CN104646054A - Solid acid catalyst supporting methane sulfonic acid, preparation method and application of same - Google Patents
Solid acid catalyst supporting methane sulfonic acid, preparation method and application of same Download PDFInfo
- Publication number
- CN104646054A CN104646054A CN201310585101.5A CN201310585101A CN104646054A CN 104646054 A CN104646054 A CN 104646054A CN 201310585101 A CN201310585101 A CN 201310585101A CN 104646054 A CN104646054 A CN 104646054A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solid acid
- acid catalyst
- highly
- olefin component
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a solid acid catalyst supporting methane sulfonic acid, a preparation method and an application of the same. In particular, the invention provides a strong acidic solid acid catalyst for removing olefin components from aromatic hydrocarbon, wherein the strong acidic solid acid catalyst is in the form of an amorphous state and includes amorphous silicon dioxide and the methane sulfonic acid supported thereon. The strong acidic solid acid catalyst is prepared through following steps: (1) under a water-free condition, mixing tetraethoxysilane (TEOS) and anhydrous formic acid to obtain a homogeneous solution; (2) adding the methane sulfonic acid and mixing the mixture continuously to form a catalyst intermediate; and (3) roasting the intermediate to obtain the strong acidic solid acid catalyst. The invention also provides the preparation method and the application of the strong acidic solid acid catalyst. The strong acidic solid acid catalyst has an excellent catalytic performance. Successful preparation and application of the catalyst develops a new way of novel green industrialization.
Description
Technical field
The present invention relates to polyester compound probability, be specifically related to a kind of highly acid solid acid catalyst for olefin component in Arene removal, especially paraxylene.This highly acid solid acid catalyst is with ethyl orthosilicate (TEOS) for silicon source, and anhydrous formic acid is hydrolyst, and Loprazolam is sour modifier, obtains in anhydrous conditions.The invention still further relates to the preparation method of described highly acid solid acid catalyst and this highly acid solid acid catalyst in the production of aromatic hydrocarbons, especially paraxylene for removing the application of olefin component.
Technical background
In recent years, along with developing rapidly and the intervention energetically of private enterprise of China's polyester industrial, the demand of China to terephthalic acid (TPA) constantly increases.Paraxylene is as the direct upstream raw material of terephthalic acid (TPA), and its demand also not whisk broom new record, all needs every year from external a large amount of import.For meeting the domestic market constantly expanded, drive economic development, country has examined a collection of paraxylene project.Because the olefin component in aromatic hydrocarbons material can have a strong impact on the carrying out of product purity and subsequent technique in the production process of paraxylene, so wherein there is a step to relate to the bromine index reducing aromatic hydrocarbons material.
The method reducing bromine index in general current art has two kinds:
(1) hydrogenation technique, this technique is very effective to reduction bromine index, but this technological operation requirement is high, difficulty large, owing to using its degree of danger of hydrogen also larger, so the scope of application is limited;
(2) clay-filtered technique, this technological operation is very simple, and safety coefficient is higher, for most of refinery adopts, but the carclazyte in this technique is easy inactivation when high bromine index, this just causes the discharge of a large amount of solid waste and the waste of national mineral resources.
For concentrating the strong point of above-mentioned two kinds of techniques, abandon its deficiency, people have studied a lot of method, such as, carry out various modification to carclazyte, extend its service life, but its effect is still limited.
In research before, it is found that the pure methane sulfonic acid of liquid has good effect for the alkylated reaction of catalyzing aromatic hydrocarbon and alkene, and Loprazolam is a kind of environmental friendliness class organic acid, within 28 days in natural environment, namely can be analyzed to carbon dioxide, water and sulfur dioxide, but be obviously restricted as its scope of application of liquid acid, be difficult to carry out commercial scale use in existing technique.
At present, have some reports that sulfonic acid group is incorporated into silica surface by some, but they otherwise need use template, need the precursor of oxidant or sulfonic acid group, and the later stage needs to wash, this causes the environmental pollution of production process, and operating process is loaded down with trivial details, is unfavorable for actual use.
In order to overcome the above-mentioned many technical problems existed in prior art, be therefore badly in need of a kind of simple to operate, be beneficial to practical application, environmental friendliness and efficiently can remove the highly acid solid acid catalyst of olefin component in aromatic hydrocarbons material.
Summary of the invention
For this reason, one aspect of the present invention provides a kind of highly acid solid acid catalyst for olefin component in Arene removal, and wherein, described highly acid solid acid catalyst is amorphous state, and comprises amorphous silica and the load Loprazolam on it; Described highly acid solid acid catalyst obtains in the following manner:
(1) in anhydrous conditions, by ethyl orthosilicate (TEOS) and anhydrous formic acid mixing, uniform solution is formed;
(2) add Loprazolam, continue mixing, form catalyst intermediate; With
(3) catalyst intermediate described in roasting, forms highly acid solid acid catalyst.
In one embodiment of the present invention, described highly acid solid acid catalyst keeps original amorphous state after 500 DEG C of roastings.
In one embodiment of the present invention, the specific area of described highly acid solid acid catalyst is 300-1000m
2/ g, pore-size distribution is at 0.81-2.17nm.
On the other hand, the present invention also provides a kind of and prepares the described method for the highly acid solid acid catalyst of olefin component in Arene removal, and described method comprises:
(1) in anhydrous conditions, mixing ethyl orthosilicate (TEOS) and anhydrous formic acid, form uniform mixed solution;
(2) add Loprazolam, continue mixing, form catalyst intermediate; With
(3) catalyst intermediate described in roasting, forms highly acid solid acid catalyst.
In one embodiment of the present invention, described ethyl orthosilicate (TEOS) and anhydrous formic acid mol ratio are 1:0.05-5.
In one embodiment of the present invention, in the dry mass of amorphous silica, the amount of described Loprazolam is 1 quality %-30 quality %.
In one embodiment of the present invention, described catalyst intermediate leaves standstill 1-6 hour at 20-100 DEG C, preferably 30 DEG C.
In one embodiment of the present invention, described catalyst intermediate at the temperature of 60-500 DEG C in Muffle furnace roasting 1-6 hour.
In one embodiment of the present invention, mixing ethyl orthosilicate (TEOS) and anhydrous formic acid carry out by stirring for 30-100 minute.
In a preferred embodiment, the stirring intensity continuing after adding Loprazolam to mix is higher than the stirring intensity mixing ethyl orthosilicate (TEOS) and anhydrous formic acid, preferred, continues mixing 1-100 minute after adding Loprazolam.
The present invention provide on the other hand described for Arene removal in the highly acid solid acid catalyst of olefin component in the production of aromatic hydrocarbons, especially paraxylene for removing the application of olefin component.
Specifically (but being not limited thereto), the present invention is with ethyl orthosilicate (TEOS) for silicon source, and anhydrous formic acid is hydrolyst, and Loprazolam is sour modifier, in anhydrous conditions, has prepared highly acid solid acid catalyst.Described highly acid solid acid catalyst shows outstanding catalytic performance in olefin component removing in high bromine index aromatic hydrocarbons material, and the green for chemical enterprise is produced and opened a new route.
In a particular embodiment, the method preparing highly acid solid acid catalyst is as follows:
(1) in stirred tank, add ethyl orthosilicate and anhydrous formic acid according to a certain percentage, preferred molar ratio is 1:0.05-5, and stirs 30-100 minute, obtains uniform mixed solution;
(2) then add Loprazolam according to the 1%-30% of amorphous silica dry mass, strengthen stirring intensity, continue to stir 1-100 minute;
(3) catalyst intermediate obtained is left standstill 1-6 hour at 30 DEG C, be then transferred in Muffle furnace, at the roasting temperature 1-6 hour of 60-500 DEG C, obtain highly acid solid acid catalyst catalyst.
In the present invention, the experiment evaluating olefin component in Arene removal material is carried out in micro fixed-bed reactor.Catalytic reaction condition is as follows:
2 grams of catalyst and 4 grams of quartz sands are loaded in reactor according to the order of quartz sand-catalyst-quartz sand, at temperature 60-300 DEG C, pressure 1.0-2.5MPa, weight space velocity 1-30h
-1condition under, react 8 hours.Sample analysis per hour, analyzes sample bromine index with bromine valency bromine index instrument.
In the present invention, evaluating catalyst method visible " for removing the acidity of the modified clay of Trace Olefins and catalytic performance and industrial test (Acidic and Catalytic Propertiesof Modified Clay for Removing Trace Olefin from Aromatics and ItsIndustrial Test) thereof from aromatic hydrocarbons "; Xin Pu, Nai-wang Liu, Zheng-hong Jiang, and LiShi.; " Chemical Engineering of American Chemical Society and industrial research (Ind.Eng.Chem.Res.) " the 2012,51st volume, 13891-13896 page.
In the present invention, described bromine index analytic process is with reference to the determination step of deolefination initial activity in chemical industry standard HG/T2825-2009.
And the concrete metering system of " N2 adsorption-desorption isothermal curve " of the present invention carries out according to GB GB/T19587-2004.
The concrete metering system of pore size distribution curve of the present invention carries out according to GB GB/T19587-2004.
The concrete metering system of XRD figure of the present invention carries out according to GB GB/T19421.1-2003.
Highly acid solid acid catalyst prepared by the present invention has the characteristic of obvious amorphous silica.Before catalyst can find out load Loprazolam after XRD analysis after and load, structure compared does not obviously change.In addition, the heat resistance of this highly acid solid acid catalyst has obvious lifting, still maintains original amorphous state through 500 DEG C of calcined catalyst.Specific surface area analysis result shows: the specific area of highly acid solid acid catalyst of the present invention is at 300-1000m
2between/g, pore-size distribution is at 0.81-2.17nm.
Accompanying drawing explanation
Fig. 1 is the nitrogen adsorption-desorption curve according to the highly acid solid acid catalyst sample of the load Loprazolam of embodiment 1 preparation in the present invention.
Wherein, in Fig. 1, the curve of top represents desorption curve, and in Fig. 1, the curve of below represents adsorption curve.
Fig. 2 is the pore size distribution curve according to the highly acid solid acid catalyst sample of the load Loprazolam of embodiment 1 preparation in the present invention.
Fig. 3 is the characteristic X-ray diffract collection of illustrative plates (XRD) of the different sample of gained in the present invention.
Wherein: a: pure silicon dioxide carrier;
B: the highly acid solid acid catalyst sample prepared according to embodiment 1;
C: the highly acid solid acid catalyst sample prepared according to embodiment 2.
Fig. 4 is the catalyst catalytic performance curve using olefin removal rate as measurement index of the highly acid solid acid catalyst sample of the load Loprazolam prepared according to embodiment 1 and embodiment 2 in the present invention.
Wherein a: the performance curve of the highly acid solid acid catalyst adopting embodiment 1 to prepare;
B: the performance curve of the highly acid solid acid catalyst adopting embodiment 2 to prepare.
Detailed description of the invention
The invention is further illustrated by the following examples.It is noted that under the condition not deviating from purport of the present invention and spirit, those of ordinary skill in the art can modify to concrete embodiment and change.These modifications and variations also drop in scope disclosed by the invention.
Embodiment 1:
In stirred tank, add ethyl orthosilicate 21g and anhydrous formic acid 50g, stir 30 minutes, obtain uniform mixed solution.Then add Loprazolam 0.7g, strengthen stirring intensity, continue stirring 50 minutes, form catalyst intermediate.The catalyst intermediate that obtains is left standstill 6 hours at 30 DEG C, is then transferred in Muffle furnace, at the roasting temperature 6 hours of 100 DEG C, obtain solid acid catalyst.
The present embodiment is obtained solid acid catalyst sample and carries out following evaluation:
(1) N
2adsorption-desorption isothermal curve,
(2) graph of pore diameter distribution,
(3) XRD figure.
The N of embodiment 1 gained solid acid catalyst sample
2adsorption-desorption isothermal curve, graph of pore diameter distribution, XRD figure is shown in Fig. 1-Fig. 3 respectively:
Wherein, the catalyst that prepared by its N2 adsorption-desorption isothermal curve explanation embodiment 1 belongs to the IV type physisorption isotherms that IUPAC (IUPAC) proposes.Along with the rising of relative pressure, there will be capillary condensation phenomenon in catalyst duct, catalyst surface can produce the multilayer absorption of gas.
Its graph of pore diameter distribution illustrates that the aperture of catalyst prepared by embodiment 1 is between 0.81-2.17nm, and duct proportion near 1.5nm is larger.Reaction object can move freely in the catalyst with this pore passage structure, and course of reaction does not control by the size of reactant molecule.
A in XRD figure, b two curves show that the solid acid catalyst sample of embodiment 1 has the identical XRD feature of pure (amorphous) silica supports, and before showing the catalyst after load Loprazolam and load, structure compared does not obviously change.
Embodiment 2:
In stirred tank, add ethyl orthosilicate 21g and anhydrous formic acid 50g, stir 30 minutes, obtain uniform mixed solution.Then add Loprazolam 0.7g, strengthen stirring intensity, continue stirring 50 minutes, form catalyst intermediate.The catalyst intermediate that obtains is left standstill 6 hours at 30 DEG C, is then transferred in Muffle furnace, at the roasting temperature 6 hours of 500 DEG C, obtain solid acid catalyst.
As described in Example 1, XRD evaluation is carried out to embodiment 2 gained solid acid catalyst.
From the b of Fig. 3, c curve is known, the solid acid catalyst sample of embodiment 2 has the identical XRD feature of pure (amorphous) silica supports equally, shows that the catalyst after 500 DEG C of baked load Loprazolams is compared silicon dioxide structure with the catalyst after the load Loprazolam of DEG C roasting of 100 in embodiment 1 and obviously do not changed.That is, the skeleton structure of catalyst can be born the temperature of 500 DEG C and be unlikely to avalanche.
Embodiment 3:
The solid acid catalyst 2ml of load Loprazolam prepared by Example 1 and embodiment 2, loads in micro fixed-bed reactor, temperature 100 DEG C, and pressure 1.0MPa, weight space velocity 30h
-1condition under, react 8 hours.Sample analysis per hour, analyzes sample bromine index with bromine valency bromine index instrument.Catalyst catalytic performance curve using olefin removal rate as measurement index is shown in Fig. 4.
This figure shows catalyst and still have considerable catalytic performance after 500 DEG C of roasting, but slightly declines relative to the catalyst catalytic performance of 100 DEG C of roastings.
Claims (10)
1. for a highly acid solid acid catalyst for olefin component in Arene removal, wherein, described highly acid solid acid catalyst is amorphous state, and comprises amorphous silica and the load Loprazolam on it; Described highly acid solid acid catalyst obtains in the following manner:
(1) in anhydrous conditions, by ethyl orthosilicate (TEOS) and anhydrous formic acid mixing, uniform solution is formed;
(2) add Loprazolam, continue mixing, form catalyst intermediate; With
(3) catalyst intermediate described in roasting, forms highly acid solid acid catalyst.
2., as claimed in claim 1 for the highly acid solid acid catalyst of olefin component in Arene removal, it is characterized in that, described highly acid solid acid catalyst keeps original amorphous state after 500 DEG C of roastings.
3., as claimed in claim 1 for the highly acid solid acid catalyst of olefin component in Arene removal, it is characterized in that, the specific area of described highly acid solid acid catalyst is 300-1000m
2/ g, pore-size distribution is at 0.81-2.17nm.
4. prepare the method for the highly acid solid acid catalyst of olefin component in Arene removal described in any one of claim 1-3, described method comprises:
(1) in anhydrous conditions, by ethyl orthosilicate (TEOS) and anhydrous formic acid mixing, uniform solution is formed;
(2) add Loprazolam, continue mixing, form catalyst intermediate; With
(3) catalyst intermediate described in roasting, forms highly acid solid acid catalyst.
5. as claimed in claim 4 for the preparation of the method for the highly acid solid acid catalyst of olefin component in Arene removal, it is characterized in that, described ethyl orthosilicate (TEOS) and anhydrous formic acid mol ratio are 1:0.05-5.
6. as claimed in claim 4 for the preparation of the method for the highly acid solid acid catalyst of olefin component in Arene removal, it is characterized in that, in the dry mass of amorphous silica, the amount of described Loprazolam is 1 quality %-30 quality %.
7. as described in any one of claim 4-6 for the preparation of the method for the highly acid solid acid catalyst of olefin component in Arene removal, it is characterized in that, described catalyst intermediate leaves standstill 1-6 hour at 20-100 DEG C, preferably 30 DEG C.
8. as described in any one of claim 4-6 for the preparation of the method for the highly acid solid acid catalyst of olefin component in Arene removal, it is characterized in that, described catalyst intermediate at the temperature of 60-500 DEG C in Muffle furnace roasting 1-6 hour.
9. as described in any one of claim 4-6 for the preparation of the method for the highly acid solid acid catalyst of olefin component in Arene removal, it is characterized in that, mixing ethyl orthosilicate (TEOS) and anhydrous formic acid by stirring within 30-100 minute, carry out; The stirring intensity continuing after adding Loprazolam to mix, higher than the stirring intensity mixing ethyl orthosilicate (TEOS) and anhydrous formic acid, preferably, continues mixing 1-100 minute after adding Loprazolam.
10. described in any one of claim 1-3 for the highly acid solid acid catalyst of olefin component in Arene removal in the production of aromatic hydrocarbons, especially paraxylene for removing the application of olefin component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310585101.5A CN104646054B (en) | 2013-11-19 | 2013-11-19 | Load solid acid catalyst, its preparation method and its application of Loprazolam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310585101.5A CN104646054B (en) | 2013-11-19 | 2013-11-19 | Load solid acid catalyst, its preparation method and its application of Loprazolam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104646054A true CN104646054A (en) | 2015-05-27 |
| CN104646054B CN104646054B (en) | 2017-10-13 |
Family
ID=53237986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310585101.5A Expired - Fee Related CN104646054B (en) | 2013-11-19 | 2013-11-19 | Load solid acid catalyst, its preparation method and its application of Loprazolam |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104646054B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825579A (en) * | 2020-07-23 | 2020-10-27 | 山东益丰生化环保股份有限公司 | Preparation method of pentaerythritol ester |
| CN113461944A (en) * | 2021-06-10 | 2021-10-01 | 佳化化学科技发展（上海）有限公司 | Solid acid and preparation method and application thereof |
| CN114471704A (en) * | 2020-10-23 | 2022-05-13 | 华东理工大学 | Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004337819A (en) * | 2003-03-20 | 2004-12-02 | Showa Denko Kk | Solid acid catalyst |
| CN102600896A (en) * | 2012-01-20 | 2012-07-25 | 山东华阳油业有限公司 | Solid catalyst of bonded type organic sulfonic acid and its preparation method |
-
2013
- 2013-11-19 CN CN201310585101.5A patent/CN104646054B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004337819A (en) * | 2003-03-20 | 2004-12-02 | Showa Denko Kk | Solid acid catalyst |
| CN102600896A (en) * | 2012-01-20 | 2012-07-25 | 山东华阳油业有限公司 | Solid catalyst of bonded type organic sulfonic acid and its preparation method |
Non-Patent Citations (3)
| Title |
|---|
| YING TIAN ET AL: ""A Novel Application of Methanesulfonic Acid as Catalyst for the Alkylation of Olefins with Aromatics"", 《IND. ENG. CHEM. RES.》 * |
| 任立国 等: ""二氧化硅负载甲烷磺酸催化酯交换制备生物柴油"", 《工业催化》 * |
| 章华桂: ""正硅酸乙酯的非水溶胶-凝胶反应与微滴乳液聚合法原位纳米复合"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825579A (en) * | 2020-07-23 | 2020-10-27 | 山东益丰生化环保股份有限公司 | Preparation method of pentaerythritol ester |
| CN114471704A (en) * | 2020-10-23 | 2022-05-13 | 华东理工大学 | Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons |
| CN113461944A (en) * | 2021-06-10 | 2021-10-01 | 佳化化学科技发展（上海）有限公司 | Solid acid and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104646054B (en) | 2017-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Alcañiz-Monge et al. | Zirconia-supported tungstophosphoric heteropolyacid as heterogeneous acid catalyst for biodiesel production | |
| Wang et al. | Improved Fischer–Tropsch synthesis for gasoline over Ru, Ni promoted Co/HZSM-5 catalysts | |
| Burattin et al. | Ni/SiO2 materials prepared by deposition− precipitation: influence of the reduction conditions and mechanism of formation of metal particles | |
| Zhao et al. | Effect of surface acidic and basic properties of the supported nickel catalysts on the hydrogenation of pyridine to piperidine | |
| CN103950951B (en) | A kind of synthetic method of heteroatoms ZSM-5 molecular sieve and application thereof | |
| CN104557423B (en) | Method for preparing arene by directly converting methane | |
| CN102101818B (en) | Method for synthesizing dimethylbenzene by alkylation of benzene and methanol | |
| CN105728018B (en) | For benzene, the ZSM-5 zeolite catalyst of methanol alkylation, its preparation method and application | |
| Li et al. | Morphology-dependent catalytic performance of mordenite in carbonylation of dimethyl ether: Enhanced activity with high c/b ratio | |
| CN107497475A (en) | A kind of aromatized catalyst and preparation method thereof | |
| CN101269340A (en) | High silicon-aluminum ratio ZSM-5 zeolite catalyst, preparation method and application thereof | |
| CN104646054A (en) | Solid acid catalyst supporting methane sulfonic acid, preparation method and application of same | |
| CN105148897B (en) | A kind of catalysis biological ethanol prepares catalyst of low-carbon alkene and preparation method and application | |
| CN109438159A (en) | One kind being based on chemical chain Lattice Oxygen Transfer Technology methane oxidation coupling method | |
| Wang et al. | Hierarchical ZSM-5 Supported CoMn Catalyst for the Production of Middle Distillate from Syngas | |
| Ren et al. | The effects of ammonium sulfate and sulfamic acid on the surface acidity of sulfated zirconia | |
| CN104549541B (en) | A kind of catalyst for heavy oil catalytic cracking carrier and catalyst and preparation method thereof | |
| CN105498827B (en) | The method for efficiently preparing biomass-based aromatic hydrocarbons | |
| Karnjanakom et al. | Selective deoxygenation of carboxylic acids to BTXs over Cu/β-zeolite prepared by ethylene glycol-assisted impregnation | |
| Wang et al. | Steam catalytic cracking of coal tar over iron‐containing mixed metal oxides | |
| Xu et al. | Zinc-assisted nanometric Pt cluster stabilized on KL zeolite via atomic layer deposition for the n-heptane aromatization | |
| Lin et al. | Studies on oxy-bromination of methane and coke deposition over FePO4/SiO2 catalysts | |
| Thaker et al. | Hydroisomerization of biomass derived n-hexadecane towards diesel pool: effect of selective removal external surface sites from Pt/ZSM-22 | |
| CN102614906A (en) | ZSM-5 molecular sieve based catalyst used for preparing ethylene through ethanol dehydration and preparation method thereof | |
| CN103551159A (en) | 2,3,6-methylphenol catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171013 Termination date: 20211119 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |