CN108772061A - A kind of solid acid catalyst and normal butane-iso-butane isomerization method for isomerization reaction - Google Patents
A kind of solid acid catalyst and normal butane-iso-butane isomerization method for isomerization reaction Download PDFInfo
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The present invention relates to a kind of solid acid catalyst for isomerization reaction and normal butane-iso-butane isomerization methods, belong to paraffin isomerization technical field.The nano bar-shape AlOOH that the present invention is prepared using template is as catalyst carrier, it has the advantages that large specific surface area, activated centre load capacity are big, in its area load activity Pb and W as catalytic active center, have the advantages that paraffin isomerization reaction conversion ratio is high, good, the catalyst service life growing way of selectivity.
Description
Technical field
The present invention relates to a kind of solid acid catalyst for isomerization reaction and normal butane-iso-butane isomerization sides
Method belongs to paraffin isomerization technical field.
Background technology
The direct steaming gasoline and catalytically cracked gasoline proportion in China are larger, and the clean gasoline component for being suitble to environmental protection to need
Proportion very little.This makes the generally existing benzene of China's gasoline product, alkene and the exceeded phenomenon of aromatic hydrocarbons equal size, therefore develops
The production of environmental-friendly gasoline component has become certainty.Isooctane typically as octane number modifier, by different
Alkylated reaction of the butane with isobutene in acidic catalyst obtains；Iso-butane is primarily present in the mixing carbon that oil refining obtains
In four, mixing carbon four usually contains normal butane, iso-butane, butene-1, cis- 2- butylene, trans- 2- butylene, also a small amount of
The components such as propylene, propane, butadiene and pentane；The separation of carbon four separation iso-butane especially from mixing carbon four, which generally uses, to be passed
The rectification process of system；But since four source of mixing carbon is different, wherein constituent content is caused to differ, it is higher for normal butane content
And when the relatively low raw material of iso-butane content, there is high energy consumption, iso-butane separation to be not thorough for the traditional handicraft, it is different to obtain
The disadvantages such as butane product purity is low, influence the effect of alkylated reaction.
It being widely used in external isomerization process, isomerization working ability, the whole world is in rising trend, wherein
North America is most widely used, and is still rapidly developing.Iso-butane has been obtained for Butane isomerization in industry at present
There is part research；At present, industrial Butane isomerization mainly uses Pt/Cl-Al2O3 Class catalyst is urged such
In agent, reaction required temperature (400~460 K) is relatively low, but catalyst is easily poisoned, Er Qie sensitive to water and aromatic hydrocarbons
Need to be continuously added chlorine-containing compound during use to keep reacting required acid strength, there are certain corrosion and environmental pollutions
Problem.
Hino etc. [1] reports WO for the first time3/ZrO2With superpower acidity, which is made of metal oxide, and heat is steady
It is qualitative that preferably component loss will not occur in high temperature and redox condition, be a kind of catalysis material with application potential,
Research in relation to the catalysis material has many reports [2~5].With SO2 4-/MxOyType solid super-strong acid compares, WO3/ZrO2
It is not high to the catalytic activity of alkane isomerization reaction.Improve WO3/ZrO2The catalytic activity and stability of type solid super-strong acid are phases
The major issue in research is closed in SO2 4-/ZrO2Suitable Al is added in solid super strong acid system2O3It is greatly improved to just
The catalytic activity and stability [6~8] of butane isomerization.Hua etc. [9] is reported in Pt/WO3A small amount of Al is adulterated in/ZrO22O3
The catalytic activity that catalyst reacts n-heptane isomerization can be improved.However above-mentioned catalyst is in isomerization reaction,
The problem of remaining not high reactivity, catalyst easy in inactivation.
[1] HinoM,ArataK. ApplCatalA . 1998
[2] WilsonRD,BartonDG,BaertschCD,IglesiaE. Journal of Catalysis . 2000
[3] Sun W D, Zhao Zh B, Guo Ch , Ye X K , Wu Y.Ind Eng Chem , Res , 2000,
39(10):3717
[4] Sun Wendong, Zhao Zhenbo, Wu Yue .WO3/ZrO2II, of alkylated reaction of iso-butane/butylene on strong solid acid catalyst
Promoting catalysis [J] catalysis journal 2000 (03) of transition metal
[5] DeRossiS,FerrarisG,ValigiM,GazzoliD. ApplCatalA . 2002
[6] Xia Yongde, Hua Weiming, height grow SO4 2-/ZrO2And SO4 2-/Al2O3-ZrO2N-pentane reaction [J] on catalyst
Chemical Journal of Chinese Universities 1999 (01)
[7] HuaWM,SommerJ. ApplCatalA . 2002
[8] MorenoJA,PonceletG. Journal of Catalysis . 2001
[9] HuaWM,XiaYD,YueYH,GaoZ. Journal of Catalysis . 2000
Invention content
The purpose of the present invention is：It provides and a kind of novel prepares the catalyst of iso-butane and different for normal butane isomerization
Structure method solves the problems, such as that catalytic activity existing for existing isomerization catalyst is low, selectivity is low, service life is short.
Technical solution is：
A kind of solid acid catalyst for isomerization reaction, preparation method include the following steps：
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the cetyl trimethylammonium bromide containing 0.2~0.4g/L
（CTAB）With the aqueous solution of the citric acid of 0.1~0.15g/L, ultrasonic disperse is uniform, as compound soft template solution, then to compound
The urea of the aluminum nitrate and 0.05~0.1mol/L of 0.1~0.15mol/L, temperature reaction, reaction knot are added in soft template solution
Shu Hou makes white depositions natural subsidence, centrifugation remove supernatant, bottom precipitation is dried in vacuo, nano bar-shape AlOOH is obtained；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made 15
The suspension of~20wt%, adds the liquor potassic permanganate of 0.1~0.15mol/L of 1~2.5 times of suspension vol, and stirring is equal
After even, four acetate hydrate manganese are added, ultrasonic disperse is uniform, and suspended matter is filtered and is washed with deionized, and obtains manganese modification
Nano bar-shape AlOOH；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.2~0.4mol/L2, make PdCl2Dilute
After cooling, pH is adjusted to 6.5~7.5, then to solution with NaOH solution for a concentration of 1.0~2.5wt% in hydrochloric acid, heating reaction
Middle addition cetyl trimethylammonium bromide（CTAB）, make a concentration of 10~20mmol/Ls of the CTAB in reaction solution, then be added dropwise
The NaBH of 50~80mmol/L4Solution carries out reduction reaction, obtains Pd nanoparticle sols；
4th step, load of the activated centre on carrier：Prepare 1~1.5wt%H8N2O4W solution, then Pd nanometers are added in the solution
Colloidal sol obtains mixed impregnant liquor after mixing；The nano bar-shape AlOOH that manganese is modified is added in mixed impregnant liquor, makes
Concentration of the nano bar-shape AlOOH that manganese is modified in mixed impregnant liquor is 2~5wt%, after being warming up to 85~90 DEG C of 3~6h of reaction,
After being dried under reduced pressure, solids is roasted, and obtains W/Pd@MnO2-Al2O3Catalyst.
In 1st step, temperature reaction refers to 1~5h of reaction at 70~80 DEG C；Centrifugal process rotating speed 2000~
5000rpm, 5~10min of centrifugation time.
In 2nd step, the weight ratio of nano bar-shape AlOOH and four acetate hydrate manganese is 3：1~1.2.
In 3rd step, the temperature for heating reaction is 95~100 DEG C, and the reaction time is 0.5~1h；Reduction reaction
Temperature is 40~45 DEG C, NaBH4And PdCl2Molar ratio be 4~6：1.
In 4th step, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 2~4：1, roasting is 850~
2~4h is roasted at 900 DEG C.
A kind of method that normal butane isomerization prepares iso-butane is to use above-mentioned W/Pd@MnO2-Al2O3Catalyst.
In the method, reaction temperature is 290~310 DEG C；100~200min of residence time.
Advantageous effect
The present invention prepares iso-butane reaction for normal butane isomerization and proposes novel W/Pd@MnO2-Al2O3Catalyst, this is urged
Agent is to use the AlOOH of nano bar-shape as carrier, after the load for having carried out W and Pd, can be shown relative to existing
The better reactivity of catalyst, while being doped with after Mn elements in AlOOH carriers, making for catalyst can be significantly improved
Use the service life.The obvious purity higher of iso-butane that isomerization reaction in through the invention obtains, it is anti-with isobutene to be more advantageous to it
It should obtain quality more preferably isooctane.In addition its can be further applicable to mixing carbon four in, through the invention in catalyst
It is that iso-butane is alkylated isooctane is obtained by the reaction again that the part normal butane isomerization in carbon four, which will be mixed, is substantially increased mixed
Close the utilization rate of carbon four.
Description of the drawings
Fig. 1 is the SEM figures for the nano bar-shape AlOOH that the present invention is prepared；
Fig. 2 is the XRD diagram for the nano bar-shape AlOOH that the present invention is prepared；
Fig. 3 is the W/Pd@MnO that the present invention is prepared2-Al2O3The XRD diagram of catalyst；
Specific implementation mode
The preparation of 1 solid acid catalyst of embodiment
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the cetyl trimethylammonium bromide containing 0.2g/L（CTAB）
With the aqueous solution of the citric acid of 0.1g/L, ultrasonic disperse is uniform, as compound soft template solution, then into compound soft template solution
The urea of the aluminum nitrate and 0.05mol/L of 0.1mol/L is added, reacts 1h at 70 DEG C, after reaction, makes white depositions certainly
So sedimentation, 2000rpm centrifuge 5min and remove supernatant, bottom precipitation is dried in vacuo, nano bar-shape AlOOH is obtained；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made
The suspension of 15wt% adds the liquor potassic permanganate of the 0.1mol/L of 1 times of suspension vol, after stirring evenly, adds four
The weight ratio of acetate hydrate manganese, nano bar-shape AlOOH and four acetate hydrate manganese is 3：1, ultrasonic disperse is uniform, and suspended matter is filtered
And be washed with deionized, obtain the nano bar-shape AlOOH of manganese modification；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.2mol/L2, make PdCl2In dilute hydrochloric acid
In a concentration of 1.0wt%, 95 DEG C reaction 0.5h, after cooling, with NaOH solution adjust pH to 6.5~7.5, then into solution plus
Enter cetyl trimethylammonium bromide（CTAB）, make a concentration of 10mmol/Ls of the CTAB in reaction solution, then 50mmol/L is added dropwise
NaBH4Solution carries out reduction reaction, and the temperature of reduction reaction is 40 DEG C, NaBH4And PdCl2Molar ratio be 4：1, obtain Pd
Nanoparticle sol；
4th step, load of the activated centre on carrier：Prepare 1wt%H8N2O4W solution, then Pd nano-particles are added in the solution
Colloidal sol, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 2：1, after mixing, obtain mixed impregnant liquor；It is mixing
The nano bar-shape AlOOH that manganese is modified is added in maceration extract, makes concentration of the nano bar-shape AlOOH of manganese modification in mixed impregnant liquor
It is 2wt%, after being warming up to 85 DEG C of reaction 3h, after being dried under reduced pressure, 2h is roasted at 850 DEG C of solids, obtains W/Pd@MnO2-Al2O3It urges
Agent.
The preparation of 2 solid acid catalyst of embodiment
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the cetyl trimethylammonium bromide containing 0.4g/L（CTAB）
With the aqueous solution of the citric acid of 0.15g/L, ultrasonic disperse is uniform, as compound soft template solution, then to compound soft template solution
The urea of the middle aluminum nitrate and 0.1mol/L that 0.15mol/L is added, reacts 5h at 80 DEG C, after reaction, makes white depositions
Natural subsidence, 5000rpm centrifuge 10min and remove supernatant, bottom precipitation is dried in vacuo, nano bar-shape AlOOH is obtained；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made
The suspension of 20wt% adds the liquor potassic permanganate of the 0.15mol/L of 2.5 times of suspension vol, after stirring evenly, then adds
Enter four acetate hydrate manganese, the weight ratio of nano bar-shape AlOOH and four acetate hydrate manganese is 3：1.2, ultrasonic disperse is uniform, will suspend
Object is filtered and is washed with deionized, and obtains the nano bar-shape AlOOH of manganese modification；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.4mol/L2, make PdCl2In dilute hydrochloric acid
In a concentration of 2.5wt%, 100 DEG C reaction 1h, after cooling, with NaOH solution adjust pH to 6.5~7.5, then into solution plus
Enter cetyl trimethylammonium bromide（CTAB）, make a concentration of 20mmol/Ls of the CTAB in reaction solution, then 80mmol/L is added dropwise
NaBH4Solution carries out reduction reaction, and the temperature of reduction reaction is 45 DEG C, NaBH4And PdCl2Molar ratio be 6：1, obtain Pd
Nanoparticle sol；
4th step, load of the activated centre on carrier：Prepare 1.5wt%H8N2O4W solution, then Pd nanoparticles are added in the solution
Sub- colloidal sol, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 4：1, after mixing, obtain mixed impregnant liquor；Mixed
It closes and the nano bar-shape AlOOH that manganese is modified is added in maceration extract, keep the nano bar-shape AlOOH that manganese is modified dense in mixed impregnant liquor
Degree is 5wt%, after being warming up to 90 DEG C of reaction 6h, after being dried under reduced pressure, 4h is roasted at 900 DEG C of solids, obtains W/Pd@MnO2-
Al2O3Catalyst.
The preparation of 3 solid acid catalyst of embodiment
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the cetyl trimethylammonium bromide containing 0.3g/L（CTAB）
With the aqueous solution of the citric acid of 0.12g/L, ultrasonic disperse is uniform, as compound soft template solution, then to compound soft template solution
The urea of the middle aluminum nitrate and 0.08mol/L that 0.12mol/L is added, reacts 3h at 75 DEG C, after reaction, makes white depositions
Natural subsidence, 3000rpm centrifuge 7min and remove supernatant, bottom precipitation is dried in vacuo, nano bar-shape AlOOH is obtained；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made 15
The suspension of~20wt% adds the liquor potassic permanganate of the 0.12mol/L of 1.5 times of suspension vol, after stirring evenly, then
It is added four acetate hydrate manganese, the weight ratio of nano bar-shape AlOOH and four acetate hydrate manganese is 3：1.1, ultrasonic disperse is uniform, will hang
Float is filtered and is washed with deionized, and obtains the nano bar-shape AlOOH of manganese modification；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.3mol/L2, make PdCl2In dilute hydrochloric acid
In a concentration of 1.5wt%, 96 DEG C reaction 1h, after cooling, with NaOH solution adjust pH be added to 6.5~7.5, then into solution
Cetyl trimethylammonium bromide（CTAB）, make a concentration of 15mmol/Ls of the CTAB in reaction solution, then be added dropwise 60mmol/L's
NaBH4Solution carries out reduction reaction, and the temperature of reduction reaction is 42 DEG C, NaBH4And PdCl2Molar ratio be 5：1, it obtains Pd and receives
Rice corpuscles colloidal sol；
4th step, load of the activated centre on carrier：Prepare 1.2wt%H8N2O4W solution, then Pd nanoparticles are added in the solution
Sub- colloidal sol, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 3：1, after mixing, obtain mixed impregnant liquor；Mixed
It closes and the nano bar-shape AlOOH that manganese is modified is added in maceration extract, keep the nano bar-shape AlOOH that manganese is modified dense in mixed impregnant liquor
Degree is 4wt%, after being warming up to 88 DEG C of reaction 4h, after being dried under reduced pressure, 3h is roasted at 880 DEG C of solids, obtains W/Pd@MnO2-
Al2O3Catalyst.
Reference examples 1
Difference with embodiment 3 is：Mn is not used to carry out surface modification treatment to carrier.
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the cetyl trimethylammonium bromide containing 0.3g/L
（CTAB）With the aqueous solution of the citric acid of 0.12g/L, ultrasonic disperse is uniform, as compound soft template solution, then to compound soft mode
The urea of the aluminum nitrate and 0.08mol/L of 0.12mol/L is added in plate solution, reacts 3h at 75 DEG C, after reaction, makes white
Sediment natural subsidence, 3000rpm centrifuge 7min and remove supernatant, bottom precipitation is dried in vacuo, nano bar-shape AlOOH is obtained；
2nd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.3mol/L2, make PdCl2In dilute hydrochloric acid
In a concentration of 1.5wt%, 96 DEG C reaction 1h, after cooling, with NaOH solution adjust pH be added to 6.5~7.5, then into solution
Cetyl trimethylammonium bromide（CTAB）, make a concentration of 15mmol/Ls of the CTAB in reaction solution, then be added dropwise 60mmol/L's
NaBH4Solution carries out reduction reaction, and the temperature of reduction reaction is 42 DEG C, NaBH4And PdCl2Molar ratio be 5：1, it obtains Pd and receives
Rice corpuscles colloidal sol；
3rd step, load of the activated centre on carrier：Prepare 1.2wt%H8N2O4W solution, then Pd nanoparticles are added in the solution
Sub- colloidal sol, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 3：1, after mixing, obtain mixed impregnant liquor；Mixed
It closes and the nano bar-shape AlOOH that manganese is modified is added in maceration extract, keep the nano bar-shape AlOOH that manganese is modified dense in mixed impregnant liquor
Degree is 4wt%, after being warming up to 88 DEG C of reaction 4h, after being dried under reduced pressure, 3h is roasted at 880 DEG C of solids, obtains W/Pd@Al2O3It urges
Agent.
Reference examples 2
Difference with embodiment 3 is：It is not loaded on the surface of carrier using Pb colloidal sols.
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the cetyl trimethylammonium bromide containing 0.3g/L
（CTAB）With the aqueous solution of the citric acid of 0.12g/L, ultrasonic disperse is uniform, as compound soft template solution, then to compound soft mode
The urea of the aluminum nitrate and 0.08mol/L of 0.12mol/L is added in plate solution, reacts 3h at 75 DEG C, after reaction, makes white
Sediment natural subsidence, 3000rpm centrifuge 7min and remove supernatant, bottom precipitation is dried in vacuo, nano bar-shape AlOOH is obtained；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made 15
The suspension of~20wt% adds the liquor potassic permanganate of the 0.12mol/L of 1.5 times of suspension vol, after stirring evenly, then
It is added four acetate hydrate manganese, the weight ratio of nano bar-shape AlOOH and four acetate hydrate manganese is 3：1.1, ultrasonic disperse is uniform, will hang
Float is filtered and is washed with deionized, and obtains the nano bar-shape AlOOH of manganese modification；
3rd step, load of the activated centre on carrier：Prepare 1.2wt%H8N2O4W solution, in H8N2O4Manganese is added in W solution to change
Property nano bar-shape AlOOH, make manganese be modified nano bar-shape AlOOH in H8N2O4Concentration in W solution is 4wt%, is warming up to 88
DEG C reaction 4h after, after being dried under reduced pressure, 3h is roasted at 880 DEG C of solids, obtains W@MnO2-Al2O3Catalyst.
Reference examples 3
Difference with embodiment 3 is：Cetyl trimethylammonium bromide is not used（CTAB）Soft template.
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the aqueous solution of the citric acid containing 0.12g/L, ultrasound point
It dissipates uniform, as soft template solution, then the urea of the aluminum nitrate and 0.08mol/L of 0.12mol/L is added into soft template solution,
3h is reacted at 75 DEG C, after reaction, makes white depositions natural subsidence, 3000rpm centrifuges 7min and removes supernatant, by bottom precipitation
Vacuum drying, obtains nano bar-shape AlOOH；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made 15
The suspension of~20wt% adds the liquor potassic permanganate of the 0.12mol/L of 1.5 times of suspension vol, after stirring evenly, then
It is added four acetate hydrate manganese, the weight ratio of nano bar-shape AlOOH and four acetate hydrate manganese is 3：1.1, ultrasonic disperse is uniform, will hang
Float is filtered and is washed with deionized, and obtains the nano bar-shape AlOOH of manganese modification；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.3mol/L2, make PdCl2In dilute hydrochloric acid
In a concentration of 1.5wt%, 96 DEG C reaction 1h, after cooling, with NaOH solution adjust pH be added to 6.5~7.5, then into solution
Cetyl trimethylammonium bromide（CTAB）, make a concentration of 15mmol/Ls of the CTAB in reaction solution, then be added dropwise 60mmol/L's
NaBH4Solution carries out reduction reaction, and the temperature of reduction reaction is 42 DEG C, NaBH4And PdCl2Molar ratio be 5：1, it obtains Pd and receives
Rice corpuscles colloidal sol；
4th step, load of the activated centre on carrier：Prepare 1.2wt%H8N2O4W solution, then Pd nanoparticles are added in the solution
Sub- colloidal sol, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 3：1, after mixing, obtain mixed impregnant liquor；Mixed
It closes and the nano bar-shape AlOOH that manganese is modified is added in maceration extract, keep the nano bar-shape AlOOH that manganese is modified dense in mixed impregnant liquor
Degree is 4wt%, after being warming up to 88 DEG C of reaction 4h, after being dried under reduced pressure, 3h is roasted at 880 DEG C of solids, obtains W/Pd@MnO2-
Al2O3Catalyst.
Reference examples 4
Difference with embodiment 3 is：Using conventional Al2O3Nano particle is as carrier.
6mol/L ammonium hydroxide is slowly dropped into 1mol/LAl (NO by the 1st step3)3In aqueous solution, until pH=9~10, generate hydroxide
Aluminum precipitation, then flow back in 90 DEG C of oil baths 12h, and precipitation is washed and filtered repeatedly with deionized water to pH=7, by filter cake in
110 DEG C of drying, obtain Al2O3Nano particle is as carrier；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made 15
The suspension of~20wt% adds the liquor potassic permanganate of the 0.12mol/L of 1.5 times of suspension vol, after stirring evenly, then
It is added four acetate hydrate manganese, the weight ratio of nano bar-shape AlOOH and four acetate hydrate manganese is 3：1.1, ultrasonic disperse is uniform, will hang
Float is filtered and is washed with deionized, and obtains the nano bar-shape AlOOH of manganese modification；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.3mol/L2, make PdCl2In dilute hydrochloric acid
In a concentration of 1.5wt%, 96 DEG C reaction 1h, after cooling, with NaOH solution adjust pH be added to 6.5~7.5, then into solution
Cetyl trimethylammonium bromide（CTAB）, make a concentration of 15mmol/Ls of the CTAB in reaction solution, then be added dropwise 60mmol/L's
NaBH4Solution carries out reduction reaction, and the temperature of reduction reaction is 42 DEG C, NaBH4And PdCl2Molar ratio be 5：1, it obtains Pd and receives
Rice corpuscles colloidal sol；
4th step, load of the activated centre on carrier：Prepare 1.2wt%H8N2O4W solution, then Pd nanoparticles are added in the solution
Sub- colloidal sol, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 3：1, after mixing, obtain mixed impregnant liquor；Mixed
It closes and the nano bar-shape AlOOH that manganese is modified is added in maceration extract, keep the nano bar-shape AlOOH that manganese is modified dense in mixed impregnant liquor
Degree is 4wt%, after being warming up to 88 DEG C of reaction 4h, after being dried under reduced pressure, 3h is roasted at 880 DEG C of solids, obtains W/Pd@MnO2-
Al2O3Catalyst.
Reference examples 5
Difference with embodiment 3 is：Using conventional ZrO2Nano particle is as carrier.
6mol/L ammonium hydroxide is slowly dropped into 1mol/LZr (NO by the 1st step3)4In aqueous solution, until pH=9~10, generate hydrogen-oxygen
Change zirconium precipitation, then flow back in 90 DEG C of oil baths 12h, and precipitation is washed and filtered repeatedly to pH=7, by filter cake with deionized water
In 110 DEG C of drying, ZrO is obtained2Nano particle is as carrier；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made 15
The suspension of~20wt% adds the liquor potassic permanganate of the 0.12mol/L of 1.5 times of suspension vol, after stirring evenly, then
It is added four acetate hydrate manganese, the weight ratio of nano bar-shape AlOOH and four acetate hydrate manganese is 3：1.1, ultrasonic disperse is uniform, will hang
Float is filtered and is washed with deionized, and obtains the nano bar-shape AlOOH of manganese modification；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.3mol/L2, make PdCl2In dilute hydrochloric acid
In a concentration of 1.5wt%, 96 DEG C reaction 1h, after cooling, with NaOH solution adjust pH be added to 6.5~7.5, then into solution
Cetyl trimethylammonium bromide（CTAB）, make a concentration of 15mmol/Ls of the CTAB in reaction solution, then be added dropwise 60mmol/L's
NaBH4Solution carries out reduction reaction, and the temperature of reduction reaction is 42 DEG C, NaBH4And PdCl2Molar ratio be 5：1, it obtains Pd and receives
Rice corpuscles colloidal sol；
4th step, load of the activated centre on carrier：Prepare 1.2wt%H8N2O4W solution, then Pd nanoparticles are added in the solution
Sub- colloidal sol, H8N2O4W solution and the volume ratio of Pd nanoparticle sols are 3：1, after mixing, obtain mixed impregnant liquor；Mixed
It closes and the nano bar-shape AlOOH that manganese is modified is added in maceration extract, keep the nano bar-shape AlOOH that manganese is modified dense in mixed impregnant liquor
Degree is 4wt%, after being warming up to 88 DEG C of reaction 4h, after being dried under reduced pressure, 3h is roasted at 880 DEG C of solids, obtains W/Pd@MnO2-
Al2O3Catalyst.
Characterization experiment
The SEM of the nano bar-shape AlOOH being prepared in embodiment 3 as shown in Figure 1, XRD spectrum as shown in Fig. 2, can from figure
To find out, carrier has the structure of nano bar-shape, specific surface area larger；It is also seen that having in XRD spectrum
14.48 °, 28.22 °, 38.34 °, 48.92 ° and 64.02 ° stronger diffraction maximums, correspond respectively to AlOOH (020),
(120), (031), (051) and (231) crystal face.
The W/Pd@MnO being prepared in embodiment 32-Al2O3The XRD spectrum of catalyst is as shown in figure 3, can therefrom see
(220), (311), (400) and (440) crystal face for providing gamma-alumina is located at 31.94 °, 37.60 °, 45.86 ° and 67.04 °
The stronger diffraction maximum at place（It is indicated with A in figure）And 22.8 ° of diffraction maximum of tungsten oxide（It is indicated with W in figure）, and manganese
37.4 ° and 66.7 ° of diffraction maximum is weaker, with gamma-alumina diffraction overlap of peaks.
Isomerization reaction is tested
Butane isomerization carries out in the miniature flow reactor of normal pressure, loaded catalyst 1.0g.450 before reaction
Be passed through air-activated 3h at DEG C, then cool the temperature to 300 DEG C and with hydrogen treat 1h, be then passed through at the reaction temperatures hydrogen and
Normal butane (V (H2)/V(n-C4)=4, WHSV=0.47h-1) reacted, reaction product is through Shimadzu GC-14C type gas chromatographs
Fid detector on-line analysis, residence time 300min.
As can be seen from the above table, catalyst of the invention compared with the existing technology in made with aluminium oxide or zirconium oxide
For the catalyst of carrier, the selectivity with higher n-butane conversion and iso-butane.Pass through embodiment 3 and reference examples
2 comparison can effectively improve catalyst for reaction process as can be seen that using Pb in the surface doping load of carrier
In iso-butane selectivity；By embodiment 3 and reference examples 3 as can be seen that preparing AlOOH carriers using CTAB soft templates
When, the specific surface area of carrier can be significantly improved, conversion ratio when catalyst being made to react normal butane has obtained significantly carrying
It is high.
After the above catalyst is carried out continuously the reaction process of 3000min, the activity change of catalyst is investigated, it is as a result as follows
It is shown：
As can be seen from the table, the catalyst that prepared by the present invention compared with the existing technology in aluminium oxide or zirconium oxide as carry
For the catalyst of body its service life is longer, by embodiment 3 and the comparison of reference examples 1 as can be seen that in alumina support
Adulterate Mn has apparent effect for improving the service life of catalyst, can significantly improve the reaction after long-play
Conversion ratio.
Claims (7)
1. a kind of solid acid catalyst for isomerization reaction, which is characterized in that preparation method includes the following steps：
1st step, the preparation of nano bar-shape AlOOH carriers：Prepare the cetyl trimethylammonium bromide containing 0.2~0.4g/L
（CTAB）With the aqueous solution of the citric acid of 0.1~0.15g/L, ultrasonic disperse is uniform, as compound soft template solution, then to compound
The urea of the aluminum nitrate and 0.05~0.1mol/L of 0.1~0.15mol/L, temperature reaction, reaction knot are added in soft template solution
Shu Hou makes white depositions natural subsidence, centrifugation remove supernatant, bottom precipitation is dried in vacuo, nano bar-shape AlOOH is obtained；
The surface manganese of 2nd step, nano bar-shape AlOOH carriers is modified：Nano bar-shape AlOOH is scattered in deionized water and is made 15
The suspension of~20wt%, adds the liquor potassic permanganate of 0.1~0.15mol/L of 1~2.5 times of suspension vol, and stirring is equal
After even, four acetate hydrate manganese are added, ultrasonic disperse is uniform, and suspended matter is filtered and is washed with deionized, and obtains manganese modification
Nano bar-shape AlOOH；
3rd step, the preparation of Pd nanoparticle sols：PdCl is added in the dilute hydrochloric acid of 0.2~0.4mol/L2, make PdCl2Dilute
After cooling, pH is adjusted to 6.5~7.5, then to solution with NaOH solution for a concentration of 1.0~2.5wt% in hydrochloric acid, heating reaction
Middle addition cetyl trimethylammonium bromide（CTAB）, make a concentration of 10~20mmol/Ls of the CTAB in reaction solution, then be added dropwise
The NaBH of 50~80mmol/L4Solution carries out reduction reaction, obtains Pd nanoparticle sols；
4th step, load of the activated centre on carrier：Prepare 1~1.5wt%H8N2O4W solution, then Pd nanometers are added in the solution
Colloidal sol obtains mixed impregnant liquor after mixing；The nano bar-shape AlOOH that manganese is modified is added in mixed impregnant liquor, makes
Concentration of the nano bar-shape AlOOH that manganese is modified in mixed impregnant liquor is 2~5wt%, after being warming up to 85~90 DEG C of 3~6h of reaction,
After being dried under reduced pressure, solids is roasted, and obtains W/Pd@MnO2-Al2O3Catalyst.
2. solid acid catalyst according to claim 1, which is characterized in that in the 1st step, temperature reaction refer to
1~5h is reacted at 70~80 DEG C；Centrifugal process 2000~5000rpm of rotating speed, 5~10min of centrifugation time.
3. solid acid catalyst according to claim 1, which is characterized in that in the 2nd step, nano bar-shape AlOOH
Weight ratio with four acetate hydrate manganese is 3：1~1.2.
4. solid acid catalyst according to claim 1, which is characterized in that in the 3rd step, heat the temperature of reaction
It it is 95~100 DEG C, the reaction time is 0.5~1h；The temperature of reduction reaction is 40~45 DEG C, NaBH4And PdCl2Molar ratio be 4
~6：1.
5. solid acid catalyst according to claim 1, which is characterized in that in the 4th step, H8N2O4W solution and Pd
The volume ratio of nanoparticle sol is 2~4：1, roasting is 2~4h of roasting at 850~900 DEG C.
6. a kind of method that normal butane isomerization prepares iso-butane, which is characterized in that use W/Pd@described in claim 1
MnO2-Al2O3Catalyst.
7. the method that normal butane isomerization according to claim 6 prepares iso-butane, which is characterized in that reaction temperature is
290~310 DEG C；100~200min of residence time.
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