CN105618083A - Application of adjuvant-containing catalyst in selective hydrogenation reaction of aromatic nitro compound - Google Patents
Application of adjuvant-containing catalyst in selective hydrogenation reaction of aromatic nitro compound Download PDFInfo
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Abstract
An application of an adjuvant-containing catalyst in a selective hydrogenation reaction of an aromatic nitro compound is disclosed. active components of the catalyst are one or more than two of Group VIII or IB metals; a carrier is iron oxide; and content of the active components is 0.01-50%. By the addition of the adjuvant alkali metal, aromatic nitro compound hydrogenation selectivity of the catalyst can be remarkably raised. In comparison with existing industrial synthetic process of aromatic nitro compound selective hydrogenation, the invention has the following remarkable advantages: reaction process is green and environmentally friendly; operation is simple; and cost is saved.
Description
Technical field
The present invention relates to containing the application in aromatic nitro compound selective hydrogenation reaction of the auxiliary agent catalyst.
Background technology
Aromatic nitro compound selective hydrogenation obtains corresponding functionalization aniline important application in many aspects, such as in pesticide, medicine, dyestuff and high molecular polymer etc. Hydrogenation for simple aromatic nitro compound, industrially there is the technology of maturation, but during for group that substituent group is reducibility, when existing such as carbon-carbon double bond, triple carbon-carbon bonds C=O bond, carbon nitrogen three key etc., optionally by nitroreduction, and retain double bond and be not hydrogenated, an or challenging problem. Industrially, for the selective hydrogenation of the aromatic nitro compound containing reducibility group, it is generally adopted the reducing agent of metering, as adopted Na2S2O4, ammonia adds Fe, Zn, Sn etc. as reducing agent, but such reducing agent, while obtaining the target product of a mole, produce the garbage of a mole to I haven't seen you for ages, in order to overcome this shortcoming, researcheres are with hydrogen for reducing agent, by PbO or H3PO2Add on loaded Pt catalyst, although reduce activity, but the selectivity for target product improves, but such catalyst can produce phenylhydroxylamine intermediate product, though this by-product under very low level it can also happen that blast danger. Researcher discovery is separately added into iron salt in this catalyst system and catalyzing or this intermediate product can be converted into target product by vitriol salt, but remains substantial amounts of transition metal salt, follow-up complex disposal process in solution after reaction, is not very economical and environmental protection. Therefore one is found for this kind of anti-emergency requirement and there is high activity, high selective heterogeneous catalyst.
Many patents and document describe selective hydrogenation load type gold and the platinum catalyst of aromatic nitro compound, and different with carrier and preparation method, its activity is also not quite similar.
Document 1 (WO2007116111-A1) finds Au/TiO2And Au/Fe2O3Catalyst shows good selectivity in the selective hydrogenation of aromatic nitro compound, and the nitro that the high selective reason of author investigation discovery is aromatic nitro compound can be preferentially adsorbed on Au and TiO2The interface of carrier, so that nitro is preferentially reduced, shows high selectivity.
Document 2 (J.Phys.Chem.C2009,113,17803 17810) is prepared for Au/Al by the method for sol deposition2O3Catalyst, equally to showing good selectivity and specific activity Au/TiO in such selective hydrogenation2High. But the shortcoming of Au catalyst is that the dissociation capability to hydrogen is poor, and the condition therefore reacted is all harsher, and reaction temperature is more than 100 DEG C, and pressure is also at more than 1Mp.
Document 3 (Adv.Synth.Catal.2011,353,1,260 1264) adopts one kettle way to be prepared for a kind of porous ion copolymer and supports Pt catalyst, and the loading of Pt is 4.9wt%, and the Pt Nanoparticle Size obtained is 2-4nm. It is at room temperature R=F, Cl, Br, I, CHO, CN, NH to substituent group2��CH3CO, OH etc. show high activity and selectivity, but are-C=C-for substituent group, and the selectivity shown is very low.
Document 4 (JournalofCatalysis265 (2009) 19 25) utilizes Au catalyst to have high selectivity for aromatic nitro compound, and Pt is the metal that a kind of hydrogenation activity is good, the two respective characteristic is combined, in such reaction, phenotype has gone out good cooperative effect, and author is at Au/TiO2Catalyst mixes 0.01%Pt, at 85 DEG C, 8barPH2The selectivity of 94.5% conversion ratio and 93.4% can be obtained under reaction condition.
Document 5 (WO2009071727) adopts infusion process to be prepared for Pt/TiO2Catalyst, at 40 DEG C, 3barPH2Reaction condition under, in the selective hydrogenation for 3-nitrostyrolene, when loading is 0.2%, it is necessary to reaction 7h could be able to obtain 92% productivity, selectivity is 93.1%.
Summary of the invention
It is an object of the invention to, by the alkali-metal interpolation of auxiliary agent, change the electronic property of catalyst, thus significantly improving the selectivity that aromatic nitro compound is hydrogenated with by catalyst, reaction condition is gentle, and catalyst stability is good, and has magnetic, easy to be recycled, easy and simple to handle. For achieving the above object, technical scheme provided by the invention is:
Containing the application in aromatic nitro compound selective hydrogenation reaction of the auxiliary agent catalyst, it is characterized in that: the active component of described catalyst is one or two or more kinds in VIII race or I B race metal, with alkali metal for auxiliary agent, carrier is ferrum oxide, active component and auxiliary agent support jointly on carrier, in catalyst, the mass content of active component is 0.5%-50%, and in catalyst, the mass content of auxiliary agent is 0.01%-40%.
Active component is one or two or more kinds in Pt, Pd and Ni, and active component content is 0.01-20wt%.
Alkali metal is one or two or more kinds in lithium, sodium and potassium, and in catalyst, the mass content of auxiliary agent is 0.01-20wt%.
The first preparation process is as follows:
1) metal active constituent solubility precursor and ferric nitrate are made into mixed aqueous solution, are designated as solution A, concentration 1 �� 10-4The ammonium carbonate solution of-1mol/L is designated as solution B; Metal active constituent solubility precursor concentration 0.1-50mg/ml in solution A, iron nitrate concentration 0.1-1mol/L;
2) solution B stirs at 50 DEG C-100 DEG C, is added drop-wise in solution B by solution A; Solution A and solution B volume ratio 0.001-1000;
3) after continuing stirring after completion of dropwise addition at 50 DEG C of-100 DEG C of temperature 1-10 hour, then 1-10 hour is stood;
4) after standing terminates, separating solid, solid deionized water sucking filtration, by solid drying;
5) dried solid catalyst is ground, impregnate alkali metal soln;
6) being dried by the catalyst after dipping alkali metal soln, baking temperature is 25-120 DEG C, and drying time is 1-24 hour; Dried solid carries out roasting, and sintering temperature is 200 DEG C-800 DEG C, and roasting time is 1-24 hour;
Described alkali metal soln be alkali-metal carbonate, nitrate, chlorate and sodium hydroxide, potassium hydroxide, Lithium hydrate etc. one or two or more kinds;
The concentration of described alkali metal soln is 0.001mol/L-10mol/L;
7) catalyst both passes through reduction treatment before being used for reaction, and reducing atmosphere is the gaseous mixture of hydrogen or the hydrogen volume concentration hydrogen be more than or equal to 10% and noble gas, and reduction temperature is 50 DEG C-800 DEG C, recovery time 10-120min.
The second preparation process is as follows,
1) metal active constituent solubility precursor and ferric nitrate are made into mixed solution, are designated as solution A, concentration 1 �� 10-4The ammonium carbonate solution of-1mol/L is designated as solution B; Metal active constituent solubility precursor concentration 0.1-50mg/ml in solution A, iron nitrate concentration 0.1-1mol/L.
2) solution B stirs at 50 DEG C-100 DEG C, is added drop-wise in solution B by solution A; Solution A and solution B volume ratio 0.001-1000;
3) after continuing stirring after completion of dropwise addition at 50 DEG C of-100 DEG C of temperature 1-10 hour, then 1-10 hour is stood;
4) after standing terminates, separating solid, solid deionized water sucking filtration, by solid drying, dried solid carries out roasting, and sintering temperature is 200 DEG C-800 DEG C, and roasting time is 1-24 hour;
5) solid catalyst after roasting is ground, impregnate alkali metal soln;
6) being dried by the catalyst after dipping alkali metal soln, baking temperature is 25-120 DEG C, and drying time is 1-24 hour; Dried solid carries out roasting, and sintering temperature is 200 DEG C-800 DEG C, and roasting time is 1-24 hour;
Described alkali metal soln be alkali-metal carbonate, nitrate, chlorate and sodium hydroxide, potassium hydroxide, Lithium hydrate etc. one or two or more kinds;
The concentration of described alkali metal soln is 0.001mol/L-10mol/L;
7) catalyst both passes through reduction treatment before being used for reaction, and reducing atmosphere is the gaseous mixture of hydrogen or the hydrogen volume concentration hydrogen be more than or equal to 10% and noble gas, and reduction temperature is 50 DEG C-800 DEG C, recovery time 10-120min.
Reacting in airtight autoclave and carry out, in reactor, initial pressure during hydrogen room temperature is 0.1-5Mpa, and reaction temperature is 20-150 DEG C, and the response time was no less than 10 minutes.
Described reacting in solvent carries out, and the solvent adopted is one or two or more kinds in ethanol, methanol, toluene, oxolane, dodecane, water, reactant liquor concentration of substrate 0.001-10mol/L;
Reaction substrate is aromatic nitro compoundSubstituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-5; Or reaction substrate isIn one, substituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-4.
The mol ratio of catalyst activity component and reaction substrate is 1 �� 10-4Between 1.
Preferred reaction temperature is 20-80 DEG C, the preferred initial pressure 0.1-1.5Mpa of hydrogen in reactor under room temperature, it is preferable that response time 0.5h-3h.
Catalyst can recycle more than 2 times, and its conversion ratio and selectivity are not decreased obviously, and catalyst easily separates with reaction solution.
The activity test method of catalyst provided by the invention is as follows:
Reactor is autoclave, reaction substrate becomes certain density reactant liquor with interior standard configuration, and every secondary response pipet takes a certain amount of reactant liquor and reacts, and in reactor, initial pressure during hydrogen room temperature is 0.1-5Mpa, reaction temperature is 20-150 DEG C, and the response time was no less than 10 minutes. After reaction end is cooled to room temperature, sampling carries out gas chromatographic analysis.
The present invention has the effect that
1. aromatic nitro compound selective hydrogenation obtains corresponding function aniline has application at numerous areas, such as agricultural, medicine, dyestuff and high molecular polymer etc. The present invention provides the alkali-metal catalyst of interpolation highly selective catalysis can obtain functionalization aniline.
2. the present invention provides the alkali-metal catalyst of interpolation in the reaction of aromatic nitro compound selective hydrogenation, can recycle more than 2 times, and activity does not substantially reduce.
3. catalyst provided by the invention is after the reaction, it is easy to separate from reaction solution, easy and simple to handle.
In a word, present invention achieves aromatic nitro compound selective conversion efficient, high and prepare functionalization aniline, compared with existing industrial catalyst system, catalyst provided by the invention is green friendly in the process of this kind of reaction, save cost, be expected to industrially be applied.
Detailed description of the invention
In following embodiment, X is 1,4/3 or 3/2;
Embodiment 1: taking the ammonium carbonate of 3.5g in the deionized water of 60mL, gained solution is designated as solution A. Take the iron nitrate solution of 20mL1M in beaker, add 9mL14.8mgPtThe H of/ml2PtCl6Solution, stirs, and gained solution is designated as solution B. Solution A being stirred under 50 DEG C of water-baths, solution B is added drop-wise in solution A with the speed of 1mL/min. After continuing stirring after completion of dropwise addition at identical temperature 3 hours, then stand 3 hours. After 500mL deionized water sucking filtration, 60 DEG C of oven drying 5h, in 400 DEG C of roasting 5h of Muffle furnace after taking-up, obtain 2.16%Pt/FeO��Catalyst.
Embodiment 2: taking the ammonium carbonate of 3.5g in the deionized water of 60mL, gained solution is designated as solution A. Take the iron nitrate solution of 20mL1M in beaker, add 9mL14.8mgPtThe H of/ml2PtCl6Solution, stirs, and gained solution is designated as solution B. Solution A being stirred under 50 DEG C of water-baths, solution B is added drop-wise in solution A with the speed of 1mL/min. After continuing stirring after completion of dropwise addition at identical temperature 3 hours, then stand 3 hours. After 500mL deionized water sucking filtration, 60 DEG C of oven drying 5h, grind after taking-up. Weigh 0.0075g sodium nitrate to be dissolved in 0.3g deionized water, weigh the catalyst after 0.4g grinds and add in sodium nitrate solution, with 60 DEG C of dry 5h after stirring, then at 400 DEG C of roasting 5h of Muffle furnace, obtain 0.75%Na-Pt/FeO��Catalyst.
Embodiment 3: taking the ammonium carbonate of 3.5g in the deionized water of 60mL, gained solution is designated as solution A. Take the iron nitrate solution of 20mL1M in beaker, add 9mL14.8mgPtThe H of/ml2PtCl6Solution, stirs, and gained solution is designated as solution B. Solution A being stirred under 50 DEG C of water-baths, solution B is added drop-wise in solution A with the speed of 1mL/min. After continuing stirring after completion of dropwise addition at identical temperature 3 hours, then stand 3 hours. After 500mL deionized water sucking filtration, 60 DEG C of oven drying 5h, grind after taking-up. Weigh 0.015g sodium nitrate to be dissolved in 0.3g deionized water, weigh the catalyst after 0.4g grinds and add in sodium nitrate solution, with 60 DEG C of dry 5h after stirring, then at 400 DEG C of roasting 5h of Muffle furnace, obtain 1.75%Na-Pt/FeO��Catalyst.
Embodiment 4: taking the ammonium carbonate of 3.5g in the deionized water of 60mL, gained solution is designated as solution A. Take the iron nitrate solution of 20mL1M in beaker, add 9mL14.8mgPtThe H of/ml2PtCl6Solution, stirs, and gained solution is designated as solution B. Solution A being stirred under 50 DEG C of water-baths, solution B is added drop-wise in solution A with the speed of 1mL/min. After continuing stirring after completion of dropwise addition at identical temperature 3 hours, then stand 3 hours. After 500mL deionized water sucking filtration, 60 DEG C of oven drying 5h, grind after taking-up. Weigh 0.03g sodium nitrate to be dissolved in 0.3g deionized water, weigh the catalyst after 0.4g grinds and add in sodium nitrate solution, with 60 DEG C of dry 5h after stirring, then at 400 DEG C of roasting 5h of Muffle furnace, obtain 3.0%Na-Pt/FeO��Catalyst.
Embodiment 5: taking the ammonium carbonate of 3.5g in the deionized water of 60mL, gained solution is designated as solution A. Take the iron nitrate solution of 20mL1M in beaker, add 9mL14.8mgPtThe H of/ml2PtCl6Solution, stirs, and gained solution is designated as solution B. Solution A being stirred under 50 DEG C of water-baths, solution B is added drop-wise in solution A with the speed of 1mL/min. After continuing stirring after completion of dropwise addition at identical temperature 3 hours, then stand 3 hours. After 500mL deionized water sucking filtration, 60 DEG C of oven drying 5h, grind after taking-up. Weigh 0.05g sodium nitrate to be dissolved in 0.3g deionized water, weigh the catalyst after 0.4g grinds and add in sodium nitrate solution, with 60 DEG C of dry 5h after stirring, then at 400 DEG C of roasting 5h of Muffle furnace, obtain 5.0%Na-Pt/FeO��Catalyst.
Application examples:
Catalyst both passes through 10%H before use2/ He reduces, reducing condition is that 10 DEG C/min is raised to 250 DEG C, after reduction 30min, 30min is purged with He, take out rapidly and weigh 0.1g and pour in reaction tube, add the 3-nitrostyrolene reactant liquor (toluene is solvent, and o-Dimethylbenzene is interior mark) of 5ml0.1M with pipet, reaction condition is 3barPH2, 40 DEG C.
Specific experiment result is as follows:
Table one Different Alkali metal addition selects the result of hydrogenation at 3-nitrostyrolene
As seen from table along with the alkali-metal increase of auxiliary agent, the selectivity of target product being significantly improved, when the addition of auxiliary agent is 3%, the selectivity of target product can be reached 96.7% by catalyst.
Table two adds Different Alkali metal and selects the result of hydrogenation at 3-nitrostyrolene
By data in table it can be seen that different alkali-metal interpolations effect that the selectivity of target product is all significantly increased.
Table three adds the cyclical stability experiment of auxiliary agent rear catalyst
Catalyst after adding alkali metal as can be seen from Table III shows good stability, and after circulating four times, its activity and selectivity does not decline.
Table four 2.16%Pt/FeOx-3.0%Na selects the result of hydrogenation at differential responses substrate
Be can be seen that this catalyst has significantly high selectivity equally for other substrates by data in table.
Claims (10)
1. containing the application in aromatic nitro compound selective hydrogenation reaction of the auxiliary agent catalyst, it is characterized in that: the active component of described catalyst is one or two or more kinds in VIII race or I B race metal, with alkali metal for auxiliary agent, carrier is ferrum oxide, active component and auxiliary agent support jointly on carrier, in catalyst, the mass content of active component is 0.5%-50%, and in catalyst, the mass content of auxiliary agent is 0.01%-40%, and surplus is carrier.
2. apply as claimed in claim 1, it is characterised in that: active component is one or two or more kinds in Pt, Pd and Ni, and active component content is 0.01-20wt%.
3. apply as claimed in claim 1, it is characterised in that: alkali metal is one or two or more kinds in lithium, sodium and potassium, and in catalyst, the mass content of auxiliary agent is 0.01-20wt%.
4. the application as described in as arbitrary in claim 1-3, it is characterised in that: its preparation process is as follows,
1) metal active constituent solubility precursor and ferric nitrate are made into mixed aqueous solution, are designated as solution A, concentration 1 �� 10-4The ammonium carbonate solution of-1mol/L is designated as solution B; Metal active constituent solubility precursor concentration 0.1-50mg/ml in solution A, iron nitrate concentration 0.1-1mol/L;
2) solution B stirs at 50 DEG C-100 DEG C, is added drop-wise in solution B by solution A; Solution A and solution B volume ratio 0.001-1000;
3) after continuing stirring after completion of dropwise addition at 50 DEG C of-100 DEG C of temperature 1-10 hour, then 1-10 hour is stood;
4) after standing terminates, separating solid, solid deionized water sucking filtration, by solid drying;
5) dried solid catalyst is ground, impregnate alkali metal soln;
6) being dried by the catalyst after dipping alkali metal soln, baking temperature is 25-120 DEG C, and drying time is 1-24 hour; Dried solid carries out roasting, and sintering temperature is 200 DEG C-800 DEG C, and roasting time is 1-24 hour;
Described alkali metal soln is alkali-metal carbonate, nitrate, chlorate and sodium hydroxide, hydroxide
Potassium, Lithium hydrate etc. one or two or more kinds;
The concentration of described alkali metal soln is 0.001mol/L-10mol/L;
7) catalyst both passes through reduction treatment before being used for reaction, and reducing atmosphere is the gaseous mixture of hydrogen or the hydrogen volume concentration hydrogen be more than or equal to 10% and noble gas, and reduction temperature is 50 DEG C-800 DEG C, recovery time 10-120min.
5. the application as described in as arbitrary in claim 1-3, it is characterised in that: its preparation process is as follows,
1) metal active constituent solubility precursor and ferric nitrate are made into mixed solution, are designated as solution A, concentration 1 �� 10-4The ammonium carbonate solution of-1mol/L is designated as solution B; Metal active constituent solubility precursor concentration 0.1-50mg/ml in solution A, iron nitrate concentration 0.1-1mol/L.
2) solution B stirs at 50 DEG C-100 DEG C, is added drop-wise in solution B by solution A; Solution A and solution B volume ratio 0.001-1000;
3) after continuing stirring after completion of dropwise addition at 50 DEG C of-100 DEG C of temperature 1-10 hour, then 1-10 hour is stood;
4) after terminating, separating solid, solid deionized water sucking filtration, by solid drying, dried solid carries out roasting, and sintering temperature is 200 DEG C-800 DEG C, and roasting time is 1-24 hour;
5) solid catalyst after roasting is ground, impregnate alkali metal soln;
6) being dried by the catalyst after dipping alkali metal soln, baking temperature is 25-120 DEG C, and drying time is 1-24 hour; Dried solid carries out roasting, and sintering temperature is 200 DEG C-800 DEG C, and roasting time is 1-24 hour;
Described alkali metal soln be alkali-metal carbonate, nitrate, chlorate and sodium hydroxide, potassium hydroxide, Lithium hydrate etc. one or two or more kinds;
The concentration of described alkali metal soln is 0.001mol/L-10mol/L;
7) catalyst both passes through reduction treatment before being used for reaction, and reducing atmosphere is the gaseous mixture of hydrogen or the hydrogen volume concentration hydrogen be more than or equal to 10% and noble gas, and reduction temperature is 50 DEG C-800 DEG C, recovery time 10-120min.
6. apply as claimed in claim 1, it is characterised in that:
Reacting in airtight autoclave and carry out, in reactor, initial pressure during hydrogen room temperature is 0.1-5Mpa, and reaction temperature is 20-150 DEG C, and the response time was no less than 10 minutes.
7. the application as described in claim 1 or 6, it is characterised in that:
Described reacting in solvent carries out, and the solvent adopted is one or two or more kinds in ethanol, methanol, toluene, oxolane, dodecane, water, reactant liquor concentration of substrate 0.001-10mol/L;
Reaction substrate is aromatic nitro compoundSubstituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-5; Or reaction substrate isIn one, substituent R is the one in hydrogen, halogen, vinyl, acetenyl, itrile group, aldehyde radical, phenolic hydroxyl group, carbonyl, methyl, isopropyl, methoxyl group, and the number of substituent R is 1-4.
8. the application as described in claim 1 or 6, it is characterised in that:
The mol ratio of catalyst activity component and reaction substrate is 1 �� 10-4Between 1.
9. the application as described in claim 1 or 6, it is characterised in that:
Preferred reaction temperature is 20-80 DEG C, the preferred initial pressure 0.1-1.5Mpa of hydrogen in reactor under room temperature, it is preferable that response time 0.5h-3h.
10. apply as claimed in claim 1, it is characterised in that: catalyst can recycle more than 2 times, and its conversion ratio and selectivity are not decreased obviously, and catalyst easily separates with reaction solution.
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Cited By (5)
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| CN106008228A (en) * | 2016-06-14 | 2016-10-12 | 中国科学院山西煤炭化学研究所 | Method for synthesizing anilines and catalyst adopted by same |
| CN106083601A (en) * | 2016-06-14 | 2016-11-09 | 中国科学院山西煤炭化学研究所 | Under a kind of normal pressure, photocatalysis synthesizes method and the catalyst of use thereof of amino benzenes compounds |
| CN112642425A (en) * | 2020-12-10 | 2021-04-13 | 西安凯立新材料股份有限公司 | Dehalogenation-preventing catalyst for nitro reduction of halogenated aromatic nitro compound and preparation method and application thereof |
| CN113522280A (en) * | 2020-04-22 | 2021-10-22 | 中国科学院大连化学物理研究所 | Catalyst, and defect regulation method and application of catalyst |
| CN115155575A (en) * | 2022-08-03 | 2022-10-11 | 中山大学 | Diatomic catalyst for efficiently catalyzing nitrobenzene hydrogenation to prepare aniline and preparation method thereof |
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| CN106008228A (en) * | 2016-06-14 | 2016-10-12 | 中国科学院山西煤炭化学研究所 | Method for synthesizing anilines and catalyst adopted by same |
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| CN112642425B (en) * | 2020-12-10 | 2023-02-28 | 西安凯立新材料股份有限公司 | Dehalogenation-preventing catalyst for nitro reduction of halogenated aromatic nitro compound and preparation method and application thereof |
| CN115155575A (en) * | 2022-08-03 | 2022-10-11 | 中山大学 | Diatomic catalyst for efficiently catalyzing nitrobenzene hydrogenation to prepare aniline and preparation method thereof |
| CN115155575B (en) * | 2022-08-03 | 2024-04-19 | 中山大学 | Double-atom catalyst for preparing aniline by efficiently catalyzing nitrobenzene hydrogenation and preparation method thereof |
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Application publication date: 20160601 |