CN104496739A - Green catalytic synthesis method of diphenylmethane - Google Patents
Green catalytic synthesis method of diphenylmethane Download PDFInfo
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- CN104496739A CN104496739A CN201410676141.5A CN201410676141A CN104496739A CN 104496739 A CN104496739 A CN 104496739A CN 201410676141 A CN201410676141 A CN 201410676141A CN 104496739 A CN104496739 A CN 104496739A
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- molecular sieve
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Abstract
The invention relates to a green catalytic synthesis method of diphenylmethane. According to the invention, benzene and benzyl chloride which are used as raw materials undergo a Fradel-Crafts alkylation reaction at the reaction temperature of 100-200 DEG C for 1-8 hours so as to obtain the product diphenylmethane, wherein the ratio of benzene to benzyl chloride is 2:1-20:1. The method provided by the invention is a diphenylmethane catalytic synthesis process with simple reaction technique and little pollution.
Description
Technical field
The present invention relates to a kind of synthesis technique of catalyzer, particularly relate to a kind of green catalysis synthetic method of ditane of environment-friendly high-efficiency.
Technical background
Ditane is commonly called as artificial musk's leaf oil, molecular formula C
6h
5cH
2c
6h
5, molecular weight 168.23, fusing point: 24.5 DEG C-25 DEG C, boiling point: 264.3 DEG C, colorless needle crystals, is dissolved in ethanol, ether, chloroform, benzene and hexanaphthene, water insoluble, and as organic synthesis intermediate, medicine industry is for the production of diphenhydramine hydrochloride.Ditane can make spiceleaf oil substitute, is suitable for preparing soap compound and perfume etc.Also for DYE PRODUCTION.Its derivative can be used for the synthesis of the medicines such as belarizine, CN, oxatomide as phenylbenzene methyl halide.
The synthesis technique of current ditane mainly with benzene and Benzyl Chloride for raw material, carry out Fradel-Crafts alkylated reaction and produce, the catalyzer of employing mainly contains: aluminium amalgam, anhydrous AlCl
3, anhydrous ZnCl
2deng lewis acid catalyst.Traditional Fradel-Crafts catalyst for alkylation reaction mainly contains: acid halide (Lewis acid), protonic acid, acidic oxide, aluminum alkyls.That commonly uses in acid halide has AlCl
3, ZnCl
2and BF
3and title complex; What protonic acid was conventional has dense H
2sO
4, HF acid.
There is a lot of shortcoming in above catalyzer, AlCl
3, ZnCl
2not high Deng acid halide catalyst selectivity, easy and benzene forms complex compound, and during product separation, catalyzer is hydrolyzed releasing heat, and produces a large amount of HCl gas and waste liquid, to equipment and environment.Dense H
2sO
4owing to having acidity and oxidisability, produce a large amount of by product in reaction process, the aftertreatment technology of product is complicated, and dense H
2sO
4, the liquid acid such as HF has serious corrodibility, to equipment and environment.Therefore find and develop the focus that a kind of novel environment-friendly catalyst is the research of Fradel-Crafts alkylated reaction.
Patent CN1876609A discloses a kind of method of ionic liquid catalyst synthesizing diphenyl methane.Ionic liquid is as a kind of novel reaction medium, non-volatile and the advantage such as to reuse and be used widely in a lot of with it, but the toxicity of ionic liquid, toxicity and the problem that affects on environment also do not obtain the deep solution of system.Therefore to realize the application of ionic liquid in engineering also to need to proceed deep research.
Patent CN1631861A has invented a kind of ZnCl
2/ clay-SA
0.1catalyze and synthesize the method for ditane.The problems such as this loading type acid halide catalyzer to some extent solves the shortcoming of acid halide and liquid acid catalyst, but still the active ingredient that there is catalyzer easily comes off, and forms complex compound with reaction raw materials, and product is not easily separated.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, provide a kind of green catalysis synthetic method of ditane, solve that solid acid catalyst reaction process in prior art is loaded down with trivial details, the problem of contaminate environment.
Process for catalytic synthesis of the present invention comprises the steps:
With benzene and Benzyl Chloride for raw material, under the effect of solid acid catalyst, carry out the preparation of Fradel-Crafts alkylated reaction; The consumption mol ratio of benzene and Benzyl Chloride is 2:1-20:1, and reaction conditions is: temperature 100 DEG C-200 DEG C, and reaction times 1-8 hour, obtains product ditane.
Solid acid catalyst of the present invention comprises molecular sieve, S
2o
4 2-/ ZrO
2, clay or silica-alumina, phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid and carried phospho-tungstic acid, phospho-molybdic acid, silicotungstic acid.
Described molecular sieve comprises X molecular sieve, Y molecular sieve, USY molecular sieve, beta-molecular sieve, mordenite, L zeolite, ZSM-5, ZSM-11, ZSM-12, ZSM-18 molecular sieve, mazzite, offretite, HX molecular sieve, HY molecular sieve, HZSM-5 molecular sieve, H beta-molecular sieve.
The carrier of described loaded catalyst adopts gac, silicon-dioxide and mesopore molecular sieve (SBA-15).
Preferred solid catalyst is: phospho-wolframic acid, phospho-molybdic acid, the silicotungstic acid of phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, USY molecular sieve, HY molecular sieve, H beta-molecular sieve or loading type.
It is 1%-60% that described loaded catalyst phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid account for vehicle weight per-cent.
It is 10%-30% that described loaded catalyst phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid account for carrier preferred weight percent.
Described loaded catalyst phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid preparation process are:
(1) carrier is carried out drying, dehydration;
(2) require to prepare the phospho-wolframic acid of different concns, phospho-molybdic acid or silicon tungsten acid solution according to different charge capacity, the volume of the aqueous solution just reaches carrier saturated extent of adsorption; Then roasting 2-12 hour at dry 12-24 hour, 200 DEG C-500 DEG C at adding selected carrier impregnation 2-24 hour, 100 DEG C.
Described alkylated reaction step is:
(1) by catalyzer, benzene and Benzyl Chloride, reactor is added successively; Then start to stir, heat, equitemperature starts timing after reaching 100 DEG C-200 DEG C, reaction 1-8 hour, and wherein catalyzer accounts for the 1%-50% of Benzyl Chloride weight, and the consumption mol ratio of benzene and Benzyl Chloride is 2:1-20:1;
(2) reaction is cooled fast to room temperature after terminating, and by reaction solution and catalyzer centrifugation, catalyst recovery, reuses;
(the 3 pairs of reaction solutions NaOH of 5% carries out alkali cleaning, then carries out being washed to neutrality with deionized water;
(4 add high-temperature solvent in reaction solution carries out rectification under vacuum, and unreacted benzene is reused after reclaiming; Collect 4.67KPa, the cut of 158 DEG C, obtain colourless liquid, crystallizing at room temperature is that white solid is ditane.
Advantageous effect of the present invention is: the invention provides the catalysis synthesizing technology that a kind of reaction process is simple, pollute the ditane of few environment-friendly high-efficiency.
Embodiment
embodiment 1
In the reactor of 200 milliliters, add 500 DEG C of baked HY molecular sieves, 1.0 grams, 6.3 grams Benzyl Chlorides (0.05 mole), 39.5 grams of benzene (0.5 mole) successively, start after sealing to stir, heat, timing is started when reaching 120 DEG C etc. temperature of reaction, react after 1 hour and stop heating and stirring, take out reactor and be quickly cooled to room temperature, open reactor.Reaction solution and catalyzer are carried out centrifugation, and catalyst recovery can be reused.The selectivity 56.24% that transformation efficiency that stratographic analysis can obtain Benzyl Chloride is 80.66% and ditane is carried out to reaction solution.
embodiment 2
According to reaction conditions and the separating step of embodiment 1, catalyzer selects 1.0 grams of 500 DEG C of baked molecular sieves (X molecular sieve, Y molecular sieve, USY molecular sieve, beta-molecular sieve, mordenite, L zeolite, ZSM-5, HX molecular sieve, HZSM-5 molecular sieve, H beta-molecular sieve etc.), 10%S successively respectively
2o
4 2-/ ZrO
2the selectivity of the transformation efficiency and product ditane that obtain Benzyl Chloride is as table 1.
embodiment 3
The raw material ratio same according to embodiment 1 and separating step, namely 6.3 grams of Benzyl Chlorides, 39.5 grams of benzene are got, temperature of reaction 120 DEG C, 1 hour reaction times, catalyzer adopts 1.0 grams, HY molecular sieve under different maturing temperature respectively, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane under the HY molecular sieve catalyst effect of different maturing temperature, acquired results is in table 2.
embodiment 4
The raw material ratio same according to embodiment 1 and separating step, namely 6.3 grams of Benzyl Chlorides, 39.5 grams of benzene are got, 1.0 grams, 800 DEG C of baked HY molecular sieves selected by catalyzer, reaction times is 1 hour, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane at differential responses temperature successively, acquired results is in table 3.
embodiment 5
The raw material ratio same according to embodiment 1 and separating step, namely 6.3 grams of Benzyl Chlorides, 39.5 grams of benzene are got, 1.0 grams, 800 DEG C of baked HY molecular sieves selected by catalyzer, temperature of reaction 140 DEG C, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane under the different reaction times successively, acquired results is in table 4.
embodiment 6
According to reaction conditions raw material ratio and the separating step of embodiment 1, namely 6.3 grams of Benzyl Chlorides, 39.5 grams of benzene are got, temperature of reaction 120 DEG C, 1 hour reaction times, catalyzer select respectively 0.2 gram, 800 DEG C of HY molecular sieves, 0.5 gram, 1.0 grams, 1.5 grams, 2.0 grams, 3.0 grams, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane under the catalyst action of different amounts successively, acquired results is in table 5.
embodiment 7
According to the reaction conditions that embodiment 6 is same, temperature of reaction 140 DEG C, in 1 hour reaction times, 800 DEG C of HY selected by catalyzer, consumption 1.5 grams, and investigated the transformation efficiency of different material than Benzyl Chloride under condition and the selectivity of ditane, acquired results is in table 6.
embodiment 8
According to the reaction conditions that embodiment 7 is same, temperature of reaction 140 DEG C, 1 hour reaction times, 6.3 grams of Benzyl Chlorides (0.05 mole), 39.5 grams of benzene (0.5 mole), catalyzer selects the consumption of phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid to be 1.0 grams successively, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane under different catalysts effect successively, acquired results is in table 7.
embodiment 9
By pickling process, phospho-wolframic acid is loaded on absorbent charcoal carrier.Load step: aqueous solution phospho-wolframic acid being configured to first respectively different concns by charge capacity 5%, 10%, 15%, 20%, 30% and 40%, floods 12 hours, then 120 DEG C of dryings 12 hours, and 300 DEG C of roastings 4 hours.According to the same raw material 6.3 grams of Benzyl Chlorides (0.05 mole) of embodiment 8,39.5 grams of benzene (0.5 mole), catalyst levels is 1 gram, temperature of reaction 120 DEG C, 1 hour reaction times, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane under the catalyzer of different loads amount successively, acquired results is in table 8.
embodiment 10
By pickling process, phospho-wolframic acid is loaded to SiO
2upper: aqueous solution phospho-wolframic acid being configured to first respectively different concns by charge capacity 5%, 10%, 15%, 20%, 30% and 40%, adds SiO
2, flood 12 hours, then 120 DEG C of dryings 12 hours, 300 DEG C of roastings 4 hours.According to the same raw material ratio 6.3 grams of Benzyl Chlorides (0.05 mole) of embodiment 8,39.5 grams of benzene (0.5 mole), catalyst levels is 1 gram, temperature of reaction 120 DEG C, 1 hour reaction times, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane under the catalyzer of different loads amount successively, acquired results is in table 9.
embodiment 11
By pickling process, phospho-wolframic acid is loaded on mesoporous molecular sieve SBA-15: aqueous solution phospho-wolframic acid being configured to first respectively different concns by charge capacity 5%, 10%, 15%, 20%, 30%, 40%, add mesoporous molecular sieve SBA-15, flood 12 hours, then 120 drying 12 hours, 300 roastings 4 hours.According to the same raw material 6.3 grams of Benzyl Chlorides (0.05 mole) of embodiment 8,39.5 grams of benzene (0.5 mole), catalyst levels is 1 gram, temperature of reaction 140 DEG C, 1 hour reaction times, investigated the transformation efficiency of Benzyl Chloride and the selectivity of ditane under the catalyzer of different loads amount successively, acquired results is in table 10.
embodiment 12
By catalyzer HY molecular sieve, benzene and Benzyl Chloride, add reactor successively; Then start to stir, heat, equitemperature starts timing after reaching 100 DEG C, and react 8 hours, wherein catalyzer HY molecular sieve accounts for 1% of Benzyl Chloride weight, and the consumption mol ratio of benzene and Benzyl Chloride is 2:1;
Be cooled fast to room temperature after reaction terminates, by reaction solution and catalyzer centrifugation, catalyst recovery, reuses;
To reaction solution with 5% NaOH carry out alkali cleaning, then carry out being washed to neutrality with deionized water;
In reaction solution, add high-temperature solvent (trolamine) carry out rectification under vacuum, unreacted benzene is reused after reclaiming; Receive 4.67KPa, the cut of 158 DEG C, obtain colourless liquid, crystallizing at room temperature is that white solid is ditane.
embodiment 13
By catalyzer silica-alumina, benzene and Benzyl Chloride, add reactor successively; Then start to stir, heat, equitemperature starts timing after reaching 200 DEG C, and react 1 hour, wherein catalyzer silica-alumina accounts for 50% of Benzyl Chloride weight, and the consumption mol ratio of benzene and Benzyl Chloride is 20:1; Other step is with embodiment 12.
embodiment 14
By phosphate-tungstic acid, benzene and Benzyl Chloride, add reactor successively; Then start to stir, heat, equitemperature starts timing after reaching 150 DEG C, and react 5 hours, wherein phosphate-tungstic acid accounts for 20% of Benzyl Chloride weight, and the consumption mol ratio of benzene and Benzyl Chloride is 10:1; Other step is with embodiment 12.
embodiment 15
By loaded catalyst phospho-molybdic acid, benzene and Benzyl Chloride, add reactor successively; Then start to stir, heat, equitemperature starts timing after reaching 200 DEG C, and react 8 hours, wherein loaded catalyst phospho-molybdic acid accounts for 25% of Benzyl Chloride weight, and the consumption mol ratio of benzene and Benzyl Chloride is 20:1;
Described loaded catalyst phospho-molybdic acid preparation process is:
Carrier active carbon is carried out drying, dehydration;
Require to prepare the phospho-molybdic acid aqueous solution that weight percent is 10% according to different charge capacity, the volume of the aqueous solution just reaches carrier saturated extent of adsorption; Then the roasting 12 hours at dry 24 hours, 200 DEG C at 24 hours, 100 DEG C of selected carrier impregnation is added; Other step is with embodiment 12.
embodiment 16
Require to prepare the silicon tungsten acid solution that weight percent is 50% according to different charge capacity, the volume of the aqueous solution just reaches carrier saturated extent of adsorption; Then the roasting 2 hours at dry 12 hours, 500 DEG C at 2 hours, 100 DEG C of selected carrier impregnation is added; Other step is with embodiment 15.
embodiment 17
Require to prepare the silicon tungsten acid solution that weight percent is 60% according to different charge capacity, the volume of the aqueous solution just reaches carrier saturated extent of adsorption; Then the roasting 6 hours at dry 18 hours, 300 DEG C at 12 hours, 100 DEG C of selected carrier impregnation is added; Other step is with embodiment 15.
The carrier of described loaded catalyst also can adopt silicon-dioxide or mesopore molecular sieve (SBA-15); Described loaded catalyst accounts for vehicle weight per-cent and can be 1%.Above about specific descriptions of the present invention, be only not limited to the technical scheme described by the embodiment of the present invention for illustration of the present invention.Those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent replacement, to reach identical technique effect.Needs are used, all in protection scope of the present invention as long as meet.
Claims (9)
1. the green catalysis synthetic method of ditane, to is characterized in that comprising the steps: with benzene and Benzyl Chloride, for raw material, under the effect of solid acid catalyst, carrying out the preparation of Fradel-Crafts alkylated reaction; The consumption mol ratio of benzene and Benzyl Chloride is 2:1-20:1, and reaction conditions is: temperature 100 DEG C-200 DEG C, and reaction times 1-8 hour, obtains product ditane.
2. the green catalysis synthetic method of ditane according to claim 1, is characterized in that described solid acid catalyst comprises molecular sieve, S
2o
4 2-/ ZrO
2, clay or silica-alumina, phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid and carried phospho-tungstic acid, phospho-molybdic acid, silicotungstic acid.
3. the green catalysis synthetic method of ditane according to claim 2, is characterized in that described molecular sieve comprises X molecular sieve, Y molecular sieve, USY molecular sieve, beta-molecular sieve, mordenite, L zeolite, ZSM-5, ZSM-11, ZSM-12, ZSM-18 molecular sieve, mazzite, offretite, HX molecular sieve, HY molecular sieve, HZSM-5 molecular sieve, H beta-molecular sieve.
4. the green catalysis synthetic method of ditane according to claim 2, is characterized in that the carrier of described loaded catalyst adopts gac, silicon-dioxide and mesopore molecular sieve (SBA-15).
5. the green catalysis synthetic method of ditane according to claim 2, is characterized in that preferred solid acid catalyst is: phospho-wolframic acid, phospho-molybdic acid, the silicotungstic acid of phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, USY molecular sieve, HY molecular sieve, H beta-molecular sieve or loading type.
6. the green catalysis synthetic method of ditane according to claim 2, it is characterized in that described loaded catalyst phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid account for vehicle weight per-cent is 1%-60%.
7. the green catalysis synthetic method of ditane according to claim 6, it is characterized in that described loaded catalyst phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid account for carrier preferred weight percent is 10%-30%.
8. the green catalysis synthetic method of the ditane according to claim 6 or 7, is characterized in that described loaded catalyst phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid preparation process are:
Carrier is carried out drying, dehydration;
Require to prepare the phospho-wolframic acid of different concns, phospho-molybdic acid or silicon tungsten acid solution according to different charge capacity, the volume of the aqueous solution just reaches carrier saturated extent of adsorption; Then roasting 2-12 hour at dry 12-24 hour, 200 DEG C-500 DEG C at adding selected carrier impregnation 2-24 hour, 100 DEG C-200 DEG C.
9. the green catalysis synthetic method of ditane according to claim 1, is characterized in that described alkylated reaction step is:
By catalyzer, benzene and Benzyl Chloride, add reactor successively; Then start to stir, heat, equitemperature starts timing after reaching 100 DEG C-200 DEG C, reaction 1-8 hour, and wherein catalyzer accounts for the 1%-50% of Benzyl Chloride weight, and the consumption mol ratio of benzene and Benzyl Chloride is 2:1-20:1;
Be cooled fast to room temperature after reaction terminates, by reaction solution and catalyzer centrifugation, catalyst recovery, reuses;
To reaction solution with 5% NaOH carry out alkali cleaning, then carry out being washed to neutrality with deionized water;
In reaction solution, add high-temperature solvent carry out rectification under vacuum, unreacted benzene is reused after reclaiming; Collect 4.67KPa, the cut of 158 DEG C, obtain colourless liquid, crystallizing at room temperature is that white solid is ditane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112023979A (en) * | 2019-06-03 | 2020-12-04 | 中石化南京化工研究院有限公司 | Catalyst for synthesizing 2-tert-butyl aniline and preparation method and application thereof |
| CN113457724A (en) * | 2021-06-17 | 2021-10-01 | 复旦大学 | Bifunctional catalyst for preparing toluene and co-producing diphenylmethane by directly converting synthesis gas and benzene, and preparation method and application thereof |
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| CN101816944A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Preparation method for solid acid catalyst for preparing diphenylmethane |
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2014
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| CN101816944A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Preparation method for solid acid catalyst for preparing diphenylmethane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112023979A (en) * | 2019-06-03 | 2020-12-04 | 中石化南京化工研究院有限公司 | Catalyst for synthesizing 2-tert-butyl aniline and preparation method and application thereof |
| CN113457724A (en) * | 2021-06-17 | 2021-10-01 | 复旦大学 | Bifunctional catalyst for preparing toluene and co-producing diphenylmethane by directly converting synthesis gas and benzene, and preparation method and application thereof |
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Application publication date: 20150408 |