CN1327960C - Method for preparing solid super strong acid in NO3/metallic oxide system - Google Patents
Method for preparing solid super strong acid in NO3/metallic oxide system Download PDFInfo
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- CN1327960C CN1327960C CNB031264484A CN03126448A CN1327960C CN 1327960 C CN1327960 C CN 1327960C CN B031264484 A CNB031264484 A CN B031264484A CN 03126448 A CN03126448 A CN 03126448A CN 1327960 C CN1327960 C CN 1327960C
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- soluble alkali
- solution
- solid super
- water soluble
- aqueous solution
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Abstract
The present invention relates to a preparation method of solid super acid in an NO3<->/ metal oxide system, which is characterized in that water solution of soluble metal salts with nitrogen and soluble alkali precipitating agents are uniformly mixed, and processed by hydrothermal treatment to obtain the hydrogel of metal salt under closed conditions, the hydrogel is aged and made to stand for delamination, the precipitates on the lower layer are dried and sintered, wherein the soluble alkali precipitating agents are organic or inorganic compounds which can make the water solution not present basic capacity when the soluble alkali precipitating agents are dissolved in water solution at normal temperature, and can make the water solution present basic capacity under hydrothermal conditions. Compared with the prior art, the present invention has the advantages that the method is convenient, and the obtained solid super acid has ultra-fine crystal grains with the length of a plurality of nanometers, and high specific surface area.
Description
Technical field
The invention relates to a kind of preparation method of solid super-strong acid, more specifically say so about a kind of NO
3 -The preparation method of/metal oxide system solid super-strong acid.
Background technology
Super acids is a kind of acid strength (H
0) than 100% sulfuric acid (H
0=-11.94) stronger acid.At room temperature, super acids just can make organic hydrocarbonylation thing carry out reactions such as alkylation, isomerization.Replace present industrial widely used liquid acid with solid super-strong acid and carry out catalytic reaction, can avoid equipment corrosion and environmental pollution, product is easy to separate with catalyst.Therefore, solid super-strong acid is considered to be in one of catalysis material the most rising in the petrochemical industry.
Synthesize SO for the first time from Hino in 1979 and Arata
4 2-/ ZrO
2Since (M.Hino, K.Arata, J.Am.Chem.Soc., 101 (2), 6439 (1979)), SO
4 2-The research work of the solid super-strong acid of/metal oxide type is very active, has reported a variety ofly, comprises the SO of noble metal
4 2-/ oxide type solid super-strong acid (EP 174836, EP 653397, EP 653398, CN 1067393, CN 1093949, CN 1075900 etc.), also useful WO
3, MoO
3Substitute SO
4 2-(catalyst, 1989,31 (6), 477), use B
2O
3Substitute SO
4 2-(H.Matsuhash, etc., Staud.Surf.Sci.Catal., 90 (1994) 251) and obtain WO
3/ ZrO
2, MoO
3/ ZrO
2, B
2O
3/ ZrO
2The report of solid super-strong acid.
SO
4 2-/ ZrO
2Be traditional solid super-strong acid, in many catalytic reactions, show good performance (J.Am.Chem.Soc., 101 (2), 6439,1079; Catal.Rev.Sci.Eng., 38 (2), 329,1996).The ZrO of platinum load
2Catalyst can be used for CO
2Reforming methane prepares in the reaction of synthesis gas (DE 9,400,513).
CN1,229,695A discloses a kind of preparation NO
3 -The preparation method of/metal oxide solid super acids.Be that the aqueous solution of slaine is regulated pH value to 7-11 with ammoniacal liquor, the metal hydroxides of precipitation is through ageing, washing, filtration, drying, dipping HNO
3, step such as roasting makes NO
3 -/ M
xO
yThe solid super-strong acid of system.
Summary of the invention
The purpose of this invention is to provide a kind of simpler NO
3 -The preparation method of/metal oxide system solid super-strong acid.
NO provided by the invention
3 -The preparation method of/metal oxide system solid super-strong acid, it is characterized in that the aqueous solution and the water soluble alkali precipitant mix of solubility nitrogen containing metal salt are carried out the hydrogel that hydrothermal treatment consists obtains slaine evenly, in confined conditions, handle through ageing, standing demix, with lower sediment thing drying, roasting, wherein, said water soluble alkali precipitating reagent is not alkalescence for do not make solution when normal-temperature dissolution is in the aqueous solution, and decomposes the organic or inorganic compound that makes the aqueous solution be alkalescence under hydrothermal condition.
More particularly, the preparation method of super acids provided by the invention may further comprise the steps:
(1) the nitrogen containing metal salt with solubility is mixed with the aqueous solution that concentration is 0.1～10.0 mol, preferred 0.2～5.0 mol, add the water soluble alkali precipitating reagent in same solution, the concentration of alkali precipitation agent is 0.1～5.0 mol, preferred 0.1～4.0 mol;
(2) with the mixed solution of slaine and water soluble alkali precipitating reagent in enclosed system, the reaction that is hydrolyzed under strong mixing and 60～190 ℃ obtains the hydrogel of slaine and carries out ageing and handle;
(3) hydrogel of the slaine after ageing is handled leaves standstill and removes supernatant liquor, with lower sediment thing drying, roasting.
In method provided by the invention, said NO
3 -/ metal oxide system solid super-strong acid consists of NO
3 -/ metal oxide, its weight percent consists of: NO
3 -=0.1～10.0%, metal oxide=99.9～90.0%; Wherein metal oxide is selected from the oxide of the metallic element in periodic table of elements IIB, IVB, VB, VIB, VIIB, VIII family and the group III A, the oxide of elements such as Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Al, Ga preferably wherein.
In the method provided by the invention, the said ageing processing time is 5～100 hours, preferred 12～80 hours; Said dry optimum condition is vacuum drying, and temperature is 45～95 ℃, preferred 50～90 ℃; Said sintering temperature is 200～700 ℃, preferred 300～600 ℃.
In the method provided by the invention, said water soluble alkali precipitating reagent is not for making during in the aqueous solution solution be alkalescence at normal-temperature dissolution, and decomposes the organic or inorganic compound that can make the aqueous solution be alkalescence under hydrothermal condition, and its typical compound is urea (H
2NCONH
2); Urea and nitrogen containing metal salt are dissolved in the same water solution system fully, and when system temperature raises gradually, since 60 ℃, urea has a small amount of decomposition, and more than 100 ℃ the time, urea begins to decomposite ammonia (NH
3), when temperature more than 130 ℃ the time, urea decomposes fully, its ammonia that decomposes fully makes the aqueous solution be strong basicity in the confined reaction system, the hydrolytic precipitation reaction takes place in nitrogen containing metal salt in the strong alkaline aqueous solution medium, the course of reaction of this hydrolytic precipitation is to occur in the very uniform water solution system of a dispersion.
Method provided by the invention is compared with prior art easier, prepared NO
3 -The solid super-strong acid of/metal oxide has the specific area of the ultra-fine grain and the Geng Gao of several nanometers.For example, in embodiment provided by the invention, prepared The grain size size is at 6.0～10.0nm, and specific surface is at 105～141m
2/ g, and according to prior art CN1,229, the grain size of the comparative sample of 695A method preparation is at 22.0～32.0nm, and specific surface is at 64～81m
2/ g.
The specific embodiment
The invention will be further described below by embodiment, but content not thereby limiting the invention.
The acid strength H of prepared sample
0Measure with indicator method.Assay method is as follows: the sample that firm roasting is good is put into measuring cup, and lid is tight, puts into drier and is cooled to room temperature, takes out about 0.3g and puts on the little surface plate, uses the indicator corresponding to different acid strengths to drip on sample, 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 solution of solvent preparation with dried cyclohexane.
Prepared The grain size is calculated (H.P.Klug and L.E.Alexander with the Scherrer method, " X-ray Di ffraction Procedure for Polycrystal line andAmorphous Materials ", 2nd Ed., Wiley, 1974), said Scherrer equation is:
In the formula: λ is the beam wavelength (_) of X-ray target; B is the halfwidth (I of hkj diffraction maximum
MaxWith the radian is unit); θ
BBe 1/2 of 2 θ of hkj diffraction maximum.
The specific area of prepared sample is measured with the nitrogen adsorption method.
Embodiment 1-3
With 20g Zr (NO
3)
45H
2(Tianjin, Tianjin fine chemistry industry research institute of section AR) is dissolved in the 80ml distilled water O, and after stirring treated that solution is limpid fully, being made into concentration was the Zr (NO of 0.74 mol
3)
4Solution.At Zr (NO
3)
4Add 5.0g H in the solution
2NCONH
2-urea (Beijing Yili Fine Chemicals Co., Ltd., AR), stirring and dissolving, the concentration of urea in solution is 1.04 mol.
Pour above-mentioned solution into the 250ml autoclave, be warmed up to 150 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 10.5.Ageing mother liquor under 150 ℃ and hydro-thermal pressure, the time of ageing process is 48 hours.Mother liquor after ageing finishes is outwelled supernatant liquor then through leaving standstill processings in 4 hours, and the lower sediment thing in vacuum drying chamber, in the vacuum of 0.09MPa and 90 ℃ drying 15 hours down, is obtained NO
3 -/ Zr (OH)
4
NO with porphyrize
3 -/ Zr (OH)
4Be divided into three parts, put into muffle furnace respectively at 350,450 and 600 ℃ of air atmosphere roastings 3 hours, the NO that obtains
3 -/ ZrO
2The solid super-strong acid sample is remembered respectively and is made N-Zr-1, N-Zr-2, N-Zr-3.
The acid strength measurement result of N-Zr-1, N-Zr-2, N-Zr-3 is listed in the table 1.Grain size size and specific surface the results are shown in the table 2.
Embodiment 4
With 80g Zr (NO
3)
45H
2O is dissolved in the 80ml distilled water, and after stirring treated that solution is limpid fully, being made into concentration was the Zr (NO of 2.94 mol
3)
4Solution.At Zr (NO
3)
4Add the 20.0g urea in the solution, stirring and dissolving, the concentration of urea in solution is 4.1 mol.
Pour above-mentioned solution into the 250ml autoclave, be warmed up to 130 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 11.9.Ageing mother liquor under 130 ℃ and hydro-thermal pressure, the time of ageing process is 32 hours.Leave standstill, dry identical with embodiment 1 with 450 ℃ of roasting process.The NO that obtains
3 -/ ZrO
2Solid super-strong acid sample note is made N-Zr-4.
N-Zr-4 acid strength measurement result is listed in the table 1, and grain size size and specific surface the results are shown in the table 2.
Embodiment 5
With 20g Ti (NO
3)
4(connection chemical reagent factory AR) is dissolved in the 160ml distilled water in Beijing, after stirring treats that solution is limpid fully.At Ti (NO
3)
4Add 25.0g urea, stirring and dissolving in the solution.Pour above-mentioned solution into the 250ml autoclave, be warmed up to 150 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 11.0.Ageing mother liquor under 150 ℃ and hydro-thermal pressure, the time of ageing process is 30 hours.
Leave standstill, dry identical with embodiment 1 with 450 ℃ of roasting process.The NO that obtains
3 -/ TiO
2Solid super-strong acid sample note is made N-Ti-1.
N-Ti-1 acid strength measurement result is listed in the table 1, and grain size size and specific surface the results are shown in the table 2.
Embodiment 6
With 20g Fe (NO
3)
39H
2O (connection chemical reagent factory AR) is dissolved in the 150ml distilled water in Beijing, stir treat solution dissolve fully limpid after.At Fe (NO
3)
4Add 25.0g urea, stirring and dissolving in the solution.Pour above-mentioned solution into the 250ml autoclave, be warmed up to 150 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 11.8.Ageing mother liquor under 150 ℃ and hydro-thermal pressure, the time of ageing process is 35 hours.
Leave standstill, dry identical with embodiment 1 with 450 ℃ of roasting process.The NO that obtains
3 -/ Fe
2O
3Solid super-strong acid sample note is made N-Fe-1.
N-Fe-1 acid strength measurement result is listed in the table 1, and grain size size and specific surface the results are shown in the table 2.
Embodiment 7
With 20g Cr (NO
3)
39H
2(Beijing Chemical Plant AR) is dissolved in the 160ml distilled water O, after stirring treats that solution is limpid fully.At Cr (NO
3)
4Add 20.0g urea, stirring and dissolving in the solution.Pour above-mentioned solution into the 250ml autoclave, be warmed up to 160 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 11.2.Ageing mother liquor under 150 ℃ and hydro-thermal pressure, the time of ageing process is 30 hours.
Leave standstill, dry identical with embodiment 1 with 450 ℃ of roasting process.The NO that obtains
3 -/ Cr
2O
3Solid super-strong acid sample note is made N-Cr-1.
N-Cr-1 acid strength measurement result is listed in the table 1, and grain size size and specific surface the results are shown in the table 2.
Embodiment 8
With 20g Mn (NO
3)
36H
2(Beijing Chemical Plant AR) is dissolved in the 80ml distilled water O, after stirring treats that solution is limpid fully.At Mn (NO
3)
3Add 25.0g urea, stirring and dissolving in the solution.Pour above-mentioned solution into the 250ml autoclave, be warmed up to 150 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 11.4.Ageing mother liquor under 150 ℃ and hydro-thermal pressure, the time of ageing process is 30 hours.
Leave standstill, dry identical with embodiment 1 with 450 ℃ of roasting process.The NO that obtains
3 -/ MnO
2Solid super-strong acid sample note is made N-Mn-1.
N-Mn-1 acid strength measurement result is listed in the table 1, and grain size size and specific surface the results are shown in the table 2.
Embodiment 9
With 20g V (NO
3)
54H
2(Beijing Chemical Plant AR) is dissolved in the 85ml distilled water O, stirs.At V (NO
3)
5Add 20.0g urea, stirring and dissolving in the solution.Pour above-mentioned solution into the 250ml autoclave, be warmed up to 150 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 11.0.Ageing mother liquor under 150 ℃ and hydro-thermal pressure, the time of ageing process is 35 hours.
Leave standstill, dry identical with embodiment 1 with 450 ℃ of roasting process.The NO that obtains
3 -/ V
2O
5Solid super-strong acid sample note is made N-V-1.
N-V-1 acid strength measurement result is listed in the table 1, and grain size size and specific surface the results are shown in the table 2.
Embodiment 10
With 20g Al (NO
3)
34H
2(Beijing Chemical Plant AR) is dissolved in the 82ml distilled water O, stirs.At Al (NO
3)
3Add 20.0g urea, stirring and dissolving in the solution.Pour above-mentioned solution into the 250ml autoclave, be warmed up to 150 ℃ under strong agitation, this moment, the pH value of gel mother liquor was 11.1.Ageing mother liquor under 150 ℃ and hydro-thermal pressure, the time of ageing process is 32 hours.
Leave standstill, dry identical with embodiment 1 with 450 ℃ of roasting process.The NO that obtains
3 -/ Al
2O
3Solid super-strong acid sample note is made N-Al-1.
N-Al-1 acid strength measurement result is listed in the table 1, and grain size size and specific surface the results are shown in the table 2.
Table 1
| The embodiment numbering | Sample | Acid strength (H 0) | |||
| -11.99 | -12.70 | -13.16 | -13.76 | ||
| 1 | N-Zr-1 | + | + | + | + |
| 2 | N-Zr-2 | + | + | + | + |
| 3 | N-Zr-3 | + | + | + | - |
| 4 | N-Zr-4 | + | + | + | + |
| 5 | N-Ti-1 | + | + | + | + |
| 6 | N-Fe-1 | Sample is a rust, can't measure | |||
| 7 | N-Cr-1 | + | + | + | - |
| 8 | N-Mn-1 | + | + | + | + |
| 9 | N-V-1 | + | + | - | - |
| 10 | N-Al-1 | + | + | + | - |
Annotate :+: indicator discoloration ,-: the indicator nondiscolouring
As can be seen from Table 1, the NO of the inventive method preparation
3 -/ metal oxide system solid super-strong acid, its acid strength all can reach-more than 12.70.
Comparative Examples 1～5
These Comparative Examples are according to CN1,229, and the method for 695A prepares the process of super acids.
Comparative Examples 1～5 prepared comparative sample is that the aqueous solution of nitrogen containing metal salt corresponding in embodiment 1,5,6,7 and 8 is regulated pH value to 9 with ammoniacal liquor, the precipitation metal hydroxides that obtains is through ageing 24 hours, washing, filters, in 100 ℃ of dryings 12 hours, 1M HNO
3Aqueous solution dipping, 700 ℃ of roastings obtain, and the comparative sample numbering is respectively DB-1, DB-2, DB-3, DB-4 and DB-5.
The crystallite dimension and the specific surface of comparative sample see Table 2.
Table 2
| The embodiment numbering | Sample number into spectrum | Crystalline phase | Crystallite dimension, nm | Specific surface, m 2/g |
| 1 | N-Zr-1 | M | 6.0 | 141 |
| Comparative Examples 1 | DB-1 | 22.0 | 81 | |
| 2 | N-Zr-2 | M | 9.0 | 135 |
| 3 | N-Zr-3 | M | 10.0 | 130 |
| 4 | N-Zr-4 | M | 7.0 | 131 |
| 5 | N-Ti-1 | M | 8.0 | 121 |
| Comparative Examples 2 | DB-2 | 29.0 | 72 | |
| 6 | N-Fe-1 | M | 8.0 | 119 |
| Comparative Examples 3 | DB-3 | 28.0 | 67 | |
| 7 | N-Cr-1 | M | 7.0 | 117 |
| Comparative Examples 4 | DB-4 | 30.0 | 70 | |
| 8 | N-Mn-1 | M | 7.0 | 124 |
| Comparative Examples 5 | DB-5 | 32.0 | 64 | |
| 9 | N-V-1 | M | 8.0 | 105 |
| 10 | N-Al-1 | M | 9.0 | 135 |
Annotate: M represents Monoclinic monocline crystalline phase.
Embodiment 11
The solid super-strong acid of example 1～10 preparation is carried out the N content analysis, and calculate NO
3 -Content.
The N content analysis is with the Japanese 3271E of Rigaku Denki Co., Ltd type Xray fluorescence spectrometer, adopts the scanning quantitative approach to measure.
Table 3 is the N and the NO of the prepared solid super-strong acid sample of embodiment 1～10
3 -Content.
Table 3
| The embodiment numbering | Sample number into spectrum | N content, heavy % | NO 3 -Content, heavy % |
| 1 | N-Zr-1 | 1.94 | 8.59 |
| 2 | N-Zr-2 | 1.29 | 5.71 |
| 3 | N-Zr-3 | 0.98 | 4.34 |
| 4 | N-Zr-4 | 2.21 | 9.79 |
| 5 | N-Ti-1 | 1.06 | 4.69 |
| 6 | N-Fe-1 | 1.12 | 4.96 |
| 7 | N-Cr-1 | 0.95 | 4.21 |
| 8 | N-Mn-1 | 0.91 | 4.03 |
| 9 | N-V-1 | 1.05 | 4.68 |
| 10 | N-Al-1 | 0.94 | 4.08 |
Claims (6)
1, a kind of NO
3 -The preparation method of/metal oxide system solid super-strong acid, it is characterized in that the aqueous solution and the water soluble alkali precipitant mix of solubility nitrogen containing metal salt are carried out the hydrogel that hydrothermal treatment consists obtains slaine evenly, in confined conditions, handle through ageing, standing demix, with lower sediment thing drying, roasting, wherein, said water soluble alkali precipitating reagent is not alkalescence for do not make solution when normal-temperature dissolution is in the aqueous solution, and decomposes the organic or inorganic compound that makes the aqueous solution be alkalescence under hydrothermal condition.
2,, it is characterized in that this method comprises the steps: according to the method for claim 1
1. the nitrogen containing metal salt with solubility is mixed with the aqueous solution that concentration is 0.1～10.0 mol, adds the water soluble alkali precipitating reagent in same solution, and the concentration of alkali precipitation agent is 0.1～5.0 mol;
2. with the mixed solution of slaine and water soluble alkali precipitating reagent in enclosed system, the reaction that is hydrolyzed under strong mixing and 60～190 ℃ obtains the hydrogel of slaine and carries out ageing and handle;
The hydrogel of the slaine after 3. ageing being handled leaves standstill removes supernatant liquor, with lower sediment thing drying, roasting.
3, according to the method for claim 1, said solid super-strong acid weight percent consists of: NO
3 -=0.1～10.0%, metal oxide=99.9～90.0%; Wherein metal oxide is selected from the oxide of the metallic element in periodic table of elements IIB, IVB, VB, VIB, VIIB, VIII family and the group III A.
4, according to the method for claim 3, wherein said metal oxide is the oxide of Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Al, Ga.
5, according to the method for claim 2,1. said step is that the nitrogen containing metal salt with solubility is mixed with the aqueous solution that concentration is 0.2～5.0 mol, adds the water soluble alkali precipitating reagent in same solution, and the concentration of alkali precipitation agent is 0.1～4.0 mol.
6, according to the method for one of 1,2 or 5 claims, said water soluble alkali precipitating reagent is a urea.
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|---|---|---|---|
| CNB031264484A CN1327960C (en) | 2003-09-28 | 2003-09-28 | Method for preparing solid super strong acid in NO3/metallic oxide system |
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|---|---|---|---|
| CNB031264484A CN1327960C (en) | 2003-09-28 | 2003-09-28 | Method for preparing solid super strong acid in NO3/metallic oxide system |
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| CN1327960C true CN1327960C (en) | 2007-07-25 |
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| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4769351A (en) * | 1986-05-06 | 1988-09-06 | Chichibu Cement Co., Ltd. | Hydrothermal process for preparing zirconia-alumina base ultra-fine powders of high purity |
| CN1229695A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工总公司 | Solid super-strong acid and its prepn. method |
-
2003
- 2003-09-28 CN CNB031264484A patent/CN1327960C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4769351A (en) * | 1986-05-06 | 1988-09-06 | Chichibu Cement Co., Ltd. | Hydrothermal process for preparing zirconia-alumina base ultra-fine powders of high purity |
| CN1229695A (en) * | 1998-03-20 | 1999-09-29 | 中国石油化工总公司 | Solid super-strong acid and its prepn. method |
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