CN1294029A - Composite catalyst and its preparing process - Google Patents
Composite catalyst and its preparing process Download PDFInfo
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- CN1294029A CN1294029A CN 99122122 CN99122122A CN1294029A CN 1294029 A CN1294029 A CN 1294029A CN 99122122 CN99122122 CN 99122122 CN 99122122 A CN99122122 A CN 99122122A CN 1294029 A CN1294029 A CN 1294029A
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Abstract
A composte catalyst for the oxidization of saturated hydrocarbon and alcohol, epoxydization of olefine, hydroxylation of acrylhydrocarbon, etc is prepared from nm-class silicon molecular sieve with MFI structure (10-91 Wt.%), non-skeleton TiO2 (0.4-3.6) and inorganic oxide through mixing the inorganic oxide or its prepcursor with silicon source, titanium source, ammonium tetra-alkylbromide and alkali and crystallizing. It features high activity.
Description
The invention relates to a kind of compound catalyze material and preparation method thereof, more specifically say so about a kind of compound catalyze material that constitutes by the nano silicone molecular sieve with MFI crystal structure, non-skeleton titanium dioxide and inorganic oxide and preparation method thereof.
USP4410501 has disclosed HTS of MFI structure and preparation method thereof, be to be template agent and alkali source with TPAOH, with colloidal silica or tetraalkyl esters of silicon acis is the silicon source, hydrolyzable titanium compound is the titanium source, they are mixed by certain mole proportioning, with mixture in autoclave under 130～200 ℃ of temperature hydrothermal crystallizing 6～30 days.
The HTS of MFI structure is in the catalytic oxidation system of oxidant as catalyst at hydrogen peroxide, has purposes and superior performance widely.It can be applicable to make the reaction condition gentleness in the reactions such as oxidation, alkene epoxidation, aromatic hydrocarbon hydroxylating, ammoxidation of cyclohexanone of oxidation, alcohol of saturated hydrocarbons, and technology is simple and safe, and is environmentally friendly, and conversion ratio is high and selectivity is good.
USP5354875 discloses a kind of olefin epoxidation process, use be the titanium-silicon molecular sieve catalyst that is carried on the titanium dioxide.The preparation method of this catalysis material is: be template agent and alkali source with the TPAOH, silicon tetraethyl acid esters and tetrabutyl titanate ester are respectively silicon source and titanium source, with the glue mixture in siliceous source, titanium source with mix with the hydrating solution in titanium source dipping and dry titania support after put into autoclave, under 150～200 ℃, the condition of 100～200psig, hydrothermal crystallizing 2～10 days.
USP5736479 has disclosed the composite catalyst of being made up of the HTS of metal oxide and in-situ crystallization generation on metal oxide.Metal oxide is meant TiO
2, SiO
2, ZrO
2, Al
2O
3Or their mixture.HTS accounts for 1～90 heavy % of composite catalyst in the catalyst.This Preparation of catalysts method is: in the presence of template agent TPAOH, the mixture in silicon source and titanium source is deposited on the metal oxide, or fully flood the metal oxide of deposition of silica with titanium compound, 150～200 ℃, self-generated pressure reaction 48～240 hours down in autoclave again.
Liquid phase selective catalytic oxidation reaction generally mostly is DIFFUSION CONTROLLED, so the size of zeolite crystal influences the performance of catalytic oxidation, and crystal grain is more little, and oxidation susceptibility is good more.
J.Chem.Soc.Chem.Commun. (1995) 2259 reported the preparation method of a kind of particle diameter less than the MFI structure molecular screen of 100 nanometers, this method is in containing the solution of ethanol, silicon tetraethyl acid esters, tetraethyl titanate esters, TPAOH is mixed the formation mole consist of 9TPAOH: x TiO
2: 25SiO
2: 404H
2The reactant mixture of O: 100EtOH (0＜x＜1.7) was 100 ℃ of following hydrothermal crystallizings 48 hours.
Do not see the report that has by the catalysis material of the nano silicone molecular sieve (being the molecular sieve of crystallite dimension size) of MFI structure, non-skeleton titanium dioxide and the compound formation of inorganic oxide so far less than 100 nanometers.
The preparation method who the objective of the invention is to provide a kind of nano silicone molecular sieve, non-skeleton titanium dioxide and the compound catalysis material that constitutes of inorganic oxide on the basis of existing technology and this catalysis material is provided by the MFI structure.
Compound catalyze material provided by the invention is made up of the inorganic oxide of the non-skeleton titanium dioxide of nano silicone molecular sieve, 0.4～3.6 (weight) % of the MFI structure of 10.0～91.0 (weight) % and surplus.
The nano silicone molecular sieve that this catalysis material preferred group becomes the MFI structure accounts for 40.0～67.0 (weight) %, and non-skeleton titanium dioxide accounts for 1.0～3.0 (weight) %.
Contained molecular sieve in this compound catalyze material is calculated 550cm by the infrared spectrum (see figure 1)
-1The absorption intensity I at place
550With 450cm
-1The absorption intensity I at place
450Ratio, I
550/ I
450＞0.7, illustrate that molecular sieve exists with the MFI crystal structure; By UV-Raman spectrum (seeing b spectral line among Fig. 2) as can be seen, this compound catalyze material does not characterize the electronic signal that titanium enters the nano zeolite skeleton near 1125cm, illustrates that titanium is present on the zeolite with non-skeleton form; By the transmission electron microscope photo (see figure 3) as can be seen, molecular sieve is a nanometer particle size, and its particle size is below 100nm.More than the compound catalyze material that provides of explanation this method is made up of the nano molecular sieve of MFI structure, non-skeleton titanium dioxide and inorganic oxide.
Wherein said inorganic oxide can be selected from TiO
2, SiO
2, ZrO
2, Al
2O
3Or two or more the mixture in them.
The preparation method of this compound catalyze material provided by the invention is: with the reaction glue of inorganic oxide or its precursor and siliceous source, titanium source, tetraalkyl ammonium bromide (TRABr), ammoniacal liquor or organic amine, according to inorganic oxide: the mixed in molar ratio of silica=0.05～6.75 in the reaction glue was even, 130～180 ℃ of following hydrothermal crystallizings 2～10 days.
The mole of said reaction glue consists of among this preparation method:
SiO
2∶TiO
2∶TRABr∶OH
-∶H
2O=1∶0．01～0．1∶0．05～0．2∶2～4∶40～60。
Inorganic oxide among this preparation method: the mol ratio of the silica of reaction in the glue is preferred 0.5～2.0, the hydrothermal crystallizing condition preferred 150～170 ℃ 5～7 days down.
Said titanium source is organic titanate or inorganic titanium salt.The general formula of organic titanate is (OR
1)
4Ti, R
1Be the alkyl of 2～4 carbon atoms, wherein preferred tetraethyl titanate; Inorganic titanium salt is selected from TiCl
4, TiOCl
2, TiOSO
4Or Ti (SO
4)
2One of, preferred TiCl
4
It is (OR that said silicon source is selected from silica gel, Ludox or general formula
2)
4The organosilicon acid esters of Si, wherein R
2It is the alkyl of 1～4 carbon atom.
The agent of said tetraalkyl ammonium bromide template is selected from one of tetraethyl, tetrapropyl or TBAB, wherein preferred 4-propyl bromide.
Said organic amine is fat amine compound or alcamine compound.
The general formula of fat amine compound wherein is R
3(NH
2)
n, R
3For having the alkyl of 1～4 carbon atom, n=1 or 2, preferred ethamine, n-butylamine, ethylenediamine or one of diamines.
The general formula of alcamine compound wherein is (HOR
4)
mN, R
4For having the alkyl of 1～4 carbon atom, m=1～3, one of preferred MEA, diethanol amine or triethanolamine.
Said inorganic oxide is TiO
2, SiO
2, ZrO
2, Al
2O
3Or two or more the mixture in them, can use their commercially available prod.SiO wherein
2Preferably handle through titanate esters before use, titanate esters can be the said organic titanate as the titanium source in front.
Said with titanate esters treatment S iO
2Method be: with SiO
2After 500～600 ℃ of roastings dehydration in 10～60 minutes, according to SiO
2With the mol ratio of titanate esters 1: 0.01～0.1, adding concentration is 0.01～O.1M titanate esters solution, after stirring, filter, and in 80～120 ℃ of oven dry.
The precursor of said inorganic oxide can be obtained by following method by their hydrolyzable salt:
TiO
2Precursor can obtain the preferred TiCl of said titanium compound by titanium compound hydrolysis in ammoniacal liquor
4, TiOCl
2, TiOSO
4, Ti (SO
4)
2One of, more preferably TiCl wherein
4
SiO
2Precursor can be by silicon compound such as SiCl
4Hydrolysis or silica gel, Ludox and NaOH contact precipitation make.
ZrO
2Precursor can be by zirconium compounds such as ZrOCl
2Or ZrCl
4Hydrolysis obtains, preferred ZrCl
4
Al
2O
3Precursor can obtain by the aluminium salt hydrolysis, said aluminium salt can be AlCl
3Or Al
2(SO
4)
3, preferred Al
2(SO
4)
3
When inorganic oxide is SiO
2And/or TiO
2The time, its precursor also can be by said silicon source and/or the preparation of titanium source that is used for crystallization in front.
Compound catalyze material provided by the invention can be used for the oxidation of saturated hydrocarbons, the reactions such as oxidation, alkene epoxidation, aromatic hydrocarbon hydroxylating, ammoxidation of cyclohexanone of alcohol under common process conditions, can be applicable to especially in the propylene ring oxidation reaction that hydrogen peroxide is an oxidant.When being used for epoxidation Reaction of Alkenes, activity is higher than the HTS of the non-compound MFI structure of prior art.For example, during with catalyst 0.4 gram, in 20 ml methanol, 2 milliliter of 30% hydrogen peroxide, 60 ℃ of temperature, under the reaction condition of 0.7Mpa, provided by the invention with TiO
2For 30,60,90 minutes hydrogen peroxide conversion ratio of the compound catalyze material of inorganic oxide is respectively 61.5%, 92.1%, 99.1%, and the analog value of the HTS of MFI structure only is 39.1%, 74.4%, 97.5%.
The preparation method of this compound catalyze material provided by the invention, crystallization is carried out in the presence of unformed oxide, on the one hand molecular sieve is evenly grown, and has limited growing up of zeolite crystal on the other hand and obtains nanocrystal.
Among the preparation method of this compound catalyze material provided by the invention, use cheap tetraalkyl ammonium bromide (TRABr) to be the template agent, and the ratio of template agent and silicon is low in the reaction glue, its TRABr: SiO
2Only be 0.05～0.2: 1, therefore can reduce the manufacturing cost of this catalysis material.
Fig. 1 is the infrared spectrum of compound catalyze material provided by the invention.
Fig. 2 is the spectrogram of UV-Raman spectrum, and wherein a and b are respectively the spectral line of MFI structure titanium silicon molecular sieve and compound catalyze material provided by the invention.
Fig. 3 is the electromicroscopic photograph of compound catalyze material provided by the invention.
Below will the present invention is further illustrated with example, but content of the present invention is not subjected to the restriction of these examples.
In the following embodiments, the infrared spectrum of compound catalyze material provided by the invention is made by Nicolet-5DX, and UV-Raman spectrum is made by the UV-DL01 ultraviolet Raman spectrometer, and electromicroscopic photograph is made by the JEM-1200EX transmission electron microscope.
Agents useful for same all adopts commercially available chemically pure reagent except that specifying.
Comparative Examples 1
This Comparative Examples is to prepare the MFI structure titanium silicon molecular sieve according to the method that embodiment among the USP4410501 1 discloses.
Get 40ml TPAOH (Japanese Fluka company) and be dissolved in the 80ml distilled water, under 0～5 ℃, slowly splash in the 46ml silicon tetraethyl acid esters, drip off the back and stir 20min, splash into 1.36ml tetraethyl titanate esters, drip off the back and stirred 1 hour.Slowly be warming up to 80 ℃, agitating heating 5 hours adds the 100ml deionized water.Above-mentioned reactant mixture is moved into band teflon-lined autoclave, be warmed up to 175 ℃, crystallization time is 10 days.After crystallization is finished, reactant is taken out, filtration, washing, drying, 540 ℃ of following roastings got product in 6 hours, were numbered V.Catalyst V has the UV-Raman spectral signature shown in the spectral line a among Fig. 2.
Embodiment 1～3 explanation inorganic oxide is TiO
2The preparation of compound catalyze material.
Embodiment 1
19 gram titanium tetrachlorides are dissolved in 30 ml deionized water, this solution slowly adds 50 milliliter 25% ammoniacal liquor under vigorous stirring, the gained white gels is washed with 200 ml deionized water after filtering, 120 ℃ of oven dry down, obtain the precursor titanium hydroxide of 8 gram titanium dioxide.
Get the Ludox (Haiyang Chemical Plant, Qingdao's product) of 23.2 grams 26%, be added dropwise to 25 milliliters of ionized waters and contain aqueous isopropanol 1.3 gram of 20 heavy % titanium tetrachlorides, obtain the homogeneous glue, the precursor titanium hydroxide that adds above-mentioned 8 gram titanium dioxide then, 4-propyl bromide 2.5 gram and 20 milliliters of ammoniacal liquor stir, this mixture is packed in the autoclave 175 ℃ of hydrothermal crystallizings 5 days, through conventional method filtration washing drying, in 540 ℃ of roastings 10 hours, obtaining 14.5 gram inorganic oxides was TiO
2Compound catalyze material, be numbered A.
Compound catalyze material A has the infrared spectrum shown in Fig. 1 spectral line a, the UV-Raman spectral signature among Fig. 2 shown in the spectral line b, and its transmission electron microscope photo is seen a of Fig. 3.
Embodiment 2
0.71 the gram titanium tetrachloride is dissolved in the low amounts of water, makes the precursor titanium hydroxide of 0.3 gram titanium dioxide by embodiment 1 step.
Get the Ludox of 17.3 grams 26%, 4-propyl bromide 3.0 gram and 30 milliliters of ammoniacal liquor, 25 milliliters of ionized waters and contain aqueous isopropanol 1.3 gram of 20 heavy % titanium tetrachlorides, add the precursor titanium hydroxide of above-mentioned 0.3 gram titanium dioxide, stir, this mixture is packed in the 100ml autoclave, 170 ℃ of hydrothermal crystallizings 5 days, through conventional method filtration washing drying, in 540 ℃ of roastings 10 hours, obtaining 4.9 gram inorganic oxides was TiO
2Compound catalyze material, be numbered B.
Compound catalyze material B has the UV-Raman spectral signature shown in the spectral line b among Fig. 2, and a's is similar among its transmission electron microscope photo and Fig. 3.
Embodiment 3
32.2 the gram titanium tetrachloride is dissolved in the low amounts of water, makes the precursor titanium hydroxide of 13.8 gram titanium dioxide by the step of embodiment 1.
Get the Ludox of 17.3 grams 26%, 4-propyl bromide 3.0 gram and 30 milliliters of ammoniacal liquor, 25 ml deionized water and contain aqueous isopropanol 1.3 gram of 20 heavy % titanium tetrachlorides, the precursor titanium hydroxide that adds above-mentioned 13.8 gram titanium dioxide, stir, this mixture is packed in the 100ml autoclave 170 ℃ of hydrothermal crystallizings 5 days, through conventional method filtration washing drying, in 540 ℃ of roastings 10 hours, obtaining 22.5 gram inorganic oxides was TiO
2Compound catalyze material, be numbered C.
Compound catalyze material C has the infrared spectrum shown in Fig. 1 spectral line c, the UV-Raman spectral signature among Fig. 2 shown in the spectral line b, and its transmission electron microscope photo is seen the b of Fig. 3.
Embodiment 4
Present embodiment explanation inorganic oxide is SiO
2The preparation of compound catalyze material.
Get 6 gram white carbon blacks (chemical plant, Shenyang product, trade mark A300), after 540 ℃ of roastings dehydration in 30 minutes, add in 80 milliliters of aqueous isopropanols that contain 0.7 gram butyl titanate, after stirring, filter, 80 ℃ of oven dry.
Get the Ludox of 23.2 grams 26%, add aqueous isopropanol 2 grams that contain 20 (weight) % titanium tetrachloride, the white carbon black that in this solution, adds the above-mentioned processing of 6 grams, add 40 milliliter 25% ammoniacal liquor, 80 ml deionized water and 3.6 gram 4-propyl bromides then and mix, the autoclave of packing into was 165 ℃ of hydrothermal crystallizings 3 days.After product washed drying after filtration, 540 ℃ of roastings 6 hours, obtaining inorganic oxide was SiO
2Compound catalyze material, be numbered D.
Compound catalyze material D has the infrared spectrum shown in Fig. 1 spectral line b, the UV-Raman spectral signature among Fig. 2 shown in the spectral line b, and a of its transmission electron microscope photo and Fig. 3 is similar.
Embodiment 5
Present embodiment explanation inorganic oxide is ZrO
2The preparation of compound catalyze material.
14 gram zirconium chlorides are dissolved in the 50ml deionized water, under agitation slowly add 50ml ammoniacal liquor, stir 30 minutes again, filter, and washing, oven dry obtain the precursor zirconium hydroxide of 8.4 gram zirconium dioxides.
Get the Ludox of 17.3 grams 26%, 4-propyl bromide 3.0 gram and 30 milliliters of ammoniacal liquor, 25 ml deionized water and contain aqueous isopropanol 1.3 gram of 20 heavy % titanium tetrachlorides, add the precursor zirconium hydroxide of above-mentioned 8.4 gram zirconium dioxides, stir, this mixture is packed in the 100ml autoclave, 170 ℃ of hydrothermal crystallizings 5 days, through conventional method filtration washing drying, in 540 ℃ of roastings 10 hours, obtaining 11.5 gram inorganic oxides was ZrO
2Compound catalyze material, be numbered E.
Compound catalyze material E has the infrared spectrum shown in Fig. 1 spectral line d, the UV-Raman spectral signature among Fig. 2 shown in the spectral line b, and a of its transmission electron microscope photo and Fig. 3 is similar.
Embodiment 6
Present embodiment explanation inorganic oxide is Al
2O
3The preparation of compound catalyze material.
50 gram Al
2(SO
4)
318H
2O is dissolved in the 100ml deionized water, under agitation slowly adds 100ml ammoniacal liquor then, stirs 30 minutes, filters, and washing, oven dry make the precursor aluminium hydroxide of 11.8 gram aluminium oxide.
Get the Ludox of 17.3 grams 26%, 4-propyl bromide 3.0 gram and 30 milliliters of ammoniacal liquor, 25 ml deionized water and contain aqueous isopropanol 1.3 gram of 20 heavy % titanium tetrachlorides, add the precursor aluminium hydroxide of above-mentioned 11.8 gram aluminium oxide, stir, this mixture is packed in the 100ml autoclave, 170 ℃ of hydrothermal crystallizings 5 days, through conventional method filtration washing drying, in 540 ℃ of roastings 10 hours, obtaining 15.5 gram inorganic oxides was Al
2O
3Compound catalyze material, be numbered F.
Compound catalyze material F has the infrared spectrum feature shown in Fig. 1 spectral line a, the UV-Raman spectral signature among Fig. 2 shown in the spectral line b, and a of its transmission electron microscope photo and Fig. 3 is similar.
Embodiment 7
Present embodiment explanation inorganic oxide is TiO
2-ZrO
2The preparation of compound catalyze material.
9.5 gram titanium tetrachloride and 7 gram zirconium chlorides are dissolved in respectively in the low amounts of water, make the precursor titanium hydroxide of 4 gram titanium dioxide and the precursor zirconium hydroxide of 4.2 gram zirconium dioxides by above-mentioned steps.
Get the Ludox of 17.3 grams 26%, 4-propyl bromide 3.0 gram and 30 milliliters of ammoniacal liquor, 30 ml deionized water and contain aqueous isopropanol 1.3 gram of 20 (weight) % titanium tetrachloride, add the precursor titanium hydroxide of 4 above-mentioned gram titanium dioxide and the precursor zirconium hydroxide of 4.2 gram zirconium dioxides, stir, this mixture is packed in the 100ml autoclave, 170 ℃ of hydrothermal crystallizings 5 days, through conventional method filtration washing drying, in 540 ℃ of roastings 10 hours, obtaining 14.0 gram inorganic oxides was TiO
2-ZrO
2Compound catalyze material, be numbered G.
Compound catalyze material G has the infrared spectrum feature shown in Fig. 1 spectral line a, the UV-Raman spectral signature among Fig. 2 shown in the spectral line b, and a of its transmission electron microscope photo and Fig. 3 is similar.
Comparative Examples 2
The activity of this Comparative Examples explanation MFI structure titanium silicon molecular sieve in epoxidation reaction of olefines.
In 200 milliliters stainless steel autoclave, add 0.4 gram catalyst V, the hydrogen peroxide of 20 ml methanol and 2 milliliter 30%, stir and feed propylene down, the 0.7MPa that keep-ups pressure, the sampling when reaction time is respectively 30,60,90 minutes, iodimetric analysis hydrogen peroxide conversion ratio.Gained the results are shown in table 1.
Embodiment 8
Present embodiment illustrates the activity of compound catalyze material provided by the invention in epoxidation reaction of olefines.
Substitute V with compound catalyze material A, carry out above-mentioned reaction, reaction result is listed in table 1.
As can be seen, the activity of compound catalyze material provided by the invention in propylene ring oxidation reaction surpassed the MFI structure titanium silicon molecular sieve with the standard method preparation.
Table 1
| The embodiment numbering | The catalysis material numbering | Reaction time (minute) | H 2O 2Conversion ratio % |
| Comparative Examples 2 | ????V | ????30 ????60 ????90 | ????39.1 ????74.4 ????97.5 |
| ?8 | ????A | ????30 ????60 ????90 | ????61.5 ????92.1 ????99.1 |
Claims (16)
1, a kind of compound catalyze material is characterized in that this catalysis material is made up of the non-skeleton titanium dioxide of nano silicone molecular sieve, 0.4～3.6 (weight) % of the MFI structure of 10.0～91.0 (weight) % and the inorganic oxide of surplus.
2, according to the described compound catalyze material of claim 1, the nano silicone molecular sieve of wherein said MFI structure accounts for 40.0～67.0 (weight) %, and non-skeleton titanium dioxide accounts for 1.0～3.0 (weight) %.
3, according to claim 1 or 2 described compound catalyze materials, wherein said inorganic oxide is selected from TiO
2, SiO
2, ZrO
2, Al
2O
3Or two or more the mixture in them.
4, the preparation method of the described compound catalyze material of claim 1, it is characterized in that reaction glue with inorganic oxide or its precursor and siliceous source, titanium source, tetraalkyl ammonium bromide (TRABr), ammoniacal liquor or organic amine, according to inorganic oxide: the mixed in molar ratio of silica=0.05～6.75 in the reaction glue was even, 130～180 ℃ of following hydrothermal crystallizings 2～10 days.
5, according to the described preparation method of claim 4, the mole of wherein said reaction glue consists of SiO
2: TiO
2: TRABr: OH
-: H
2O=1: 0.01～0.1: 0.05～0.2: 2～4: 40～60.
6, according to the described preparation method of claim 4, it is characterized in that according to inorganic oxide: the mixed in molar ratio of silica=0.5～2.0 of reaction in the glue was even, 150～170 ℃ of following hydrothermal crystallizings 5～7 days.
7, according to the described preparation method of claim 4, wherein said titanium source is that general formula is (OR
1)
4The organic titanate of Ti, wherein R
1It is the alkyl of 2～4 carbon atoms.
8, according to the described preparation method of claim 7, wherein said organic titanate is a tetraethyl titanate.
9, according to the described preparation method of claim 4, wherein said titanium source is for being selected from TiCl
4, TiOCl
2, TiOSO
4Or Ti (SO
4)
2One of inorganic titanium salt.
10, according to the described preparation method of claim 4, it is (OR that wherein said silicon source is selected from silica gel, Ludox or general formula
2)
4The organosilicon acid esters of Si, wherein R
2It is the alkyl of 1～4 carbon atom.
11, according to the described preparation method of claim 4, wherein said tetraalkyl ammonium bromide is selected from one of tetraethyl, tetrapropyl or TBAB.
12, according to the described preparation method of claim 11, wherein said tetraalkyl ammonium bromide is a 4-propyl bromide.
13, according to the described preparation method of claim 4, wherein said organic amine is that general formula is R
3(NH
2)
nFat amine compound, R wherein
3For having the alkyl of 1～4 carbon atom, n=1 or 2.
14, according to the described preparation method of claim 13, wherein said fat amine compound is selected from one of ethamine, n-butylamine, ethylenediamine or hexamethylene diamine.
15, according to the described preparation method of claim 4, wherein said organic amine is that general formula is (HOR
4)
mThe alcamine compound of N, wherein R
4For having the alkyl of 1～4 carbon atom, m=1～3.
16, according to the described preparation method of claim 15, wherein said alcamine compound is selected from one of MEA, diethanol amine or triethanolamine.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109847772A (en) * | 2018-12-17 | 2019-06-07 | 中南民族大学 | Ammonia oxidation prepares the special-purpose catalyst and preparation method and purposes to 6-chlorophenyl nitrile |
| CN109876837A (en) * | 2018-12-17 | 2019-06-14 | 中南民族大学 | The special-purpose catalyst and preparation method and purposes of preparing chlorobenzonitrile by using ammoxidation method |
-
1999
- 1999-10-27 CN CN 99122122 patent/CN1128671C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109847772A (en) * | 2018-12-17 | 2019-06-07 | 中南民族大学 | Ammonia oxidation prepares the special-purpose catalyst and preparation method and purposes to 6-chlorophenyl nitrile |
| CN109876837A (en) * | 2018-12-17 | 2019-06-14 | 中南民族大学 | The special-purpose catalyst and preparation method and purposes of preparing chlorobenzonitrile by using ammoxidation method |
| CN109847772B (en) * | 2018-12-17 | 2022-02-18 | 中南民族大学 | Special catalyst for preparing parachlorobenzonitrile by ammoxidation method, preparation method and application |
| CN109876837B (en) * | 2018-12-17 | 2022-02-22 | 中南民族大学 | Special catalyst for preparing o-chlorobenzonitrile by ammoxidation method, preparation method and application thereof |
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