CN109382119A - A kind of research method of novel solid acid catalyst and application and its catalytic active center - Google Patents

A kind of research method of novel solid acid catalyst and application and its catalytic active center Download PDF

Info

Publication number
CN109382119A
CN109382119A CN201811443991.5A CN201811443991A CN109382119A CN 109382119 A CN109382119 A CN 109382119A CN 201811443991 A CN201811443991 A CN 201811443991A CN 109382119 A CN109382119 A CN 109382119A
Authority
CN
China
Prior art keywords
solid acid
acid catalyst
ardealite
acetal
novel solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811443991.5A
Other languages
Chinese (zh)
Inventor
谭建红
蒋达波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangtze Normal University
Original Assignee
Yangtze Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangtze Normal University filed Critical Yangtze Normal University
Priority to CN201811443991.5A priority Critical patent/CN109382119A/en
Publication of CN109382119A publication Critical patent/CN109382119A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of novel solid acid catalyst and application and its research methods of catalytic active center, the present invention is using industrial by-product ardealite as novel solid acid catalyst, ardealite is directly used in the synthesis of catalysis acetal (ketone), operation is simple by simply washing after dry.And ardealite has many advantages, such as that catalytic activity is high in the synthesis of catalysis acetal (ketone), is easily isolated, subsequent processing is simple and repeat performance is excellent.Raw material sources are extensive, and preparation is simple, at low cost, while realizing the recycling and recycling treatment of phosphoric acid industry by-product, also mitigate ardealite to pressure caused by environment.The present invention is easily achieved large-scale industrialized production, provides new theoretical direction and technical support for easy, low cost solid acid catalyst, while improving the value added applications of ardealite, with good economic efficiency.

Description

A kind of research method of novel solid acid catalyst and application and its catalytic active center
Technical field
The present invention relates to solid acid catalyst technical field, in particular to a kind of novel solid acid catalyst and application and The research method of its catalytic active center.
Background technique
Acetal (ketone) is a kind of important fine chemical product, has fragrance mostly, is widely used in food as fragrance With the industries such as daily use chemicals, it is also commonly used for organic synthesis intermediate or solvent, is had a wide range of applications.The side of conventional synthesis acetal (ketone) Method is condensed by inorganic acid catalysis aldehyde ketone and alcohol, usually to remove catalyst by washing, there is that environmental pollution is serious, and equipment is rotten Erosion is strong, and product purification process is complicated and catalyst is difficult to the disadvantages of recycling.Therefore, new can be recycled is researched and developed Catalyst be of great significance to the green syt of acetal (ketone).
In recent years, people are devoted to the solid acid catalyst of research environment friendly, such as the immobilized phosphorus of improved silica Wolframic acid, Ga2O3Concave convex rod solid acid, modified activated carbon load aluminium dihydrogen tripolyphosphate etc., but all there is synthesis in these catalyst The disadvantages of route complexity and high production cost, repeat performance is poor.
Ardealite is the solid waste of industrial production phosphoric acid, and Wet-process phosphoric acid (WPPA) is acted on sulfuric acid and ground phosphate rock, warp Washing filtering obtains phosphoric acid, and remaining waste residue is exactly ardealite after filtering, and the main component of ardealite is CaSO4•2H2O, In also contain remaining sulfuric acid, sulfate, the silicate of the metals such as Fe, Al, the impurity such as microelement.The accumulation of ardealite is to water Serious harm is caused with soil.Therefore, extremely urgent to the recycling and recycling treatment of phosphoric acid industry by-product.
Summary of the invention
In view of the above shortcomings of the prior art, the object of the present invention is to provide a kind of novel solid acid catalyst and answer With and its catalytic active center research method, solving existing solid acid catalyst, there are complex synthetic route and production costs The problems such as height, repeat performance is poor, while further promoting the resource utilization and value added applications of ardealite.
In order to solve the above-mentioned technical problem, present invention employs the following technical solutions: a kind of novel solid acid catalyst, The catalyst is ardealite, and the ardealite is phosphoric acid industry byproduct, is washed to neutrality, then in 70 ~ 90 DEG C dry 2 ~ 4h.
If above-mentioned novel solid acid catalyst is catalyzing and synthesizing the application in acetal or ketal, specifically includes the following steps: Aldehydes or ketones, dihydric alcohol, solid acid catalyst and water entrainer are fitted into water segregator and reflux condensing tube, in heated at reflux temperature It is stirred to react 2 ~ 4h, reflux water-dividing enters water segregator to anhydrous, that is, catalyzed and synthesized acetal or ketal.
Further, the dihydric alcohol is ethylene glycol, 1,2-PD and 1, one of 2- butanediol or a variety of.
Further, the aldehyde is one of n-butanal, benzaldehyde and furfural or a variety of；The ketone is cyclohexanone, benzene second Ketone,Acetone, one of butanone and 2 pentanone or a variety of.
Further, the water entrainer is hexamethylene.
Further, the molar ratio of the ketone or aldehyde and dihydric alcohol is 1 ~ 2:1, the molar ratio of preferred ketone or aldehyde and dihydric alcohol For 1.5:1；Solid acid catalyst dosage is the 6 ~ 15% of aldehydes or ketones quality, and preferred solid acid catalyst dosage is aldehydes or ketones matter The 10% of amount.
The yield of acetal (ketone) gradually rises with the increase of dihydric alcohol dosage.This may be because ethylene glycol dosage increases Add, increases the collision probability between aldehyde (ketone) and glycol molecule.But the dosage of ethylene glycol is continued growing, the yield of acetal (ketone) Appearance downward trend.This is mainly due to the dosages for continuing growing ethylene glycol to have diluting effect to reaction system, thus Decline yield.
The research method of the catalytic active center of above-mentioned novel solid acid catalyst, comprising the following steps:
S1: being analyzed by X-ray diffraction spectra, determines the composition and main catalytic specie of the solid acid catalyst；
S2: the acid amount and catalytic efficiency of the solid acid catalyst are measured at a temperature of different disposal, determines solid acid catalyst In the crystallization water and its acid relationship；
S3: solid acid catalyst is divided into 2 parts, a copy of it poisons all acid in solid acid catalyst by poisonous agent 1 Center, while another poisons the acid site B in solid acid catalyst by poisonous agent 2, then determines the solid acid catalysis Acid centre type and its ratio in agent.
Further, the treatment temperature in the step S2 is 100 ~ 500 DEG C.
Further, the poisonous agent 1 is pyridine, and poisonous agent 2 is 2,6- lutidines or 2,6- di-tert-butyl pyridine
Compared with prior art, the invention has the following beneficial effects:
1, the present invention is using industrial by-product ardealite as novel solid acid catalyst, and ardealite is by simply washing, after dry It is directly used in the synthesis of catalysis acetal (ketone), operation is simple.And ardealite has in the synthesis of catalysis acetal (ketone) Catalytic activity is high, preferable applicability, is easily isolated, the advantages that subsequent processing is simple and repeat performance is excellent.Overcome Consersion unit requires the disadvantages of high, product separation is difficult, catalyst is difficult to recycle and environmental pollution is serious in the prior art.
2, used catalyst of the present invention is industry byproduct, from a wealth of sources, and preparation is simple, at low cost, is had environmental-friendly The potential quality of type solid acid catalyst, while realizing the recycling and recycling treatment of phosphoric acid industry by-product, to mitigate ardealite To pressure caused by environment.The present invention is easily achieved large-scale industrialized production, for the solid acid catalyst of easy low cost New theoretical direction and technical support are provided, while improving the value added applications of ardealite, it is with good economic efficiency.
3, the present invention combines X-ray fluorescence spectra analysis, X-ray diffraction spectra analysis and infrared spectrum analysis to determine phosphorus stone Catalytic active center in cream, wherein ardealite is primarily present the acid site B, and a small amount of metal sulfate constitutes the acid site L, And the acid site B and the acid site L proportion are respectively 92.4% and 7.6%.This provides certain theory for the surface modification of ardealite Basis, to realize that modified ardealite is applied in organic composite material as inorganic filler.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectra figure of ardealite.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
One, ardealite is catalyzing and synthesizing the application in acetal or ketal
Embodiment 1
1) ardealite directly is taken from the solid waste stockyard of Zhonghua Chongqing Fulin Chemical Co., Ltd.'s phosphoric acid production workshop, is washed to neutrality Afterwards in 80 DEG C of 2 h of drying to get the solid acid catalyst (ardealite) for catalyzing and synthesizing acetal or ketal；
2) 0.05mol benzaldehyde, 0.075mol ethylene glycol, a certain amount of ardealite are sequentially added in the three-neck flask of 100 mL It is fitted into water segregator and reflux condensing tube with 10 mL hexamethylenes, is stirred to react 2h, reflux water-dividing to nothing in heated at reflux temperature Water enters water segregator, that is, has catalyzed and synthesized two acetal of benzaldehyde second.Ardealite dosage is benzaldehyde quality 10%.
Quantitative analysis is carried out to product using gas chromatograph, gas chromatograph-mass spectrometer (GC-MS) determines condensation product Property analysis.The yield of two acetal of result product benzaldehyde second is 98.4%.
2 ~ 13 operating procedure of embodiment is with embodiment 1, and only aldehyde (ketone) is different from the type of dihydric alcohol, is specifically shown in Table 1.
Table 1
Embodiment Dihydric alcohol Aldehyde (ketone) Yield %
Embodiment 1 Ethylene glycol Benzaldehyde 98.4
Embodiment 2 Ethylene glycol N-butanal 98.1
Embodiment 3 Ethylene glycol Benzaldehyde 98.4
Embodiment 4 Ethylene glycol Furfural 77.0
Embodiment 5 Ethylene glycol Cyclohexanone 98.8
Embodiment 6 1,2-PD N-butanal 98.2
Embodiment 7 1,2-PD Benzaldehyde 90.5
Embodiment 8 1,2-PD Furfural 79.5
Embodiment 9 1,2-PD Cyclohexanone 95.8
Embodiment 10 1,2- butanediol N-butanal 99.8
Embodiment 11 1,2- butanediol Benzaldehyde 85.3
Embodiment 12 1,2- butanediol Furfural 83.1
Embodiment 13 1,2- butanediol Cyclohexanone 98.8
As shown in Table 1, ardealite shows preferable catalytic activity in catalyzing and synthesizing different types of acetal ketone, in addition to benzene Outside formaldehyde, furfural and diol reaction, the yield of remaining acetal (ketone) is up to 98% or more.This may be due to benzaldehyde and chaff Contain phenyl ring and furan nucleus in aldehyde respectively, the two is connected directly with carbonyl, and the two is in the pi-conjugated system of π-, and phenyl is power supply Subbase, the electropositive for reducing carbonyl carbon reduce yield, are unfavorable for the attack of alcoholic extract hydroxyl group.In addition furfural itself is unstable, easily Generate self-polymerization.Therefore, ardealite has preferable applicability to acetal (ketone) is catalyzed and synthesized.Ardealite has environmental-friendly The potential quality of type solid acid catalyst is expected to realize the recycling and recycling treatment of phosphoric acid industry by-product.
Two, the reusability of ardealite
1) ardealite directly is taken from the solid waste stockyard of Zhonghua Chongqing Fulin Chemical Co., Ltd.'s phosphoric acid production workshop, is washed to neutrality Afterwards in 80 DEG C of 2 h of drying to get the solid acid catalyst (ardealite) for catalyzing and synthesizing acetal or ketal；
2) 0.05mol benzaldehyde, 0.075mol ethylene glycol, ardealite and 10 mL are sequentially added in the three-neck flask of 100 mL Hexamethylene is fitted into water segregator and reflux condensing tube, and ardealite dosage is benzaldehyde quality 10%, is stirred in heated at reflux temperature 2h is reacted, reflux water-dividing enters water segregator to anhydrous, then carries out quantitative analysis, gas phase color to product using gas chromatograph Spectrum-mass spectrometer carries out qualitative analysis to condensation product, and calculates the yield of product.Simultaneously by high speed centrifugation, decantation is anti- Liquid is answered, washs recycling ardealite with hexamethylene；
3) ardealite that step 2 recycles is continued repetition step 2 to carry out repeating test, the results are shown in Table 2.
Table 2
Number of repetition 1 2 3 4 5 6 7 8 9
Yield/% 94.1 98.5 96.9 98.7 97.8 98.9 96.3 97.9 98.7
As shown in Table 2, ardealite shows preferable repeat performance, phosphorus in the synthesis of catalysis benzaldehyde ethylene glycol acetal Gypsum is used continuously 9 times, and significantly reducing do not occur in catalytic activity and stability.
Three, the research method of the catalytic active center of ardealite
1, the ardealite that embodiment 1 obtains is carried out X-ray fluorescence spectra to analyze to determine forming for ardealite, as a result such as chart Shown in 3.
Table 3
Compound Content/% Compound Content/%
CaO 34.35 SO3 42.40
P2O5 0.72 Al2O3 0.39
Fe2O3 0.28 SiO2 4.32
MgO 0.03 TiO2 0.07
ZrO2 0.01 SrO 0.10
K2O 0.07 H2O 17.26
As shown in Table 3, the main component in ardealite is calcium sulphate dihydrate, also the sulfate containing metals such as a small amount of aluminium, iron. In addition, there is also the microelements such as Sr, Ti, Zr.
2, the ardealite for obtaining embodiment 1 carries out X-ray diffraction spectra analysis, as a result as shown in Figure 1.It can be with from Fig. 1 Find out, the diffraction maximum at 11.619 °, 20.736 °, 29.062 °, 31.120 ° be respectively calcium sulphate dihydrate (020), (021), (041), (200) crystal face are distributed in the diffraction peak intensity highest of (021) crystal face appearance, illustrate the main component in PG For calcium sulphate dihydrate.In conjunction with table 3 it is found that main component in ardealite is calcium sulphate dihydrate, wherein also containing a small amount of aluminium, The disulfate or sulfate of iron, this just constitutes the L acid centre in ardealite.
3, the ardealite that embodiment 1 obtains is handled into 4 h at 100 DEG C, 200 DEG C, 300 DEG C, 400 DEG C and 500 DEG C respectively, Treated ardealite is tied according to the synthesis for being used to be catalyzed benzaldehyde ethylene glycol acetal the step of implementing 1 with studying in ardealite Brilliant water is to acid influence, as a result as shown in table 4 below.
Table 4
Treatment temperature/DEG C 100 200 300 400 500
Sour amount/mmolg-1 0.32 0.32 0.29 0.19 0.09
Yield/% 99.03 99.43 99.91 63.32 1.14
As shown in Table 4, with the raising of ardealite treatment temperature, the acid amount of ardealite is gradually decreased with the removing of the crystallization water, The catalytic activity of ardealite under corresponding temperature is also substantially reduced.When treatment temperature rises to 500 DEG C, the acid amount of ardealite Level off to 0, and acetal yield is also only 1.14%.The result shows that the crystallization water in ardealite lives to the acidity of ardealite and catalysis Property has a significant impact, this is because the crystallization water in ardealite can provide the acid site B, this also implies the acid site B in gypsum For main catalytic center.
4, ardealite is divided into 2 parts, a copy of it poisons whole acid sites in ardealite by pyridine, makes ardealite Loss of catalytic activity；Another poisons the acid site B in ardealite by 2,6- lutidines simultaneously, this is because 2,6- bis- Two methyl can only poison the B acid in ardealite there are steric hindrance in picoline.Then the phosphorus after above-mentioned 2 parts being poisoned Gypsum is used to be catalyzed the synthesis of acetal (ketone), as a result as shown in table 5 below.
Table 5
Poisonous agent Yield/%
Nothing 98.4
Pyridine 0
2,6- lutidines 7.6
As shown in Table 5, the ardealite not poisoned is used for the synthesis of acetal, and acetal yield is 98.4%.Phosphorus after pyridine is poisoned Gypsum is used for the synthesis of acetal, and acetal yield is 0；And the ardealite after being poisoned with 2,6- lutidines corresponds to acetal yield is 7.6%.The result shows that being primarily present B acid and the acid site L in ardealite, and the acid site B and the acid site L proportion are respectively 92.4% and 7.6%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not limitation with the present invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (10)

1. a kind of novel solid acid catalyst, which is characterized in that the catalyst is ardealite, and the ardealite is phosphoric acid industry pair Product is washed to neutrality, then in 70 ~ 90 DEG C of dry 2 ~ 4h.
2. novel solid acid catalyst as described in claim 1 is catalyzing and synthesizing the application in acetal or ketal.
3. novel solid acid catalyst exists catalyzing and synthesizing the application in acetal or ketal, feature according to claim 2 In, comprising the following steps: aldehydes or ketones, dihydric alcohol, solid acid catalyst and water entrainer are fitted into water segregator and reflux condensing tube, It is stirred to react 2 ~ 4h in heated at reflux temperature, reflux water-dividing enters water segregator to anhydrous, that is, catalyzed and synthesized acetal or ketal.
4. novel solid acid catalyst exists catalyzing and synthesizing the application in acetal or ketal, feature according to claim 3 In the dihydric alcohol is ethylene glycol, 1,2-PD and 1, one of 2- butanediol or a variety of.
5. novel solid acid catalyst exists catalyzing and synthesizing the application in acetal or ketal, feature according to claim 3 In the aldehyde is one of n-butanal, benzaldehyde and furfural or a variety of；The ketone be cyclohexanone, acetophenone,Acetone, butanone With one of 2 pentanone or a variety of.
6. novel solid acid catalyst exists catalyzing and synthesizing the application in acetal or ketal, feature according to claim 3 In the water entrainer is hexamethylene.
7. novel solid acid catalyst exists catalyzing and synthesizing the application in acetal or ketal, feature according to claim 3 In the molar ratio of, the ketone or aldehyde and dihydric alcohol be 1 ~ 2:1；Solid acid catalyst dosage is the 6 ~ 15% of aldehydes or ketones quality.
8. the research method of the catalytic active center of novel solid acid catalyst as described in claim 1, which is characterized in that including Following steps:
S1: being analyzed by X-ray diffraction spectra, determines the composition and main catalytic specie of the solid acid catalyst；
S2: the acid amount and catalytic efficiency of the solid acid catalyst are measured at a temperature of different disposal, determines solid acid catalyst In the crystallization water and its acid relationship；
S3: solid acid catalyst is divided into 2 parts, a copy of it poisons all acid in solid acid catalyst by poisonous agent 1 Center, while another poisons the acid site B in solid acid catalyst by poisonous agent 2, then determines the solid acid catalysis Acid centre type and its ratio in agent.
9. the research method of the catalytic active center of novel solid acid catalyst according to claim 8, which is characterized in that institute Stating the treatment temperature in step S2 is 100 ~ 500 DEG C.
10. the research method of the catalytic active center of novel solid acid catalyst according to claim 8, which is characterized in that The poisonous agent 1 is pyridine, and poisonous agent 2 is 2,6- lutidines or 2,6- di-tert-butyl pyridine.
CN201811443991.5A 2018-11-29 2018-11-29 A kind of research method of novel solid acid catalyst and application and its catalytic active center Pending CN109382119A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811443991.5A CN109382119A (en) 2018-11-29 2018-11-29 A kind of research method of novel solid acid catalyst and application and its catalytic active center

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811443991.5A CN109382119A (en) 2018-11-29 2018-11-29 A kind of research method of novel solid acid catalyst and application and its catalytic active center

Publications (1)

Publication Number Publication Date
CN109382119A true CN109382119A (en) 2019-02-26

Family

ID=65429930

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811443991.5A Pending CN109382119A (en) 2018-11-29 2018-11-29 A kind of research method of novel solid acid catalyst and application and its catalytic active center

Country Status (1)

Country Link
CN (1) CN109382119A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006289158A (en) * 2005-04-05 2006-10-26 Mitsubishi Heavy Ind Ltd Catalyst for synthesis of acetal and method of manufacturing acetal
CN102079740A (en) * 2010-12-07 2011-06-01 尹华芳 Method for preparing butyraldehyde glycol acetal
CN107790191A (en) * 2017-10-17 2018-03-13 江苏大学 The preparation method of the solid acid catalyst reacted for cyclohexanone and ethylene ketal

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006289158A (en) * 2005-04-05 2006-10-26 Mitsubishi Heavy Ind Ltd Catalyst for synthesis of acetal and method of manufacturing acetal
CN102079740A (en) * 2010-12-07 2011-06-01 尹华芳 Method for preparing butyraldehyde glycol acetal
CN107790191A (en) * 2017-10-17 2018-03-13 江苏大学 The preparation method of the solid acid catalyst reacted for cyclohexanone and ethylene ketal

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
将达波等: "磷石膏催化合成缩醛（酮)", 《石油化工》 *
蒋达波等: "磷石膏在合成缩醛( 酮) 中的催化作用研究", 《广州化工》 *

Similar Documents

Publication Publication Date Title
CN101274922B (en) Preparation for epoxypropane
da Silva Rocha et al. Phosphotungstic heteropoly acid as efficient heterogeneous catalyst for solvent-free isomerization of α-pinene and longifolene
Song et al. Highly selective synthesis of methyl ethyl ketone oxime through ammoximation over Ti-MWW
CN103418432A (en) Hierarchical-pore titanium silicon molecular sieve catalyst synthesized with assistance of aerosol and preparation method of hierarchical-pore titanium silicon molecular sieve catalyst
Vilanculo et al. One-pot synthesis at room temperature of epoxides and linalool derivative pyrans in monolacunary Na 7 PW 11 O 39-catalyzed oxidation reactions by hydrogen peroxide
CN1858048A (en) Method for preparing ketal in ionic liquid
CN105601490B (en) Efficiently catalyzing and oxidizing α isophorones prepare ketoisophorone
CN110343078A (en) A kind of preparation method of furans ether compound
CN105665002A (en) Method for regenerating deactivated titanium silicon molecular sieve catalyst
CN102309983B (en) Method for regenerating inactivated titanium silicon molecular sieve
CN101116810A (en) Modified coal-radicle activated charcoal solid catalyst and method for preparing the same and the application in the aldehyde acetal/ketone building-up reactions
Feliczak-Guzik et al. Mesoporous niobosilicates serving as catalysts for synthesis of fragrances
Davies et al. Nanoporous alumino-and borosilicate-mediated Meinwald rearrangement of epoxides
Bao et al. Efficient procedure for oxathioacetalization using the novel ionic liquid
de Meireles et al. Heteropoly acid catalysts for the valorization of biorenewables: Isomerization of caryophyllene oxide in green solvents
CN102256919A (en) Continuous method for producing substituted cyclohexylmethanols
CN109382119A (en) A kind of research method of novel solid acid catalyst and application and its catalytic active center
Chávez et al. Sulfuric acid adsorbed on silica gel. An efficient catalyst for the tetrahydropyranylation of alcohols
EP2487150B1 (en) Process for producing a lactone
CN111978274A (en) Method for preparing butylene oxide
CN1680032A (en) Tungsten-contained mesic porous molecular sieve catalyst for synthesis of glutaraldehyde and its production
CN107021969A (en) The method that catalysis oxidation prepares biotin precursor ketone acid
CN103373903B (en) Method for preparing methylphenol by hydroxylating methylbenzene
CN105111044A (en) Method for synthesizing isopentenol from butenol
CN113651776A (en) Purifying agent for compound containing aldehyde impurities and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190226