CN1304294C - Big pore volume and high specific surface gamma-Al2O3 nanometer fibre powder preparation method - Google Patents
Big pore volume and high specific surface gamma-Al2O3 nanometer fibre powder preparation method Download PDFInfo
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- CN1304294C CN1304294C CNB2004100701440A CN200410070144A CN1304294C CN 1304294 C CN1304294 C CN 1304294C CN B2004100701440 A CNB2004100701440 A CN B2004100701440A CN 200410070144 A CN200410070144 A CN 200410070144A CN 1304294 C CN1304294 C CN 1304294C
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- boehmite
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Abstract
The present invention relates to a method for preparing gamma-Al2O3 nanometer fiber powder with large pore volume and high specific surface area, which comprises: H2O2 solution is added into sodium aluminate solution to obtain precipitates of pseudo thin diaspore; the precipitates of pseudo thin diaspore are aged, filtered and then washed in water to neutrality; obtained filter cakes of the pseudo thin diaspore are immediately uniformly mixed with azeotropic solvent, and then, azeotropic distillation and back flow are carries out; products generated in the azeotropy are orderly cooled, separated in a centrifugal mode, dried and then roasted at 400 to 550 DEG C for 1 to 4 h to obtain the gamma-Al2O3 nanometer fiber powder with large pore volume and high specific surface area. The method has the advantages of simple preparing technology, moderate reaction condition and low cost and is suitable for scale industrial production. The prepared gamma-Al2O3 powder is in the shape of nanometer fiber, no hard aggregation exists, and the proportion of large pores to small pores is reasonable. Besides, the method does not need any surface active agents, template agents and pore expanding agents, and azeotropic agents used in azeotropic distillation can also be recovered for use, which is economical and practical.
Description
Technical field
The present invention relates to a kind of γ-Al
2O
3The preparation method of nanometer fibre powder specifically relates to a kind of for heavy oil hydrodesulfurization and Hydrodemetalation catalyst, that have structure of double peak holes, large pore volume and high specific surface gamma-Al
2O
3The preparation method of nano-powder.
Background technology
γ-Al
2O
3Cause has certain surface acidity, the higher good characteristics such as specific surface, absorption property and Heat stability is good are widely used in fields such as catalyst carrier, catalyst, adsorbent, multi-hole filtering film, buffing material and coating materials.γ-Al
2O
3Generally obtain 400～700 ℃ of lower roastings by boehmite, therefore, the particle size of boehmite, coherent condition and pattern have determined γ-Al to a great extent
2O
3Texture character and serviceability.At present, along with the raising heavy and that deep processing requires of becoming gradually of crude oil in China and the world wide, an urgent demand heavy distillate, especially residuum hydrodesulfurization and Hydrodemetalation catalyst adopt the γ-Al of the structure of double peak holes that has simultaneously large aperture and large pore volume
2O
3Be carrier, can reach provides the Uniform Dispersion active component with the mesopore that catalytic action is provided and the macropore that satisfies the metal oxide molecular migration simultaneously, deposits the catalysqt deactivation that causes because of beavy metal impurities such as coking and vanadium, nickel with effective reduction.In addition, because catalyst for heavy oil hydrogenation demetal is disposable products, be difficult to regeneration, this just requires γ-Al
2O
3The preparation cost of carrier is cheap.And the main preparation process of pseudoboehmite such as the domestic acid system that extensively adopts at present and alkaline process are subjected to the restriction of cost and pore volume, are difficult to satisfy simultaneously the requirement of large pore volume, high-ratio surface and low preparation cost.Therefore, from improving the pore passage structure of catalyst, the angle in extending catalyst service life is set out large pore volume, high specific surface gamma-Al
2O
3Exploitation be subjected to researcher's extensive concern.
γ-Al
2O
3Middle bore portion in the pore structure is generally determined by the character of its predecessor boehmite, and big bore portion often will could form by adding various expanding agents.By adjusting γ-Al
2O
3The pore structure of carrier, especially improve the aperture greater than pore volume shared ratio in total pore volume in the above hole of 100nm, be conducive to hold the migration of big molecular metal oxide, thereby take full advantage of the inner surface of catalyst and improve the metal removal activity of hydrotreating catalyst.Relevant large pore volume γ-Al
2O
3And the existing many reports of the exploitation of predecessor boehmite.
EP 237240 has reported that a kind of adding charcoal fiber preparation has structure of double peak holes γ-Al
2O
3Method, pore-size distribution concentrates on above two zones of 1.0～5.0nm and 100nm.The shortcoming of this method is that aperture part aperture is too little, and that the aperture pore volume accounts for the ratio of total pore volume is bigger, both has been unfavorable for the diffusion of macromolecular compound, also is easy to be stopped up by the metal accumulation thing; In addition, use the charcoal fiber also to cause γ-Al
2O
3Production cost higher.
CN 1103009A has reported a kind of γ-Al with structure of double peak holes
2O
3The preparation method, at first with two kinds of aluminium oxide or its predecessor and carbon black powder, surfactant, peptizing agent and water mixed-formings that pore-size distribution is different, behind roasting 1～4h in 550～650 ℃ of air, γ-Al
2O
3Mesoporous be the pore volume in 10～20nm hole account for total pore volume 50%, the aperture accounts for 5.0～30.0% of total pore volume greater than the pore volume in 100nm hole, but with total pore volume that mercury injection method records 0.99ml/g is only arranged.
CN 1044337C has reported that two kinds of different aluminium hydrate powders of pore-size distribution of a kind of usefulness make predecessor, does the expanding agent preparation with carbon black and surfactant and has structure of double peak holes γ-Al
2O
3Method.But the aperture only accounts for 14.0～40.0% of total pore volume greater than the pore volume in 10nm hole in this carrier, also less than 5.0% of total pore volume, therefore is difficult to remove the macromole of arsenic one class greater than the pore volume in 100nm hole; In addition, it is best unazotized linear primary alcohol polyethers or polyester nonionogenic tenside that this method requires tensio-active agent, and add-on is about 5.0～6.0% (in mass) of alumina raw material, thereby production cost is higher.
CN 1047957C has reported that the dried glue preparation of a kind of boehmite that adopts two or more different material route to prepare has structure of double peak holes γ-Al
2O
3Method.Have a kind of aluminium chloride---Ammonia Process that is in the syntheti c route of this method requirement boehmite at least, the hydrochloric acid of use is serious to equipment corrosion, discharging NH
4 +The cleaning solution that content is very high also can be to environment.Obviously, this method complex process, cost is higher, and environmental pollution is serious.
H
2O
2The method that the precipitation of aluminium acid sodium solution prepares boehmite also has report at RU 2124478.Its process conditions are 0～30 ℃ of decomposition temperatures, Na
2O/Al
2O
3=0.5～2.0 (mol ratios), Al
2O
3Concentration be 1.0～50.0% (in mass), H
2O
2/ Al
2O
3=6.7～50.0 (mol ratios).Although adopt this method can access the purer boehmite of crystalline phase, because H
2O
2Solution is extremely weak acid medium, produce strong interaction by hydrogen bond between the great amount of hydroxy group that the boehmite particle surface is rich in and hydrone and link together, cause boehmite and product of roasting thereof to produce very serious hard aggregation, γ-Al when being ground to the 250 μ m left and right sides
2O
3Specific surface be generally less than 200m
2/ g, pore volume is less than 0.4ml/g.Obviously, above-mentioned γ-Al
2O
3Can't directly be used as catalyst carrier for hydrgenating heavy oil.
Summary of the invention
The objective of the invention is to overcome existing structure of double peak holes γ-Al
2O
3γ-the Al that exists in the technology of preparing
2O
3Size boring ratio example is unreasonable, production cost is high, complex process, environmental pollution are serious; and produce easily hard aggregation and be unfavorable for the defective of commercial Application, thereby large pore volume and the high specific surface gamma-Al that a kind of big or small boring ratio example is reasonable, technology is simple, with low cost and suitable large-scale industrial is produced is provided
2O
3The preparation method of nanometer fibre powder.
The objective of the invention is to realize by the following technical solutions:
Large pore volume provided by the invention and high specific surface gamma-Al
2O
3The preparation method of nanometer fibre powder, process chart as shown in Figure 1 comprises following step:
1) under 0～90 ℃ to containing 50～250g/L-Al
2O
3With the causticization factor alpha
KBe that to add mass percent concentration in 1.30～2.00 the sodium aluminate solution be 8.0～30.0% H
2O
2Solution, H
2O
2Addition be Al in the sodium aluminate solution
2O
33.0～7.0 times of molal quantity, feed time is no less than 25min, obtains the boehmite precipitation, and is no less than the aging of 30min;
2) step 1) is obtained behind aged pseudo-boehmite sedimentation and filtration, the water washing of adopting 60～95 ℃ obtains wet pseudo-boehmite filter cake to neutral;
3) with step 2) the wet boehmite filter cake that obtains mixes making beating with the azeotropic organic solvent immediately, and powerful mechanical agitation is dispersed to it and forms complete homodisperse solidliquid mixture, it is transferred in the azeotropic distillation device afterwards; Described wet boehmite filter cake mixes making beating with the azeotropic organic solvent volume ratio is 1: 2～10;
4) the finely dispersed solidliquid mixture that step 3) is obtained carries out component distillation under powerful mechanical stirring, described component distillation comprises: the azeotropic mixture that the moisture between azeotropic organic solvent and pseudo-boehmite particle surface is formed evaporates, with the boiling point that it is warmed up to azeotropic solvent, and after the 10～40min that refluxes, again the azeotropic product is cooled off successively, separates and drying, just obtain the pseudo-boehmite nanometer fibre powder of large pore volume and high-ratio surface;
Described centrifugation or the vacuum filtration of being separated into; Described drying is that filter cake is dry under 60～80 ℃ still air, perhaps is with filter cake dry 6～12h under 30～80 ℃ of vacuum;
5) with step 4) the boehmite powder that obtains is at 400～550 ℃ of roasting 1～4h, obtains having γ-Al structure of double peak holes, large pore volume and high-ratio surface
2O
3Nanometer fibre powder;
The azeotropic organic solvent of described step 3) and step 4) is the organic solvent that energy and water form azeotropic mixture and contained hygroscopic water in the pseudo-boehmite particle can be removed to greatest extent.
Described azeotropic organic solvent is propyl carbinol, isopropylcarbinol, sec-butyl alcohol, Pentyl alcohol, Virahol, n-propyl alcohol, ethanol, toluene or benzene.
The present invention adopts H
2O
2The mode of precipitation of aluminium acid sodium solution and azeotropic distillation coupling prepares the γ-Al of large pore volume and high-ratio surface
2O
3Compared with the prior art nanometer fibre powder, this method have following outstanding advantages:
1, preparation technology is simple, reaction conditions is gentle, easy to control, without any need for complex apparatus, be fit to suitability for industrialized production;
2, preparation process does not need to add any surfactant, template and expanding agent, and the azeotropic solvent that uses during azeotropic distillation can not pollute product, can also reclaim use, economically feasible;
3, the γ-Al that makes
2O
3There is not hard aggregation in powder, and it is nanometer fibrous that morphology microstructure is, and average thickness and length are respectively about 5nm and about 100nm; Powder has very high specific area, and pore structure is bimodal distribution, and mercury injection method pore volume and BET specific surface are up to 4.21cm
3/ g and 396.3m
2/ g.
4, H
2O
2The pH of precipitation of aluminium acid sodium solution postprecipitation filtrate generally greater than 11 and free from admixture introduce, it is in addition recycling it can be turned back to the alkaline process bauxite stripping stage;
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is boehmite and the γ-Al that embodiment 1 makes
2O
3The XRD collection of illustrative plates;
Fig. 3 is γ-Al that embodiment 1 makes
2O
3The TEM photo.
Embodiment
Embodiment 1,
Be the 100g/L-Al of 80ml to volume under 30 ℃, stirring arm rotating speed 300r/min
2O
3, the causticization factor alpha
KBe at the uniform velocity to squeeze into 12.0%H with pump in 1.30 the sodium aluminate solution
2O
2Solution, H
2O
2/ Al
2O
3=5: 1 (mol ratio), charging rate are 4.2ml/min (feed time 25.4min).To separate out the aging 30min final vacuum suction filtration of precipitation, and be neutral with 60 ℃ water washing to filtrate, obtain wet boehmite filter cake; With this filter cake immediately with the azeotropic solvent of 2 times of volumes---n-butanol mixes making beating, powerful mechanical agitation makes its dispersion, until transfer in the ground conical flask after forming complete homodisperse solidliquid mixture, under powerful mechanical agitation, carry out azeotropic distillation and partial reflux thoroughly to remove moisture wherein and the pattern of crystal induced.Treat that the azeotropic mixture that moisture between n-butanol and boehmite particle surface forms evaporates, when the temperature of system rises to 117 ℃ of the boiling points of n-butanol gradually, continue backflow 10min; The azeotropic product obtains the boehmite nanometer fibre powder of large pore volume and high-ratio surface through cooling, centrifugation with behind 80 ℃ of air drying 12h; With this boehmite powder roasting 1h under 550 ℃ of air atmospheres,, obtain the γ-Al of large pore volume and high-ratio surface
2O
3Nanometer fibre powder.
The XRD collection of illustrative plates of precipitation and product of roasting is respectively boehmite mutually and γ-Al as shown in Figure 2
2O
3, do not have other impurity diffraction maximum, according to halfwidth and the γ-Al of Scherrer husband formula by the diffraction crystal face (200) of boehmite
2O
3The halfwidth of diffraction crystal face (440) can calculate that the average diameter of particle is respectively 14.4nm and 15.6nm before and after the roasting.
Product of roasting N
2The BET specific surface that the adsorption desorption method records is 396.3m
2/ g, the pore volume that records with mercury injection method is 4.21cm
3/ g, its pore-size distribution is as shown in table 1, as shown in Table 1, by the γ-Al of the present invention's preparation
2O
3, the pore volume of bore dia between 3～50nm is 1.44cm
3/ g accounts for 34.3% of total pore volume, and bore dia is 2.40cm at the pore volume of the above macropore of 100nm
3/ g accounts for 57.0% of total pore volume.
By γ-Al among Fig. 3
2O
3The TEM photo, it is fibrous to can clearly be seen that granule-morphology is.
Table 1, the γ-Al that obtains by embodiment
2O
3Nanometer fibre powder mercury penetration method pore size distribution data
| γ-Al 2O 3Pore size distribution | Embodiment 1 | Embodiment 2 | Embodiment 3 | |||
| Pore volume (cm 3/g) | Pore volume (%) | Pore volume (cm 3/g) | Pore volume (%) | Pore volume (cm 3/g) | Pore volume (%) | |
| Aperture (nm) 3-25 25-50 50-100 100-500＞500 Total | 1.02 0.42 0.37 1.11 1.29 4.21 | 24.2 10.1 8.7 26.3 30.7 100 | 0.93 0.51 0.56 0.55 0.08 2.63 | 35.4 19.4 21.3 20.9 3.0 100 | 0.96 0.45 0.35 1.13 1.14 4.03 | 23.8 11.2 8.7 28.0 28.3 100 |
Embodiment 2,
Be the 250g/L-Al of 80ml to volume under 0 ℃, stirring arm rotating speed 300r/min
2O
3, the causticization factor alpha
KBe at the uniform velocity to squeeze into 30.0%H with pump in 2.00 the sodium aluminate solution
2O
2Solution, H
2O
2/ Al
2O
3=3: 1 (mol ratio), charging rate is 2.0ml/min (feed time 30.0min), separate out that precipitation is aging through 30min, vacuum filtration and with 95 ℃ water washing to neutrality, pulling an oar to solid with the ethanol mixing of 10 times of volumes immediately is uniformly dispersed fully.Subsequently, under powerful mechanical agitation, be warmed up to 78.37 ℃ (the second alcohol and water forms the boiling point of azeotropic mixture) and carry out azeotropic distillation and partial reflux, treat that azeotropic mixture evaporates, after system temperature rises to 78.40 ℃ of the boiling points of ethanol, continue backflow 40min; The azeotropic product is through cooling, vacuum filtration with behind dry 12h under 60 ℃ of vacuum, and roasting 4h under 400 ℃ of air atmospheres obtains the γ-Al of large pore volume and high-ratio surface
2O
3Nanometer fibre powder, its average diameter is about 9.6nm.Product of roasting N
2The BET specific surface that the adsorption desorption method records is 373.1m
2/ g, the pore volume that records with mercury penetration method is 2.47cm
3/ g, its pore size distribution is as shown in table 1, and the pore volume of bore dia between 3～50nm is 1.44cm
3/ g accounts for 54.8% of total pore volume; The pore volume of bore dia between 50～100nm is 0.56cm
3/ g accounts for 21.3% of total pore volume; Bore dia is 0.63cm at the pore volume of the above macropore of 100nm
3/ g accounts for 23.9% of total pore volume.
Embodiment 3,
Be the 160g/L-Al of 80ml to volume under 90 ℃, stirring arm rotating speed 300r/min
2O
3, the causticization factor alpha
KBe at the uniform velocity to squeeze into 8.0%H with pump in 1.60 the sodium aluminate solution
2O
2Solution, H
2O
2/ Al
2O
3=7: 1 (mol ratio), charging rate is 14.3ml/min (feed time 25.4min), separate out that precipitation is aging through 30min, vacuum filtration and with 80 ℃ water washing to neutrality, pulling an oar to solid with the ethanol mixing of 5 times of volumes immediately is uniformly dispersed fully.Subsequently, be warmed up to 69.3 ℃ (benzene and water form the boiling points of azeotropic mixture) and carry out azeotropic distillation and partial reflux under powerful mechanical agitation, treat that azeotropic mixture evaporates, system temperature continues backflow 20min after rising to 80.2 ℃ of the boiling points of benzene; The azeotropic product is through cooling, vacuum filtration with behind dry 6h under 80 ℃ of vacuum, and roasting 2h under 500 ℃ of air atmospheres obtains the γ-Al of large pore volume and high-ratio surface
2O
3Nanometer fibre powder, its average diameter is about 14.8nm.Product of roasting N
2The BET specific surface that the adsorption desorption method records is 382.5m
2/ g, the pore volume that records with mercury penetration method is 4.03cm
3/ g, its pore size distribution is as shown in table 1, and the pore volume of bore dia between 3～50nm is 1.41cm
3/ g accounts for 35.0% of total pore volume; The pore volume of bore dia between 50～100nm is 0.35cm
3/ g accounts for 8.7% of total pore volume; Bore dia is 2.27cm at the pore volume of the above macropore of 100nm
3/ g accounts for 56.3% of total pore volume.
As seen from the above-described embodiment, γ-Al provided by the invention
2O
3Nanometer fibre powder has very big pore volume and higher specific surface and pore structure is bimodal distribution; petrochemical industry be can be widely used in and the environmental protection industry is used as catalyst carrier and adsorbent, heavy oil hydrodesulfurization that pore volume and pore-size distribution have relatively high expectations and the carrier of Hydrodemetalation catalyst especially are used as.
Claims (1)
1, a kind of large pore volume and high specific surface gamma-Al
2O
3The preparation method of nanometer fibre powder comprises the steps:
1) under 0～90 ℃ to containing 50～250g/L-Al
2O
3With the causticization factor alpha
KBe that to add mass percent concentration in 1.30～2.00 the sodium aluminate solution be 8.0～30.0% H
2O
2Solution, H
2O
2Addition be Al in the sodium aluminate solution
2O
33.0～7.0 times of molal quantity, feed time is no less than 25min, obtains the boehmite precipitation, and is no less than the aging of 30min;
2) step 1) is obtained behind aged pseudo-boehmite sedimentation and filtration, the water washing of adopting 60～95 ℃ obtains wet pseudo-boehmite filter cake to neutral;
3) with step 2) the wet boehmite filter cake that obtains mixes making beating with the azeotropic organic solvent immediately, and powerful mechanical agitation is dispersed to it and forms complete homodisperse solidliquid mixture, it is transferred in the azeotropic distillation device afterwards; Described wet boehmite filter cake mixes making beating with the azeotropic organic solvent volume ratio is 1: 2～10;
4) the finely dispersed solidliquid mixture that step 3) is obtained carries out component distillation under powerful mechanical stirring, described component distillation comprises: the azeotropic mixture that the moisture between azeotropic organic solvent and pseudo-boehmite particle surface is formed evaporates, with the boiling point that is warmed up to the azeotropic organic solvent, and the 10～40min that refluxes; Afterwards, again the azeotropic product is cooled off successively, separates and drying, just obtain the pseudo-boehmite nanometer fibre powder of large pore volume and high-ratio surface;
Described centrifugation or the vacuum filtration of being separated into; Described drying is that filter cake is dry under 60～80 ℃ still air, perhaps is with filter cake dry 6～12h under 30～80 ℃ of vacuum;
5) with step 4) the boehmite powder that obtains is at 400～550 ℃ of roasting 1～4h, obtains having γ-Al structure of double peak holes, large pore volume and high-ratio surface
2O
3Nanometer fibre powder;
The azeotropic organic solvent of described step 3) and step 4) is propyl carbinol, isopropylcarbinol, sec-butyl alcohol, Pentyl alcohol, Virahol, n-propyl alcohol, ethanol, toluene or benzene.
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|---|---|---|---|
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|---|---|---|---|
| CNB2004100701440A CN1304294C (en) | 2004-08-03 | 2004-08-03 | Big pore volume and high specific surface gamma-Al2O3 nanometer fibre powder preparation method |
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| CN1304294C true CN1304294C (en) | 2007-03-14 |
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| CN103831138B (en) * | 2014-03-27 | 2015-09-23 | 辽宁科隆精细化工股份有限公司 | A kind of preparation method of high-specific surface area gamma-aluminium oxide carrier |
| CN106276993B (en) * | 2015-05-27 | 2017-08-11 | 裕祥化工（大连）有限公司 | A kind of nano aluminium oxide thickened pulp and preparation method thereof |
| CN108383143A (en) * | 2018-03-30 | 2018-08-10 | 沈阳航空航天大学 | A method of preparing nanometer γ-AlOOH with sodium aluminate solution |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097351A (en) * | 1993-07-16 | 1995-01-18 | 中国石油化工总公司 | The preparation method of microspheroidal gama-alumina |
| RU2124478C1 (en) * | 1996-07-01 | 1999-01-10 | Мельников Вячеслав Борисович | Aluminum hydroxide production process |
| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN1477059A (en) * | 2003-06-05 | 2004-02-25 | 上海大学 | Preparation method of nano alumina material |
-
2004
- 2004-08-03 CN CNB2004100701440A patent/CN1304294C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097351A (en) * | 1993-07-16 | 1995-01-18 | 中国石油化工总公司 | The preparation method of microspheroidal gama-alumina |
| RU2124478C1 (en) * | 1996-07-01 | 1999-01-10 | Мельников Вячеслав Борисович | Aluminum hydroxide production process |
| CN1398787A (en) * | 2002-05-31 | 2003-02-26 | 中国石油化工集团公司 | Prepn of gamma-alumina |
| CN1477059A (en) * | 2003-06-05 | 2004-02-25 | 上海大学 | Preparation method of nano alumina material |
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