CN104492407A - Preparation method of long-chain alkane dehydrogenation catalyst carrier with large pore volume and low specific surface area - Google Patents
Preparation method of long-chain alkane dehydrogenation catalyst carrier with large pore volume and low specific surface area Download PDFInfo
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- CN104492407A CN104492407A CN201410818697.3A CN201410818697A CN104492407A CN 104492407 A CN104492407 A CN 104492407A CN 201410818697 A CN201410818697 A CN 201410818697A CN 104492407 A CN104492407 A CN 104492407A
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Abstract
The invention discloses a preparation method of a long-chain alkane dehydrogenation catalyst carrier with large pore volume and low specific surface area. The preparation method disclosed by the invention comprises the following steps of: gelatinizing aluminum sulphate solution and sodium metaaluminate solution in a stainless steel reaction kettle by taking NaAlO2-Al2(SO4)3 as the raw material in a continuous parallel flow manner, then, pressing in a plate-and-frame filter press by using a pressing pump after aging in a stainless steel aging water-washing tank for a certain time, continuously washing, after washing is qualified, acidizing, forming, drying and activating a discharged filter cake, and forming by adopting ammonium hydroxide containing a surface active agent through an optimization process. By means of the preparation method disclosed by the invention, the long-chain alkane dehydrogenation catalyst carrier of a bimodal pore structure can be prepared; the pore volume of the long-chain alkane dehydrogenation catalyst carrier is 1.8-2.2 ml/g; the specific surface area is 80-100 m<2>/g; compared with the existing catalyst carrier, the long-chain alkane dehydrogenation catalyst carrier prepared by the invention is more excellent in technical index and lower in cost; and thus, various technical indexes of the long-chain alkane dehydrogenation catalyst carrier (above C10) can be comprehensively increased.
Description
Technical field
The present invention relates to fine chemistry industry synthesis field, particularly relate to the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of a kind of large pore volume.
Background technology
γ-Al
2o
3as a kind of catalysis, sorbing material, because it has high temperature resistant, wear-resistant, compressive resistance, high activity and loose structure characteristic, and pore structure has controllability, make it divide at sky, the commercial Application such as hydrogen peroxide, daily use chemicals, pottery, medicine, chemical industry, membrane material and Aero-Space is more and more extensive, the research of people to it is also more and more deep.Large pore volume, low ratio table γ-Al
2o
3due to the pore size distribution of its uniqueness, make its application in enzymatic, dehydrogenation of long-chain alkane and other industry be subject to people and pay close attention to greatly.At present at home, foreign minister's paraffin dehydrogenation catalyst carrier leading indicator is: pore volume 1.0-1.5 ml/g, specific area 120-150 m
2/ g, pore size distribution has unimodal, also has bimodal.Main in preparation method be hydrolyzed to master with aluminium alcoholates abroad, this method environmental pollution is less, product purity is high, and technical indicator is excellent, and aperture belongs to Unimodal Distribution, but production cost is higher, domestic main employing AlCl
3-NH
4oH method, this method pore volume is larger, specific surface is lower, aperture belongs to bimodal distribution, as CN 87101513 A carry out neutralizing with this raw material, aging, filter, washing, acidifying are shaping, dry, prepared by calcination activation dehydrogenation of long-chain alkane catalyst carrier, pore volume at 1.2-1.4 ml/g, specific surface 120 ~ 160 m
2/ g, its technical indicator is suitable with international most advanced level, but this method equipment corrosion is serious, comparatively large to soil, water pollutions, produces and is subject to a definite limitation, with NaAlO
2-Al
2(SO
4)
3for activated alumina prepared by raw material, low because having cost, equipment corrosion is little, the advantages such as wastewater treatment is easy, attract domestic, scientific research personnel a large amount of outward studies, also many patents have been applied for, its production process mostly through in and the step such as plastic → aging → washing → shaping → drying → calcination for activation, because process conditions are different, the alumina support performance difference of preparation is larger, its mesopore volume, specific area and pore size distribution all do not meet the requirement of dehydrogenation of long-chain alkane catalyst to its carrier, therefore, be badly in need of exploitation larger than current technical indicator pore volume, the less more excellent dehydrogenation of long-chain alkane catalyst carrier of specific area.
Summary of the invention
The technical problem that the present invention mainly solves is to provide the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of a kind of large pore volume, with NaAlO
2-Al
2(SO
4)
3for raw material, preparing pore volume is 1.8-2.2 ml/g, and specific area is 80-100 m
2/ g, and there is the carrier of the dehydrogenation of long-chain alkane catalyst of bimodal pattern pore structure, the macropore volume more excellent than current catalyst carrier technical indicator, cost is lower, low specific surface area dehydrogenation of long-chain alkane catalyst carrier, thus improve all technical of activated alumina comprehensively, be particularly suitable for as long-chain (C
10alkane dehydrogenating catalyst carrier above).
For solving the problems of the technologies described above, the invention provides the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of a kind of large pore volume, comprising the following steps:
(1) by NaOH and Al (OH)
3be made into certain mass concentration, causticity factor alpha preparing in still
kbe the NaAlO of 1.1 ~ 1.3
2solution; Then Al is used
2(SO
4)
318H
2o is made into the Al of certain mass concentration in dissolving tank
2(SO
4)
3solution;
(2) under mechanical stirring, by Al
2(SO
4)
3solution and NaAlO
2solution is with 1 ~ 10 ml/min flow velocity continuous gel formation, and control reaction temperature and pH value of solution neutralize within the specific limits;
(3), after neutralization terminates, reactant liquor is all put into ageing can, at 30 ~ 50 DEG C of temperature, aging enough time;
(4) the liquid binder after aging is pumped into plate and frame filter press, then washs with the water of 50 ~ 60 DEG C, until use Ba
2+inspection does not measure the SO in the filtrate in filtrate
4 2-till;
(5) wet cake after washing is put into souring tank, first add appropriate water, surfactant and expanding agent to stir, then add dust technology, being made into sour aluminum ratio is by mass percentage 0.1 ~ 0.5, proportion is the solution of 1.1 ~ 1.5, then shaping in the ammoniacal liquor containing surfactant;
(6) wet bulb after shaping carries out drying in drying box, and temperature controls at 120 ~ 150 DEG C, time 2 ~ 6 h;
(7) roasting is carried out, temperature 600 ~ 900 DEG C, time 5 h in dried bead loading roaster.
In the present invention's preferred embodiments, NaAlO in described step (1)
2solution concentration is with Al
2o
3count 5 ~ 50 g/L, Al
2(SO
4)
3solution concentration is with Al
2o
3count 10 ~ 100 g/L; In in step (2) and PH be 6 ~ 9, neutralization reaction temperature is 20 ~ 85 DEG C; In step (3), ageing time is 10 ~ 180 min.
In the present invention's preferred embodiments, NaAlO in described step (1)
2solution concentration is with Al
2o
3count 10 ~ 40 g/L, Al
2(SO
4)
3solution concentration is with Al
2o
3count 25 ~ 85 g/L; In in step (2) and PH be 7 ~ 8, neutralization reaction temperature is 30 ~ 80 DEG C; In step (3), ageing time is 20 ~ 120 min.
In the present invention's preferred embodiments, NaAlO in described step (1)
2solution concentration is with Al
2o
3count 15 ~ 20 g/L, Al
2(SO
4)
3solution concentration is with Al
2o
3count 35 ~ 80 g/L; In in step (2) and PH be 7.2 ~ 7.8, neutralization reaction temperature is 40 ~ 60 DEG C; In step (3), ageing time is 30 ~ 90 min.
In the present invention's preferred embodiments, described surfactant is one or more in APG, alcohol ether carboxylate, triethanolamine quaternary ammonium salt, glucose amide, monoalkyl phosphoric acid esters.
The invention has the beneficial effects as follows:
1, in and with ageing process, prepare the bulky grain of primary particle 20-40 nanometer, uniform boehmite by changing neutralization and aging technique parameter;
2, in ammoniacal liquor forming process, pass into and add surfactant, utilize surfactant can reduce the capillary characteristic of water, guarantee that the sphericity of spherical carrier of catalyst is better;
3, pore volume 1.8-2.2 ml/g is prepared, specific area 80-100 m
2/ g, and the carrier with the dehydrogenation of long-chain alkane catalyst of bimodal pattern pore structure are more excellent than current catalyst carrier technical indicator.
Detailed description of the invention
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1:
NaAlO
2prepared by solution: under mechanical stirring, added in 500 ml deionized waters by 40 g caustic soda, be then warming up to boiling, slowly add 50 g Al (OH)
3, after all dissolving, be incubated 100 ~ 105 DEG C of 3 h, be then naturally down to room temperature, add water and be made into 500 ml, concentration is that 15 g/L are (with Al
2o
3meter) solution.
Al
2(SO
4)
31200 ml deionized waters are added thermic 30 ~ 40 DEG C, then add 100 gAl by the preparation of solution: under mechanical stirring
2(SO
4)
318H
2o, after all dissolving, is down to room temperature, adds water and be made into 600 ml, concentration is that 15 g/L are (with Al
2o
3meter) solution.
First in 10000 ml stainless steel cauldrons, add 500 ml deionized waters, under mechanical agitation, be heated to 70 DEG C, then carry out and flow plastic.Stablize NaAlO
2solution flow rate 2 ~ 8 ml/min, adjustment Al
2(SO
4)
3solution flow rate to solution ph is start overflow after 7.5,25 min, keeps the level stability of reactor.About about 3 h, neutralize complete, reactant liquor are all put into ageing can, control aging temperature 45 DEG C, start binder after aging 30 min, then carry out successive washing, control plate and frame filter press inlet pressure 0.2 ~ 0.4 MPa, washing temperature is 55 DEG C, until the SO in filtrate
4 2-use Ba
2+till inspection does not measure, being dropped into by wet cake has in appropriate amount of deionized water souring tank, under constantly stirring, adds a certain amount of nitric acid acidifying, be made into that sour aluminum ratio is 0.1 ~ 0.5, the solution of proportion 1.1 ~ 1.5, then shaping in containing the ammoniacal liquor of alkyl glucoside surfactant through dripping dish device.Bead after shaping is dry in drier, and temperature controls at 130 DEG C, time 4 h.Activate in dried bead loading activation furnace, temperature controls at 650 DEG C, roasting 3 h, and gained sample analysis data are in table 1.Wherein specific surface is by low temperature N
2physisorphtion calculates through BET and tries to achieve; Pore volume and pore size distribution are recorded by mercury injection method.
Example 1 comparative example:
By the method for embodiment 1, difference does not add alkyl glucoside surfactant in ammoniacal liquor forming process, and gained sample analysis data are in table 1.
Embodiment 2:
Will with Al
2o
3meter concentration is the NaAlO of 25 g/L
2solution 1000 ml and with Al
2o
3meter concentration is the Al of 35g/L
2(SO
4)
3solution 1200 ml in a kettle. continuously and flow plastic, stablizes NaAlO
2solution flow rate 3 ~ 5ml/min, regulates Al
2(SO
4)
3solution flow rate to solution ph is 7.4, and equilibrium temperature 75 DEG C, start overflow after 30 min, keep the level stability of neutralizing tank, neutralization terminates rear aging 45 min, in shaping ammoniacal liquor, add glucose amide, other condition is same as Example 1, and gained sample analysis data are in table 1.
Example 2 comparative example:
By the method for embodiment 2, difference does not add glucose amide surfactant in ammoniacal liquor forming process, and gained sample analysis data are in table 1.
Embodiment 3:
Will with Al
2o
3meter concentration is the NaAlO of 20g/L
2solution 1000 ml and with Al
2o
3meter concentration is the Al of 45.5g/L
2(SO
4)
3solution 1200 ml in a kettle. continuously and flow plastic, stablizes NaAlO
2solution flow rate 4 ~ 7 ml/min, regulates Al
2(SO
4)
3solution flow rate to solution ph is 7.6, and equilibrium temperature 70 DEG C, start overflow after 30 min, keep the level stability of neutralizing tank, neutralization terminates rear aging 40 min, in shaping ammoniacal liquor, add alcohol ether carboxylate, other condition is same as Example 1, and gained sample analysis data are in table 1.
Example 3 comparative example:
Will with Al
2o
3meter concentration is the NaAlO of 50 g/L
2solution 1000ml and with Al
2o
3meter concentration is the Al of 100g/L
2(SO
4)
3solution 1200 ml in a kettle. continuously and flow plastic, stablizes NaAlO
2solution flow rate 9 ~ 10 ml/min, regulates Al
2(SO
4)
3solution flow rate to solution ph is 7.8 and equilibrium temperature 85 DEG C, starts overflow after 30 min, keeps the level stability of neutralizing tank, neutralization terminates rear aging 180 min, other condition is same as Example 1, and in described example 3 comparative example, above-mentioned technical parameter is maximum, and gained sample analysis data are in table 1.
Table 1 example analyzes data
Claims (5)
1. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of large pore volume, is characterized in that, comprise the following steps:
(1) by NaOH and Al (OH)
3be made into certain mass concentration, causticity factor alpha preparing in still
kbe the NaAlO of 1.1 ~ 1.3
2solution; Then Al is used
2(SO
4)
318H
2o is made into the Al of certain mass concentration in dissolving tank
2(SO
4)
3solution;
(2) under mechanical stirring, by Al
2(SO
4)
3solution and NaAlO
2solution is with 1 ~ 10 ml/min flow velocity continuous gel formation, and control reaction temperature and pH value of solution neutralize within the specific limits;
(3), after neutralization terminates, reactant liquor is all put into ageing can, at 30 ~ 50 DEG C of temperature, aging enough time;
(4) the liquid binder after aging is pumped into plate and frame filter press, then washs with the water of 50 ~ 60 DEG C, until use Ba
2+inspection does not measure the SO in the filtrate in filtrate
4 2-till;
(5) wet cake after washing is put into souring tank, first add appropriate water, surfactant and expanding agent to stir, then add dust technology, being made into sour aluminum ratio is by mass percentage 0.1 ~ 0.5, proportion is the solution of 1.1 ~ 1.5, then shaping in the ammoniacal liquor containing surfactant;
(6) wet bulb after shaping carries out drying in drying box, and temperature controls at 120 ~ 150 DEG C, time 2 ~ 6 h;
(7) roasting is carried out, temperature 600 ~ 900 DEG C, time 5 h in dried bead loading roaster.
2. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of large pore volume according to claim 1, is characterized in that, NaAlO in described step (1)
2solution concentration is with Al
2o
3count 5 ~ 50 g/L, Al
2(SO
4)
3solution concentration is with Al
2o
3count 10 ~ 100 g/L; In in step (2) and PH be 6 ~ 9, neutralization reaction temperature is 20 ~ 85 DEG C; In step (3), ageing time is 10 ~ 180 min.
3. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of large pore volume according to claim 1, is characterized in that, NaAlO in described step (1)
2solution concentration is with Al
2o
3count 10 ~ 40 g/L, Al
2(SO
4)
3solution concentration is with Al
2o
3count 25 ~ 85 g/L; In in step (2) and PH be 7 ~ 8, neutralization reaction temperature is 30 ~ 80 DEG C; In step (3), ageing time is 20 ~ 120 min.
4. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of large pore volume according to claim 1, is characterized in that, NaAlO in described step (1)
2solution concentration is with Al
2o
3count 15 ~ 20 g/L, Al
2(SO
4)
3solution concentration is with Al
2o
3count 35 ~ 80 g/L; In in step (2) and PH be 7.2 ~ 7.8, neutralization reaction temperature is 40 ~ 60 DEG C; In step (3), ageing time is 30 ~ 90 min.
5. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of large pore volume according to claim 1, it is characterized in that, described surfactant is one or more in APG, alcohol ether carboxylate, triethanolamine quaternary ammonium salt, glucose amide, monoalkyl phosphoric acid esters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107081149A (en) * | 2017-05-16 | 2017-08-22 | 武汉理工大学 | A kind of anthraquinone simplification preparation method for preparing hydrogen peroxide low energy consumption hydrogenation catalyst |
| CN111432925A (en) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | Catalyst and process for the selective conversion of hydrocarbons |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
| CN103055786A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Alumina ball, preparation method of aluminum ball, and supergravity reactor |
-
2014
- 2014-12-25 CN CN201410818697.3A patent/CN104492407B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055786A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Alumina ball, preparation method of aluminum ball, and supergravity reactor |
| CN102730724A (en) * | 2012-05-31 | 2012-10-17 | 江苏晶晶新材料有限公司 | Preparation process for large pore volume and light bulk density activated alumina |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107081149A (en) * | 2017-05-16 | 2017-08-22 | 武汉理工大学 | A kind of anthraquinone simplification preparation method for preparing hydrogen peroxide low energy consumption hydrogenation catalyst |
| CN111432925A (en) * | 2017-11-02 | 2020-07-17 | 环球油品有限责任公司 | Catalyst and process for the selective conversion of hydrocarbons |
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| CN104492407B (en) | 2017-06-20 |
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