CN109772287A - A kind of alkane isomerization catalyst carrier and preparation method thereof, the catalyst and preparation method thereof - Google Patents
A kind of alkane isomerization catalyst carrier and preparation method thereof, the catalyst and preparation method thereof Download PDFInfo
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- CN109772287A CN109772287A CN201711132843.7A CN201711132843A CN109772287A CN 109772287 A CN109772287 A CN 109772287A CN 201711132843 A CN201711132843 A CN 201711132843A CN 109772287 A CN109772287 A CN 109772287A
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Abstract
The present invention provides a kind of alkane isomerization catalyst carrier and preparation method thereof.Method includes the following steps: zirconates is dissolved, weak aqua ammonia is added dropwise under stiring and adjusts pH to 7-10, then carries out hydro-thermal reaction；Reaction is completed to be cooled to room temperature, and to neutrality, and after can not check chloride ion with silver nitrate inspection, washing terminates for washing filtering；By gained filtration cakes torrefaction, yttrium salt solution is then added, after stirring impregnates, washs, filters, it is dry；Cerium solution is continuously added, after stirring impregnates, washs, filters, it is dry；Then sulfate radical and tungstate radicle are successively loaded using equi-volume impregnating, is finally roasted 2-4 hours at 350~750 DEG C, mediated extrusion forming, obtain the nanometer grade tetragonal crystal phase Zirconia carrier of bimetallic-modified.The present invention also provides a kind of alkane isomerization catalysts and preparation method thereof.Not only reaction temperature is low for catalyst made from this method, and isomerization activity and selectivity are high, and repeatability and catalytic stability are good.
Description
Technical field
The present invention relates to catalyst field, it is related to a kind of alkane isomerization catalyst carrier and preparation method thereof, also relates to
And alkane isomerization catalyst comprising the carrier and preparation method thereof.
Background technique
Increasingly strict with environmental requirement, the specification of quality of mogas production requires higher and higher.Aromatic hydrocarbons, drop drop
Sulphur, Olefin decrease are that quality of gasoline improves the measure for having to take.Clean gasoline standard is towards low-sulfur, low alkene, low aromatic hydrocarbons
Direction is developed.Adopt people constantly from the pretreatment of raw material, the new process development of catalytic cracking, catalytic gasoline post-processing etc.
Measure is taken to further decrease catalytic gasoline sulfur content and alkene.And said from product blending angle, increase isomerization, researches and develops environment-friendly type
Isomerization new process can be improved the octane number of its product and reduce benzene and olefin(e) centent.Alkene in gasoline pool, arene content by
Limitation；Octane number wretched insufficiency, therefore it is most important to develop antiknock component.Thus exploitation alkane isomerization catalyst
It is the research of a production important in inhibiting to clean gasoline.
Isomerization catalyst uses chloride oxidation aluminium profiles catalyst more.It is well known that chloride oxidation aluminium profiles catalyst is to anti-
Answer the requirement of raw material very stringent, water, sulphur, nitrogen, oxygen content be less than 0.1ppm.Chloride oxidation aluminium profiles catalyst it is another
A fatal defects are can not to regenerate.And chloride oxidation aluminium profiles catalyst is in catalytic reaction process, chlorine can with reaction into
Journey is largely lost, in order to guarantee that catalytic quantity needs constantly mend chlorine into reaction.Corruption since content of Cl element is higher, to equipment
Lose fairly obvious, this is resulted in again needs to pay higher equipment repair and maintenance cost using chloride oxidation aluminium profiles catalyst.
The environment that chlorine element in chloride oxidation aluminium profiles catalyst will cause the catalyst simultaneously is unfriendly, and it is impossible to meet greenizations
Learn the requirement to catalyst.
The nanometer grade tetragonal crystal phase zirconium oxide of bimetallic-modified is the C of carrier4~C7Alkane isomerization catalyst then can will be upper
The problem of stating is readily solved, and requirement of the catalyst to raw material is loose；It does not need to mend chlorine during catalytic production；And it can be again
It is raw, meet the standard of Green Chemistry, is more efficient, more friendly C4~C7Alkane isomerization catalyst.
The pore diameter range and ratio that the physical parameter of carrier such as specific surface area, average pore size and pore size distribution are mainly concentrated are to institute
Catalyst activity, selectivity, stability and the regenerability used plays an important role.Therefore it is required that the specific surface of carrier is big,
To guarantee the selectivity and stability of catalyst.Therefore above-mentioned C4~C7Bimetallic-modified used in alkane isomerization catalyst
Nanometer grade tetragonal crystal phase zirconium oxide large specific surface area, catalyst activity is high, and stability and regenerability are good, and following patent reveals
The preparation method of carrier or catalyst.
CN104117369A discloses a kind of preparation method of catalyst for normal paraffin isomerization.With γ-Al2O3For carrier
It is impregnated with the aqueous solution of compound containing platinum, drying and roasting carries out reduction treatment with hydrogen, and gasifies respectively under hydrogen and nitrogen
Catalyst is made in aluminium chloride and carbon tetrachloride.The aperture of aluminium oxide is all bigger than normal, be distributed it is wider, chloride oxidation aluminium profiles catalyst without
Method regeneration, and chlorine can be lost in reaction process, and in order to guarantee that the quality of catalyst needs constantly to mend chlorine, this makes catalysis not
It is able to satisfy environmental requirement, not environmentally type catalyst.
CN1524616A discloses a kind of preparation method of strong solid acid catalyst, is to mix zirconium saline solution and ammonium hydroxide
It is aged the hydroxide that zirconium is made, then the oxide mixed-forming with the oxide of aluminium and silicon, is roasted at a certain temperature.This is specially
The pH value that benefit is controlled when preparing zirconium hydroxide is 6~10, and digestion time is longer, it is therefore an objective to so that zirconium hydroxide is converted into list as far as possible
Monoclinic phase.Being compared as shared by the oxide of aluminium in butt and the oxide of silicon higher keeps catalyst easy to form.The catalyst
The oxide of a large amount of silicon and the oxide of aluminium are added in forming process, sulfate radical is caused to load based on monoclinic phase for carrier
The sulfur content that amount reduces the catalyst is low, and only 1.0%~2.0% is acid weak.
CN105413743A discloses one kind by Ce-SAPO-41 molecular sieve, and kaolin and aluminium phosphate sol are by a certain percentage
Straight chain alkane isomerization catalyst made of 1.0:0.1:0.1.The catalyst of molecular sieve type needs higher reaction temperature, energy
Consumption is big.
Summary of the invention
To solve the above-mentioned problems, the object of the present invention is to provide a kind of alkane isomerization catalyst carrier and its preparation sides
Method also provides a kind of alkane isomerization catalyst and preparation method thereof comprising above-mentioned carrier.Catalyst made from this method is not
Only reaction temperature is low, and isomerization activity and selectivity are high, and repeatability and catalytic stability are good.
For this purpose, the preparation method of alkane isomerization catalyst carrier of the invention, comprising the following steps:
S1 dissolves zirconates, and weak aqua ammonia is added dropwise under stiring and adjusts pH to 7-10, it is anti-then to carry out still aging or hydro-thermal
It answers；
S2 ageing or reaction are completed and system temperature is cooled to room temperature, washing filtering to neutrality, and is checked not with silver nitrate
Out after chloride ion, washing terminates；
Then yttrium salt solution or cerium solution is added in gained filtration cakes torrefaction by S3, after stirring impregnates, wash, filter, do
It is dry, obtain metal-modified nanometer grade tetragonal crystal phase Zirconia carrier.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein the zirconates is preferably selected from oxygen chlorine
Change at least one of zirconium, zirconyl nitrate and zirconium sulfate.
The preparation method of alkane isomerization catalyst carrier of the present invention, in step S1, the time of stirring is preferably
0.5~5 hour, the still aging time was preferably 12~36 hours, and hydrothermal temperature is preferably 100~190 DEG C.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein preferably, further includes: S4 after
It is continuous that a kind of metal salt solution different from step S3 is added, it after stirring impregnates, washs, filters, it is dry, it obtains bimetallic-modified and receives
Meter level tetragonal-phase zirconia carrier；The metal salt solution is yttrium salt solution or cerium solution.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein the condition of the drying is preferred
Are as follows: 50~150 DEG C of temperature, the time 12~36 hours.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein the yttrium salt is preferably selected from nitric acid
At least one of yttrium, yttrium chloride, yttrium carbonate, yttrium sulfate, yttrium oxalate and yttrium acetate.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein the cerium salt is preferably selected from nitric acid
At least one of cerium, cerium chloride, cerous carbonate, cerous sulfate, cerium oxalate and cerous acetate.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein the time of the stirring dipping is equal
Preferably 0.5~10 hour.
It is the load as prepared by above-mentioned method the present invention also provides a kind of alkane isomerization catalyst carrier
150~240m of surface area of body2/ g, 3~20nm of partial size, 100-1000 μm of ol/g of Surface acidity.
The present invention also provides a kind of alkane isomerization catalyst, which is the support type for including active component and carrier
Catalyst, the active component are group VIII metal, and the carrier is as prepared by above-mentioned method.
Alkane isomerization catalyst of the present invention, it is preferred that in the catalyst, on the basis of butt zirconium oxide
It calculates, the yttrium comprising 0.5~5.0 mass %, the cerium of 0.5~5.0 mass %, the sulphur of 0.5~2.5 mass %, 0.5~2.5 matter
Measure the tungsten of % and the group VIII metal of 0.01~5.0 mass %.
The present invention also provides a kind of preparation methods of alkane isomerization catalyst, comprising the following steps:
The carrier as prepared by above-mentioned method is successively loaded sulfate radical and/or wolframic acid using equi-volume impregnating by C1
Root finally roasts 2-4 hours at 350~750 DEG C, mediates extrusion forming, obtains the nanoscale of containing sulfate radicals and/or tungstate radicle
Tetragonal-phase zirconia carrier；
C2 prepares the maceration extract of the metallic element containing group VIII, using equi-volume impregnating, by the containing sulfate radicals and/or
The nanometer grade tetragonal crystal phase Zirconia carrier of tungstate radicle, which is put into maceration extract, to be impregnated, and is then dried, is roasted to obtain the catalyst.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein the containing sulfate radicals solution is preferred
Selected from sulfuric acid, ammonium sulfate, the solution containing tungstate radicle is selected from wolframic acid, ammonium tungstate solution.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein sulfuric acid in the sulfate radical solution
The concentration of root is preferably 0.1~5mol/L, and the concentration of tungstate radicle is preferably 0.1~5mol/L in the tungstate radicle solution.
The preparation method of alkane isomerization catalyst carrier of the present invention, wherein on the basis of every gram of zirconium oxide, institute
The dosage for stating sulfate radical solution is preferably 5~50ml, and the dosage of the tungstate radicle solution is preferably 5~50ml.
The preparation method of alkane isomerization catalyst of the present invention, wherein the maceration extract preferably contains chlorine platinum
Acid, ammonium chloroplatinate, platinous chloride or platinum tetrachloride solution.
The preparation method of alkane isomerization catalyst of the present invention, wherein the time of the dipping is both preferably 0.5
~10 hours；In step C2, the condition of the drying is preferred are as follows: 50~150 DEG C of temperature, the time 12~36 hours；The roasting
Condition it is preferred are as follows: 450~700 DEG C of temperature, the time 2~4 hours.
Details are as follows for the preparation method of alkane isomerization catalyst of the invention.
The preparation and compound pickling of bimetallic-modified catalyst carrier of the invention, leaching platinum prepare alkane isomerization catalyst
Method carry out as follows:
(1) zirconates deionized water dissolving will be contained, weak aqua ammonia is added dropwise under stiring, adjust pH to 7-10, stirring 0.5~5
Hour；
(2) it moves into water heating kettle, reacts 12~48 hours at 100~190 DEG C, washed after being cooled to room temperature with Buchner funnel
Chloride ion is washed away, air dry oven is packed into, it is dry at 110 DEG C；
(3) carrier after dry, introduces yttrium salt using infusion process, is added a certain amount of yttrium salt solution, and stirring dipping 0.5~
10 hours, the product after filtering lotion dipping, 110 DEG C of dryings；
(4) cerium salt is introduced using infusion process, a certain amount of cerium solution is added, stirring dipping crosses diafiltration in 0.5~10 hour
Product after agent dipping, 50~150 DEG C of dryings obtain the yttrium and cerium bimetallic-modified nanometer grade tetragonal crystal phase that partial size is 3~20nm
Zirconia carrier；
(5) by after drying yttrium and cerium bimetallic-modified nanometer grade tetragonal crystal phase Zirconia carrier grind, with containing sulfuric acid
The solution stirring that root concentration is 0.1~5mol/L dipping 0.5~10 hour；
(6) product after filtering lotion dipping, then dipping is stirred with containing the solution that tungstate radicle concentration is 0.1~5mol/L
0.5~10 hour；
(7) product after filtering lotion dipping, 50~150 DEG C of dryings
(8) it is roasted 2~4 hours at 350~750 DEG C, obtains the nanometer grade tetragonal crystal phase oxidation of containing sulfate radicals and tungstate radicle
Zirconium carrier；
(9) product after roasting is extruded into strip or other shapes；
(10) maceration extract of the compound containing group VIII metal is prepared, the carrier of dipping (9) step preparation, then dry, 450~
700 DEG C of roastings, time are to obtain catalyst in 2~4 hours.
The present invention is a kind of with simple zirconates, prepares C using bimetallic-modified and compound infusion process4~C7Alkane isomery
Change the method for catalyst carrier.Resulting vehicle is the nanometer grade tetragonal crystal phase Zirconia carrier of containing sulfate radicals and tungstate radicle.
Emphasis of the invention be to provide it is a kind of with acid relatively strong (100-1000 μm of ol/g of Surface acidity), surface area 150~
240m2/ g, alkane isomerization catalyst of the partial size based on the bimetallic-modified nanometer grade tetragonal crystal phase zirconium oxide of 3~20nm
Preparation method.The method can be required according to isomerization catalyst difference, introduce different containing sulfate radicals solution, tungstate radicle solution is to adjust
Acid strength, partial size and the specific surface property of catalyst, furthermore appropriate adjustment maturing temperature condition, prepares different crystallization degrees
Zirconia carrier for prepare heterogeneous catalyst use.
The present invention prepares the hydroxide of zirconium using coprecipitation in the preparation process of carrier and catalyst, at hydro-thermal
It is dry after reason, yttrium salt and the modified ratio to improve tetragonal phase of cerium salt are introduced by the method impregnated respectively, obtain abundant crystalline substance
The zirconium oxide of tetragonal phase is turned to, is roasted after dip loading sulfate radical and tungstate radicle, catalyst acid intensity is improved, then forms again
Soak platinum.The tetragonal-phase zirconia carrier of the bimetallic-modified of load sulfate radical and tungstate radicle can provide more isomerization reaction
Site.Synthesis has been obtained using the tetragonal-phase zirconia of bimetallic-modified as the alkane isomerization catalyst of carrier, thermal stability
Height is still able to maintain higher alkane isomerization activity under high temperature.
The technology of the present invention key is filling for the bimetallic-modified that introducing yttrium salt and cerium salt prepare zirconium in dipping normal direction zirconium oxide
Dividing crystallization is the Zirconia carrier of nanometer grade tetragonal crystal phase.With containing sulfate radicals solution and solution impregnating carrier containing tungstate radicle and adjust
Maturing temperature makes catalyst obtain the acid strength most beneficial for alkane isomerization
The convenient preparation method of carrier of the present invention is the oxide that zirconium is made with hydro-thermal method.Suitable zirconates includes oxygen chlorine
Change zirconium, zirconium sulfate, zirconyl nitrate etc., preferably zirconium oxychloride and zirconyl nitrate.By above-mentioned molten ammonium hydroxide adjusting pH to 7~10
Afterwards, sufficient high degree of agitation, to guarantee to obtain the hydroxide of uniform zirconium.The hydroxide of zirconium is moved into water after stirring sufficiently
Solution is removed reaction kettle, after removing supernatant liquor, uses Bu Shi by heat, hydro-thermal reaction natually cooled to room temperature after a certain period of time
Funnel washs repeatedly repeatedly, and the purpose of washing is to remove impurity (NO3 2-And Cl-), conventional method is pressed at 50-150 DEG C after washing
It is dry.
It impregnates and introduces yttrium salt and cerium salt in normal direction zirconium oxide, a certain amount of yttrium salt solution, stirring dipping 0.5~10 is first added
Hour, the product after filtering lotion dipping, 110 DEG C of dryings；A certain amount of cerium solution is being added, stirring dipping 0.5~10 is small
When filtering lotion dipping after product, 50~150 DEG C of dryings.Suitable yttrium salt includes yttrium nitrate, yttrium chloride, yttrium carbonate, sulfuric acid
Yttrium, yttrium oxalate, yttrium acetate, most preferably yttrium nitrate and yttrium chloride.Suitable cerium salt includes cerous nitrate, cerium chloride, cerous carbonate, sulphur
Sour cerium, cerium oxalate, cerous acetate, most preferably cerous nitrate and chlorination.Partial size is converted into the bimetallic-modified nanoscale of 3~20nm
Tetragonal-phase zirconia carrier.
Bimetallic-modified nanometer grade tetragonal crystal phase zirconia material of the partial size that the present invention obtains in 3~20nm is a kind of tool
There is the catalyst carrier of excellent performance.Sulphation can be carried out to the carrier and noble metal supports, be used to prepare alkane isomerization
Catalyst.
Partial size is made after the bimetallic-modified nanometer grade tetragonal crystal phase Zirconia carrier of 3~20nm in the present invention, with containing
The solution stirring dipping of sulfate radical is supported on sulfate radical sufficiently on the nanometer grade tetragonal crystal phase Zirconia carrier of bimetallic-modified,
The sulfate radical on unsupported is washed away, keeps solution evaporation dry.Sulphur needed for sulfate radical content in mixed liquor should reach catalyst
Content, dip time 0.5~10 hour.With the solution stirring dipping containing tungstate radicle it is supported on tungstate radicle sufficiently after filtering double
On metal-modified nanometer grade tetragonal crystal phase Zirconia carrier, the tungstate radicle on unsupported is washed away, keeps solution evaporation dry.Mixing
W content needed for molybdic acid radical content in liquid should reach catalyst, dip time 0.5~10 hour.Solid exists after immersion filtration
It is roasted 2~4 hours at 350~750 DEG C, obtains the nanometer grade tetragonal crystal phase oxidation of the bimetallic-modified of containing sulfate radicals and tungstate radicle
Zirconium, by the nanometer grade tetragonal crystal phase zirconium oxide extruded moulding of the bimetallic-modified of containing sulfate radicals and tungstate radicle.
Chloroplatinic acid that the present invention is prepared with predetermined amounts, liquid impregnated carrier, platinum needed for platinum content should reach catalyst contain
Amount, dip time 0.5~10 hour.Solid is roasted at 450~700 DEG C after immersion filtration, and the time is to be catalyzed for 2~4 hours
Agent.
Detailed description of the invention
Fig. 1 is the electromicroscopic photograph of the nanometer grade tetragonal crystal phase Zirconia carrier of bimetallic-modified prepared by embodiment 1.
Fig. 2 is the XRD of the nanometer grade tetragonal crystal phase Zirconia carrier of bimetallic-modified prepared by embodiment 1.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, it is to be noted that the content of present invention is simultaneously
It is not limited to this.
Embodiment 1
(1) the nanometer grade tetragonal crystal phase Zirconia carrier of bimetallic-modified is prepared
Zirconium oxychloride is taken to be dissolved in deionized water (concentration of zirconium be 0.4mol/L), 10% ammonium hydroxide is added dropwise in stirring while
Adjust pH, pH value of solution=7~8 made to move into water heating kettles, 170 DEG C hydro-thermal reaction 24 hours；It is washed after cooling with filtered on buchner funnel,
110 DEG C drying 24 hours, with yttrium nitrate solution oxide impregnation zirconium (content of yttrium be 0.2% (w)), stirring dipping 0.5~10 is small
When, the product after filtering lotion dipping, 110 DEG C of dryings, then (content of cerium is 0.3% (w)), stirring are impregnated with cerous nitrate solution
The nanometer grade tetragonal crystal phase of bimetallic-modified is made in dipping 0.5~10 hour, the product after filtering lotion dipping, 110 DEG C of dryings
Zirconia carrier, electromicroscopic photograph is shown in Figure 1, and XRD is shown in Figure 2.
150~240m of surface area of resulting vehicle2/ g, 3~20nm of partial size, 100-1000 μm of ol/g of Surface acidity.
(2) compound pickling molding
By nanometer grade tetragonal crystal phase Zirconia carrier predetermined amounts (every gram of nanometer grade tetragonal crystal phase oxygen made from step (1)
Change zirconium carrier to be impregnated with 20ml dilute sulfuric acid (0.5mol/L)) configuration dilute sulfuric acid maceration extract, stirs dipping 1 hour, washes away unsupported
On sulfate radical, then predetermined amounts (every gram of nanometer grade tetragonal crystal phase Zirconia carrier with the dilute wolframic acid of 20ml (0.5mol/L) soak
Stain) the dilute wolframic acid maceration extract of configuration, stirring dipping 1 hour washes away the tungstate radicle on unsupported, and 110 DEG C 650 DEG C after drying 24 hours
Roasting 3 hours, is extruded into strip or other shapes.
(3) dipping carries platinum
Containing sulfate radicals made from step (2) and the nanometer grade tetragonal crystal phase Zirconia carrier predetermined amounts of molybdate are configured
Chloroplatinic acid maceration extract, stirring dipping 1 hour, washes away the platinum on unsupported, 110 DEG C of 550 DEG C of roastings, 3 hours systems after drying 24 hours
Catalyst A must be changed (content of platinum is 0.2% (w)).It the results are shown in Table 1.
Embodiment 2
It is identical as 1 operating method of embodiment, unlike, step (1) does not introduce bimetallic-modified, and (content of yttrium is
0.2% (w), the content of cerium is 0% (w)).Catalyst B is made, the results are shown in Table 1.
Embodiment 3
It is identical as 1 operating method of embodiment, unlike, step (1) does not introduce bimetallic-modified, and (content of yttrium is 0%
(w), the content of cerium is 0.3% (w)).Catalyst C is made, the results are shown in Table 1.
Embodiment 4
It is identical as 1 operating method of embodiment, unlike, hydro-thermal reaction in step (1) is changed to, is added dropwise after ammonium hydroxide directly
Still aging 24 hours；Washed after cooling with filtered on buchner funnel, 110 DEG C drying 24 hours.Catalyst D is obtained, the results are shown in Table 1.
Embodiment 5
It is identical as 1 operating method of embodiment, unlike, step (2) predetermined amounts (every gram of nanometer grade tetragonal crystal phase oxygen
Change zirconium carrier and impregnate (0.5mol/L) with 20ml dilute sulfuric acid) configuration dilute sulfuric acid maceration extract, stirs dipping 1 hour, washes away unsupported
On sulfate radical after no longer load tungstate radicle, after direct 110 DEG C of dryings 24 hours 650 DEG C roast 3 hours, be extruded into strip or other
Shape.Catalyst E is made, the results are shown in Table 1.
Embodiment 6
It is identical as 1 operating method of embodiment, unlike, step (2) predetermined amounts configure dilute wolframic acid maceration extract, maceration extract
In wolframic acid radical content should reach catalyst needed for molybdenum content, stirring dipping 1 hour washes away after the tungstate radicle on unsupported not
Sulfate radical is loaded again, is roasted 3 hours for 650 DEG C after direct 110 DEG C of dryings 24 hours, is extruded into strip or other shapes (every gram of nanometer
Grade tetragonal-phase zirconia carrier impregnates (0.5mol/L) with the dilute wolframic acid of 20ml).Catalyst F is made, the results are shown in Table 1.
Comparative example 1
It is identical as 1 operating method of embodiment, unlike, step (1) does not introduce modified metal dipping, and (content of yttrium is
0% (w), the content of cerium is 0% (w)).Catalyst G is made, the results are shown in Table 1.
Comparative example 2
It is identical as 1 operating method of embodiment, unlike, step (1) takes zirconium oxychloride, and yttrium nitrate and cerous nitrate are dissolved in
Deionized water (concentration of zirconium be 0.4mol/L), the ammonium hydroxide that stirring while is added dropwise 10% adjust pH, move pH value of solution=7~8
Enter water heating kettle, 170 DEG C hydro-thermal reaction 24 hours；Washed after cooling with filtered on buchner funnel, 110 DEG C drying 24 hours.It is made and urges
Agent H (content of yttrium is 0.2% (w), and the content of cerium is 0.3% (w)), the results are shown in Table 1.
Table 1
Embodiment 7
Catalyst made from embodiment 1-6 and comparative example 1-2 is subjected to isomeric hexane with small fixed reaction unit
Reaction test.Isomerization catalyst is fitted into small fixed reactor, charge weight is 10 milliliters, in 190 DEG C, 2.1MPa item
The mixed preparing oil that n-hexane and pentane are passed through under part carries out isomerization reaction, and reaction feed weight space velocity is 1.0 hours-1,
Hydrogen hydrocarbon molar ratio is 1.2.
The evaluation property with liquefaction used, referring to being shown in Table 2.Evaluating catalyst the results are shown in Table 3.
Table 2
Table 3
From table 3 it can be seen that using the alkane isomerization catalyst of the method for the present invention preparation to C5 n-alkane and C6 just
The catalytic activity of structure alkane isomerization reaction is higher, and the isomerisation selectivity of C6 n-alkane is also higher.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (17)
1. a kind of preparation method of alkane isomerization catalyst carrier, which comprises the following steps:
S1 dissolves zirconates, and weak aqua ammonia is added dropwise under stiring and adjusts pH to 7-10, then carries out still aging or hydro-thermal reaction；
S2 ageing or reaction are completed and system temperature is cooled to room temperature, washing filtering to neutrality, and can not check chlorine with silver nitrate inspection
After ion, washing terminates；
Then yttrium salt solution or cerium solution is added in gained filtration cakes torrefaction by S3, after stirring impregnates, wash, filter, dry, is obtained
To metal-modified nanometer grade tetragonal crystal phase Zirconia carrier.
2. the preparation method of alkane isomerization catalyst carrier according to claim 1, which is characterized in that the zirconates choosing
From at least one of zirconium oxychloride, zirconyl nitrate and zirconium sulfate.
3. the preparation method of alkane isomerization catalyst carrier according to claim 1, which is characterized in that in step S1,
The time of stirring is 0.5~5 hour, and the still aging time is 12~36 hours, and hydrothermal temperature is 100~190 DEG C.
4. the preparation method of alkane isomerization catalyst carrier according to claim 1, which is characterized in that further include: S4
A kind of metal salt solution different from step S3 is continuously added, after stirring impregnates, washs, filters, it is dry, obtain bimetallic-modified
Nanometer grade tetragonal crystal phase Zirconia carrier；The metal salt solution is yttrium salt solution or cerium solution.
5. the preparation method of alkane isomerization catalyst carrier according to claim 1 or 4, which is characterized in that described dry
Dry condition is equal are as follows: 50~150 DEG C of temperature, the time 12~36 hours.
6. the preparation method of alkane isomerization catalyst carrier according to claim 1 or 4, which is characterized in that the yttrium
Salt is selected from least one of yttrium nitrate, yttrium chloride, yttrium carbonate, yttrium sulfate, yttrium oxalate and yttrium acetate.
7. the preparation method of alkane isomerization catalyst carrier according to claim 1 or 4, which is characterized in that the cerium
Salt is selected from least one of cerous nitrate, cerium chloride, cerous carbonate, cerous sulfate, cerium oxalate and cerous acetate.
8. the preparation method of alkane isomerization catalyst carrier according to claim 1 or 4, which is characterized in that described to stir
The time for mixing dipping is 0.5~10 hour.
9. a kind of alkane isomerization catalyst carrier is the spy as prepared by claim 1-8 described in any item methods
Sign is, 150~240m of surface area of the carrier2/ g, 3~20nm of partial size, 100-1000 μm of ol/g of Surface acidity.
10. a kind of alkane isomerization catalyst, which is characterized in that the catalyst be include that the support type of active component and carrier is urged
Agent, the active component are group VIII metal, and the carrier is as prepared by the described in any item methods of claim 1-8
's.
11. alkane isomerization catalyst according to claim 10, which is characterized in that in the catalyst, with butt oxygen
It is calculated on the basis of change zirconium, the yttrium comprising 0.5~5.0 mass %, the cerium of 0.5~5.0 mass %, the sulphur of 0.5~2.5 mass %,
The group VIII metal of the tungsten of 0.5~2.5 mass % and 0.01~5.0 mass %.
12. a kind of preparation method of alkane isomerization catalyst, which comprises the following steps:
The carrier as prepared by claim 1-8 described in any item methods is successively loaded sulfuric acid using equi-volume impregnating by C1
Root and/or tungstate radicle finally roast 2-4 hours at 350~750 DEG C, mediate extrusion forming, obtain containing sulfate radicals and/or tungsten
The nanometer grade tetragonal crystal phase Zirconia carrier of acid group；
C2 prepares the maceration extract of the metallic element containing group VIII, using equi-volume impregnating, by the containing sulfate radicals and/or wolframic acid
The nanometer grade tetragonal crystal phase Zirconia carrier of root, which is put into maceration extract, to be impregnated, and is then dried, is roasted to obtain the catalyst.
13. the preparation method of alkane isomerization catalyst carrier according to claim 12, which is characterized in that the sulfur-bearing
Acid group solution is selected from sulfuric acid, ammonium sulfate, and the solution containing tungstate radicle is selected from wolframic acid, ammonium tungstate solution.
14. the preparation method of alkane isomerization catalyst carrier according to claim 12, which is characterized in that the sulfuric acid
The concentration of sulfate radical is 0.1~5mol/L in root solution, and the concentration of tungstate radicle is 0.1~5mol/L in the tungstate radicle solution.
15. the preparation method of alkane isomerization catalyst carrier according to claim 12, which is characterized in that with every gram of oxygen
On the basis of changing zirconium, the dosage of the sulfate radical solution is 5~50ml, and the dosage of the tungstate radicle solution is 5~50ml.
16. the preparation method of alkane isomerization catalyst according to claim 12, which is characterized in that the maceration extract is
Solution containing chloroplatinic acid, ammonium chloroplatinate, platinous chloride or platinum tetrachloride.
17. the preparation method of alkane isomerization catalyst according to claim 12, which is characterized in that the dipping when
Between be 0.5~10 hour；In step C2, the condition of the drying are as follows: 50~150 DEG C of temperature, the time 12~36 hours；It is described
The condition of roasting are as follows: 450~700 DEG C of temperature, the time 2~4 hours.
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