CN1772385A - Prepn of n-heptane hydroisomerizing catalyst - Google Patents

Prepn of n-heptane hydroisomerizing catalyst Download PDF

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CN1772385A
CN1772385A CN 200510095236 CN200510095236A CN1772385A CN 1772385 A CN1772385 A CN 1772385A CN 200510095236 CN200510095236 CN 200510095236 CN 200510095236 A CN200510095236 A CN 200510095236A CN 1772385 A CN1772385 A CN 1772385A
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catalyst
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isomerization
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CN100528360C (en
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王军
魏瑞平
顾焰波
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Nanjing Tech University
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Abstract

The present invention relates to the preparation process of one supported super strong acid catalyst and the application of the catalyst in isomerizing reaction, and is especially the preparation process of ultrastable Y(USY) zeolite supported SO42-/ZrO2 catalyst and bimetallic catalyst and the application of the catalyst in n-heptane hydroisomerizing reaction. The present invention prepares super strong acid catalyst with great specific surface area on the basis of available SO42-/ZrO2 super strong acid catalyst and by adopting widely applied USY as carrier, and prepares Pt containing bimetallic catalyst with the support super strong acid as carrier. The catalyst of the present invention has high n-heptane hydroisomerizing reaction activity, high hydroisomerized product selectivity and excellent catalytic stability.

Description

A kind of preparation method of n-heptane hydroisomerizing catalyst
Technical field
The present invention relates to a kind of preparation method and the application of this catalyst in isomerization reaction of support type super acidic catalyst, relate in particular to the zeolite-loaded SO of a kind of super steady Y (USY) 4 2-/ ZrO 2And the preparation method of bimetallic catalyst and the application of this catalyst in the n-heptane hydroisomerizing reaction.
Background technology
The alkane isomerization process is that low-octane linear paraffin is converted into high-octane branched paraffin.C 5/ C 6Hysomer system lightweight isoparaffin has been a kind of technology of maturation at present, is subjected to the promotion of global clean gasoline demand, and the raw material of alkane isomerization expands to C 7And the trend (Marcilly C.Stud.Surf.Sci.Catal., 2001,135,3) of higher carbon number alkane.C 7And higher carbon number isomerization of paraffins will be the important measures that following clean gasoline is produced.
C 5/ C 6Isomerization catalyst has experienced from early stage Friedel-Crafts catalyst, to the differentiation of bifunctional catalyst.Bifunctional catalyst is divided into low temperature, middle gentle high temperature catalyst, wherein present industrial extensive use be warm type catalyst in noble metal/h-mordenite (US35079321, US4018711, US4735929).Yet this noble metal/h-mordenite catalyst directly applies to n-heptane hydroisomerizing, will make normal heptane be cracked into C 4Below little molecule, cause hydrogen consumption to increase, yield descends, catalysqt deactivation is accelerated.Therefore seek high activated catalyst, and improve the focus that normal heptane isomerization product selectivity becomes people's concern.
Researchers (J.Catal, 1999,187,167) such as Corma A. have studied modenite, SSZ-24, USY, and SCB, H β, SAPO-5 even load precious metals pt catalyst are 5.13h for the hysomer activity of normal heptane in air speed (WSHV) -1, stagnation pressure is 20bar, hydrogen/hydrocarbon than for 15mol/mol, when reaction temperature is 240-400 ℃, zeolite molecular sieve (as USY, H β, SSZ-33) with larger aperture of 12 yuan of ring three-dimensional channels has higher activity, especially a kind of have that to receive the zeolite-loaded Pt catalyst performance of β of crystal structure best, when reaction temperature is 270 ℃, the normal heptane conversion ratio is about at 75% o'clock, has the isomerized products selectivity about 70%; And the Pt catalyst of modenite load only shows very strong cracking activity.
(AppL Catal.A:General such as Campelo J.M., 1997,152,53) studied the n-heptane hydroisomerizing reactivity worth of Pt/SAPO-5 and Pt/SAPO-11, the result shows that in reaction temperature be 400 ℃, and reaction pressure is 5bar, when catalyst amount is 0.12g, the conversion ratio of normal heptane isomerization reaction is respectively 98.4% and 41.5% on two kinds of catalyst of Pt/SAPO-5 and Pt/SAPO-11, and the selectivity of isomerization product is respectively 3.8% and 76.5%.As seen Pt/SAPO-11 has normal heptane conversion ratio and isomerization product yield preferably.
It is that required reaction temperature and pressure ratio is higher that noble metal/zeolite molecular sieve class catalyst is used for the main weak point of normal heptane isomerization reaction, the selectivity of isomerization product is not high, carrier acidity itself and pore passage structure are had relatively high expectations, thereby also limited its further industrial applications.
Super acids is meant the acid that acid strength also is eager to excel than 100% sulfuric acid, from Hino in 1979 and Arata reported first SO 4 2-/ ZrO 2Since the solid super-strong acid (Hino M., Arata K., J.Am.Chem.Soc., 1979,101,21,6439), the catalytic applications of solid super-strong acid just causes people's extensive concern.Compare with traditional halogen-containing super acids, it is simple that solid super-strong acid has the preparation method, acid strength height, not advantage such as etching reactor.But because of its poor stability, specific area is little, so far not yet in industrial large-scale application.
(Garin F., Andriamasinoro D., Abdulsamad A., Sommer J., J.Catal.1991,131 (1), 199) such as Garin F. have prepared the SO of supporting Pt 4 2-/ ZrO 2Solid super acid catalyst, and be used for normal butane isomerization reaction, find to add precious metals pt and use the hydrogen reducing catalyst, reaction 500min still has good active later on, as seen by adding precious metals pt and can improving its stability with hydrogen reducing.
Lei T. etc. makes γ-Al 2O 3And SiO 2Load SO 4 2-/ ZrO 2Catalyst, and use it for normal butane isomerization reaction (Lei T., Xu J.S., Tang Y., Hua W.M., Gao Z., Appl.Catal.A:General, 2000,192,181); Patent CN1040846C has reported a kind of with γ-Al 2O 3Or there is not a silica supported SO of sodium 4 2-/ ZrO 2Method, and be used for the isomerization reaction of n-hexane; Patent CN1030288C has reported a kind of with HM load SO 4 2-/ ZrO 2Method, and be used for the isomerization reaction of n-hexane.More than various load SO 4 2-/ ZrO 2Catalyst makes the specific area of catalyst increase, and the conversion ratio of low-carbon (LC) n-alkane increases, but still is easy to generate pyrolysis product.
(F ttinger K., Zom K., Vinek H., Appl.Catal.A:Generl, 2005,284,69) such as F ttinger K. have prepared the Pt-SO that contains 2.5%Pt 4 2-/ ZrO 2Catalyst is used for the hydroisomerization reaction of normal heptane, at 200 ℃, the reaction stagnation pressure is 1bar, and the dividing potential drop of normal heptane is 15mbar, and overall flow rate is 40mL/min, reaction 1h afterreaction speed is 0.55 μ mol/gs, and the isomerization product selectivity is 63%, as seen directly uses SO 4 2-/ ZrO 2The selectivity of loaded Pt catalyst in the normal heptane isomerization is not high.
CN1094787 adopts unbodied ZrO (OH) x and H 2WO 4Mechanical mixture is prepared WOx-ZrO 2Solid super acid catalyst, and be used for n-heptane hydroisomerizing reaction, when reaction temperature was respectively 320 ℃ and 400 ℃, the conversion ratio of normal heptane was 44.3% and 48.7%, the simultaneous isomerization product selectivity is respectively 88.9% and 81.4%.As seen this class super acidic catalyst is used for the normal heptane isomerization reaction, though can effectively improve the selectivity of isomerization product, the reaction temperature that needs is still higher.
Summary of the invention
Technical problem to be solved by this invention: provide a kind of prior art that is different from, the higher and stable zeolite-loaded SO of USY that better is used for the n-heptane hydroisomerizing reaction of the selectivity of catalytic activity, isomerization product 4 2-/ ZrO 2And the preparation method who contains the bimetallic catalyst of Pt.
Technical scheme of the present invention is:
The preparation method of the support type super acidic catalyst that a kind of N-alkanes isomerization reaction is used, its concrete preparation process is as follows:
A) zirconates with solubility is dissolved in the deionized water, and being made into concentration is 0.1-1.0mol/L solution, stirs, and adds the USY zeolite, stirs 1-24 hour, mixes; Wherein the addition of zirconates is: ZrO wherein 2Amount account for the 15%-30% of USY zeolite quality;
B) dripping concentration expressed in percentage by weight is the ammoniacal liquor of 5-25%, regulates pH value to 7-11, stirs 5-10 hour, leaves standstill aging 1-24 hour, washs the above-mentioned no zirconates anion that is precipitated to, and descends dry 1-24 hour at 80-150 ℃;
C) be sulfuric acid or the ammonium sulfate dipping of 0.2-2.0mol/L with concentration, descended dry 1-24 hour at 80-150 ℃, at 500-700 ℃ of roasting 1-10 hour;
D) be immersed in the solution that contains precious metals pt or Pd compound and metal promoter compound with conventional infusion process, make the quality percentage composition of precious metals pt in the catalyst or Pd account for the 0.2-2.0% of USY zeolite quality, the mol ratio of metal promoter and noble metal is 0.5-20: 1,80-150 ℃ dry 1-10 hour down, 200-600 ℃ roasting 1-5 hour.
Wherein used zirconates is ZrOCl among the step a 2, Zr (NO 3) 4Or ZrO (NO 3) 2, preferred ZrOCl 2The metal promoter compound is a kind of salt among Al, Cr, Zn, Cu, Zn, Se, Fe or the Sn in the steps d, any nitrate of preferred Al, Cr, Zn, Cu, Zn, Se, Fe or Sn; Preferred size is the above USY zeolites (Zhou village catalyst plant, n (Si)/n (Al)=8.2) of 200 orders; PH value is 8-10 among the step b; The sulfuric acid among the step c or the concentration of ammonium sulfate are 0.5-1.0mol/L, and the catalyst behind sulfuric acid or the ammonium sulfate dipping was at 550-650 ℃ of following roasting 2-5 hour.Wherein the content of noble metal is the heavy % of 0.4-0.8 of USY zeolite quality in the steps d, and the mol ratio of metal promoter and noble metal is 1-8: 1; Noble metal and metal promoter step impregnation or simultaneously the dipping.
Wherein in catalyst preparation process, also can carry out steps d earlier, carry out step c again.
The catalyst that makes with the inventive method is applicable to C 4-C 10The alkane isomerization reaction especially is fit to C 7Hydroisomerization reaction is produced high-octane isoparaffin.
C 7The hydroisomerization reaction condition is: reaction temperature is 150 ℃-350 ℃, and preferred 200 ℃-250 ℃, the mol ratio of hydrogen and feed n-heptane is 5.0-10.0: 1, and weight space velocity is 1.0-10.0h -1
Adopt the catalyst of the present invention's preparation to have higher normal heptane isomerization reaction activity, particularly have the selectivity of higher isomerization product, also have good catalytic stability simultaneously.
Beneficial effect:
(1) adopting the present invention's USY zeolite commonly used in petroleum refining process is carrier, preparation contains the bimetallic catalyst of Pt or Pd and metal promoter, second kind of metal mixes in catalyst, further improve its decentralization, make this catalyst have high specific surface area and effective stability that improves this class super acidic catalyst simultaneously, be 250 ℃ in reaction temperature for example, the mol ratio of hydrogen and feed n-heptane is 5: 1, and the weight space velocity of normal heptane is 2.0h -1, successive reaction 100 hours, the conversion ratio of normal heptane remains on more than 60%, and the isomerization product selectivity is greater than 93% (seeing example 16);
(2) the present invention is in containing the minute amount of noble metal catalyst, introduce other cheap metal promoters, when improving normal heptane isomerization reaction conversion ratio, can obviously improve the selectivity of isomerization product, particularly have high-octane polysubstituted product selectivity (seeing Table 2); Improve the effective rate of utilization of noble metal simultaneously, reduce cost;
(3) method for preparing catalyst provided by the present invention is simple, is convenient to operation, and still is preparation process from the component of catalyst itself no matter, all is free of contamination to environment, has tangible prospects for commercial application.
Description of drawings
Fig. 1: the XRD figure of different catalysts.is cubic phase among the figure, and zero is the monocline phase.
Fig. 2: the conversion ratio of catalyst Q and selectivity graph of a relation.■ is single substitution product yield % among the figure, ● be polysubstituted product yield %, ▲ be isomerization product selectivity %.
Fig. 3: the stability experiment figure of catalyst Q.● be the normal heptane conversion ratio,  is the isomerization product selectivity.
The specific embodiment
Example 1
ZrOCl with 0.48g 28H 2O is dissolved in the deionized water, being made into concentration is 0.2mol/L solution, under the strong agitation, add 2g USY zeolite, stirring mixes it, drip the ammoniacal liquor of 20 heavy %, regulate pH value to 9, continue to stir 10 hours, left standstill aging 12 hours, wash the above-mentioned no chlorion that is precipitated to, drying is 12 hours under 110 ℃.With concentration is the sulfuric acid solution dipping of 0.5mol/L, and drying was 12 hours under 110 ℃, 600 ℃ of roastings 5 hours.Get the 0.033g chromic nitrate and be dissolved in the 6ml water, add the 0.02mol/L chloroplatinic acid of 2.16ml, be made into mixed solution, above-mentioned precursor is ground the back dipping, 110 ℃ dry 10 hours down, catalyst A is made in 500 ℃ of roastings 2 hours, its composition sees Table 7.
The isomerization reaction performance test of catalyst A is to carry out on a cover Continuous Flow actuating miniature catalyst reaction device, raw material is squeezed into vaporizer with the micro-measurement pump, and with enter reactor after hydrogen fully mixes, catalyst (40-60 order) loadings is 0.5g, before catalyst uses in reactor 300 ℃ of in-situ reducing 3 hours, reaction temperature is got 200 ℃, 220 ℃, 230 ℃, 250 ℃ respectively.The GC112 gas chromatograph on-line analysis that product is produced with Shanghai analytical instrument factory, chromatographic column is the SE30 capillary column of 50m * 0.25mm * 0.3 μ m, detector is a flame ionization ditector, product GC-MS (ThermoFinnigan) qualitative analysis.Reaction result sees Table 1.
Comparative Examples 1-4 has investigated the performance with the catalyst of different carriers preparation
Comparative Examples 1
Method for preparing catalyst is consistent with example 1, difference is that used carrier replaces the USY zeolite by Hydrogen ZSM-5 zeolite powder (Catalyst Factory, Nankai Univ), is designated as catalyst A 1, and its composition sees Table 7, the isomerization reaction performance test condition of catalyst B is consistent with example 1, and reaction result sees Table 1.
Comparative Examples 2
Method for preparing catalyst is consistent with example 1, and difference is that used carrier replaces the USY zeolite by SBA-15, is designated as catalyst A 2, and its composition sees Table 7, and the isomerization reaction performance test condition of catalyst B is consistent with example 1, and reaction result sees Table 1.
Comparative Examples 3
Method for preparing catalyst is consistent with example 1, and difference is that used carrier replaces the USY zeolite by HM, is designated as catalyst A 3, and its composition sees Table 7, and the isomerization reaction performance test condition of catalyst B is consistent with example 1, and reaction result sees Table 1.
Comparative Examples 4
Method for preparing catalyst is consistent with example 1, and difference is that used carrier replaces the USY zeolite by H β stone, is designated as catalyst A 4, and its composition sees Table 7, and the isomerization reaction performance test condition of catalyst B is consistent with example 1, and reaction result sees Table 1.
Table 1
Embodiment Catalyst Carrier Normal heptane conversion ratio/weight % Single substitution product rate/weight % Polysubstituted product rate/weight % Isomerization product selectivity/weight %
Example 1 A USY 53.6 35.3 10.6 85.6
Comparative Examples 1 A1 HZSM-5 60.0 7.2 1.0 13.7
Comparative Examples 2 A2 SBA-15 5.7 2.5 0 43.9
Comparative Examples 3 A3 HM 8.2 2.9 0 35.4
Comparative Examples 4 A4 Hβ 12.5 8.3 0 66.4
As can be seen from Table 1, adopt the present invention prepared be that the isomerization performance of catalyst of carrier is best with USY, HZSM-5 is the catalyst of preparing carriers, though conversion ratio very high (60%), but be pyrolysis product mostly, the selectivity of isomerization product very low (13.7%), and other several carrier conversion ratios and selectivity are all very low.
Comparative Examples 5
The preparation method is consistent with example 1, when difference is impregnating metal, carrier impregnation in the 0.02mol/L of 2.16ml platinum acid chloride solution, and is not added second kind of metal promoter, is designated as catalyst B, and its composition sees Table 7.The isomerization reaction performance test condition of catalyst B is consistent with example 1, and reaction result sees Table 2.
Comparative Examples 6
The preparation method is consistent with example 1, and difference is not add the USY zeolite when beginning to stir, and makes catalyst C, and its composition sees Table 7.The isomerization reaction performance test condition of catalyst C is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 2.
Comparative Examples 7
With 2g USY zeolite direct impregnation in example 1 described chloroplatinic acid and chromic nitrate mixed solution, 110 ℃ dry 10 hours down, catalyst D is made in 500 ℃ of roastings 2 hours, its composition sees Table 7.The isomerization reaction performance test condition of catalyst C is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 2.
Table 2
Embodiment Catalyst Reaction temperature/℃ Normal heptane conversion ratio/weight % Single substitution product rate/weight % Polysubstituted product rate/weight % Isomerization product selectivity/weight %
Example 1 A 200 30.0 22.6 5.5 93.5
220 44.3 30.6 8.7 88.9
230 53.6 35.3 10.6 85.6
250 72.1 36.5 13.2 68.9
Comparative Examples 5 B 200 19.2 12.2 3.3 80.5
230 30.6 18.2 4.8 74.8
250 42.1 14.7 6.7 69.6
Comparative Examples 6 C 230 10.8 6.5 0 60.2
Comparative Examples 7 D 230 75.7 19.1 9.0 37.2
Catalyst A is for containing the bimetallic USY load of Pt, Cr super acidic catalyst, the conversion ratio of its n-heptane hydroisomerizing and selectivity are best with respect to the B-D catalyst, in the time of 230 ℃, when conversion ratio reached 53.6%, the isomerization product selectivity reached 85.6%.Catalyst C is pure SZ supported bimetal catalyst, and conversion ratio has only 10.8% in the time of 230 ℃.Catalyst D is the direct supported bimetal catalyst of USY carrier, though its activity very high (75.7%), isomerization product selectivity very low (37.2%), product mostly is pyrolysis product.Catalyst B has been load super acids and precious metals pt, but the catalyst of the second kind of metal promoter that do not mix, its combination property all has greatly improved with respect to catalyst C and catalyst D.When conversion ratio is suitable (42%-44%), relatively find during the performance of catalyst A and B, the conversion ratio of catalyst B is 42.1% o'clock, the reaction temperature that needs is 250 ℃, the selectivity of isomerization product only is 69.6%, and during the conversion ratio 44.3% of catalyst A, the reaction temperature that needs then has only 220 ℃, and the selectivity of isomerization product can be up to 88.9%.Optionally improve and be not only, and polysubstituted isomerization product yield also is significantly improved because single isomerization product yield that replaces improves.This catalyst that proves absolutely that the present invention prepares has the isomerization product selectivity of good low temperature active and Geng Gao, particularly has high-octane polysubstituted product selectivity and is able to obvious raising.
Example 2-3 has compared ZrO 2Content for the influence of catalyst performance of the present invention.
Example 2
The preparation method is consistent with example 1, and difference is with ZrOCl in the example 1 28H 2The consumption of O changes 0.32g into, makes catalyst E, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 3.
Example 3
The preparation method is consistent with example 1, and difference is with ZrOCl in the example 1 28H 2The consumption of O changes 0.96g into, makes catalyst F, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 3.
Table 3
Embodiment Catalyst ZrO 2/ weight % Normal heptane conversion ratio/weight % Single substitution product rate/weight % Polysubstituted product rate/weight % Isomerization product selectivity/weight %
Example 1 A 15 53.6 35.3 10.6 85.6
Example 2 E 10 37.1 25.4 5.2 82.5
Example 3 F 30 30.0 20.5 4.6 83.7
Fig. 1 has provided with the Bruker D8 ADVANCE of company X-ray diffractometer and has measured catalyst A, C, E, the XRD spectra of F and carrier USY, 3 °～50 ° of 2 θ scopes.As can be seen from Figure 1, pure SO 4 2-/ ZrO 2Supported bimetal catalyst C has four directions and two kinds of ZrO of monocline 2Crystalline phase, and with the USY load SO 4 2-/ ZrO 2And the later catalyst A of bimetallic, E, F compares with the XRD of USY carrier, has kept the characteristic peak of USY well, and does not observe ZrO 2, precious metals pt and doping metals Cr oxide characteristic peak occur, even ZrO 2The heavy % of content to 25 do not have ZrO yet 2Characteristic peak occurs, and the catalyst with the present invention's preparation is described, can keep the crystalline structure of USY well, and super acids and metal are disperseed at its apparent height.
Reaction result from table 3 as can be seen, ZrO 2Content is preferably in about 15 heavy %, load capacity too low (10 weight %), and isomerized reaction conversion ratio of normal heptane and selectivity all descend.Load capacity too high (30 weight %), though the selectivity of isomerization product has only descended 2%, conversion ratio declines to a great extent 20%.Example 4-6 has compared in the preparation process pH value to the influence of catalyst performance.
Example 4
The preparation method is consistent with example 1, when difference is dropping ammonia the pH value is transferred to 7, makes catalyst G, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 4.
Example 5
The preparation method is consistent with example 1, when difference is dropping ammonia the pH value is transferred to 8, makes catalyst H, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 4.
Example 6
The preparation method is consistent with example 1, when difference is dropping ammonia the pH value is transferred to 11, makes catalyst I, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 4.
Table 4
Embodiment Catalyst pH Normal heptane conversion ratio/weight % Single substitution product rate/weight % Polysubstituted product rate/weight % Isomerization product selectivity/weight %
Example 1 A 9 53.6 35.3 10.6 85.6
Example 4 G 7 44.7 30.1 6.7 82.1
Example 5 H 8 42.5 29.1 6.2 83.1
Example 6 I 11 31.2 21.3 4.9 83.9
Reaction result from table 4 as can be seen, optimal pH is 9, the pH value is too low or too high, the selectivity of isomerization product slightly descends (about 2%), and is more but the normal heptane conversion ratio descends, when particularly the pH value was too high, conversion ratio descended about 20%.
Example 7-10 has compared the influence of different second kind of metal for catalyst performance of the present invention of mixing.
Example 7
The preparation method is consistent with example 1, and difference is to change chromic nitrate in the example 1 into aluminum nitrate, makes catalyst J, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 5.
Example 8
The preparation method is consistent with example 1, and difference is to change chromic nitrate in the example 1 into lanthanum nitrate, makes catalyst K, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 5.
Example 9
The preparation method is consistent with example 1, and difference is to change chromic nitrate in the example 1 into cerous nitrate, makes catalyst L, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 5.
Example 10
The preparation method is consistent with example 1, and difference is to change chromic nitrate in the example 1 into zinc nitrate, makes catalyst M, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1,230 ℃ of reaction temperatures, and reaction result sees Table 5.
Table 5
Embodiment Catalyst Metal Normal heptane conversion ratio/weight % Single substitution product rate/weight % Polysubstituted product rate/weight % Isomerization product selectivity/weight %
Example 1 A Cr 53.6 35.3 10.6 85.6
Example 7 J Al 56.6 35.6 11.3 82.9
Example 8 K La 46.5 31.1 8.9 86.1
Example 9 L Ce 50.4 33.2 9.4 84.6
Example 10 M Zn 10.2 6.1 1.7 76.9
As can be seen from Table 5, Al has mixed, La, the catalyst of Ce and Cr has reasonable isomerization reaction performance, conversion ratio also has higher selectivity simultaneously, more than 82% all more than 45%, and the isomerization effect of doping of Zn catalyst is poor, and is best with the combination property of the catalyst of doping Cr.Example 11-13 has compared the influence of the amount of the second kind of metal that mix for catalyst performance of the present invention.
Example 11
The preparation method is consistent with example 1, and difference is that the amount with chromic nitrate in the example 1 changes 0.016g into, makes catalyst n, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1, and difference is 230 ℃ of reaction temperatures, and reaction result sees Table 6.
Example 12
The preparation method is consistent with example 1, and difference is that the amount with chromic nitrate in the example 1 changes 0.128g into, makes catalyst O, and its composition sees Table 7.Isomerization reaction performance test condition is consistent with example 1, and difference is 230 ℃ of reaction temperatures, and reaction result sees Table 6.
Example 13
The preparation method is consistent with example 1, and difference is that the amount with chromic nitrate in the example 1 changes 0.24g into, makes catalyst P, and its composition sees Table 1.Isomerization reaction performance test condition is consistent with example 1, and difference is 230 ℃ of reaction temperatures, and reaction result sees Table 6.
Table 6
Embodiment Catalyst Cr∶Pt/ mol∶mol Normal heptane conversion ratio/weight % Single substitution product rate/weight % Polysubstituted product rate/weight % Isomerization product selectivity/weight %
Example 1 A 2∶1 53.6 35.3 10.6 85.6
Example 11 N 1∶1 47.6 31.5 8.7 84.6
Example 12 O 8∶1 43.7 27.9 9.1 84.5
Example 13 P 15∶1 40.5 25.9 8.8 85.7
Table 6 provides is that the mol ratio of Cr and Pt is to normal heptane isomerization reaction Effect on Performance.As can be seen from Table 6, there is optimum value (2: 1) in mol ratio, and the too high or too low normal heptane isomerization reaction performance that all can influence is especially remarkable to the influence of conversion ratio.
Example 14
The preparation method is consistent with example 1, and difference is that the consumption with chloroplatinic acid in the example 1 changes 4.32ml into, and the consumption of chromic nitrate changes 0.128g into, makes catalyst Q, and its composition sees Table 7.For the catalyst that further specifies the present invention preparation has higher isomerization product selectivity, adopt the method identical with example 1, carry out the isomerization reaction performance test of catalyst Q.Change hydrogen and feed n-heptane mol ratio and weight space velocity, make the conversion ratio of normal heptane between 10-75%.Relation between resulting conversion ratio and the selectivity is seen Fig. 2.As can be seen from Figure 2, this class catalyst has very high isomerization selectivity, even conversion ratio reaches 70%, the isomerization product selectivity still has 93%.
Example 15
The acid strength of catalyst A-I is measured with the Hammett indicator method.Indicator comprises para-nitrotoluene (H 0=-11.35), para-nitrochloro-benzene (H 0=-12.70), a nitro Benzene Chloride (H 0=-13.60), 2,4-dinitrofluorobenzene (H 0=-14.52).It the results are shown in Table 7.The result shows that the catalyst that adopts the inventive method to prepare all has superpower acidity.
Example 16
For the catalyst that further specifies the present invention preparation has good stability, adopt the method identical with example 1, carry out the isomerization reaction performance test of catalyst Q.Reaction temperature is 250 ℃, and the mol ratio of hydrogen and feed n-heptane is 5: 1, and the weight space velocity of normal heptane is 2.0h -1, successive reaction 100 hours, the result is as shown in Figure 3.As seen from Figure 3, the conversion ratio of normal heptane remains on more than 60%, and the isomerization product selectivity is reacted running 100 hours greater than 93%, catalyst still has higher activity, further illustrates the prepared catalyst of the inventive method and has good stability.
Table 7
Embodiment Catalyst Acid strength/H 0 Kind of carrier Carrier quality/g ZrO 2/ weight % The pH value Pt/ weight % Auxiliary agent M M∶Pt/mol∶ mol
Example 1 A ＜-12.70 USY 2 15 9 0.4 Cr 2∶1
Comparative Examples 1 A1 ＜-12.70 HZSM-5 2 15 9 0.4 Cr 2∶1
Comparative Examples 2 A2 ＜-12.70 SBA-15 2 15 9 0.4 Cr 2∶1
Comparative Examples 3 A3 ＜-12.70 HM 2 15 9 0.4 Cr 2∶1
Comparative Examples 4 A4 ＜-12.70 Hβ 2 15 9 0.4 Cr 2∶1
Comparative Examples 5 B ＜-12.70 USY 2 15 9 0.4 - -
Comparative Examples 6 C ＜-13.60 - - 100 9 0.4 Cr 2∶1
Comparative Examples 7 D - USY 2 - - 0.4 Cr 2∶1
Example 2 E ＜-12.70 USY 2 20 9 0.4 Cr 2∶1
Example 3 F ＜-12.70 USY 2 30 9 0.4 Cr 2∶1
Example 4 G ＜-12.70 USY 2 15 7 0.4 Cr 2∶1
Example 5 H ＜-12.70 USY 2 15 8 0.4 Cr 2∶1
Example 6 I ＜-12.70 USY 2 15 11 0.4 Cr 2∶1
Example 7 J ＜-12.70 USY 2 15 9 0.4 Al 2∶1
Example 8 K ＜-12.70 USY 2 15 9 0.4 La 2∶1
Example 9 L ＜-12.70 USY 2 15 9 0.4 Fe 2∶1
Example 10 M ＜-12.70 USY 2 15 9 0.4 Zn 2∶1
Example 11 N ＜-12.70 USY 2 15 9 0.4 Cr 1∶1
Example 12 O ＜-12.70 USY 2 15 9 0.4 Cr 8∶1
Example 13 P ＜-12.70 USY 2 15 9 0.4 Cr 15∶1
Example 14 Q ＜-12.70 USY 2 15 9 0.8 Cr 8∶1

Claims (10)

1, a kind of preparation method of n-heptane hydroisomerizing catalyst, its preparation process is as follows:
A) zirconates with solubility is dissolved in the deionized water, and being made into concentration is 0.1-1.0mol/L solution, stirs, and adds the USY zeolite, stirs 1-24 hour, mixes; Wherein the addition of zirconates is: wherein the amount of ZrO2 accounts for the 15%-30% of USY zeolite quality;
B) dripping concentration expressed in percentage by weight is the ammoniacal liquor of 5-25%, regulates pH value to 7-11, stirs 5-10 hour, leaves standstill aging 1-24 hour, washs the above-mentioned no zirconates anion that is precipitated to, and descends dry 1-24 hour at 80-150 ℃;
C) be sulfuric acid or the ammonium sulfate dipping of 0.2-2.0mol/L with concentration, descended dry 1-24 hour at 80-150 ℃, at 500-700 ℃ of roasting 1-10 hour;
D) contain in the solution of precious metals pt or Pd compound and metal promoter compound with conventional infusion process dipping, make the quality percentage composition of precious metals pt in the catalyst or Pd account for the 0.2-2.0% of USY zeolite quality, the mol ratio of metal promoter and noble metal is 0.5-20: 1,80-150 ℃ dry 1-10 hour down, 200-600 ℃ roasting 1-5 hour.
2, preparation method according to claim 1 is characterized in that zirconates used among the step a is ZrOCl 2, Zr (NO 3) 4Or ZrO (NO 3) 2
3, preparation method according to claim 2 is characterized in that zirconates is ZrOCl 2
4, preparation method according to claim 1 is characterized in that metal promoter compound in the steps d is a kind of salt among Al, Cr, Zn, Cu, Zn, Se, Fe or the Sn, any nitrate of preferred Al, Cr, Zn, Cu, Zn, Se, Fe or Sn.
5, preparation method according to claim 1 is characterized in that pH value is 8-10 among the step b.
6, preparation method according to claim 1 is characterized in that the sulfuric acid among the step c or the concentration of ammonium sulfate are 0.5-1.0mol/L.
7, preparation method according to claim 1 is characterized in that catalyst behind sulfuric acid among the step c or the ammonium sulfate dipping was at 550-650 ℃ of following roasting 2-5 hour.
8, preparation method according to claim 1, the content that it is characterized in that noble metal in the steps d is the 0.4-0.8% that accounts for USY zeolite quality, the mol ratio of metal promoter and noble metal is 1-8: 1.
9, preparation method according to claim 1 is characterized in that in the steps d noble metal and metal promoter step impregnation or dipping simultaneously.
10, preparation method according to claim 1 is characterized in that Preparation of Catalyst carries out steps d earlier, carries out step c again.
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CN103611552A (en) * 2013-11-07 2014-03-05 复旦大学 Solid superacid catalyst for n-heptane isomerization reaction and preparation method thereof
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