CN1137773C - Solid super acid and its prepn. - Google Patents

Solid super acid and its prepn. Download PDF

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Publication number
CN1137773C
CN1137773C CNB011060212A CN01106021A CN1137773C CN 1137773 C CN1137773 C CN 1137773C CN B011060212 A CNB011060212 A CN B011060212A CN 01106021 A CN01106021 A CN 01106021A CN 1137773 C CN1137773 C CN 1137773C
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solid super
strong acid
noble metal
preparation
described solid
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CN1362283A (en
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段维宇
南军
唐林
李崇慧
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to solid super acid containing noble metals, ZrO2, r-Al2O3 and WO3, and a preparation method thereof. The solid super acid has the following components by weight percentage: 0.1 to 2.0% of noble metal, 15 to 25% of WO3, 33 to 84.4% of ZrO2 and 0.5 to 40% of r-Al2O3, wherein the noble metals comprise Pt and Pd or the mixture of Pt and Pd. The solid super acid in the present invention has an acidity (H0) that can be-13.76 or lower, and is used for catalysts in the process of n-pentane isomerisation reaction. Indicated by results, the solid super acid has high activity and provides a new variety for the field of solid super acids.

Description

A kind of solid super-strong acid and preparation method thereof
The present invention relates to a kind of solid super-strong acid and preparation method thereof, specifically is about a kind of noble metal/ZrO 2-r-Al 2O 3/ WO 3System solid super-strong acid and preparation method thereof.
Super acids is a kind of acid strength (H 0) than 100% sulfuric acid (H 0=-11.94) stronger acid.At room temperature, they just can make the organic hydrocarbon compound carry out reactions such as alkylation, isomerization.The liquid acid that replaces present industrial use with solid super-strong acid is carried out catalytic reaction, can avoid equipment corrosion and environmental pollution, and product is easy to separate with catalyst.Therefore, solid super-strong acid is considered at present at one of rising catalyst of chemical field [Kazusli Arata, Advanced in Catalysis, Vol.37.P165].
From Hino in 1979 and the synthetic for the first time SO of Arata 4 2-/ ZrO 2Since [M.Hino, K.Arata, J.Am.Chem.Soc., 101 (21), 6439 (1979)], SO 4 2-The research of/oxide type solid super-strong acid is very active, has reported a variety ofly, comprises the SO that contains noble metal 4 2-/ oxide type solid super-strong acid [CN1093949A, CN 1075900A, EP 174836, EP 653397, EP 653398 etc.], also useful WO 3, MoO 3Replace SO 4 2-[catalyst, 1989,31 (6), 477] and the WO that obtains 3/ ZrO 2, MoO 3/ ZrO 2Solid super-strong acid, and use Al 2O 3, SiO 2Load ZrO 2Support type zirconia solid super acids [CN1094995A, CN 1229368A].
Support type zirconia solid super acids, Al 2O 3, SiO 2It is zirconic stable to help tetragonal crystal system.For example, if at 600 ℃ of amorphous zirconium hydroxides of roasting or hydrous zirconium oxide(HZO), the formed most of zirconia of crystallization takes place for it is monoclinic.But, through using Al 2O 3, SiO 2Load, then owing to the improvement of crystallization effect, formed crystal of zirconium oxide is a tetragonal crystal system, does not find monoclinic zirconia.And specific area also increases to some extent, and L acid amount is obviously improved.But it lacks the B acid position that helps the low-carbon alkanes isomerization reaction.
WO 3/ ZrO 2, MoO 3/ ZrO 2Solid super-strong acid has improved SO 4 2-/ ZrO 2Catalyst stability is relatively poor, the shortcoming that the catalyst surface sulfate radical easily runs off during high temperature.Use WO 3And MoO 3Replace sulfate radical can obtain the solid super-strong acid of anti-800 ℃ of roastings.SO 4 2-/ ZrO 2Has only L acid position, no B acid position, and WO 3/ ZrO 2, MoO 3/ ZrO 2Existing L is sour on the sample, and the B acid position of a great deal of is also arranged, and this point is to needing the catalytic reaction of sour of B, and is very favourable as the low-carbon alkanes isomerization.But it lacks the enough big enough strong L acid amount that specific area produced again.
Isomerization reaction has very high activity and selectivity to solid super acid catalyst to low-carbon alkanes low temperature, but in high-temperature reaction process, then is very easy to inactivation [Pinna F, Siganoretto M, StrukulG.Catal Lett, 1994,26:339].Gain once reported SO 4 2-/ ZrO 2Face H after carrying Pt 2Use, can suppress inactivation, improve its stability [Garin F.J Catal, 1991,131:199].The existence of Pt makes SO 4 2-/ ZrO 2Catalyst becomes a kind of bifunctional catalyst, is facing H 2The time can make hydrogen be dissociated into hydrogen atom, increase the Bronsted acid amount, reduce carbon deposit.But Pt-SO 4 2-/ ZrO 2Catalyst more lacks enough stable and strong B, L acid amount.
This shows, although above-mentioned catalyst all has its characteristics separately, but still the inevitable limitation that exists separately.Purpose of the present invention is exactly with the organically combination of above-mentioned catalyst characteristics separately, forms a kind of stable tetragonal crystal system zirconia structure, existing B acid position that has, and L acid position, high temperature resistant roasting is arranged again, H is faced in isomerization reaction to low-carbon alkanes low temperature 2Use, can suppress the high activity solid super acid catalyst of inactivation, for solid super-strong acid provides a kind of new kind.
The characteristics of solid super-strong acid of the present invention are: consist of noble metal/ZrO 2-r-Al 2O 3/ WO 3, its weight percent consists of: noble metal=0.1-2.0%, 0.2-1.0% preferably, WO 3=15-25%, 15-20% preferably, ZrO 2=33-84.4%, 59-84.3% preferably, r-Al 2O 3=0.5-40%, preferably 0.5-20%.
Said noble metal is the noble metal that is selected from group VIII, as Pt, Ru, Pd, Ir etc., preferably Pt, Pd or the mixture of the two.
The acid strength of above-mentioned solid super-strong acid can reach H 0=more than-13.76.
The preparation method of solid super-strong acid of the present invention is:
Zirconates is dissolved in the water (preferably deionized water), adds r-Al 2O 3, regulating pH value with ammoniacal liquor is 6-7, generates the zirconium hydroxide coating at carrier surface, then through washing, filter, dry, soak WO 3, drying, roasting, soak noble metal, drying, roasting, H 2Step such as reduce under the atmosphere makes noble metal/ZrO 2-r-Al 2O 3/ WO 3The system super acidic catalyst.
The said zirconates of the present invention is meant the zirconates that energy is water-soluble, as ZrOCl 28H 2O, ZrO (NO 3) 2, Zr (NO 3) 2Deng.
The said zirconates concentration of the present invention is: 10-90w%, preferably 15%-70%.
The said r-Al of the present invention 2O 3Granular size be generally the 80-200 order, 100-200 order preferably.R-Al 2O 3Precursor be Al 2O 3H 2O (false boehmite).
The said WO of the present invention 3The source is (NH 4) 3H 5(H 2(WO 4) 6) H 2The O deionized water solution.
The said noble metal of the present invention is Pt, Pd or the mixture of the two.Said noble metal source is H 2PtCl 6Deionized water solution or with PdCl 2Be dissolved in the H that makes in the hydrochloric acid 2PdCl 4Deionized water solution also can be the mixture of the two.
The concentration of described ammoniacal liquor is: 4%-28%, preferably 8%-20%.
The present invention mentioned soaks WO 3And noble metal, can step impregnation, also can a step dipping, can also soak noble metal earlier, soak WO again 3, after the roasting again at H 2Reduce under the atmosphere.Dipping method can be saturated dipping, also can be the supersaturation dipping.
It is Fe that the said preparation method of the present invention also can be used for oxide 2O 3, TiO 2, SnO 2, or use SiO 2The load oxide, and use MO 3The preparation of the solid super strong acid system of dipping.
During concrete preparation solid super-strong acid of the present invention, can carry out with reference to following steps:
1. zirconates is dissolved in the deionized water, makes the solution that zirconates concentration is 20-80w%;
2. with 80-200 purpose r-Al 2O 3Join in the zirconium salt solution, make ZrO in the catalyst 2Content is 33-84.4w%, r-Al 2O 3Content is 0.5-40w%;
3. under stirring ammoniacal liquor being added drop-wise in the 2 step gains, is 6-7 up to PH, makes carrier surface generate the zirconium hydroxide coating, leaves standstill aging, washing, in 100-120 ℃ of oven dry, obtains uniform zirconium hydroxide-carrier granular;
4. soak WO with saturated infusion process 3, make WO in the catalyst 3Content is the heavy % of 15-25, drying;
5. in 550-750 ℃ of roasting 0.5-5 hour;
6. soak noble metal with saturated infusion process, making in the catalyst bullion content is the heavy % of 0.1-2.0, drying;
7. in 250-550 ℃ of roasting 0.5-3 hour;
8. at H 2Reduced 0.5-2 hour in 200-350 ℃ under the atmosphere.
Noble metal/ZrO provided by the present invention 2-r-Al 2O 3/ WO 3The system solid super-strong acid, its acid strength can reach H 0=more than-13.76.Make pentane carry out isomerization reaction, higher activity is arranged.The present invention provides a kind of new kind for solid super-strong acid.
The following examples will the present invention is described further.
Embodiment 1
With 40gZrOCl 2H 2O (Jiaozhuo, Henan chemical general factory, technical grade descend together) is dissolved in the deionized water, makes to contain ZrOCl 2Be the solution of 40 heavy %, take by weighing 5 gram 140-200 purpose r-Al then 2O 3(the import Germany Ke Diya SB of company powder, its chemical composition is Al 2O 3H 2O (false boehmite) becomes r-Al through 650 ℃ of roastings after 2 hours 2O 3) join in the zirconium salt solution, stirring drips the ammonia spirit of 6 heavy % down, up to PH=6-7, makes carrier surface generate the zirconium hydroxide coating, leaves standstill, wears out 24 hours, is washed till no Cl with deionized water -,, make about 70-80 purpose Zr (OH) in 110 ℃ of dryings 24 hours 4-Al 2O 3Particle.Take by weighing this particulate samples 5 grams, soak 28% weight (NH with saturated infusion process 4) 3H 5(H 2(WO 4) 6) H 225 milliliters of O solution left standstill 5 hours, in 110 ℃ of dryings 24 hours, 650 ℃ of roastings 3 hours, soaked the H of 25 milliliter of 0.1 heavy % with saturated infusion process 2PtCl 6Solution, in 110 ℃ of dryings 24 hours, 550 ℃ give handle 2 hours after in 300 ℃ at H 2Reduction is 1 hour under the atmosphere, makes catalyst A.
Embodiment 2
The preparation method just adds 20 gram r-Al with embodiment 1 2O 3Make catalyst B.
Embodiment 3
The preparation method just soaks 40% weight (NH with embodiment 1 4) 3H 5(H 2(WO 4) 6) H 2O solution makes catalyst C for 25 milliliters.
Embodiment 4
The preparation method just soaks the H of 25 milliliter of 0.5 heavy % with embodiment 1 2PtCl 6Solution makes catalyst D.
Embodiment 5
The preparation method just adds 10 gram r-Al with embodiment 1 2O 3, soak 25 milliliter of 35% weight (NH 4) 3H 5(H 2(WO 4) 6) H 2O solution soaks 25 milliliter of 0.25 H that weighs % 2PtCl 6Solution makes catalyst E.
Embodiment 6
The preparation method just soaks the H of 25 milliliter of 0.25 heavy % with embodiment 5 2PdCl 4Solution makes catalyst F.
Comparative Examples 1
The preparation method does not just add r-Al with embodiment 5 2O 3, do not soak (NH 4) 3H 5(H 2(WO 4) 6) H 2O solution, and flood 25 milliliter of 20% weight (NH 4) 3SO 4Solution makes catalyst G.
Comparative Examples 2
The preparation method does not just add r-Al with embodiment 5 2O 3, do not soak H 2PtCl 6Solution makes catalyst H.
Comparative Examples 3
The preparation method does not just soak (NH with embodiment 5 4) 3H 5(H 2(WO 4) 6) H 2O solution, and flood 25 milliliter of 20% weight (NH 4) 3SO 4Solution does not soak H 2PtCl 6Solution makes catalyst I.
Comparative Examples 4
The preparation method does not just add r-Al with embodiment 5 2O 3, do not soak (NH 4) 3H 5(H 2(WO 4) 6) H 2O solution, and flood 25 milliliter of 20% weight (NH 4) 3SO 4Solution does not soak H 2PtCl 6Solution makes catalyst J.
Embodiment 7
Present embodiment illustrates the acid strength of solid super-strong acid provided by the invention.
The foregoing description 1～6 and Comparative Examples 1～4 solid super-strong acid are carried out acid strength H 0Measure.Assay method is as follows:
Take by weighing above-mentioned sample 1g in 650 ℃ of roastings 2 hours, the sample that roasting is good was put into drier cool 20 minutes, taking out sample moves in the separatory funnel, add the dry good cyclohexane solvent of 15ml rapidly, after shaking up with its mean allocation in five test tubes, drip the indicator corresponding to different acid strengths respectively, concussion is 30 minutes on ultrasonic cleaner, observation sample change color situation.If corresponding to the indicator generation change color of a certain acid strength, show that then sample has this acid strength.Indicator is to be the corresponding solution of 0.3 heavy % of solvent preparation with dried cyclohexane.Table 1 is the acid strength (H of sample 0) measurement result.
Table 1 result shows that solid super-strong acid provided by the invention has the H of being better than 0=-13.76 acid strength is better than the solid super-strong acid of Comparative Examples.
Embodiment 8
Present embodiment illustrates that solid super-strong acid provided by the invention is to n-C 5Isomerization activity.
On continuous reaction apparatus, with n-C 5Be raw material, estimate the isomerization activity of the foregoing description 1～6 and Comparative Examples 1～4 solid super-strong acid.Reaction condition is: 140 ℃ of reaction temperatures, and 2 milliliters of 40-80 order catalyst fillings, the liquid air speed is 1.5 o'clock -1, H 2/ n-C 5Mol ratio is 2.0, reaction pressure 10 kilograms per centimeter 2, get 4 hours analysis data of sample introduction, reaction result sees Table 2.
As can be seen from Table 2: solid super-strong acid n-C provided by the invention 5Conversion ratio be 83.5-85.6 mole %, the isomerization product yield is 80.7-84.1 mole %, obviously is better than the solid super-strong acid of Comparative Examples.
Table 1
Figure C0110602100111
Annotate :+: indicator discoloration
-: the indicator nondiscolouring
±: indicator has variable color slightly but is not obvious
Table 2
Sample number into spectrum Conversion ratio mole % Product distribution (mole %)
Cracking Isomery
A 83.5 2.8 80.7
B 83.9 2.9 81.0
C 84.5 3.1 81.4
D 85.6 2.5 84.1
E 85.1 3.0 82.1
F 85.3 2.9 82.4
G 73.2 0 73.2
H 79.8 1.6 78.2
I 75.3 1.9 73.4
J 70.2 0 70.2

Claims (14)

1. a solid super-strong acid is characterized in that it consists of noble metal/ZrO 2-r-Al 2O 3/ WO 3, its weight percent consists of: noble metal=0.1-2.0%, WO 3=15-25%, ZrO 2=33-84.4%, r-Al 2O 3=0.5-40%.
2. according to the solid super-strong acid of claim 1, it is characterized in that described noble metal is Pt, Pd or the mixture of the two.
3. according to the described solid super-strong acid of claim 1, it is characterized in that the weight percent of described solid super-strong acid consists of: noble metal=0.2-1.0%, WO 3=15-20%, ZrO 2=59-84.3%, r-Al 2O 3=0.5-20% is better.
4, the preparation method of the described solid super-strong acid of claim 1 comprises: zirconates is dissolved in the water, adds r-Al 2O 3, regulating pH value with ammoniacal liquor is 6-7, generates the zirconium hydroxide coating at carrier surface, then through washing, filter, dry, soak WO 3, drying, roasting, soak noble metal, drying, roasting, H 2Reduction makes noble metal/ZrO under the atmosphere 2-r-Al 2O 3/ WO 3The system super acidic catalyst wherein soaks WO 3After sintering temperature be 550～750 ℃, the sintering temperature that soaks behind the noble metal is 250～550 ℃.
5,, it is characterized in that described zirconates is to be selected from ZrOCl according to the preparation method of the described solid super-strong acid of claim 4 28H 2O, ZrO (NO 3) 2, Zr (NO 3) 2In one or more.
6,, it is characterized in that described r-Al according to the preparation method of the described solid super-strong acid of claim 4 2O 3Granular size be the 80-200 order.
7,, it is characterized in that described WO according to the preparation method of the described solid super-strong acid of claim 4 3The source is (NH 4) 3H 5(H 2(WO 4) 6) H 2The O deionized water solution.
8,, it is characterized in that described noble metal is Pt, Pd or the mixture of the two according to the preparation method of the described solid super-strong acid of claim 4.
9,, it is characterized in that described noble metal source is H according to the preparation method of the described solid super-strong acid of claim 4 2PtCl 6Deionized water solution or with PdCl 2Be dissolved in the H that makes in the hydrochloric acid 2PdCl 4Deionized water solution, or the mixture of the two.
10,, it is characterized in that the described WO of soaking according to the preparation method of the described solid super-strong acid of claim 4 3And noble metal, be step impregnation, soak WO earlier 3, after super-dry, roasting, soak noble metal more then.
11,, it is characterized in that the described WO of soaking according to the preparation method of the described solid super-strong acid of claim 4 3And noble metal, be step impregnation, soak noble metal earlier, after super-dry, roasting, soak WO again 3, after the roasting again at H 2Reduce under the atmosphere.
12,, it is characterized in that the described WO of soaking according to the preparation method of the described solid super-strong acid of claim 4 3With the noble metal dipping is to flood in a step, then through super-dry, roasting, H 2Reduction obtains described solid super-strong acid under the atmosphere.
13,, it is characterized in that described dipping method is saturated dipping according to the preparation method of the described solid super-strong acid of claim 4.
14,, it is characterized in that described preparation method's concrete steps are as follows according to the preparation method of the described solid super-strong acid of claim 4:
(1) zirconates is dissolved in the deionized water, makes the solution that zirconates concentration is 10-90w%;
(2) with 80-200 purpose r-Al 2O 3Join in the zirconium salt solution, make ZrO in the catalyst 2Content is 33-84.4w%, r-Al 2O 3Content is 0.5-40w%;
(3) stirring is added drop-wise to ammoniacal liquor down in (2) step gains, is 6-7 up to PH, makes carrier surface generate the zirconium hydroxide coating, leaves standstill aging, washing, in 100-120 ℃ of oven dry, obtains uniform zirconium hydroxide-carrier granular;
(4) soak WO with saturated infusion process 3, make WO in the catalyst 3Content is the heavy % of 15-25, drying;
(5) in 550-750 ℃ of roasting 0.5-5 hour;
(6) soak noble metal with saturated infusion process, making in the catalyst bullion content is the heavy % of 0.1-2.0, drying;
(7) in 250-550 ℃ of roasting 0.5-3 hour;
(8) at H 2Reduced 0.5-2 hour in 200-350 ℃ under the atmosphere.
CNB011060212A 2001-01-05 2001-01-05 Solid super acid and its prepn. Expired - Lifetime CN1137773C (en)

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CN103059911B (en) * 2011-10-18 2015-03-18 中国石油化工股份有限公司 Isomerization reaction method of straight-chain paraffin
CN103055912B (en) * 2011-10-18 2015-07-29 中国石油化工股份有限公司 Solid superacid bifunctional catalyst and preparation method thereof
CN103031133B (en) * 2012-12-27 2014-12-03 余俊杰 Flame-retardant inorganic composition
CN107344124B (en) * 2016-05-06 2020-02-28 中国石油化工股份有限公司 In-situ regeneration method of solid super acidic catalyst
CN108722406B (en) * 2018-06-04 2020-10-23 山东麟丰化工科技有限公司 Tungsten-based catalyst, preparation method and application thereof in isobutane-butylene alkylation reaction

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