CN1733606A - Large pore volume and high specific surface gamma-Al 2O 3The preparation method of nanometer fibre powder - Google Patents

Large pore volume and high specific surface gamma-Al 2O 3The preparation method of nanometer fibre powder Download PDF

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CN1733606A
CN1733606A CN 200410070144 CN200410070144A CN1733606A CN 1733606 A CN1733606 A CN 1733606A CN 200410070144 CN200410070144 CN 200410070144 CN 200410070144 A CN200410070144 A CN 200410070144A CN 1733606 A CN1733606 A CN 1733606A
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pore volume
boehmite
azeotropic
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large pore
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CN1304294C (en
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蔡卫权
李会泉
张懿
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Institute of Process Engineering of CAS
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Abstract

The present invention relates to a kind of large pore volume and high specific surface gamma-Al 2O 3The preparation method of nanometer fibre powder comprises: add H in sodium aluminate solution 2O 2Solution obtains the boehmite precipitation; Filter after this boehmite precipitation is aging, be washed to neutrality; The wet boehmite filter cake that obtains is mixed with azeotropic solvent immediately, carry out then azeotropic distillation and backflow; The azeotropic product after cooling, centrifugation, drying, namely obtains the γ-Al of large pore volume of the present invention and high-ratio surface successively at 400～550 ℃ of roasting 1～4h 2O 3Nanometer fibre powder.The standby technology of the party's legal system is simple, reaction condition is gentle, with low cost and suitable large-scale industrial production; γ-the Al that makes 2O 3It is nanometer fibrous that powder is, and do not have hard aggregation, and big or small boring ratio example rationally; And this method do not need to add any surfactant, template and expanding agent, and the azeotropic solvent that uses during azeotropic distillation can also reclaim use, economically feasible.

Description

Large pore volume and high specific surface gamma-Al 2O 3The preparation method of nanometer fibre powder
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 it is warmed up to the boiling point of azeotropic 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 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 bore dia is 1.44cm at the pore volume of asking of 3～50nm 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 (2)

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 it is warmed up to the boiling point of azeotropic 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 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.
2, large pore volume as claimed in claim 1 and high specific surface gamma-Al 2O 3The preparation method of nanometer fibre powder is characterized in that, described azeotropic organic solvent is n-butanol, isobutanol, sec-butyl alcohol, n-amyl alcohol, isopropyl alcohol, normal propyl alcohol, ethanol, toluene or benzene.
CNB2004100701440A 2004-08-03 2004-08-03 Big pore volume and high specific surface gamma-Al2O3 nanometer fibre powder preparation method Expired - Fee Related CN1304294C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103831138A (en) * 2014-03-27 2014-06-04 辽宁科隆精细化工股份有限公司 Preparation method of gamma-alumina supporter with high specific surface area
CN106276993A (en) * 2015-05-27 2017-01-04 裕祥化工（大连）有限公司 A kind of nano aluminium oxide concentrated 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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1040845C (en) * 1993-07-16 1998-11-25 中国石油化工总公司 Preparation of micro-ball gamma aluminum oxide
RU2124478C1 (en) * 1996-07-01 1999-01-10 Мельников Вячеслав Борисович Aluminum hydroxide production process
CN1164494C (en) * 2002-05-31 2004-09-01 中国石油化工集团公司 Prepn of gamma-alumina
CN1186261C (en) * 2003-06-05 2005-01-26 上海大学 Preparation method of nano alumina material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103831138A (en) * 2014-03-27 2014-06-04 辽宁科隆精细化工股份有限公司 Preparation method of gamma-alumina supporter with high specific surface area
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
CN106276993A (en) * 2015-05-27 2017-01-04 裕祥化工（大连）有限公司 A kind of nano aluminium oxide concentrated 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

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