CN102371178A - Catalyst for preparing arene by methanol conversion and preparation method thereof - Google Patents
Catalyst for preparing arene by methanol conversion and preparation method thereof Download PDFInfo
- Publication number
- CN102371178A CN102371178A CN2010102617309A CN201010261730A CN102371178A CN 102371178 A CN102371178 A CN 102371178A CN 2010102617309 A CN2010102617309 A CN 2010102617309A CN 201010261730 A CN201010261730 A CN 201010261730A CN 102371178 A CN102371178 A CN 102371178A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hzsm
- methanol conversion
- gram
- hmcm
- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a catalyst for preparing arene by methanol conversion and a preparation method thereof. The problems of complex process route flow and low selectivity of a target product in the prior art are mainly solved. The problems are well solved by adopting the technical scheme that: the catalyst comprises the following components in part by weight: a) 20 to 80 parts of molecular sieve carrier, b) 0.1 to 12 parts of zinc element or oxide thereof carried on the molecular sieve carrier, c) 0.1 to 10 parts of nickel or phosphorus element or oxide thereof and d) 20 to 80 parts of adhesive, wherein the molecular sieve comprises a mixture of HZSM-5 and at least one of HZSM-11 and HMCM-22 molecular sieves, and the weight ratio of the HZSM-5 to the at least one of the HZSM-11 and the HMCM-22 is (0.1-10): 1. The catalyst can be used in the field of industrially producing the arene by methanol conversion.
Description
Technical field
The present invention relates to the Catalysts and its preparation method that a kind of methanol conversion prepares aromatic hydrocarbons.
Background technology
Since China's oil and natural gas resource shortage, and coal resources are abundant relatively.In recent years, burning hot situation appears in China Coal Chemical Industry cause, the various places various Coal Chemical Industry projects that start one after another.As comparatively ripe coal chemical technology, coal-based synthesizing methanol becomes the first-selected project of most coal chemical industry enterprises.In recent years; China is that raw material production methyl alcohol is towards maximization, energy-saving development with coal; Output constantly increases, and therefore the production capacity of methyl alcohol will actively carry out the exploitation of Downstream Products of Methanol considerably beyond actual demand; Increase new methyl alcohol application, improve the production technology level of existing Downstream Products of Methanol, the development of methanol industry is had crucial meaning.
The methanol conversion research contents is very abundant.External Uop Inc., Lurgi company have developed MTO (methanol conversion system alkene respectively; Comprise ethene and propylene) and MTP (preparing propylene by methanol transformation) technology, Exxon-Mobil company has developed MTG (methanol conversion system gasoline) technology and MOGD (methanol conversion system petrol and diesel oil) technology.Domestic such as the Dalian Chemistry and Physics Institute and Shanxi coalification etc. also methanol conversion has been carried out a large amount of research, and aspect two of catalyst and reaction process, obtained breakthrough.But no matter see from present circumstances, be to be high-quality gasoline with methanol conversion, still is converted into alkene, and the economy of process is all hindered owing to the restriction that receives added value of product makes its industrialization process.
Aromatic hydrocarbons (especially benzene (Benzene), toluene (Toluene) and xylenes (Xylene) are referred to as BTX) is important petrochemical industry basic raw material, has high added value.The aromatic hydrocarbons of China is mainly derived from petroleum resources, and the present situation of China's oil shortage of resources has determined the scarcity of aromatic hydrocarbon resource, and therefore, it is most important to seek a kind of new technology that can replace petrochemical industry to produce aromatic hydrocarbons.From the direct preparing aromatic hydrocarbon by converting of resourceful methyl alcohol,, has significant values for the shortage of alleviating aromatic hydrocarbons, the added value that improves Downstream Products of Methanol, prolongation Coal Chemical Industry and gas chemical industry's industrial chain.
CN 1880288A has introduced a kind of technology and catalyst of methanol conversion for preparing arene; This catalyst is carrier with the ZSM-5 molecular sieve with small crystal grains; Load active component gallium and lanthanum are that 0.1～5.0MPa, 300～460 ℃ of operating temperatures, raw material liq air speed are 0.1～6.0h at operating pressure
-1Catalyzed conversion is for aromatic hydrocarbons being main product under the condition, and the process refrigerated separation is with gas-phase product lower carbon number hydrocarbons and liquid product C
5 +Hydrocarbon separates, liquid product C
5 +Hydrocarbon obtains aromatic hydrocarbons and non-aromatic hydrocarbons through extract and separate.This technological essence is the methanol conversion technique for preparing gasoline, promptly on the basis of original methanol conversion technique for preparing gasoline, through the performance modulation of catalyst, makes that the arene content in the product increases.But the used ZSM-5 molecular sieve of this specification requirement is little crystal grain, and the gas-phase product lower carbon number hydrocarbons of one section reaction get into second stage reactor continue to react the second-stage reaction product, the process route flow process is comparatively complicated.
Summary of the invention
One of technical problem to be solved by this invention is complicated and target product aromatic hydrocarbons (especially BTX) problem that selectivity is not high of the process route flow process that exists in the prior art, and a kind of catalyst of new methanol conversion for preparing arene is provided.This catalyst is used for methanol conversion and prepares aromatic hydrocarbons and have the high and high advantage of BTX selectivity of product of catalyst activity.Two of technical problem to be solved by this invention provides one of a kind of and technical solution problem corresponding methanol conversion and prepares the preparation method of arenes catalytic agent.
For one of solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of methanol conversion prepares the catalyst of aromatic hydrocarbons, comprises in parts by weight: a) 20～80 parts of molecular sieve carriers; With the b that carries on it) 0.1～12 part of zinc element or its oxide; C) 0.1～10 part is selected from nickel or P elements or its oxide; D) 20～80 parts of binding agents, wherein molecular sieve comprises HZSM-5 and is selected from least a mixture in HZSM-11 or the HMCM-22 molecular sieve, HZSM-5 be selected from HZSM-11 or at least a weight ratio of HMCM-22 is 0.1～10: 1.
In the technique scheme, the binding agent preferred version is Al
2O
3HZSM-5 be selected from HZSM-11 or at least a weight ratio preferable range of HMCM-22 is 0.2～5: 1; In parts by weight, contain zinc element or its oxide preferable range in the catalyst being 0.5～8 part is 0.5～5 part with being selected from nickel or P elements or its oxide preferable range.
For solve the problems of the technologies described above two, the technical scheme that the present invention adopts is following:
(1) with the HZSM-5 of aequum and at least a and binding agent that is selected from HZSM-11 or HMCM-22 molecular sieve mix mixture I; In mixture I, add the expanding agent of gained catalyst weight 0.5～5% and the aqueous solution of nitric acid of aequum; Pinch through mixing, moulding, drying, 500～600 ℃ of roastings be after 2～8 hours; Process catalyst carrier, wherein expanding agent is selected from the sesbania powder; (2) with the acid or the salt that are selected from nickel nitrate or phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate of the zinc nitrate of said catalyst carrier load aequum and aequum; Through dry and 450～600 ℃ of roastings 2～6 hours, process said methanol conversion for preparing arene catalyst.
Contain two kinds of cross one another pore canal system in the ZSM-5 framework of molecular sieve; (pore structure has tangible shape selectivity to mononuclear aromatics to its duct size for 0.56nm * 0.53nm, 0.55nm * 0.51nm) approaching with the kinetic diameter of aromatic hydrocarbon molecule; So be widely used in aromatization; But because the acidity of ZSM-5 is stronger, catalyst is prone to coking deactivation, and therefore single molecular sieve catalyst is difficult to take into account acid matter of methanol conversion for preparing arene reaction pair and the synergistic requirement of pore passage structure.The ZSM-11 molecular sieve is applied in the aromatization owing to its unique pore passage structure and acid centre, and shows higher active and stable.MCM-22 has two kinds of independently pore passage structures; Except that the two-dimentional dextrorotation duct of a kind of ZSM-5 of being similar to ten-ring; Also have the inner space and be respectively two supercages of 0.71nm * 0.71nm * 1.82nm and 0.71nm * 0.71nm * 0.91nm; The existence of supercage has improved the appearance carbon ability of catalyst, and aromatisation stability is improved.ZSM-5 be selected from least a of ZSM-11 or MCM-22 molecular sieve and mix the intermodulation that can realize catalyst acid character and pore passage structure, thereby more help bringing into play both synergies.Adopt catalyst of the present invention, be used for the methanol conversion for preparing arene reaction, in continuous fixed bed reactors, 390 ℃ of pressure 0.3MPa, temperature, weight space velocity 2h
-1Under the condition, its methanol conversion can reach 100%, and the BTX selectivity of product can reach more than 35%, has obtained better technical effect, and technological process is merely one section reaction, and is fairly simple.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
[embodiment 1]
The present embodiment preparation comprises: in total catalyst weight, and 2%NiO, 3%ZnO, 45%HZSM-5,15%HZSM-11,15%HMCM-22,20%Al
2O
3Catalyst A.
Take by weighing 45 gram HZSM-5 molecular sieves, 15 gram HZSM-11 molecular sieves, 15 gram HMCM-22 molecular sieves, 20 gram Al
2O
3, 3.8 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 15 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 14 milliliters of zinc nitrate aqueous solutions that contain 0.63 gram ZnO,, process catalyst intermediate in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours.
Above-mentioned catalyst intermediate impregnated in 14 milliliters of nickel nitrate aqueous solutions that contain 0.42 gram NiO,, process catalyst A in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours.
Adopt this catalyst to be used for the methanol conversion for preparing arene reaction, in continuous fixed bed reactors, 390 ℃ of pressure 0.3MPa, temperature, weight space velocity 2h
-1Under the condition, its methanol conversion is 100%, and the BTX selectivity of product is 38.61%.
[embodiment 2]
The present embodiment preparation comprises: in total catalyst weight, and 5%P
2O
5, 8%ZnO, 30%HZSM-5,30%HZSM-11,7%HMCM-22,20%Al
2O
3Catalyst B.
Take by weighing 30 gram HZSM-5 molecular sieves, 30 gram HZSM-11 molecular sieves, 7 gram HMCM-22 molecular sieves, 20 gram Al
2O
3, 3.5 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 520 ℃ of roastings.
20 gram said catalyst carrier impregnated in 14 milliliters of zinc nitrate aqueous solutions that contain 1.84 gram ZnO,, process catalyst intermediate in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours.
Above-mentioned catalyst intermediate impregnated in 14 milliliters contain 1.15 gram P
2O
5Ammonium dihydrogen phosphate aqueous solution in, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, process catalyst B.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
[embodiment 3]
The present embodiment preparation comprises: in total catalyst weight, and 3%NiO, 5%ZnO, 20%HZSM-5,12%HZSM-11,20%HMCM-22,40%Al
2O
3Catalyst C.
Take by weighing 20 gram HZSM-5 molecular sieves, 12 gram HZSM-11 molecular sieves, 20 gram HMCM-22 molecular sieves, 40 gram Al
2O
3, 3.7 gram sesbania powder, it is mixed, add 43 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 4 hours, process the catalyst carrier of 2～3 millimeters long through drying, 550 ℃ of roastings.
20 gram said catalyst carrier impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 1.09 gram ZnO,, process catalyst intermediate in leaving standstill 24 hours, dry, 500 ℃ of roastings under the room temperature after 4 hours.
Above-mentioned catalyst intermediate impregnated in 15 milliliters of nickel nitrate aqueous solutions that contain 0.65 gram NiO,, process catalyst C in leaving standstill 24 hours, dry, 500 ℃ of roastings under the room temperature after 4 hours.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
[embodiment 4]
The present embodiment preparation comprises: in total catalyst weight, and 1%NiO, 2%ZnO, 10%HZSM-5,7%HZSM-11,20%HMCM-22,60%Al
2O
3Catalyst D.
Take by weighing 10 gram HZSM-5 molecular sieves, 7 gram HZSM-11 molecular sieves, 20 gram HMCM-22 molecular sieves, 60 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 44 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 6 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 0.41 gram ZnO,, process catalyst intermediate in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours.
Above-mentioned catalyst intermediate impregnated in 15 milliliters of nickel nitrate aqueous solutions that contain 0.21 gram NiO,, process catalyst D in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
[embodiment 5]
The present embodiment preparation comprises: in total catalyst weight, and 1%P
2O
5, 0.5%ZnO, 5%HZSM-5,3.5%HZSM-11,10%HMCM-22,80%Al
2O
3Catalyst E.
Take by weighing 5 gram HZSM-5 molecular sieves, 3.5 gram HZSM-11 molecular sieves, 10 gram HMCM-22 molecular sieves, 80 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 6 hours, process the catalyst carrier of 2～3 millimeters long through drying, 600 ℃ of roastings.
20 gram said catalyst carrier impregnated in 16 milliliters of zinc nitrate aqueous solutions that contain 0.10 gram ZnO,, process catalyst intermediate in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours.
Above-mentioned catalyst intermediate impregnated in 16 milliliters contain 0.20 gram P
2O
5Phosphate aqueous solution in, in leaving standstill 24 hours, dry, 550 ℃ of roastings under the room temperature after 3 hours, process catalyst E.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 1]
The preparation of this Comparative Examples comprises: in total catalyst weight, and 0.5%NiO, 1%ZnO, 68.5%HZSM-5,30%Al
2O
3Catalyst F.
Take by weighing 68.5 gram HZSM-5 molecular sieves, 30 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 42 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 5 hours, process the catalyst carrier of 2～3 millimeters long through drying, 520 ℃ of roastings.
20 gram said catalyst carrier impregnated in 14 milliliters of zinc nitrate aqueous solutions that contain 0.20 gram ZnO,, process catalyst intermediate in leaving standstill 24 hours, dry, 600 ℃ of roastings under the room temperature after 2 hours.
Above-mentioned catalyst intermediate impregnated in 14 milliliters of nickel nitrate aqueous solutions that contain 0.10 gram NiO,, process catalyst F in leaving standstill 24 hours, dry, 600 ℃ of roastings under the room temperature after 2 hours.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 2]
The preparation of this Comparative Examples comprises: in total catalyst weight, and 1%P
2O
5, 2%ZnO, 30%HZSM-5,17%HZSM-11,50%Al
2O
3Catalyst G.
Take by weighing 30 gram HZSM-5 molecular sieves, 17 gram HZSM-11,50 gram A1
2O
3, 3.9 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 5 hours, process the catalyst carrier of 2～3 millimeters long through drying, 520 ℃ of roastings.
20 gram said catalyst carrier impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 0.41 gram ZnO,, process catalyst intermediate in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours.
Above-mentioned catalyst intermediate impregnated in 15 milliliters contain 0.21 gram P
2O
5Ammonium phosphate solution in, in leaving standstill 24 hours, dry, 480 ℃ of roastings under the room temperature after 4 hours, process catalyst G.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
[comparative example 3]
The preparation of this Comparative Examples comprises: in total catalyst weight, and 3%ZnO, 40%HZSM-5,10%HZSM-11,17%HMCM-22,30%Al
2O
3Catalyst H.
Take by weighing 40 gram HZSM-5 molecular sieves, 10 gram HZSM-11,17 gram HMCM-22 molecular sieves, 30 gram Al
2O
3, 3.9 gram sesbania powder, it is mixed, add 45 gram mass concentration and be 5% aqueous solution of nitric acid, fully mix and be extruded into the cylindrical of 1.5 millimeters of diameters after pinching, after 6 hours, process the catalyst carrier of 2～3 millimeters long through drying, 550 ℃ of roastings.
20 gram said catalyst carrier impregnated in 15 milliliters of zinc nitrate aqueous solutions that contain 0.62 gram ZnO,, process catalyst H in leaving standstill 24 hours, dry, 450 ℃ of roastings under the room temperature after 6 hours.
Catalyst examination condition is identical with embodiment 1, and reaction result is listed in table 2.
Table 1 catalyst weight is formed (%)
| Example | Catalyst | HZSM-5 | HZSM-11 | HMCM-22 | Al 2O 3 | ZnO | NiO | P 2O 5 |
| Embodiment 1 | A | 45 | 15 | 15 | 20 | 3 | 2 | - |
| Embodiment 2 | B | 30 | 30 | 7 | 20 | 8 | - | 5 |
| Embodiment 3 | C | 20 | 12 | 20 | 40 | 5 | 3 | - |
| Embodiment 4 | D | 10 | 7 | 20 | 60 | 2 | 1 | - |
| Embodiment 5 | E | 5 | 3.5 | 10 | 80 | 0.5 | - | 1 |
| Comparative example 1 | F | 68.5 | - | - | 30 | 1 | 0.5 | - |
| Comparative example 2 | G | 30 | 17 | - | 50 | 2 | - | 1 |
| Comparative example 3 | H | 40 | 10 | 17 | 30 | 3 | - | - |
The methanol conversion for preparing arene reaction result (wt%) of table 2 catalyst
Claims (5)
1. a methanol conversion prepares the catalyst of aromatic hydrocarbons, comprises following component in parts by weight:
A) 20～80 parts of molecular sieve carriers; With carry on it
B) 0.1～12 part of zinc element or its oxide;
C) 0.1～10 part is selected from nickel or P elements or its oxide;
D) 20～80 parts of binding agents;
Wherein molecular sieve comprises HZSM-5 and is selected from least a mixture in HZSM-11 or the HMCM-22 molecular sieve, HZSM-5 be selected from HZSM-11 or at least a weight ratio of HMCM-22 is 0.1～10: 1.
2. prepare the catalyst of aromatic hydrocarbons according to the said methanol conversion of claim 1, it is characterized in that binding agent is selected from Al
2O
3HZSM-5 be selected from HZSM-11 or at least a weight ratio of HMCM-22 is 0.2～5: 1.
3. prepare the catalyst of aromatic hydrocarbons according to the said methanol conversion of claim 1, it is characterized in that, contain 0.5～8 part of zinc element or its oxide in the catalyst in parts by weight.
4. prepare the catalyst of aromatic hydrocarbons according to the said methanol conversion of claim 1, it is characterized in that, contain 0.5～5 part in the catalyst and be selected from nickel or P elements or its oxide in parts by weight.
5. the described methanol conversion of claim 1 prepares the preparation method of arenes catalytic agent, may further comprise the steps successively:
(1) with the HZSM-5 of aequum and at least a and binding agent that is selected from HZSM-11 or HMCM-22 molecular sieve mix mixture I; In mixture I, add the expanding agent of gained catalyst weight 0.5～5% and the aqueous solution of nitric acid of aequum; Pinch through mixing, moulding, drying, 500～600 ℃ of roastings be after 2～8 hours, processes catalyst carrier; Wherein expanding agent is selected from the sesbania powder;
(2) with the acid or the salt that are selected from nickel nitrate or phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate of the zinc nitrate of said catalyst carrier load aequum and aequum; Through dry and 450～600 ℃ of roastings 2～6 hours, process said methanol conversion for preparing arene catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102617309A CN102371178B (en) | 2010-08-23 | 2010-08-23 | Catalyst for preparing arene by methanol conversion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102617309A CN102371178B (en) | 2010-08-23 | 2010-08-23 | Catalyst for preparing arene by methanol conversion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102371178A true CN102371178A (en) | 2012-03-14 |
| CN102371178B CN102371178B (en) | 2013-10-16 |
Family
ID=45790732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102617309A Active CN102371178B (en) | 2010-08-23 | 2010-08-23 | Catalyst for preparing arene by methanol conversion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102371178B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2540333C1 (en) * | 2013-12-24 | 2015-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет тонких химических технологий имени М.В. Ломоносова" (МИТХТ им. М.В. Ломоносова) | Method of initiated continuous catalytic obtaining aromatic hydrocarbons from ethanol |
| CN104549474A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst and preparation method thereof |
| RU2594564C1 (en) * | 2015-05-18 | 2016-08-20 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Catalyst and method of converting ethanol, methanol or mixture thereof |
| CN105949019A (en) * | 2016-04-29 | 2016-09-21 | 浙江大学 | Catalyst and method for improving selectivity of preparation of aromatic hydrocarbon products from methanol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088614A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aromatized eutectic superfine zeolite grain catalyst and its prepn process and application |
| CN101172250A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| CN101596461A (en) * | 2008-06-02 | 2009-12-09 | 中国石油化工股份有限公司 | A kind of aromatizing catalyst for light hydrocarbon and preparation method thereof |
-
2010
- 2010-08-23 CN CN2010102617309A patent/CN102371178B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088614A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Aromatized eutectic superfine zeolite grain catalyst and its prepn process and application |
| CN101172250A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| CN101596461A (en) * | 2008-06-02 | 2009-12-09 | 中国石油化工股份有限公司 | A kind of aromatizing catalyst for light hydrocarbon and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549474A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst and preparation method thereof |
| RU2540333C1 (en) * | 2013-12-24 | 2015-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Московский государственный университет тонких химических технологий имени М.В. Ломоносова" (МИТХТ им. М.В. Ломоносова) | Method of initiated continuous catalytic obtaining aromatic hydrocarbons from ethanol |
| RU2594564C1 (en) * | 2015-05-18 | 2016-08-20 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Catalyst and method of converting ethanol, methanol or mixture thereof |
| CN105949019A (en) * | 2016-04-29 | 2016-09-21 | 浙江大学 | Catalyst and method for improving selectivity of preparation of aromatic hydrocarbon products from methanol |
| CN105949019B (en) * | 2016-04-29 | 2019-12-03 | 浙江大学 | A kind of catalyst and method improving methanol preparing aromatic hydrocarbon selectivity of product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102371178B (en) | 2013-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102372535B (en) | Method for preparing aromatic hydrocarbon through methanol transformation | |
| CN102371177B (en) | Catalyst for preparing aromatic hydrocarbons by methanol conversion and preparation method thereof | |
| CN102380415B (en) | Catalyst for preparing methylbenzene by methanol conversion and preparation method and application thereof | |
| CN102266793A (en) | Catalyst for producing propylene and producing method and application thereof | |
| CN102199446A (en) | Method for producing aromatic hydrocarbon by adopting raw materials containing methanol | |
| CN102416342A (en) | Catalyst for preparing aromatic hydrocarbon through methanol conversion as well as preparation method and application thereof | |
| CN102371178B (en) | Catalyst for preparing arene by methanol conversion and preparation method thereof | |
| CN104557416A (en) | Method for producing arene by employing oxygenated compound as raw material | |
| CN105195211B (en) | A kind of methanol and C4Hydrocarbon aromatizing catalyst and aromatization method | |
| CN104549481B (en) | Composite molecular sieve catalyst for preparing aromatics by use of methanol | |
| CN103623859B (en) | Catalyst for producing propylene with methanol of high third second ratio and preparation method thereof is obtained under high-speed | |
| CN102371176B (en) | Catalyst for preparing aromatic hydrocarbon through methanol conversion and preparation method thereof | |
| CN107398294B (en) | Preparation method and application of modified binder-free ZSM-11 molecular sieve catalyst | |
| CN104557432A (en) | Aromatization method of oxygenated compound | |
| CN103028436B (en) | The Catalysts and its preparation method of Methanol aromatic hydrocarbons | |
| CN102372536B (en) | Method for producing aromatic hydrocarbons by methanol conversion | |
| CN105418345B (en) | A kind of preparation method of biology base aromatic hydrocarbons | |
| CN104557364B (en) | The method of oxygenatedchemicals aromatisation | |
| CN104549444B (en) | The catalyst of oxygenatedchemicals aromatic hydrocarbons and its application | |
| CN103623862B (en) | A kind of Catalysts and its preparation method being produced gasoline component by oil refinery dry gas | |
| CN113385215B (en) | Preparation method and application of catalyst for preparing propane by hydro-upgrading | |
| CN103657707A (en) | Preparation method of low carbon hydrocarbon aromatization catalyst | |
| CN104557419A (en) | Method for preparing aromatic hydrocarbon from methanol or dimethyl ether | |
| CN105272797A (en) | Benzene and methanol alkylation reaction method | |
| CN104437596A (en) | Methanol to arene 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |