Liquid, the hydrosol is dried 3 days at room temperature through filtered on buchner funnel.Dry glue hot water surname extraction 8 hours, product is done at 120 DEG C
Dry 6 hours, and be calcined 6 hours in 500 DEG C of air streams.It is not difficult to find out from preparation process, the manufacturing cycle of this method compares
Long, wherein room temperature normal pressure Aging Step needs 3 days.In addition, niffy concentrated ammonia liquor is the method use, not only pollution operation
Environment, can also be detrimental to health.
CN 101239328A disclose one kind using sodium aluminate and sodium metasilicate as aluminium, silicon source, and carbonizatin method prepares amorphous silicon
The method of aluminium.CO2Reaction raw materials are served not only as herein, while being also equipped with disturbing, stirring, make the full and uniform mixing of reactant
Effect.But, CO2It is notorious greenhouse gases, if CO2Dosage control is inaccurate, the excessive CO added2Without recycling
Environment is directly discharged into, then can aggravate greenhouse gases pollution.
CN 101491774A disclose a kind of first with inorganic silicon silicon source co-precipitation plastic, add organic-silicon-modified preparation
The method of amorphous silica-alumina.The drawbacks of coprecipitation method has itself, in order that sial is precipitated and settling velocity is close, then simultaneously
Need to be controlled by deposition condition, and the condition be generally not one-component precipitation when optimum condition.
Yao Nan is in Chinese Academy of Sciences Ph.D. Dissertation《The non-template agent synthesis and sign research of mesopore nano catalytic material》In
Propose the method that " ultrasonic sol-gal process " prepares mesoporous amorphous sial.Can be at ambient temperature with inorganic by this method
Aluminium salt is that raw material passes through precipitation, dispergation process, and dispergation process carries out preparing in the presence of ultrasonic disperse to be needed to exist originally
The getable Alumina gel of ability under hot conditions.On the premise of without using template and other additives, by homogeneous
The control of the sol particles of size distribution, makes these sol particleses regularly reunite and be packed together in gel process, from
And successfully prepared the alumina material of middle pore distribution concentration.Although this paper make use of the cavitation of ultrasonic wave or divides
Effect is dissipated, the preferable mesopore amorphous silicon aluminium product of mass is prepared, but ultrasonic wave main function used is to a certain degree
On realize the homogenization of solution and the stabilisation of colloidal sol, it is difficult to realize the finer control of silica-alumina supports particulate and pore structure.
Also need to add ammonium nitrate in the preparation process ageing process, to prevent in drying process the contraction of sial skeleton and cave in.
The content of the invention
In view of the shortcomings of the prior art, the present invention is prepared using the method for heavy silicon after first heavy aluminium, is used in ageing process
Dual-frequency ultrasonic wave, in drying process by the way of pressurization, can not only prepare Distribution of silicon and aluminium uniformly, dioxide-containing silica
The big high-quality amorphous silica-alumina of height, pore volume and specific surface area, while making raw material using cheap inorganic salts, being not added with adjusting hole agent, also
The preparation cost of amorphous silica-alumina can be reduced.
A kind of preparation method of macropore amorphous silicon alumina supporter of the present invention, including following content：
（1）Acid aluminium salt solution is mixed with Alumina gel with sodium aluminate solution；
（2）To step（1）Sodium silicate solution is added in the Alumina gel of gained；
（3）To step（2）Material carry out burin-in process, ageing process uses dual-frequency ultrasonic wave aging, frequency point first
Not Wei 20~50kHz and 30~100kHz, preferably 25~45kHz, 35~80kHz, two frequency-splittings control in 1~50kHz, it is excellent
Select 5~35kHz, ultrasonic radiation time control in 10~60min, preferably 10~15min, ultrasonic aging terminate after at room temperature after
Continuous aging；
（4）By step（3）Resulting material is filtered, washed；
（5）By step（4）Resulting material is dried, and drying temperature is 100~150 DEG C, 1~20 hour drying time,
Then it is fired to produce macropore amorphous silicon aluminum.
The inventive method, step（1）Described in acid aluminium salt solution include AlCl3、Al(NO3)3、Al2(SO4)3Solution
In one or more.
The inventive method, step（2）Middle addition sodium silicate solution process is carried out in the presence of stirring or ultrasound, and is adjusted
System pH is in the range of 4.0~9.5, and temperature control is at 20~80 DEG C；
The inventive method, step（3）Middle dual-frequency ultrasonic wave aging can be carried out simultaneously can also be alternately.Ultrasonic wave work(
Rate presses step（1）In acid aluminium salt liquor capacity be calculated as 0.01~20W/mL, preferably 0.05~10W/mL.Temperature during ultrasonic radiation
Degree control is at 20~80 DEG C, preferably 40~60 DEG C.It is 30~300min to continue ageing time at room temperature.
The inventive method, step（4）In filtering, washing using conventional method carry out.Step（5）In drying process can
To carry out under an increased pressure, it is 0.05~0.2MPa to control to dry gauge pressure.High-pressure drying serves further reaming effect.
Described roasting is calcined 0.5~10 hour at 300~750 DEG C.
The inventive method adds sodium metaaluminate in Alumina gel and prepares silicon-aluminum sol；Double frequency is used in colloidal sol ageing process
Ultrasonic wave；In drying process use high-pressure drying, the two synergy can effectively suppress and avoid silicon-aluminum sol drying,
Framework shrinkage in roasting process and cave in, influence amorphous silicon alumina supporter.Relative to use single-frequency ultrasound and conventional drying side
The preparation process of method, prepared amorphous silicon aluminum has larger aperture and larger specific surface area, and pore size distribution
More concentrate.Preparation method described in this patent has that raw material is cheap and easy to get, it is simple to add pore regulator, preparation process,
The features such as easily operated, good product quality.The material is especially suited as load type metal catalyst in catalytic hydrogenation application
Carrier.
The present invention introduces dual-frequency ultrasonic wave during sial dry glue is prepared.Ultrasonic wave triggers sol particle or micelle
Rapid motion, can avoid caking from causing sol particle or micelle size to increase；By controlling double-frequency ultrasound wave frequency rate and energy level,
The sol particle larger and smaller than aimed dia can be made to produce resonance, cause movement velocity too fast and crush or dissolve, obtain
The sial colloid that particle diameter distribution is more single, pore size distribution is more concentrated, is realized by the adjustment of preparation method and finely controlled
The purpose of pore structure and property.
In addition, in the presence of ultrasonic wave, being also possible to prevent or reducing that agglomeration is produced between particle or micelle, reduce
The generation of abnormal large-volume particulate, so as to be effectively controlled the generation of super big hole.
Embodiment
A kind of detailed process of amorphous silica-alumina of the present invention is as follows：
（1）AlCl3The preparation of solution：General aluminum oxide is reacted with hydrochloric acid at 90 ~ 120 DEG C, it is de- with activated carbon
Iron so that Fe/Al by weight2O3Value is less than 0.005%, and essence AlCl is made3Solution, then be diluted, concentration is 10 ~ 60g
Al2O3/ L can be used as working solution during plastic.
（2）NaAlO is respectively configured2Solution and sodium silicate solution, respectively with Al2O3Count the Al containing 5~80g2O3/ L, with SiO2
Count the SiO containing 5~120g2/L。
（3）Plastic process：By AlCl3Solution and NaAlO2Solution is added in plastic cans with certain flow velocity simultaneously, is gone forward side by side
Row stirring, gelling temperature is controlled at 20~80 DEG C, is preferably controlled in 50~70 DEG C.Formed after Alumina gel, in 25kHz, 2W/mL
（With AlCl3Liquor capacity meter）In the presence of ultrasonic wave, the sodium silicate solution prepared is added, and adjust pH value in 4.0~9.5 models
In enclosing, temperature control is at 20~80 DEG C, and gelation time control is in 30~60min.
（4）Ageing process：Using dual-frequency ultrasonic wave, frequency is respectively 20~50kHz and 30~100kHz, preferably 25~
45kHz and 35~80kHz, two frequency-splittings control presses AlCl in 1~50kHz, preferably 5~35kHz, ultrasonic power3Solution
Volume is calculated as 0.01~20W/mL, preferably 0.05~10W/mL.Ultrasonic radiation time control in 10~60min, preferably 10~
15min, temperature control is at 20~80 DEG C during ultrasonic radiation, preferably 40~60 DEG C.Then, at room temperature stand aging 30~
300min。
（5）Filtering, washing：Aging slurries are filtered, mother liquor is separated, obtained filter cake is washed with deionized, washed
Temperature is controlled when washing between 60~80 DEG C, wash time is 20~50min, washing times are 3~5 times.
（6）Dry：Filtration cakes torrefaction after washing is produced into sial dry glue, drying temperature is 100~150 DEG C, preferably 120
DEG C, dry 1~20 hour, dry and carried out preferably in the case where there is appropriate pressure, it is 0.05~0.2MPa to dry gauge pressure, preferably
0.1MPa。
Comparative example 1
Prepare contained amorphous silica-alumina dry glue（SiO2：Al2O3Mass ratio is 50:50）2L is contained into Al2O3 30g/L AlCl3Solution
Contain Al with 1.5L2O3 120g/L NaAlO2Solution cocurrent plastic, reaction temperature is 60 DEG C.After plastic, what addition was prepared contains SiO2
20g/L Na2SiO3Solution, control ph is 8.0, and temperature control is in 50 DEG C, reaction contact time 45min.In temperature 60 C,
Aging is carried out under the conditions of pH 9.0, ageing time is 2 hours, and ageing process uses single-frequency ultrasonic wave, and frequency is 80kHz, power
For 2W/mL.Product is filtered, is then 1 with solid-to-liquid ratio:20 deionized water washing, 60 DEG C of wash temperature, washing 3
It is secondary, about 10min every time.Gained filter cake is dried 3 hours at 120 DEG C.
Embodiment 1
The plastic process of comparative example 1 is under ultrasonic environment, ultrasonic instrument is controlled（Double frequency constant temperature is selected in this experiment
Numerical control supersonic device）Frequency is 30kHz and 60kHz, and ultrasonic power presses AlCl3Liquor capacity be calculated as respectively 2W/mL and
5W/mL, two kinds of frequencies are alternately radiated, and each radiation 60s constitutes a transformation period, 12min is radiated altogether, radiative process temperature control is 60
℃.Then, aging 2 hours are stood at room temperature.Other same comparative examples 1.
Embodiment 2
The drying process of embodiment 1 is under pressurized conditions, gauge pressure 0.1MPa, the other the same as in Example 1.
Embodiment 3
Ageing process is using dual-frequency ultrasonic wave aging simultaneously, and ultrasonic frequency is respectively 50kHz and 100kHz, ultrasonic wave
Power presses AlCl3Liquor capacity is calculated as respectively 6W/mL and 12W/mL, and ultrasonic radiation time control is in 120S, radiation altogether
30min, temperature control stands aging 60min at room temperature after 75 DEG C, ultrasonic aging during ultrasonic radiation, control pressure when drying
0.2MPa, remaining is with comparative example 1.
Embodiment 4
Prepare contained amorphous silica-alumina dry glue（SiO2：Al2O3Mass ratio is 30:70）Other same examples 2.
Product property is shown in Table 1 after sial dry glue prepared by example 1 ~ 4 is calcined 3 hours at 400 DEG C
Table 1
Claims (11)
1. a kind of preparation method of macropore amorphous silicon alumina supporter, it is characterised in that including following content：
（1）Acid aluminium salt solution is mixed with Alumina gel with sodium aluminate solution；
（2）To step（1）Sodium silicate solution is added in the Alumina gel of gained；
（3）To step（2）Material carry out burin-in process, ageing process uses dual-frequency ultrasonic wave aging first, and frequency is respectively
20~50kHz and 30~100kHz, two frequency-splittings are controlled in 1~50kHz, and ultrasonic radiation time control surpasses in 10~60min
Sound aging continues aging at room temperature after terminating；
（4）By step（3）Resulting material is filtered, washed；
（5）By step（4）Resulting material is dried, and drying temperature is 100~150 DEG C, 1~20 hour drying time, then
Fired to produce macropore amorphous silicon aluminum, the drying process is carried out under an increased pressure, and it is 0.05 to control to dry gauge pressure
~0.2MPa.
2. according to the method described in claim 1, it is characterised in that：Step（2）The microwave frequency of middle use is respectively 25~
45kHz, 35~80kHz, two frequency-splittings are controlled in 5~35kHz, and ultrasonic radiation time control is in 10~15min.
3. according to the method described in claim 1, it is characterised in that：Step（1）Described in acid aluminium salt solution include AlCl3、
Al(NO3)3、Al2(SO4)3One or more in solution.
4. according to the method described in claim 1, it is characterised in that：Step（2）It is middle addition sodium silicate solution process stirring or
Carried out in the presence of ultrasound, and regulation system pH value, in the range of 4.0~9.5, temperature control is at 20~80 DEG C.
5. according to the method described in claim 1, it is characterised in that：Step（3）The different frequencies that middle dual-frequency ultrasonic wave aging is used
The ultrasonic wave of rate is carried out or alternately simultaneously.
6. according to the method described in claim 1, it is characterised in that：Step（3）Middle ultrasonic power presses step（1）In acidity
Aluminum salt solution volume is calculated as 0.01~20W/mL.
7. the method according to claim 1 or 6, it is characterised in that：Ultrasonic power presses step（1）In acid aluminium salt it is molten
Liquid product is calculated as 0.05~10W/mL.
8. according to the method described in claim 1, it is characterised in that：Step（3）Temperature control is 20~80 during middle ultrasonic radiation
℃。
9. the method according to claim 1 or 8, it is characterised in that：Temperature control is at 40~60 DEG C during ultrasonic radiation.
10. according to the method described in claim 1, it is characterised in that：Step（3）In continue at room temperature ageing time for 30~
300min。
11. according to the method described in claim 1, it is characterised in that：Step（5）In roasting be calcined at 300~750 DEG C
0.5~10 hour.
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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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| CN1210755A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Amorphous silica-alumina and its preparing method |
| CN102836747A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method for alumina oxide carrier |
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| CN101491774B (en) * | 2008-01-23 | 2011-05-18 | 中国石油化工股份有限公司 | High-silicon amorphous silica aluminum and preparation method thereof |
| CN102309999B (en) * | 2010-07-07 | 2013-05-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and preparation method thereof |
| CN102218351B (en) * | 2011-04-20 | 2012-09-26 | 山东浩霖石油化工科技股份有限公司 | Titanium-containing amorphous silicon-aluminum dry gel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1210755A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Amorphous silica-alumina and its preparing method |
| CN102836747A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method for alumina oxide carrier |
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