CN104492407B - A kind of low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume - Google Patents
A kind of low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume Download PDFInfo
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Abstract
The invention discloses a kind of low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume, with NaAlO2‑Al2(SO4)3It is raw material, by aluminum sulfate solution and sodium aluminate solution in stainless steel cauldron with the method plastic of continuous cocurrent, then after the stainless steel aging certain hour of aging water washing tank, plate and frame filter press is pumped into binder, carries out serialization washing, after washing is qualified, the filter cake that will be unloaded carries out acidifying shaping, dries, activation process, by optimize technique, it is molded using the ammoniacal liquor containing surfactant.This method can prepare pore volume for 1.8 2.2 ml/g, specific surface area are 80 100 m2The carrier of/g and the dehydrogenation of long-chain alkane catalyst with bimodal pattern pore structure, cost more excellent than current catalyst carrier technical indicator is lower, so as to improve long-chain comprehensively（C10More than）The all technical of alkane dehydrogenating catalyst carrier.
Description
Technical field
The present invention relates to fine chemistry industry synthesis field, more particularly to a kind of big pore volume is low to be catalyzed than table dehydrogenation of long-chain alkane
The preparation method of agent carrier.
Background technology
γ-Al2O3As one kind catalysis, sorbing material, due to its have high temperature resistant, wear-resistant, compressive resistance, high activity and
The characteristic of loose structure, and pore structure has controllability, makes it in space division, hydrogen peroxide, daily use chemicals, ceramics, medicine, chemical industry, film
The commercial Application such as material and Aero-Space is more and more extensive, and research of the people to it is also more and more deep.Big pore volume, low compare table
γ-Al2O3Due to its unique pore size distribution, its application in enzymatic, dehydrogenation of long-chain alkane and other industry is set to be subject to people
Greatly concern.At present at home, foreign minister's paraffin dehydrogenation catalyst carrier leading indicator be：Pore volume 1.0-1.5 ml/g,
Specific surface area 120-150 m2/ g, pore size distribution has unimodal, also there is bimodal.Foreign countries are mainly hydrolyzed to aluminium alcoholates in preparation method
Main, the method environmental pollution is smaller, product purity is high, and technical indicator is excellent, aperture category Unimodal Distribution, but production cost is higher；
The country mainly uses AlCl3-NH4OH methods, the method pore volume is larger, and specific surface is relatively low, aperture category bimodal distribution, such as CN 87101513
A neutralized with this raw material, aging, filtering, washing, acidifying shaping, dry, dehydrogenation of long-chain alkane catalysis prepared by calcination activation
Agent carrier, pore volume is in 1.2-1.4 ml/g, the m of specific surface 120~1602/ g, its technical indicator is suitable with international most advanced level, but
The method equipment corrosion is serious, larger to soil, water pollution, and production is subject to a definite limitation；With NaAlO2-Al2(SO4)3For raw material system
Standby activated alumina, because having low cost, equipment corrosion is small, the advantages of wastewater treatment is easy, has attracted the substantial amounts of section in home and abroad
The personnel of grinding are studied, and have also applied for many patents, and its production process is mostly by neutralizing plastic → aging → washing → shaping
The steps such as → drying → calcination for activation, because process conditions are different, the alumina support performance difference of preparation is larger, wherein hole body
Product, specific surface area and pore size distribution do not meet requirement of the dehydrogenation of long-chain alkane catalyst to its carrier, therefore, it is badly in need of exploitation ratio
Current technical indicator pore volume bigger, the smaller more excellent dehydrogenation of long-chain alkane catalyst carrier of specific surface area.
The content of the invention
The present invention solves the technical problem of providing, a kind of big pore volume is low than table dehydrogenation of long-chain alkane catalyst carrier
Preparation method, with NaAlO2-Al2(SO4)3It is raw material, prepares pore volume for 1.8-2.2 ml/g, specific surface area is 80-100
m2/ g, and the dehydrogenation of long-chain alkane catalyst with bimodal pattern pore structure carrier, than current catalyst carrier technical indicator more
Plus the lower macropore volume of excellent, cost, low specific surface area dehydrogenation of long-chain alkane catalyst carrier, so as to improve active oxygen comprehensively
Change all technical of aluminium, be particularly suitable as long-chain（C10More than）Alkane dehydrogenating catalyst carrier.
In order to solve the above technical problems, the present invention to provide a kind of big pore volume low than table dehydrogenation of long-chain alkane catalyst carrier
Preparation method, comprises the following steps：
（1）By NaOH and Al (OH)3Certain mass concentration, causticity factor alpha are made into kettle is preparedkIt is 1.1~1.3
NaAlO2Solution；Then Al is used2(SO4)3·18H2O is made into the Al of certain mass concentration in dissolving tank2(SO4)3Solution；
（2）Under mechanical stirring, by Al2(SO4)3Solution and NaAlO2Solution with 1~10 ml/min flow velocity continuous gel formations,
Controlling reaction temperature and pH value of solution are neutralized within the specific limits；
（3）After neutralization terminates, reaction solution is all put into ageing can, at a temperature of 30~50 DEG C, aging enough time；
（4）Liquid binder after will be aging is pumped into plate and frame filter press, is then washed with 50~60 DEG C of water,
Until using Ba2+Inspection does not measure the SO in the filtrate in filtrate4 2-Untill；
（5）Wet cake after washing is put into souring tank, first adds appropriate water, surfactant and expanding agent to carry out
Stirring, is subsequently adding dust technology, and it is 0.1~0.5 that sour aluminum ratio is made into by mass percentage, and proportion is 1.1~1.5 solution, so
It is molded in the ammoniacal liquor containing surfactant afterwards；
（6）Wet bulb after shaping is dried in drying box, and temperature control is in 120~150 DEG C, the h of time 2~6；
（7）Dried bead is calcined in being fitted into roaster, 600~900 DEG C of temperature, the h of time 5.
In a preferred embodiments of the invention, the step（1）Middle NaAlO2Solution concentration is with Al2O3It is calculated as 5~50 g/
L, Al2(SO4)3Solution concentration is with Al2O3It is calculated as 10~100 g/L；Step（2）It is 6~9 to neutralize PH, and neutralization reaction temperature is
20~85 DEG C；Step（3）Middle ageing time is 10~180 min.
In a preferred embodiments of the invention, the step（1）Middle NaAlO2Solution concentration is with Al2O3It is calculated as 10~40 g
/ L, Al2(SO4)3Solution concentration is with Al2O3It is calculated as 25~85 g/L；Step（2）It is 7~8 to neutralize PH, and neutralization reaction temperature is
30~80 DEG C；Step（3）Middle ageing time is 20~120 min.
In a preferred embodiments of the invention, the step（1）Middle NaAlO2Solution concentration is with Al2O3It is calculated as 15~20 g
/ L, Al2(SO4)3Solution concentration is with Al2O3It is calculated as 35~80 g/L；Step（2）It is 7.2~7.8, neutralization reaction temperature to neutralize PH
Spend is 40~60 DEG C；Step（3）Middle ageing time is 30~90 min.
In a preferred embodiments of the invention, the surfactant is APG, alcohol ether carboxylate, triethanolamine season
One or more in ammonium salt, glucose amide, monoalkyl phosphoric acid esters.
The beneficial effects of the invention are as follows：
1st, in neutralization and ageing process, primary particle 20-40 is prepared by changing neutralization with aging technique parameter
Bulky grain, the uniform boehmite of nanometer；
2nd, in ammoniacal liquor forming process, addition surfactant is passed through, the surface of water can be reduced using surfactant
The characteristic of tension force, it is ensured that the sphericity of spherical carrier of catalyst is preferable；
3rd, pore volume 1.8-2.2 ml/g, specific surface area 80-100 m are prepared2/ g, and with the long-chain of bimodal pattern pore structure
The carrier of alkane dehydrogenating catalyst, it is more excellent than current catalyst carrier technical indicator.
Specific embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
All other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
Embodiment 1：
NaAlO2It is prepared by solution：Under mechanical stirring, by 40 g caustic soda, 500 ml deionized waters of addition, then heat up
To seething with excitement, 50 g Al (OH) are slowly added to3, after after all dissolvings, 100~105 DEG C of 3 h is incubated, room temperature is then down to naturally,
Add water be made into 500 ml, concentration for 15 g/L (with Al2O3Meter) solution.
Al2(SO4)3The preparation of solution：Under mechanical stirring, the heating of 1200 ml deionized waters is caused 30~40 DEG C, then
Add 100 gAl2(SO4)3·18H2O, after all dissolving after, be down to room temperature, add water be made into 600 ml, concentration for 15 g/L (with
Al2O3Meter) solution.
First add 500 ml deionized waters, under mechanical agitation, be heated to 70 DEG C in 10000 ml stainless steel cauldrons,
Then cocurrent plastic is carried out.Stabilization NaAlO2The ml/min of solution flow rate 2~8, adjusts Al2(SO4)3Solution flow rate is to solution ph
It is to start overflow after 7.5,25 min, keeps the level stability of reactor.About 3 h or so, neutralization is complete, and reaction solution is all put
Enter ageing can, control 45 DEG C of aging temperature, binder is started after aging 30 min, then carry out successive washing, control sheet frame pressure
The MPa of filter inlet pressure 0.2~0.4, washing temperature is 55 DEG C, until the SO in filtrate4 2-Use Ba2+Untill inspection is not measured, will
Wet cake input has in appropriate amount of deionized water souring tank, in the case where being stirred continuously, adds a certain amount of nitric acid acidifying, and being made into sour aluminum ratio is
0.1~0.5, the solution of proportion 1.1~1.5, is then molded through drip tray device in the ammoniacal liquor containing alkyl glucoside surfactant.
Bead after shaping is dried in drier, and temperature control is in 130 DEG C, the h of time 4.Dried bead is fitted into activation furnace
Activation, temperature control is calcined 3 h at 650 DEG C, and gained sample analysis data are shown in Table 1.Wherein specific surface is by low temperature N2Physics is inhaled
Attached method is calculated through BET and tried to achieve；Pore volume and pore size distribution are measured by mercury injection method.
The comparative example of example 1：
As described in Example 1, except that being added without alkyl glucoside surfactant in ammoniacal liquor forming process, institute
Obtain sample analysis data and be shown in Table 1.
Embodiment 2：
Will be with Al2O3Meter concentration is the NaAlO of 25 g/L2The ml of solution 1000 and with Al2O3Meter concentration is the Al of 35g/L2
(SO4)3The ml of solution 1200 continuous cocurrent plastics in a kettle., stabilization NaAlO23~5ml/min of solution flow rate, adjusts Al2
(SO4)3Solution flow rate to solution ph is 7.4, and 75 DEG C of equilibrium temperature, and overflow is started after 30 min, keeps the liquid level of neutralizing tank
Stabilization, neutralization terminates rear aging 45 min, and glucose amide is added in the ammoniacal liquor of shaping, and other conditions are same as Example 1, institute
Obtain sample analysis data and be shown in Table 1.
The comparative example of example 2：
As described in Example 2, except that being added without glucose amide surfactant in ammoniacal liquor forming process,
Gained sample analysis data are shown in Table 1.
Embodiment 3：
Will be with Al2O3Meter concentration is the NaAlO of 20g/L2The ml of solution 1000 and with Al2O3Meter concentration is the Al of 45.5g/L2
(SO4)3The ml of solution 1200 continuous cocurrent plastics in a kettle., stabilization NaAlO2The ml/min of solution flow rate 4~7, adjusts Al2
(SO4)3Solution flow rate to solution ph is 7.6, and 70 DEG C of equilibrium temperature, and overflow is started after 30 min, keeps the liquid level of neutralizing tank
Stabilization, neutralization terminates rear aging 40 min, and alcohol ether carboxylate is added in the ammoniacal liquor of shaping, and other conditions are same as Example 1, gained
Sample analysis data are shown in Table 1.
The comparative example of example 3：
Will be with Al2O3Meter concentration is the NaAlO of 50 g/L2Solution 1000ml and with Al2O3Meter concentration is the Al of 100g/L2
(SO4)3The ml of solution 1200 continuous cocurrent plastics in a kettle., stabilization NaAlO2The ml/min of solution flow rate 9~10, adjusts Al2
(SO4)3Solution flow rate to solution ph is 7.8 and 85 DEG C of equilibrium temperature, and overflow is started after 30 min, keeps the liquid level of neutralizing tank
Stabilization, neutralization terminates rear aging 180 min, and other conditions are same as Example 1, and above-mentioned technical parameter is in the comparative example of the example 3
Maximum, gained sample analysis data are shown in Table 1.
The example analyze data of table 1
Claims (4)
1. a kind of low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume, it is characterised in that the step of the method
Suddenly it is：
（1）By NaOH and Al (OH)3Certain mass concentration, causticity factor alpha are made into kettle is preparedkIt is 1.1~1.3 NaAlO2
Solution；Then Al is used2(SO4)3·18H2O is made into the Al of certain mass concentration in dissolving tank2(SO4)3Solution；
（2）Under mechanical stirring, by Al2(SO4)3Solution and NaAlO2Solution is with 1~10 ml/min flow velocity continuous gel formations, control
Reaction temperature and pH value of solution are neutralized within the specific limits；
（3）After neutralization terminates, reaction solution is all put into ageing can, at a temperature of 30~50 DEG C, aging enough time；
（4）Liquid binder after will be aging is pumped into plate and frame filter press, is then washed with 50~60 DEG C of water, until
Use Ba2+Inspection does not measure the SO in filtrate4 2-Untill；
（5）Wet cake after washing is put into souring tank, first adds appropriate water, surfactant and expanding agent to be stirred
Mix, be subsequently adding dust technology, it is 0.1~0.5 that sour aluminum ratio is made into by mass percentage, and proportion is 1.1~1.5 solution, then
It is molded in the solution being made up of surfactant and ammoniacal liquor；
（6）Wet bulb after shaping is dried in drying box, and temperature control is in 120~150 DEG C, the h of time 2~6；
（7）Dried bead is calcined in being fitted into roaster, 600~900 DEG C of temperature, the h of time 5；
The step（1）Middle NaAlO2Solution concentration is with Al2O3It is calculated as 5~50 g/L, Al2(SO4)3Solution concentration is with Al2O3It is calculated as
10~100 g/L；Step（2）It is 6~9 to neutralize pH, and neutralization reaction temperature is 20~85 DEG C；Step（3）Middle ageing time is
10~180 min.
2. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume according to claim 1, its feature
It is, the step（1）Middle NaAlO2Solution concentration is with Al2O3It is calculated as 10~40 g/L, Al2(SO4)3Solution concentration is with Al2O3
It is calculated as 25~85 g/L；Step（2）It is 7~8 to neutralize pH, and neutralization reaction temperature is 30~80 DEG C；Step（3）In it is aging when
Between be 20~120 min.
3. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume according to claim 1, its feature
It is, the step（1）Middle NaAlO2Solution concentration is with Al2O3It is calculated as 15~20 g/L, Al2(SO4)3Solution concentration is with Al2O3
It is calculated as 35~80 g/L；Step（2）It is 7.2~7.8 to neutralize pH, and neutralization reaction temperature is 40~60 DEG C；Step（3）In it is old
The change time is 30~90 min.
4. the low preparation method than table dehydrogenation of long-chain alkane catalyst carrier of big pore volume according to claim 1, its feature
It is that the surfactant is APG, alcohol ether carboxylate, triethanolamine quaternary ammonium salt, glucose amide, single alkyl phosphonic acid
One or more in ester.
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