CN104971706B - A kind of method and its application for preparing titanium oxide alumina compound - Google Patents
A kind of method and its application for preparing titanium oxide alumina compound Download PDFInfo
- Publication number
- CN104971706B CN104971706B CN201410140884.0A CN201410140884A CN104971706B CN 104971706 B CN104971706 B CN 104971706B CN 201410140884 A CN201410140884 A CN 201410140884A CN 104971706 B CN104971706 B CN 104971706B
- Authority
- CN
- China
- Prior art keywords
- solution
- compound
- catalyst
- titanium oxide
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a kind of method for preparing titanium oxide alumina compound, including:Step I:Aluminum soluble salt is dissolved in the water, solution A is obtained;Tetraethyl titanate is dissolved in benzene, solution B is obtained;Ammonium hydrogen carbonate and ammoniacal liquor are configured to mixed aqueous ammonium C;And step II:At a temperature of 65 95 DEG C, by solution A, tri- kinds of solution parallel-flow precipitations of B and C, by controlling the flow of solution C, the pH value of solution A, B and C mixed solution is set to be alternately present in 5.0 6.5 and 8.0 9.5 two scopes, and 6 10min are stopped respectively, obtain sediment;Step III, the sediment is calcined, obtains the compound.Catalyst using the titanium oxide alumina compound of the present invention as carrier is in the application of pyrolysis gasoline hydrogenation desulphurization reaction, and the low temperature active of catalyst is high, and hydrogenation conversion is high, and hydrodesulfurization rate can reach 99.9%.
Description
Technical field
The present invention relates to inorganic composite materials field, and in particular to a kind of preparation method of Titanium oxide-aluminum oxide compound
And its application.
Background technology
Titanium oxide and aluminum oxide are the conventional carrier materials of chemical reaction catalyst.Titanium oxide is separately as carrier with passing
The aluminum oxide of system is compared, and its specific surface area is smaller(BET specific surface area is about 50m2/g), bad mechanical strength(About γ-Al2O3's
1/5th), heat endurance is poor.Titanium dioxide-aluminum oxide composite carrier, both maintains Al2O3It is the high-specific surface area of carrier, high-strength
The advantages of degree and good heat endurance, there is TiO again2Special performance.Meanwhile, incorporation titanium oxide is modified to carrier
Afterwards, the structure and property of the active phase of catalyst can also be affected, so as to improve catalytic activity, the anticaking carbon of catalyst
Property and the ability of anti-poisoning.
The existing many reports of the preparation method of Titanium oxide-aluminum oxide compound, Titanium oxide-aluminum oxide compound can be direct
As catalyst, for a gram Lloyd's(Clause)In Catalytic processes, petrochemical industry hydrorefining catalyst for hydrocarbon can also be used as
Carrier.
The preparation method of traditional Titanium oxide-aluminum oxide compound be typically by alumina dry glue and titanium salt solution, and
Appropriate peptizing agent and water is sufficiently mixed aftershaping, dries, and roasting is made.As disclosed in the specification of European patent EP 0199399
The preparation method of Titanium oxide-aluminum oxide compound, the preparation method be by a certain proportion of titanium oxide, aluminum oxide, acetic acid and
Water mixes extrusion forming, then high-temperature roasting and obtain.The catalyst that the titanium dioxide-aluminum oxide is prepared as carrier, has
The high feature of initial activity, but the decentralization and mechanical strength of titanium oxide be not high.
Disclosed in the specification of European patent EP 0399640 with titanium trichloride or titanyl sulfate or titanium oxychloride and meta-aluminic acid
Sodium solution co-precipitation prepares Titanium oxide-aluminum oxide compound, the catalysis prepared with the Titanium oxide-aluminum oxide compound as carrier
Agent has to CS in Clause Catalytic processes2Desulphurizing activated height, stability is high and the advantages of strong resistance to SO_2.But, its work
Industry production cost is high, and the specific surface area of Titanium oxide-aluminum oxide compound and pore size distribution need further raising.
A kind of preparation method of titanium dioxide-aluminum oxide bi-component is disclosed in Chinese patent application CN1273878A, is used
By soluble titanium salt and the mixture and NaAlO of aluminum soluble salt2It is prepared by the method for solution co-precipitation.The Ti-Al is double
Component has preparation method simple, and raw material is easy to get, and specific surface area is big and the advantages of high decentralization of titanium.But, the Ti-Al is double
The pore size distribution of component needs to improve.
A kind of preparation method of titania-alumina compound is disclosed in Chinese patent application CN101204671A,
Metatitanic acid is dissolved into titanium solution by the method in acid condition, then by its inorganic salt solution with sodium metaaluminate or aluminium strong
Stirring is lower to be mixed, and is adjusted the pH value of mixture to 6.5-9.5, is dried, Titanium oxide-aluminum oxide compound is made in roasting.This method
Obtained Titanium oxide-aluminum oxide compound has high Ti content and high specific surface area.But, the titanium dioxide-aluminum oxide is answered
The pore size distribution of compound is difficult to control, it is impossible to obtain the Titanium oxide-aluminum oxide compound of suitable pore size distribution.
The present inventor is in Chinese patent prospectus(Application number 02146005.1)In disclose it is a kind of using titanium oxide-
Alumina compound as the drippolene selective hydrogenation of carrier catalyst, with and its production and use.Urged at this
The use of specific surface area is 100-200m in the preparation method of agent2/ g, pore volume is 0.5-1.5ml/g, and most probable pore size is 80-
200 angstroms of aluminum oxide dipping compound titanium solution, is dried, Titanium oxide-aluminum oxide compound is made in roasting.The compound is soaked
The appropriate active component palladium of stain, is made catalyst.When the catalyst is for during drippolene selective hydrogenation refining, liquid air
Speed than existing catalyst improve 30-40%, selectivity be more than 99%, continuously run 1500 hours it is activity stabilized.But, the catalysis
The pore size distribution of the titanium dioxide-aluminum oxide composite carrier of agent still needs improvement, to obtain more preferable catalytic performance.
Although in the prior art, people have done to Titanium oxide-aluminum oxide compound and preparation method thereof and much ground
Study carefully, still, how further to optimize the performance of compound, to improve its application value, for example, improve the catalysis using it as carrier
The catalytic performances such as the activity of agent, are always direction and the focus of research of the area research.
The content of the invention
In view of above prior art situation, the present inventor to the preparation method of Titanium oxide-aluminum oxide compound and
Its application in Hydrobon catalyst is conducted in-depth research, and is as a result found, in soluble aluminum salting liquid and metatitanic acid four
During ethyl ester solution co-precipitation, using mixed ammonium salt solution by the regulation of the pH value of mixed solution 5.0-6.5 and 8.0-9.5 it
Between when being alternately present, can obtain the Titanium oxide-aluminum oxide compound being substantially distributed in Based on Dual-Aperture.With the titanium dioxide-aluminum oxide system
Standby catalyst is high with low temperature active in the application process of pyrolysis gasoline hydrogenation desulfurization, the high feature of desulfurization degree, the present invention
The above is based on to find to be accomplished.
It is therefore an object of the present invention to provide a kind of preparation of the Titanium oxide-aluminum oxide compound with double hole channel structure
Method, the compound can be used as Hydrobon catalyst or the carrier of other chemical reaction catalysts.
It is a further object to provide a kind of application of compound as described above.
According to an aspect of the invention, there is provided a kind of method for preparing Titanium oxide-aluminum oxide compound, including:
Step I:Aluminum soluble salt is dissolved in the water, solution A is obtained;Tetraethyl titanate is dissolved in benzene, obtains molten
Liquid B;Ammonium hydrogen carbonate and ammoniacal liquor are configured to mixed aqueous ammonium C;With
Step II:At a temperature of 65~95 DEG C, by solution A, tri- kinds of solution parallel-flow precipitations of B and C, by controlling solution C
Flow, the pH value of solution A, B and C mixed solution is alternately present in 5.0~6.5 and 8.0~9.5 two scopes, and
6-10min is stopped respectively, obtains sediment;
Step III:The sediment is calcined, the compound is obtained.
According to method of the present invention preferred embodiment, make the mixed solution pH value in 5.0~6.0 Hes
It is alternately present in 8.5~9.5 two scopes.In another preferred embodiment, the mixed solution pH value is made in described two models
Enclose interior stop 7~9 minutes respectively.
According in method of the present invention specific embodiment, the concentration of the solution A is 0.5~2.5mol/
L.The concentration of the solution B is 0.1~1.5mol/L.The concentration of ammonium hydrogen carbonate in the solution C is 0.1~0.3mol/L.
The concentration of the ammoniacal liquor is 15~25 volume %.
According to method of the present invention, the aluminum soluble salt is selected from aluminum dialkyl, dialkylaluminum chloride, alkyl dichloro
Change the one or more in aluminium, dialkyl group alchlor, and aluminum sulfate, aluminium chloride and aluminum nitrate.
In the above-mentioned methods, in the step III, the sediment is in roasting(Such as 300~700 DEG C)Before can be as needed
Washed and dried.Specifically, for example with the deionized water of 10-20 times of sediment volume by sediment cyclic washing, filter
Four times, acid ion is removed, filter cake is small in 400-600 DEG C of roasting temperature 4-6 in being dried 10-12 hours at 100-120 DEG C
When, obtain Titanium oxide-aluminum oxide compound.
The compound prepared according to the above method of the present invention, the compound contains 0.3-25wt% titanium oxide, wherein institute
The aperture for stating compound is distributed in double hole channel.Wherein, in a specific embodiment, the aperture of the double hole channel is respectively 20
~40 angstroms and 80~130 angstroms.
According to the specific embodiment of the present invention, in the compound, the aperture in 30~50% hole is 20~40
Angstrom, the aperture in 30~50% hole is 80~130 angstroms.
According to the specific embodiment of the present invention, the specific surface area of the compound is 200~350m2/ g, pore volume is
0.4~0.7m3/ g, intensity is 14~20N/mm.
There is provided the Titanium oxide-aluminum oxide compound that a kind of above method is obtained according to another aspect of the present invention
It is used as the application of catalyst carrier.
In above-mentioned application, included in the catalyst:Based on overall catalyst weight gauge, 12.0~25.0wt% oxidation
The molybdenum oxide of molybdenum and 1.0~5.0wt% cobalt oxide or 12.0~25.0wt%, 1.0~5.0wt% nickel oxide and 1.0~
5.0wt% cobalt oxide.
Above-mentioned catalyst is preferably used for the catalyst of pyrolysis gasoline hydrogenation desulphurization reaction.
Method in the present invention, using tetraethyl titanate and benzene, is compared with other systems, using obtained compound as
Carrier, which obtains catalyst, is used for hydrodesulfurization, with higher low temperature active, more preferable hydrogenation conversion and hydrodesulfurization rate.
According to the preparation method of the Titanium oxide-aluminum oxide compound of the present invention, its technique is simple, and reaction condition is gentle, nothing
Surfactant, peptizing agent etc. is needed to prepare the nanometer micropore that is distributed in uniform pore diameter in several particular ranges
Composite.Titanium oxide-aluminum oxide compound prepared by the method that the present invention is provided:(1)Micropore is distributed in double hole channel, and this is special
Pore structure the compound is more applicable in some specific applications, such as the preparation of interim discharge active component
Carrier, while the structure can also bring some special advantages, for example, can improve the mass-and heat-transfer efficiency of catalyst;(2)Machine
Tool intensity is high;(3)It is as the Hydrobon catalyst of carrier, and low temperature active is high, hydrogenation conversion and hydrodesulfurization rate compared with
It is high(Hydrodesulfurization rate can reach 99.9%).
Embodiment
Below by embodiment, the invention will be further elaborated, it will be appreciated that following examples be merely to illustrate and
The present invention is explained, is not limited the invention anyway.
Wherein, hydrodesulfurization rate is calculated as follows:
Hydrodesulfurization rate=(Sulfur content in feed sulphur content-product)/ feed sulphur content × 100%
Embodiment 1
Take analytically pure AlCl3·6H2O201.3g, is dissolved in 1000ml deionized water, obtained solution A1;Take chemistry pure
Ti (OCH2CH3)421.7g, is dissolved in 500ml benzene(Benzene content is 99.8 (Wt) %)In, obtained solution B1;Take analytically pure
NH4HCO318g, is dissolved in 600ml deionized water, adds the ammoniacal liquor that 250ml concentration is 24-28wt%, is uniformly mixed, then
Add the solution C that deionized water is configured to 1000ml1。
In normal pressure, temperature is under conditions of 70-75 DEG C, by A1、B1And C1Three kinds of solution co-precipitations.Control solution C1
Flow, the pH value of sediment is kept in the range of 5.0-6.0 8 minutes, then increase solution C1Flow, make mixed solution
PH value is kept 8 minutes in the range of 8.5-9.5, then reduces solution C1Flow, make the pH value of mixed solution in 5.0-6.0 models
Interior holding 8 minutes is enclosed, then increases solution C1Flow, make the pH value of sediment in the range of 8.5-9.5, so repeatedly, until
Solution A1And B1All drip.Reaction solution stands 30 minutes at 70 DEG C, filtering, with 15 times of deionized water of filter cake volume
Wash filter cake 30 minutes, refilter, then wash, this process is repeated four times, filter cake is finally dried to 8-12 at 100-120 DEG C small
When, in being calcined 5 hours at 450 DEG C, obtain 42.7g Titanium oxide-aluminum oxide compounds Z1, its structure and results of property are shown in Table 1.
Embodiment 2
The experimentation in embodiment 1 is repeated, unlike, take the pure Al of analysis2(SO4)3·18H2O samples 277.6g, it is molten
In 1000ml deionized waters, solution A is obtained2, replace the A in embodiment 11;Take chemical pure Ti (OCH2CH3)421.4g, it is dissolved in
500ml benzene(Benzene content is 99.8 (Wt) %)In, obtain solution B2, replace the B in embodiment 11.As a result be made 42.4g titanium oxide-
Alumina compound Z2, its structure and results of property are shown in Table 1.
Embodiment 3
The experimentation in embodiment 1 is repeated, unlike, take the pure AlCl of analysis3·6H2O235.8g, is dissolved in 1000ml
In deionized water, solution A is obtained3, replace the A in embodiment 11;Take chemical pure Ti (OCH2CH3)40.7g, is dissolved in 500ml benzene(Benzene
Content is 99.8 (Wt) %)In, obtain solution B3, replace the B in embodiment 11.As a result 42.5g titanium dioxide-aluminum oxides are made to be combined
Thing Z3, its structure and results of property are shown in Table 1.
Embodiment 4
The experimentation in embodiment 1 is repeated, unlike, take the pure AlCl of analysis3·6H2O221.5g, is dissolved in 1000ml
In deionized water, solution A is obtained4, replace the A in embodiment 11;The chemical pure Ti (OCH for taking chemistry pure2CH3)42.7g, is dissolved in
500ml benzene(Benzene content is 99.8 (Wt) %)In, obtain solution B4, replace the B in embodiment 11.As a result be made 40.7g titanium oxide-
Alumina compound Z4, its structure and results of property are shown in Table 1.
Embodiment 5
The experimentation in embodiment 1 is repeated, unlike, take the pure AlCl of analysis3·6H2O214.3g, is dissolved in 1000ml
In deionized water, solution A is obtained5, replace the A in embodiment 11;Take analytically pure Ti (OCH2CH3)46.8g, is dissolved in 500ml benzene
(Benzene content is 99.8 (Wt) %), obtain solution B5, replace the B in embodiment 11.As a result 40.8g titanium dioxide-aluminum oxides are made to answer
Compound Z5, its structure and results of property are shown in Table 1.
Embodiment 6
The experimentation in embodiment 1 is repeated, unlike, take the pure AlCl of analysis3·6H2O213.8g, is dissolved in 1000ml
In deionized water, solution A is obtained6, replace the A in embodiment 11;Take chemical pure Ti (OCH2CH3)414.3g, is dissolved in 500ml benzene
(Benzene content is 99.8 (Wt) %)In, obtain solution B6.As a result 43.1g Titanium oxide-aluminum oxide compounds Z is made6, its structure and property
1 can be the results are shown in Table.
Embodiment 7
The experimentation in embodiment 1 is repeated, unlike, take the pure AlCl of analysis3·6H2O189.1g, is dissolved in 1000ml
In deionized water, solution A is obtained7, replace the A in embodiment 11;Take chemical pure Ti (OCH2CH3)428.7g, is dissolved in 500ml benzene
(Benzene content is 99.8 (Wt) %)In, obtain solution B7, replace the B in embodiment 11.As a result 43.2g titanium dioxide-aluminum oxides are made
Compound P7, its structure and results of property are shown in Table 1.
Embodiment 8
The experimentation in embodiment 1 is repeated, unlike, take the pure AlCl of analysis3·6H2O178.5g, is dissolved in 1000ml
In deionized water, solution A is obtained8, replace the A in embodiment 11;Take chemical pure Ti (OCH2CH3)437.0g, is dissolved in 500ml benzene
(Benzene content is 99.8 (Wt) %)In, obtain solution B8, replace the B in embodiment 11.As a result 43.4g titanium dioxide-aluminum oxides are made to answer
Compound Z8, its structure and results of property are shown in Table 1.
Comparative example 1
Titanium oxide-aluminum oxide compound is prepared according to the method disclosed in European patent EP 03396407, concrete operations are such as
Under:
Take 70g NaAlO2It is dissolved in deionized water and is diluted to 1000ml, filters off insoluble matter, obtain solution A9, by 13g
TiOCl2It is dissolved in deionized water and is diluted to 1000ml, obtains solution B9.By A9And B9Solution is respectively with 25ml/min speed
Add simultaneously in reactor, controlling reaction temperature is 68-72 DEG C, and the ammoniacal liquor for being 10wt% with concentration adjusts the pH value of reaction solution
To 9.0-9.5.After mixing is finished, solution left standstill 30 minutes, filtering, with 20 times of deionized water of filter cake volume by Washing of Filter Cake
30 minutes, refilter, then wash, this process is repeated four times, filter cake is dried 8 hours in 110 DEG C, and the nitric acid for then adding 5wt% is molten
Liquid kneading, cloverleaf pattern is extruded into banded extruder, is dried 8 hours in 110 DEG C, is calcined 4 hours in 450 DEG C, and 49.7g oxidations are made
Titanium-alumina compound Z9, its structure and results of property are shown in Table 1.
Comparative example 2
The sulfuric acid solution for taking 14ml volumetric concentrations to be 85%, 11g H are added in the case where being stirred continuously2TiO3In, then heat
To 130 DEG C, it is completely dissolved, 1000ml is diluted to deionized water, obtain Ti (SO4)2Solution B10.Take 70g NaAlO2It is molten
Solution is in deionized water and is diluted to 1000ml, filters off insoluble matter, obtains solution A10。
In normal pressure, reaction temperature is 68-72 DEG C, and under conditions of stirring, by solution A10And B10Respectively with 25ml/
Min flow velocity is added in reactor simultaneously, and the pH value of mixed solution is adjusted to 9.0-9.5 by the ammoniacal liquor for being 25wt% with concentration.It is molten
After liquid mixing is finished, 30 minutes are stood at a temperature of 70 DEG C, filtering, with 20 times of deionized waters of filter cake volume by Washing of Filter Cake 30
Minute, refilter, then wash, this process is repeated four times, and filter cake is dried 8 hours in 110 DEG C, and the salpeter solution for adding 5wt% is mixed
Pinch, cloverleaf pattern is extruded into banded extruder, dried 8 hours in 110 DEG C, is calcined 4 hours in 450 DEG C, 49.3g titanium oxide-oxygen is made
Change aluminium compound Z10, its structure and results of property are shown in Table 1.
The preparation of catalyst:Embodiment 9, comparative example 3~5
Embodiment 9
The Titanium oxide-aluminum oxide compound Z of Example 1140g is added with MoO as carrier3Meter concentration is 0.351g/
Ml ammonium molybdate aqueous solution 23ml, stirs 30 minutes under normal temperature, normal pressure, is then dried 8 hours at 110 DEG C, at 500 DEG C
Roasting 5 hours, obtains 47.2g catalyst precarsors Pr1。
Take the catalyst precarsor Pr of above-mentioned preparation140g, addition counts cobalt nitrate solution of the concentration as 0.08g/ml using CoO
24ml, stirs 30 minutes under normal temperature, normal pressure, is then dried 8 hours at 110 DEG C, be calcined 5 hours, obtain at 500 DEG C
49.2g catalyst Cat1.The property of catalyst is shown in Table 2.
Comparative example 3
The preparation process of embodiment 9 is repeated, unlike, use the Titanium oxide-aluminum oxide compound Z of comparative example 19Substitute
Z1, 49.1g catalyst Cat is made2.The property of catalyst is shown in Table 2.
Comparative example 4
The preparation process of embodiment 9 is repeated, unlike, use the Titanium oxide-aluminum oxide compound Z of comparative example 210Substitute
Z1, 49.2g catalyst Cat is made3.The property of catalyst is shown in Table 2.
Comparative example 5
Take the titanium solution and aluminum soluble salt configured in CN201110358513.6 patents using titanium tetrachloride and isopropanol
The titanium dioxide-aluminum oxide composite carrier P of preparation2, prepare MoO3(Wt) %'s of content 14.95 (Wt) %, CoO content 3.01 urges
Agent H2.The property of catalyst is shown in Table 2.
Application of the catalyst in pyrolysis gasoline hydrogenation desulphurization reaction:Embodiment 10, comparative example 6~8
Embodiment 10
Catalyst Cat in Example 91Continuously evaluated on 10g, the hydrogenation plant for being seated in 30ml reactors.Catalysis
Agent is passed through drippolene under the conditions of hydrodesulfurization reaction and carries out hydrodesulfurization after vulcanization, wherein:
The conditions of vulcanization of catalyst:280 DEG C of temperature, Hydrogen Vapor Pressure 2.5MPa, hydrogen gas-oil ratio 400:1, sulfurized oil(Sulphur
Carburetion is carbon disulfide+kerosene mixture, and carbon disulfide content is 1.5 (wt) %)Liquid phase air speed be 1.5h-1, cure time 8
Hour, hydrogen flowing quantity 150ml/ hours;
The property of drippolene raw material:Boiling range is 83-163 DEG C, and sulfur content is 350ppm, and bromine valency is 36.8 grams of bromine/100 gram
Oil.
Hydrodesulfurization reaction condition:Pressure 3.0MPa, 240 DEG C of temperature, air speed 3.0h-1, hydrogen-oil ratio(Volume ratio)400:1.
It the results are shown in Table 3.
Comparative example 6
The experimental procedure in embodiment 10 is repeated, unlike, use the catalyst Cat in comparative example 32Substitute Cat1.Knot
Fruit is shown in Table 3.
Comparative example 7
The experimental procedure in embodiment 10 is repeated, unlike, use the catalyst Cat in comparative example 43Substitute Cat1.Knot
Fruit is shown in Table 3.
Comparative example 8
Then hydrodesulfurization is carried out using drippolene raw material same as in Example 10 and experiment condition, the results are shown in Table 3.
The pore structure of the Titanium oxide-aluminum oxide compound of table 1
As it can be seen from table 1 being concentrated mainly on 20- according to the pore-size distribution of the Titanium oxide-aluminum oxide compound of the present invention
40 angstroms and 80-130 angstroms, respectively 30~45%, the characteristics of with double hole channel, and the Titanium oxide-aluminum oxide compound in comparative example
Then solely concentrate in the range of 40-80 angstroms;Even if the Titanium oxide-aluminum oxide compound in the embodiment of the present invention contains in titanium oxide
Amount is relatively low(Such as little as 0.47wt%)In the case of, intensity of its intensity also than comparative example is big.
The catalyst property of table 2
The hydrodesulfurization activity of table 3
From table 3 it can be seen that in pyrolysis gasoline hydrogenation Refining tests, with the aluminium oxide-titanium oxide compound of the present invention
For the catalyst Cat of carrier1Aluminium oxide-titanium oxide apparently higher than in comparative example of hydrogenation saturated activity and desulfurization degree be combined
Thing is the catalyst Cat of carrier2、Cat3And H2.Relative in the prior art, prepared by the compound provided according to the present invention urges
The hydrogenation saturated activity of agent is higher, and desulfurization degree is higher, with significant progressive.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein word used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of method for preparing Titanium oxide-aluminum oxide compound, including:
Step I:Aluminum soluble salt is dissolved in the water, solution A is obtained;Tetraethyl titanate is dissolved in benzene, solution B is obtained;
Ammonium hydrogen carbonate and ammoniacal liquor are configured to mixed aqueous ammonium C;
Step II:At a temperature of 65~95 DEG C, by solution A, tri- kinds of solution parallel-flow precipitations of B and C, by the stream for controlling solution C
Amount, makes the pH value of solution A, B and C mixed solution be alternately present in 5.0~6.5 and 8.0~9.5 two scopes, and respectively
6-10min is stopped, sediment is obtained;With
Step III:The sediment is calcined, the compound is obtained.
2. according to the method described in claim 1, it is characterised in that make the mixed solution pH value 5.0~6.0 and 8.5~
It is alternately present, and stops 7~9 minutes respectively in 9.5 two scopes.
3. according to the method described in claim 1, it is characterised in that the concentration of the solution A is 0.5~2.5mol/L, described
The concentration of solution B is 0.1~1.5mol/L, and the concentration of the ammonium hydrogen carbonate in the solution C is 0.1~0.3mol/L, the ammonia
The concentration of water is 15~25 volume %.
4. the method according to any one in claim 1-3, it is characterised in that the compound contains 0.3-25wt%
Titanium oxide, wherein the aperture of the compound in double hole channel be distributed.
5. method according to claim 4, it is characterised in that the aperture of the double hole channel is respectively 20~40 angstroms and 80~
130 angstroms.
6. the method according to any one in claim 1-3, it is characterised in that in the compound, 30~50%
The aperture in hole be 20~40 angstroms, the aperture in 30~50% hole is 80~130 angstroms.
7. the method according to any one of claim 1-3, it is characterised in that the specific surface area of the compound is 200
~350m2/ g, pore volume is 0.4~0.7m3/ g, intensity is 14~20N/mm.
8. the Titanium oxide-aluminum oxide compound that the method according to any one of claim 1-7 is obtained is as catalyst carrier
Application.
9. application according to claim 8, it is characterised in that included in the catalyst:Based on overall catalyst weight gauge,
12.0~25.0wt% molybdenum oxide and 1.0~5.0wt% cobalt oxide, or 12.0~25.0wt% molybdenum oxide, 1.0~
5.0wt% nickel oxide and 1.0~5.0wt% cobalt oxide.
10. application according to claim 9, it is characterised in that the catalyst is anti-for pyrolysis gasoline hydrogenation desulfurization
The catalyst answered.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410140884.0A CN104971706B (en) | 2014-04-09 | 2014-04-09 | A kind of method and its application for preparing titanium oxide alumina compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410140884.0A CN104971706B (en) | 2014-04-09 | 2014-04-09 | A kind of method and its application for preparing titanium oxide alumina compound |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104971706A CN104971706A (en) | 2015-10-14 |
CN104971706B true CN104971706B (en) | 2017-09-29 |
Family
ID=54268998
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410140884.0A Active CN104971706B (en) | 2014-04-09 | 2014-04-09 | A kind of method and its application for preparing titanium oxide alumina compound |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104971706B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106955746A (en) * | 2017-03-17 | 2017-07-18 | 钦州学院 | A kind of complex carrier of the aluminum oxide containing zinc oxide and preparation method thereof |
CN106925264A (en) * | 2017-03-17 | 2017-07-07 | 钦州学院 | A kind of catalyst and preparation method for producing cyclohexane by adding hydrogen in benzene |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0199399A2 (en) * | 1985-04-24 | 1986-10-29 | Shell Internationale Researchmaatschappij B.V. | Improved hydroconversion catalyst and process |
CN103100379A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Production method of titanium oxide-alumina composite |
-
2014
- 2014-04-09 CN CN201410140884.0A patent/CN104971706B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0199399A2 (en) * | 1985-04-24 | 1986-10-29 | Shell Internationale Researchmaatschappij B.V. | Improved hydroconversion catalyst and process |
CN103100379A (en) * | 2011-11-14 | 2013-05-15 | 中国石油化工股份有限公司 | Production method of titanium oxide-alumina composite |
Also Published As
Publication number | Publication date |
---|---|
CN104971706A (en) | 2015-10-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103721693B (en) | A kind of Titanium oxide-aluminum oxide compound and its preparation method and application | |
CN104383923B (en) | A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof | |
CN104209142B (en) | Hydrocarbon oil desulfurization catalyst and application method thereof | |
CN103100379B (en) | Production method of titanium oxide-alumina composite | |
CN106622204B (en) | A kind of zinc oxide material and preparation method containing gahnite | |
CN107051420B (en) | N-butane isomerization catalyst and preparation method thereof | |
CN1782031A (en) | Slag oil hydro-demetallization catalyst and its preparing method | |
CN104741071B (en) | A kind of preparation method of the nano combined desulfurizing agent of concave convex rod ground mass | |
CN100364663C (en) | Supported nano Au catalyst and method for preparing the same | |
CN105268459A (en) | Sulfur-containing low-carbon alkane dehydrogenation catalyst and preparation method thereof | |
CN106635135A (en) | Hydrodesulfurization method of catalytic cracking gasoline | |
CN105728027A (en) | Adsorption desulphurization catalyst and preparation method thereof | |
CN104971706B (en) | A kind of method and its application for preparing titanium oxide alumina compound | |
CN105363496B (en) | Dehydrogenating low-carbon alkane producing light olefins catalyst and preparation method thereof | |
CN104941639B (en) | A kind of selective hydrogenation catalyst and its preparation method and application | |
CN107970918B (en) | Spherical denitration catalyst and preparation method thereof | |
CN102527367B (en) | Catalyst for selective hydrogenation of cracked gasoline and preparation and application thereof | |
CN102039154B (en) | Hydrogenation sweetening catalyst, preparing method and application thereof | |
CN104711011B (en) | Uses of hydrotalcite-like compound as mercaptan removing catalyst, and use method of hydrotalcite-like compound | |
CN104549345B (en) | Active hydrocracking proppant and preparation method thereof | |
CN105214677B (en) | nickel-base catalyst | |
CN106622319B (en) | A kind of zinc-aluminium stratified material and preparation method | |
CN110038581A (en) | A method of preparing Hydrobon catalyst | |
CN112705220B (en) | Catalyst for skeletal isomerization reaction of carbon tetra-alkane, preparation method and application thereof | |
CN107670661B (en) | For the catalyst and its preparation method of crude naphthalene hydrodesulfurization production decahydronaphthalene and application |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |