CN1073886C - Solid super-strong acid and its prepn. method - Google Patents

Solid super-strong acid and its prepn. method Download PDF

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CN1073886C
CN1073886C CN98100763A CN98100763A CN1073886C CN 1073886 C CN1073886 C CN 1073886C CN 98100763 A CN98100763 A CN 98100763A CN 98100763 A CN98100763 A CN 98100763A CN 1073886 C CN1073886 C CN 1073886C
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solid super
strong acid
preparation
oxide
metal oxide
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CN1229695A (en
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冯铱
何奕工
何鸣元
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

The present invention relates to a solid super acid of an NO3<->/metallic oxide system and a preparation method thereof. The solid super acid comprises components (by weight): 0.1 to 10.0% of NO3<-> and 99.9 to 90.0% of metallic oxide, wherein the metallic oxide is the oxide of a metallic element selected from IIB group, IVB group, VB group, VIB group, VIIB group, VIIIB group and IIIA group of the element periodic table, the oxides of elements of Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Al, Ga, etc. are preferably selected, and the oxides of Ti, Zr, Fe, V, Cr, Mo, W, Mn and Al are particularly preferably selected. The solid super acid provided by the present invention has higher acidity than that of 100% sulfuric acid, the acid strength can reach more than-13.16, n-pentane can carry out isomerizing reaction and cracking reaction, and the solid super acid has higher activity.

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 NO 3 -/ metal oxide system 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.About 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 to be in one of rising catalyst of chemical field.
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 (CN1067393A, CN1093949A, CN1075900A, EP174836, EP653397, EP653398 etc.), also useful WO 3, MoO 3Replace SO 4 2-(catalyst, 1989,31 (6), 477), use B 2O 3Replace SO 4 2-(H.Matsuhash, etc., Stud.Surf.Sci.Catal., 90 (1994) 251) and obtain WO 3/ ZrO 2, MoO 3/ ZrO 2And B 2O 3/ ZrO 2The report of solid super-strong acid.
Known to the inventor, up to the present also there is not NO 3The report of/oxide system solid super-strong acid.
The purpose of this invention is to provide a kind of new solid super-strong acid and preparation method thereof.
It consists of NO solid super-strong acid provided by the present invention 3 -/ metal oxide, its weight percent consists of: NO 3 -=0.1～10.0%, metal oxide=99.9～90.0%; Wherein metal oxide is the oxide that is selected from the metallic element in periodic table of elements II B, IV B, V B, VI B, VII B, VIII family and the group IIIA, the oxide of elements such as Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Al, Ga preferably wherein, particularly preferred is the oxide of Ti, Zr, Fe, V, Cr, Mo, W, Mn and Al.
One of preparation method of said solid super-strong acid provided by the present invention comprises:
(1). with a kind of concentration of salt of said metal is that the aqueous solution of 1～30 heavy % adds the ammoniacal liquor hydrolysis, obtains precipitation of hydroxide, after ageing, washing, filtration, drying, obtains hydroxide;
(2). with (1) gained hydroxide HNO 3Aqueous solution dipping filters and drying, makes products therefrom contain the NO of 0.1～10 heavy % by butt 3 -
(3). with (2) products therefrom in 500～1000 ℃ of roastings 1～4 hour.
The salt of said metal is water-soluble any salt among one of preparation method of solid super-strong acid provided by the present invention.
Can also comprise among one of preparation method of solid super-strong acid provided by the present invention that the said step of repetition (2) is to improve NO 3 -Load capacity.
The preparation method's of said solid super-strong acid provided by the present invention two comprises:
(1). the nitrate of said metal or carbonate are added thermal decomposition obtain corresponding metal oxide;
(2). with (1) gained oxide HNO 3Aqueous solution dipping filters and drying, makes products therefrom contain the NO of 0.1～10 heavy % by butt 3 -
(3). with (2) products therefrom in 500～1000 ℃ of roastings 1～4 hour.
The preparation method of said solid super-strong acid provided by the present invention two in can also comprise that the said step of repetition (2) is to improve NO 3 -Load capacity.
The preparation method's of solid super-strong acid provided by the present invention three comprises:
(1). with commercially available said metal oxide HNO 3Aqueous solution dipping filters and drying, makes products therefrom contain the NO of 0.1～10 heavy % by butt 3 -
(2). with (1) products therefrom in 500～1000 ℃ of roastings 1～4 hour.
The preparation method of said solid super-strong acid provided by the present invention three in can also comprise that the said step of repetition (1) is to improve NO 3 -Load capacity.
NO provided by the present invention 3 -/ oxide system solid super-strong acid has than 100% sulfuric acid (H 0=-11.94) stronger acidity, its acid strength can reach-and more than 13.16, can make pentane carry out isomerization and cracking reaction, and 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 1～3
With 40g ZrOCl 28H 2O (Beijing Chemical Plant, analyze pure, down with) be dissolved in the 400mL distilled water, be stirred to solution limpid fully after, to gained ZrOCl 2Dropping ammonia in the aqueous solution (concentration is 25～28%, and Beijing Yili Fine Chemicals Co., Ltd. produces, and analyzes pure, together following) is until solution PH=9.Stop to stir, still aging 24 hours of room temperature is washed with distilled water to no Cl then -Ion filters, in 100 ℃ of dryings 12 hours, below porphyrize to 100 order, zirconium hydroxide.With this zirconium hydroxide 2MHNO 3Dipping (10mL/g zirconium hydroxide) 1 hour under the aqueous solution room temperature filters, in 100 ℃ of dryings 12 hours, NO 3 -/ zirconium hydroxide is divided equally into three parts with it, respectively 700 ℃, 750 ℃, 800 ℃ roastings 3 hours, gets NO 3 -/ ZrO 2Solid super-strong acid Zr-A, Zr-B, Zr-C.
Embodiment 4～6
With 40g ZrOCl 28H 2O is dissolved in the 400mL distilled water, makes zirconium hydroxide by the same procedure among the embodiment 1～3, and it is divided equally into three parts, uses the HNO of 1M, 4M and dense (65 heavy %) respectively 3Aqueous solution room temperature dipping (10mL/g zirconium hydroxide) 1 hour filters, in 100 ℃ of dryings 12 hours, and 750 ℃ of roastings 3 hours, respectively NO 3 -/ ZrO 2Solid super-strong acid Zr-D, Zr-E, Zr-F.
Embodiment 7
According to the method among the embodiment 1, with 10g ZrOCl 28H 2O is dissolved in the 100mL distilled water, stirs dropping ammonia down, and until solution PH=8, ageing 48 hours is washed to no Cl -, 100 ℃ of dryings 12 hours, porphyrize is used 2M HNO 3Aqueous solution dipping (10mL/g) 1 hour filters, 100 ℃ of dryings 8 hours, 750 ℃ of roastings 3 hours, NO 3 -/ ZrO 2Solid super-strong acid Zr-G.
Embodiment 8
Same procedure by embodiment 7 makes NO 3 -/ ZrO 2Solid super-strong acid Zr-H, different is that dropping ammonia is to solution PH=10.
Embodiment 9
With 50g Fe (NO 3) 39H 2O is dissolved in the 500mL distilled water, be stirred to solution fully limpid after, stop to stir until solution PH=8 to dropping ammonia wherein, room temperature ageing 24 hours is filtered, in 100 ℃ of dryings 12 hours, porphyrize, iron hydroxide, it is used 2M HNO 3Aqueous solution room temperature dipping (10mL/g iron hydroxide) 1 hour filters, 100 ℃ of dryings 12 hours, NO 3 -/ iron hydroxide 600 ℃ of roastings 2 hours, gets NO with it 3 -/ Fe 2O 3Solid super-strong acid Fe-A.
Embodiment 10
With 25g Fe (NO 3) 39H 2O gets Fe 200 ℃ of roastings 5 hours 2O 3It is used 2M HNO 3Aqueous solution dipping (10mL/g) 1 hour filters, 100 ℃ of dryings 10 hours, NO 3 -/ Fe 2O 3, it 600 ℃ of roastings 3 hours, is got NO 3 -/ Fe 2O 3Solid super-strong acid Fe-B.
Embodiment 11
Stir down 50gTiCl 4(connection chemical reagent factory in the Chaoyang District, Beijing City, chemical pure) slowly joining the 500mL temperature is in 0 ℃ the distilled water, get milky white liquid, room temperature leaves standstill and made the solution clarification in 12 hours, stir dropping ammonia in this clarified solution down,, stop to stir until solution PH=8, room temperature ageing 24 hours is washed to no Cl -Ion filters, 100 ℃ of dryings 12 hours, porphyrize, titanium hydroxide 20g, get this titanium hydroxide of 10g (residue 10g stays embodiment 12～13 usefulness) and use 2M HNO 3Aqueous solution room temperature dipping (10mL/g titanium hydroxide) 1 hour filters, 100 ℃ of dryings 12 hours, with it 650 ℃ of roastings 2 hours, NO 3 -/ TiO 2Solid super-strong acid Ti-A.
Embodiment 12～13
With remaining 10g titanium hydroxide 1M HNO among the embodiment 11 3Aqueous solution dipping (10mL/g titanium hydroxide) 1 hour filters, and 100 ℃ of dryings 12 hours are divided equally into two parts with it, respectively 650 ℃, 700 ℃ roastings 3 hours, NO 3 -/ TiO 2Solid super-strong acid Ti-B, Ti-C.
Embodiment 14
With 10g γ-Al 2O 3(Chang Ling oil-refining chemical factory catalyst plant is produced, down together) is put in the beaker, to wherein adding 100mL0.5M HNO 3The aqueous solution filters, 100 ℃ of dryings 12 hours, with it 900 ℃ of roastings 2 hours, NO 3 -/ Al 2O 3Solid super-strong acid Al-A.
Embodiment 15～16
With each 5g γ-Al 2O 3Be put in the beaker, add 50mL1M, 4M HNO respectively 3The aqueous solution filters, and 100 ℃ in dry 8 hours, 900 ℃ of roastings 2 hours, makes NO then 3 -/ Al 2O 3Solid super-strong acid Al-B, Al-C.
Embodiment 17
With 20g Cr (NO 3) 39H 2O (analyze pure, Beijing Chemical Plant) is dissolved in the 200mL distilled water, and it is limpid fully to be stirred to solution, then to slow dropping ammonia wherein, up to the solution pH value is 9, and the room temperature ageing was washed, filtered after 24 hours, and in 100 ℃ of dryings 12 hours, porphyrize was then with the HNO of products therefrom with 1M 3Aqueous solution room temperature dipping (10mL/g) 1 hour filters, 100 ℃ of dryings 12 hours, and, make NO 650 ℃ of roastings 3 hours 3 -/ Cr 2O 3Solid super-strong acid Cr-A.
Embodiment 18
With 20g Mn (NO 3) 26H 2O (analyze pure, Beijing Chemical Plant) is dissolved in the 200mL distilled water, makes NO by the same procedure of embodiment 21 3 -/ MnO solid super-strong acid Mn-A.
Embodiment 19
With 20gNH 4VO 3(analyze pure, Li Jiadian chemical plant, Beijing) is dissolved in the 200mL distilled water, makes NO by the same procedure of embodiment 21 3 -/ V 2O 5Solid super-strong acid V-A.
Embodiment 20
Present embodiment illustrates the acid strength of solid super-strong acid provided by the invention.
With the NO that makes in the above-mentioned example 1～19 3 -Acid strength H is carried out in the acid of/oxide solid super 0Measure.Assay method is as follows:
The sample that firm roasting is good is put into measuring cup, and lid is tight, and it is cool to put into drier, takes out about 0.5g 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 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 and is better than-13.16 acid strength.
Table 1.
Sample -11.99 -12.70 -13.16 -13.76
Zr-A + + + +
Zr-B + + + +
Zr-C + + + +
Zr-D + + + ±
Zr-E + + + +
Zr-F + + + +
Zr-G + + + +
Zr-H + + + -
Al-A + + + +
Al-B + + + ±
Al-C + + + +
Fe-A～B Sample is a rust, can't measure
Ti-A～C It is faint yellow that sample is, and is difficult for judging
Cr-A Sample is yellow, is difficult for judging
Mn-A It is dark that sample is, and can't measure
V-A It is faint yellow that sample is, and is difficult for judging
Annotate :+: indicator discoloration
-: the indicator nondiscolouring
±: indicator has variable color slightly, but not obvious
Embodiment 21
Present embodiment illustrates the n-pentane reaction performance of solid super-strong acid provided by the invention.
The solid super-strong acid of above-mentioned example 1～19 preparation is carried out n-pentane isomerization and cracking reaction.Reaction method is a static little reactor of the 0.5g sample being put into about 3mL, injects 5 μ L pentanes, leaves standstill reaction at 40 ℃, after certain reaction time, takes out product and analyzes with chromatogram.Table 2 has been listed the n-pentane reaction situation of each sample.
Embodiment 22
Present embodiment illustrates the NO of solid super-strong acid provided by the invention 3 -Content data.
The solid super-strong acid of above-mentioned example 1～19 preparation is carried out the N analysis on Content, and calculate NO 3 -Content.The N analysis on Content is analyzed with REN-1 type apparatus for nitrogen examination.Table 3 has been listed the N and the NO of each sample 3 -Content.
Table 2.
Sample Reaction time (h) Conversion ratio (%) Product distribution (%)
Cracking Isomerization
Zr-A 47 9.65 5.51 4.14
Zr-B 47 31.72 24.38 7.34
Zr-C 46 19.73 13.97 5.76
Zr-D 48 8.16 4.00 4.16
Zr-E 48 11.03 5.83 5.20
Zr-F 48 10.80 5.66 5.14
Zr-G 50 26.13 17.60 8.53
Zr-H 50 17.33 12.91 4.42
Ti-A 51 7.90 3.78 4.12
Ti-B 51 10.01 5.60 4.41
Ti-C 51 5.36 3.37 1.99
Fe-A 43 9.73 4.01 5.27
Fe-B 46 5.95 3.66 2.29
Al-A 48 5.65 2.28 3.37
Al-B 47 6.77 2.03 4.74
Al-C 47 6.16 2.19 3.97
Cr-A 52 11.45 6.91 4.54
Mn-A 52 9.44 5.37 4.07
V-A 51 11.21 6.53 4.68
Table 3.
Sample N content (W%) NO 3 -Content (W%)
Zr-A 0.57 2.52
Zr-B 0.42 1.86
Zr-C 0.30 1.33
Zr-D 0.35 1.55
Zr-E 0.59 2.61
Zr-F 1.03 4.51
Zr-G 0.55 2.44
Zr-H 0.58 2.57
Ti-A 0.86 3.81
Ti-B 1.01 4.47
Ti-C 0.87 3.85
Fe-A 0.75 3.32
Fe-B 0.42 1.86
Al-A 0.21 0.93
Al-B 0.25 1.11
Al-C 0.37 1.64
Cr-A 0.73 3.23
Mn-A 0.70 3.10
V-A 0.76 3.37

Claims (10)

1. a solid super-strong acid is characterized in that it 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 the oxide that is selected from the metallic element in periodic table of elements II B, IV B, V B, VI B, VII B, VIII family and the group IIIA.
2. according to the solid super-strong acid of claim 1, wherein said metal oxide is the oxide of Zn, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Al or Ga.
3. according to the solid super-strong acid of claim 1, wherein said metal oxide is the oxide of Ti, Zr, Fe, V, Cr, Mo, W, Mn or Al.
4. the preparation method of the described solid super-strong acid of claim 1 is characterized in that this method comprises:
(1). with a kind of concentration of salt of said metal is that the aqueous solution of 1～30 heavy % adds the ammoniacal liquor hydrolysis, obtains precipitation of hydroxide, after ageing, washing, filtration, drying, obtains hydroxide;
(2). with (1) gained hydroxide HNO 3Aqueous solution dipping filters and drying, makes products therefrom contain the NO of 0.1～10 heavy % by butt 3 -
(3). with (2) products therefrom in 500～1000 ℃ of roastings 1～4 hour.
5. according to the preparation method of claim 4, wherein the salt of said metal is water-soluble salt.
6. according to the preparation method of claim 4, comprise also that wherein the said step of repetition (2) is to improve NO 3 -Load capacity.
7. the preparation method of the described solid super-strong acid of claim 1 is characterized in that this method comprises:
(1). the nitrate of said metal or carbonate are added thermal decomposition obtain corresponding metal oxide;
(2). with (1) gained oxide HNO 3Aqueous solution dipping filters and drying, makes products therefrom contain the NO of 0.1～10 heavy % by butt 3 -
(3). with (2) products therefrom in 500～1000 ℃ of roastings 1～4 hour.
8. according to the preparation method of claim 7, comprise also that wherein the said step of repetition (2) is to improve NO 3 -Load capacity.
9. the preparation method of the described solid super-strong acid of claim 1 is characterized in that this method comprises:
(1). with commercially available said metal oxide HNO 3Aqueous solution dipping filters and drying, makes products therefrom contain the NO of 0.1～10 heavy % by butt 3 -
(2). with (1) products therefrom in 500～1000 ℃ of roastings 1～4 hour.
10. according to the preparation method of claim 9, comprise also that wherein the said step of repetition (2) is to improve NO 3 -Load capacity.
CN98100763A 1998-03-20 1998-03-20 Solid super-strong acid and its prepn. method Expired - Lifetime CN1073886C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1651118B (en) * 1996-06-05 2010-05-26 世嘉股份有限公司 Image processor for a game

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CN1327960C (en) * 2003-09-28 2007-07-25 中国石油化工股份有限公司 Method for preparing solid super strong acid in NO3/metallic oxide system
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
CN112007665B (en) * 2019-11-22 2023-08-04 南京林业大学 High-activity sulfuric acid-promoted solid super-strong composite acid and preparation method thereof

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Publication number Priority date Publication date Assignee Title
JPS5945391A (en) * 1982-09-07 1984-03-14 Nippon Mining Co Ltd Purification of slack wax
CN1093949A (en) * 1993-04-23 1994-10-26 中国石油化工总公司 Noble metal/zirconia/S0 42-The preparation method of system super acids
JPH0769955A (en) * 1993-08-27 1995-03-14 Inoue Koryo Seizosho:Kk Production of acetal
JPH1175946A (en) * 1997-09-09 1999-03-23 Takahashi Kanamono Corp Attaching structure for shelf

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5945391A (en) * 1982-09-07 1984-03-14 Nippon Mining Co Ltd Purification of slack wax
CN1093949A (en) * 1993-04-23 1994-10-26 中国石油化工总公司 Noble metal/zirconia/S0 42-The preparation method of system super acids
JPH0769955A (en) * 1993-08-27 1995-03-14 Inoue Koryo Seizosho:Kk Production of acetal
JPH1175946A (en) * 1997-09-09 1999-03-23 Takahashi Kanamono Corp Attaching structure for shelf

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1651118B (en) * 1996-06-05 2010-05-26 世嘉股份有限公司 Image processor for a game

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