CN104801332A - Preparation method of catalyst for methanol to aromatics - Google Patents
Preparation method of catalyst for methanol to aromatics Download PDFInfo
- Publication number
- CN104801332A CN104801332A CN201410035193.4A CN201410035193A CN104801332A CN 104801332 A CN104801332 A CN 104801332A CN 201410035193 A CN201410035193 A CN 201410035193A CN 104801332 A CN104801332 A CN 104801332A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- methanol
- zsm
- roasting
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a preparation method of a catalyst for methanol to aromatics. The preparation method of the catalyst includes the following steps: (a) providing a hydrogen-type ZSM-5 molecular sieve; (b) modifying the hydrogen-type ZSM-5 molecular sieve in the step (a) with an acid solution, and conducting separation, washing, drying, and roasting to obtain a modified hydrogen-type ZSM-5 molecular sieve; (c) dipping a solution containing metal cobalt to the modified hydrogen-type ZSM-5 molecular sieve in step (b), drying and calcining to obtain the catalyst for methanol to aromatics. The invention also provides the catalyst for methanol to aromatics and application thereof.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, relate to a kind of for the Catalysts and its preparation method by methanol-fueled CLC aromatic hydrocarbons particularly.
Background technology
The aromatic hydrocarbons being representative with benzene,toluene,xylene (be referred to as BTX) is large petrochemicals of a class high added value, its chemical industry, medicine and other fields all tool have been widely used.Along with the scarcity of petroleum resources, the price of aromatic hydrocarbons also remains high.Be converted into aromatic hydrocarbons from resourceful methyl alcohol, be a very valuable alternative route, caused increasingly extensive concern.
Originate from preparing gasoline by methanol technique the earliest by methyl alcohol preparing aromatic hydrocarbon, first this technique succeeded in developing by Mobil company, and realized industrialization in 1979 in New Zealand.
CN201010261674.9 reports a kind of method for preparing catalyst of methyl alcohol preparing aromatic hydrocarbon, the method use molecular sieve carrier in ZSM-5, ZSM-11 and beta-molecular sieve one or several, adopt the modifications such as La and P, the aromatics yield obtained is about 60wt%, and the yield of described BTX is 24-35%.
CN1880288A discloses the small-grain ZSM-5 catalyst of a kind of load gallium and lanthanum, and proposes the two-stage method reaction process of the further aromatisation of accessory substance alkene of reaction.The yield of aromatic hydrocarbons reaches more than 65wt%.
CN200910135643.6 discloses a kind of method for preparing catalyst of aromatization of methanol, adopts Ga, Zn, Cu, Cr, Ag of variable concentrations to be carried on ZSM-5 molecular sieve, at pressure 2.3Mpa, 400 DEG C, raw material liq air speed 4.0h
-1under reaction condition, the yield of aromatic hydrocarbons is 60-65wt%.
In sum, CN1880288A, CN200910135643.6 refer to how to improve aromatics yield to 60 ~ 65%, but fail to improve BTX; And the aromatics yield of CN201010261674.9 is 60wt%, and BTX also to improve and to reach yield be 24-35% compared to prior art, but the content of described BTX still has much room for improvement.
Therefore, this area lacks the methyl alcohol that can improve aromatics yield and BTX content and produces arenes catalytic agent and preparation method thereof.
Summary of the invention
The first object of the present invention is that obtaining the methyl alcohol that can improve aromatics yield and BTX content produces arenes catalytic agent and preparation method thereof.
The second object of the present invention is to obtain the method that can improve the methyl alcohol preparing aromatic hydrocarbon of aromatics yield and BTX content.
The third object of the present invention is that obtaining the methyl alcohol that can improve aromatics yield and BTX content produces arenes catalytic agent.
The fourth object of the present invention is to obtain the purposes that the described methyl alcohol that can improve aromatics yield and BTX content produces arenes catalytic agent.
In a first aspect of the present invention, provide the preparation method of a kind of Methanol arenes catalytic agent, described method for preparing catalyst comprises the steps:
A () provides Hydrogen ZSM-5 molecular sieve;
B the Hydrogen ZSM-5 molecular sieve of () described step (a) adopts acid solution to carry out modification, obtain the Hydrogen ZSM-5 molecular sieve of modification after separation, washing, drying and roasting;
C (), by the Hydrogen ZSM-5 molecular sieve of the modification of step (b) described in the solution impregnation of containing metal cobalt, obtains described Methanol arenes catalytic agent after drying and roasting.
In a specific embodiment of the present invention, the silica alumina ratio (SiO of described Hydrogen ZSM-5 molecular sieve
2/ Al
2o
3) be 20-200, be preferably 30-150, described silica alumina ratio is that mol ratio calculates.
In a specific embodiment of the present invention, described acid solution can be nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid one or several.
In a specific embodiment of the present invention, the concentration of described acid solution is 0.05-1mol/L.
In a specific embodiment of the present invention, in step (b), during modification, the Hydrogen ZSM-5 of described step (a) and the mixing temperature of acid solution are 20-100 DEG C; Incorporation time is 1-24h.
In a specific embodiment of the present invention, in step (c), the solution impregnation of described containing metal cobalt is 20-100 DEG C to the dipping temperature on the modified hydrogen ZSM-5 of described step (c); Dip time is 1-24h.
In a specific embodiment of the present invention, described metallic cobalt source can be one or several of cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate etc.
In a specific embodiment of the present invention, the content of metallic cobalt is the 0.1-10% of total catalyst weight, is preferably 0.1-8%.
In a specific embodiment of the present invention, the sintering temperature of described ZSM-5 molecular sieve is 300-800 DEG C, is preferably 400-600 DEG C.
A second aspect of the present invention provides a kind of method of Methanol aromatic hydrocarbons, and described method comprises: when there is catalyst of the present invention, and methyl alcohol is with gas phase and catalyst exposure, thus reaction generates the hydrocarbon compound containing aromatic hydrocarbons.
In a specific embodiment of the present invention, preferably carry out under the following conditions: reaction temperature is 300-550 DEG C, is more preferably 350-500 DEG C; Reaction pressure is 0.1-5MPa, is more preferably 0.1-2Mpa; Methanol feed liquid air speed is 0.1-20h
-1, be more preferably 0.1-10h
-1, most preferably be 0.1-5h
-1.
The Methanol arenes catalytic agent that a third aspect of the present invention provides a kind of method of the present invention to obtain.
A fourth aspect of the present invention provides the application of a kind of Methanol arenes catalytic as described in the present invention agent in the reaction of Methanol aromatic hydrocarbons.
Detailed description of the invention
The present inventor, through extensive and deep research, by improving preparation technology, obtains a kind of Catalysts and its preparation method improving Methanol aromatic hydrocarbons activity, can improve Methanol especially for the yield of aromatic hydrocarbons and BTX content.Complete the present invention on this basis.
Technical conceive of the present invention is:
Method for preparing catalyst all more complicated of current Methanol aromatic hydrocarbons, generally all adopt various metals load on ZSM-5 molecular sieve, and less for the study on the modification of ZSM-5 molecular sieve self.The present invention proposes a kind of method of modifying of effective ZSM-5 molecular sieve, then the single metallic cobalt of load is on the ZSM-5 molecular sieve of modification, achieves the simplification of catalyst preparing, and improves the activity of Methanol aromatic hydrocarbons of catalyst.
Technological means of the present invention or obtain effect and comprise:
Preparation method provided by the invention first adopts certain density acid solution to carry out modification to ZSM-5 molecular sieve, then ZSM-5 molecular sieve is dry, roasting; Again with the above-mentioned modified ZSM-5 of solution impregnation containing metallic cobalt, complete preparation process by steps such as drying, roastings.
Catalyst powder prepared by preparation method provided by the invention can adopt extruded moulding or spray shaping more further, therefore goes for fixed bed or fluidized-bed process, and method for preparing catalyst has good versatility.
Below describe in detail to various aspects of the present invention:
In the present invention, term " contains " or " comprising " represents that various composition can be applied in mixture of the present invention or composition together.Therefore, term " primarily of ... composition " and " by ... form " be included in term and " contain " or in " comprising ".
The preparation method of catalyst
The invention provides the preparation method of a kind of Methanol arenes catalytic agent, described method for preparing catalyst comprises the steps:
A () provides Hydrogen ZSM-5 molecular sieve;
B the Hydrogen ZSM-5 molecular sieve of () described step (a) adopts acid solution to carry out modification, obtain the Hydrogen ZSM-5 molecular sieve of modification after separation, washing, drying and roasting;
C (), by the Hydrogen ZSM-5 molecular sieve of the modification of step (b) described in the solution impregnation of containing metal cobalt, obtains described Methanol arenes catalytic agent after drying and roasting.
Described " Hydrogen ZSM-5 molecular sieve " is commercially, also can by being obtained by ammonium nitrate ion-exchange of sodium form that be commercially available or oneself synthesis." Hydrogen ZSM-5 molecular sieve " the former powder of NaZSM-5 should be can be after high-temperature roasting removing template, carry out ion-exchange in the solution such as ammonium nitrate after through drying, roasting and obtaining.
Concrete example is as (but being not limited thereto): take a certain amount of NaZSM-5 molecular screen primary powder (Catalyst Factory, Nankai Univ, silica alumina ratio SiO
2/ Al
2o
3=38), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
In a specific embodiment of the present invention, the silica alumina ratio (SiO of described Hydrogen ZSM-5 molecular sieve
2/ Al
2o
3) be 20-200, be preferably 30-150.Described silica alumina ratio is that mol ratio calculates.
In a detailed description of the invention, the ZSM-5 molecular sieve of this Hydrogen is mixed at a certain temperature with certain density acid solution, then ZSM-5 molecular sieve is separated and wash, dry, roasting; Last again by the solution impregnation of containing metal cobalt on ZSM-5 molecular sieve, and drying, roasting and obtain final catalyst.
In a specific embodiment of the present invention, described acid solution can be nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid one or several.These are only citing, acid solution of the present invention is not limited thereto, and also can be inorganic acid solution or the organic acid soln of other solubilities, only otherwise to goal of the invention of the present invention produces and limits.Preferably, this acid solution is strong acid solution, such as hydrochloric acid, sulfuric acid, nitric acid etc., and it easily can ionize out hydrogen ion, facilitates dealuminzation, and therefore effect is better.Secondly, this acid solution also can be weak acid, such as acetic acid, citric acid etc.
In a specific embodiment of the present invention, the concentration of described acid solution is 0.05-1mol/L.The concentration of described acid solution can regulate further according to actual conditions, and this is all in protection scope of the present invention.Preferably, when described acid solution is strong acid, the concentration of strong acid solution is 0.05-1mol/L.The concentration of acid solution is selected also very important, when acid solutions is too large, catalyst backbone can be caused to cave in because of excessive dealuminzation; When concentration is too little, the effect of modification can not had because of too rare.Certainly, described acid solution also can be weak acid.
In a specific embodiment of the present invention, in step (b), during modification, the Hydrogen ZSM-5 of described step (a) and the mixing temperature of acid solution are 20-100 DEG C, preferred 30-80 DEG C, more preferably 40-60 DEG C; Incorporation time is 1-24h, preferred 2-10 hour.During modification mixing temperature choose very important, the too high then dealuminzation of temperature is serious, and cause catalyst backbone to cave in, the too low then effect of temperature is bad.In addition, during modification incorporation time choose also very important.Study discovery through the present inventor, product generation cracking is easily caused in excessively strong acid site, and cause accessory substance alkane many, hydrogen transfer reaction is violent; And than being easier to carbon distribution on acid site.The acid site that these are excessively strong is taken off, and leaves stronger acid site, be then conducive to the formation of aromatic hydrocarbons.And the present inventor finds, has a reasonable time scope at a suitable temperature, excessively strong acid site can be taken off in this time range, thus dredging duct.Overlong time then dealuminzation is serious, time too short DeGrain.
In a specific embodiment of the present invention, in step (c), the solution impregnation of described containing metal cobalt is 20-100 DEG C to the temperature on the modified hydrogen ZSM-5 of described step (c); Dip time is 1-24h, and for ensureing dipping effect, dip time can not be too short, at least 1-12 hour.
In a specific embodiment of the present invention, described metallic cobalt source can be one or several of cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate etc.
In a specific embodiment of the present invention, the content of metallic cobalt is the 0.1-10% of total catalyst weight, is preferably 0.1-8%.In this dipping process, may the ion-exchange of generating portion, but the deposition of mainly cobalt salt.
In a specific embodiment of the present invention, in order to improve activity, the sintering temperature of described ZSM-5 molecular sieve is 300-800 DEG C, is preferably 400-600 DEG C.Roasting after dipping is necessary step, and in this roasting process, cobalt salt becomes cobalt oxide state.
The invention provides a kind of Methanol arenes catalytic agent preparation method of ZSM-5 molecular sieve structure of containing metal cobalt.Method for preparing catalyst provided by the invention is for first to use acid solution modified zsm-5 zeolite, and then by metallic cobalt load on the ZSM-5 molecular sieve of modification, catalyst prepared by the method reacts the content of the arene content, particularly BTX that can significantly improve in product for Methanol aromatic hydrocarbons.
Specifically, a certain amount of NaZSM-5 molecular screen primary powder (Catalyst Factory, Nankai Univ, silica alumina ratio SiO is taken
2/ Al
2o
3=38), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.Or this Hydrogen ZSM-5 molecular sieve is bought from market.
By the ZSM-5 molecular sieve of this Hydrogen and certain density acid solution, preferred concentration be the strong acid solution of 0.05-1mol/L at a certain temperature, such as, at 20-100 DEG C mix, incorporation time is 1-24h, then ZSM-5 molecular sieve is separated and wash, drying, roasting; Last again by the solution impregnation of containing metal cobalt on ZSM-5 molecular sieve, and drying, roasting and obtain final catalyst, sintering temperature is 300-800 DEG C, is preferably 400-600 DEG C.
The Methanol arenes catalytic agent that the present invention also provides a kind of described method to obtain.
The method of Methanol aromatic hydrocarbons
A method for Methanol aromatic hydrocarbons, described method comprises: when catalyst of the present invention, and methyl alcohol is with gas phase and catalyst exposure, thus reaction generates aromatic hydrocarbons and other hydro carbons.Do not add water in methyl alcohol or add little water.
Described method has no particular limits type of reactor and reaction condition, as used fixed bed or fluidized-bed reactor etc.
In a specific embodiment of the present invention, preferably carry out under the following conditions: reaction temperature is 300-550 DEG C, is more preferably 350-500 DEG C; Reaction pressure is 0.1-5MPa, is more preferably 0.1-2Mpa; Methanol feed liquid air speed is 0.1-20h
-1, be more preferably 0.1-10h
-1, most preferably be 0.1-5h
-1.Described reaction condition can improve the content of BTX further.
Preferred embodiment
The invention discloses the preparation method of a kind of Methanol arenes catalytic agent, described method for preparing catalyst is specific as follows:
The ZSM-5 molecular sieve of Hydrogen is mixed at a certain temperature with certain density acid solution, then ZSM-5 molecular sieve is separated and wash, dry, roasting; Last again by the solution impregnation of containing metal cobalt on ZSM-5 molecular sieve, and drying, roasting and obtain final catalyst.
Described ZSM-5 molecular sieve requires as Hydrogen, silica alumina ratio (SiO
2/ Al
2o
3) be 20-200, be preferably 30-150.
Described acid solution can be one or several in nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid etc.Be preferably the strong acid such as nitric acid, hydrochloric acid, sulfuric acid, the concentration of described acid solution is 0.05-1mol/L.
The mixing temperature of Hydrogen ZSM-5 molecular sieve and acid solution is 20-100 DEG C; Incorporation time is 1-24h.
The cobalt-carrying solution temperature be impregnated on ZSM-5 is 20-100 DEG C; Dip time is 1-24h.Metallic cobalt source can be one or several of cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate etc.The content of metallic cobalt is the 0.1-10% of total catalyst weight, is preferably 0.1-8%.
In catalyst preparation process, the sintering temperature of ZSM-5 molecular sieve is 300-800 DEG C, is preferably 400-600 DEG C.
When there is aforesaid catalyst, methyl alcohol is with gas phase and catalyst exposure, thus reaction generates aromatic hydrocarbons and other hydro carbons.Described method has no particular limits type of reactor and reaction condition, as used fixed bed or fluidized-bed reactor etc., preferably carries out under the following conditions: reaction temperature is 300-550 DEG C; Reaction pressure is 0.1-5MPa; Methanol feed liquid air speed is 0.1-20h
-1.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the conventional method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the meaning be familiar with identical.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight portion, and all percentage is weight percentage, and described polymer molecular weight is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the meaning be familiar with identical.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
Take a certain amount of NaZSM-5 molecular screen primary powder (Catalyst Factory, Nankai Univ, silica alumina ratio SiO
2/ Al
2o
3=38), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 50 DEG C, put into the hydrochloric acid solution of 200ml0.3mol/L, be uniformly mixed 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.2g cobalt nitrate, 30ml water, mixes, and the cobalt nitrate solution then ZSM-5 after roasting being put into 40 DEG C floods 12h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter) be 1.2wt%.
Methanol aromatic hydrocarbons reacts:
Catalyst breakage after roasting is sieved as 20-40 order.
Taking 8 grams of Catalyst packings, to enter internal diameter be in the stainless steel fixed bed reactors of 12mm, at reaction conditions, passes into methanol vapor wherein, to react.Concrete reaction condition is: reaction temperature: 420 DEG C, pressure: 0.5Mpa, the liquid air speed of methyl alcohol: 2.0h
-1.Methyl alcohol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 300 DEG C, makes methanol liquid gasify and form steam in this preheater, and then insulation enters reactor and reacts.Product uses gas-chromatography to carry out on-line analysis under the condition of insulation, and gas-chromatography adopts PLOT Q capillary column and hydrogen flame detector.
Embodiment 2
Take a certain amount of NaZSM-5 molecular screen primary powder (Catalyst Factory, Nankai Univ, silica alumina ratio SiO
2/ Al
2o
3=38), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 60 DEG C, put into the citric acid solution of 200ml0.3mol/L, be uniformly mixed 6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.5g cobalt nitrate, 30ml water, mixes, and then the ZSM-5 after roasting is put into 20 DEG C of cobalt nitrate solutions and floods 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter, accounts for total amount) be 1.8wt%.
The reaction of Methanol aromatic hydrocarbons and analysis condition are with embodiment 1.
Embodiment 3
Take a certain amount of NaZSM-5 molecular screen primary powder (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO
2/ Al
2o
3=50), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 55 DEG C, put into the hydrochloric acid solution of 200ml0.2mol/L, be uniformly mixed 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.8g cobaltous sulfate, 30ml water, mixes, and the cobalt sulfate solution then ZSM-5 after roasting being put into 30 DEG C floods 15h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter, accounts for total amount) be 2.1wt%.
The reaction of Methanol aromatic hydrocarbons and analysis condition are with embodiment 1.
Embodiment 4
Take a certain amount of NaZSM-5 molecular screen primary powder (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO
2/ Al
2o
3=50), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 50 DEG C, put into the salpeter solution of 200ml0.1mol/L, be uniformly mixed 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.7g cobalt nitrate, 30ml water, mixes, and the cobalt nitrate solution then ZSM-5 after roasting being put into 20 DEG C floods 12h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter, accounts for total amount) be 1.9wt%.
The reaction of Methanol aromatic hydrocarbons and analysis condition are with embodiment 1.
Embodiment 5
Take a certain amount of NaZSM-5 molecular screen primary powder (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO
2/ Al
2o
3=50), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 20 DEG C, put into the sulfuric acid solution of 200ml0.2mol/L, be uniformly mixed 6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.5g cobaltous sulfate, 30ml water, mixes, and then the ZSM-5 after roasting is put into 25 DEG C of cobalt sulfate solutions and floods 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter, accounts for total amount) be 2.0wt%.
The reaction of Methanol aromatic hydrocarbons and analysis condition are with embodiment 1.
Embodiment 6
Take a certain amount of NaZSM-5 molecular screen primary powder (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO
2/ Al
2o
3=50), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 30 DEG C, put into the sulfuric acid solution of 200ml0.1mol/L, be uniformly mixed 6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.5g cobalt chloride, 30ml water, mixes, and then the ZSM-5 after roasting is put into 40 DEG C of cobalt chloride solutions and floods 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter, accounts for total amount) be 2.2wt%.
The reaction of Methanol aromatic hydrocarbons and analysis condition are with embodiment 1.
Embodiment 7
Take a certain amount of NaZSM-5 molecular screen primary powder (Catalyst Factory, Nankai Univ, silica alumina ratio SiO
2/ Al
2o
3=38), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 30 DEG C, put into the phosphoric acid solution of 200ml0.3mol/L, be uniformly mixed 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.5g cobalt chloride, 30ml water, mixes, and then the ZSM-5 after roasting is put into 25 DEG C of cobalt chloride solutions and floods 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter, accounts for total amount) be 2.1wt%.
The reaction of Methanol aromatic hydrocarbons and analysis condition are with embodiment 1.
Embodiment 8
Hydrogen type catalyst used is commercial HZSM-5 molecular sieve (the silica alumina ratio SiO bought from Tianjin Nankai university
2/ Al
2o
3=38).Take 20 grams of above-mentioned HZSM-5 molecular sieves, at 40 DEG C, put into the phosphoric acid solution of 200ml0.1mol/L, be uniformly mixed 6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h;
Take 1.5g cobalt chloride, 30ml water, mixes, and then the ZSM-5 after roasting is put into 40 DEG C of cobalt chloride solutions and floods 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, measure the content of metal Co (by Co through ICP
2o
3meter, accounts for total amount) be 1.9wt%.
Comparative example 1
Take a certain amount of NaZSM-5 molecular screen primary powder (Catalyst Factory, Nankai Univ, silica alumina ratio SiO
2/ Al
2o
3=38), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Be 20-40 order by the HZSM-5 molecular sieve catalyst crushing and screening after above-mentioned roasting.
Taking 8 grams of Catalyst packings, to enter internal diameter be in the stainless steel fixed bed reactors of 12mm, at reaction conditions, passes into methanol vapor wherein, to react.Concrete reaction condition is: reaction temperature: 420 DEG C, pressure: 0.5Mpa, the liquid air speed of methyl alcohol: 2.0h
-1.Methyl alcohol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 300 DEG C, makes methanol liquid gasify and form steam in this preheater, and then insulation enters reactor and reacts.Product uses gas-chromatography to carry out on-line analysis under the condition of insulation, and gas-chromatography adopts PLOT Q capillary column and hydrogen flame detector.
Comparative example 2
Take a certain amount of NaZSM-5 molecular screen primary powder (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO
2/ Al
2o
3=50), roasting removing template at 550 DEG C, in 80 DEG C of water-baths, exchange 2 times with the ammonium nitrate solution of 1mol/L, the molecular sieve after exchange is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieve of Hydrogen.
Be 20-40 order by the HZSM-5 molecular sieve catalyst crushing and screening after above-mentioned roasting.
Taking 8 grams of Catalyst packings, to enter internal diameter be in the stainless steel fixed bed reactors of 12mm, at reaction conditions, passes into methanol vapor wherein, to react.Concrete reaction condition is: reaction temperature: 420 DEG C, pressure: 0.5Mpa, the liquid air speed of methyl alcohol: 2.0h
-1.Methyl alcohol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 300 DEG C, makes methanol liquid gasify and form steam in this preheater, and then insulation enters reactor and reacts.Product uses gas-chromatography to carry out on-line analysis under the condition of insulation, and gas-chromatography adopts PLOT Q capillary column and hydrogen flame detector.
Result gathers and is listed in the table below.
Table 1
* note: aromatics yield is based on THC product
Conclusion
From above-described embodiment, the catalyst of Methanol aromatic hydrocarbons of the present invention obtains higher aromatics yield, is more valuablely that of obtaining higher BTX content, thus greatly improves the value of Methanol for aromatic hydrocarbons route as an alternative.
In addition, when to reach mol ratio be 35 ~ 40 to silica alumina ratio of the present invention, can arrive best effect, its aromatics yield is not less than 65%, even reaches more than 70%, BTX yield and is not less than 43%, even reach more than 50%.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (13)
1. a preparation method for Methanol arenes catalytic agent, described method for preparing catalyst comprises the steps:
A () provides Hydrogen ZSM-5 molecular sieve;
B the Hydrogen ZSM-5 molecular sieve of () described step (a) adopts acid solution to carry out modification, obtain the Hydrogen ZSM-5 molecular sieve of modification after separation, washing, drying and roasting;
C the solution impregnation of containing metal cobalt on the Hydrogen ZSM-5 molecular sieve of the modification of described step (b), is obtained described Methanol arenes catalytic agent after drying and roasting by ().
2. the method for claim 1, is characterized in that, the silica alumina ratio (SiO of described Hydrogen ZSM-5 molecular sieve
2/ Al
2o
3) be 20-200, be preferably 30-150, described silica alumina ratio calculates with mol ratio.
3. the method for claim 1, is characterized in that, described acid solution is one or several in nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid.
4. the method for claim 1, is characterized in that, the concentration of described acid solution is 0.05-1mol/L.
5. the method for claim 1, is characterized in that, in step (b), during modification, the Hydrogen ZSM-5 of described step (a) and the mixing temperature of acid solution are 20-100 DEG C; Incorporation time is 1-24h.
6. the method for claim 1, is characterized in that, in step (c), the solution impregnation of described containing metal cobalt is 20-100 DEG C to the temperature on the modified hydrogen ZSM-5 of described step (b); Dip time is 1-24h.
7. the method for claim 1, is characterized in that, the metallic cobalt source of the solution of described containing metal cobalt is one or several in cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate.
8. the method for claim 1, is characterized in that, in described catalyst, the content of metallic cobalt is the 0.1-10% of total catalyst weight, is preferably 0.1-8%.
9. the method for claim 1, is characterized in that, after dipping, the sintering temperature of described ZSM-5 molecular sieve is 300-800 DEG C, is preferably 400-600 DEG C.
10. a method for Methanol aromatic hydrocarbons, described method comprises: when there is the catalyst as described in any one in claim 1-9, and methyl alcohol is with gas phase and catalyst exposure, thus reaction generates the hydrocarbon compound containing aromatic hydrocarbons.
11. methods as claimed in claim 10, is characterized in that, preferably carry out under the following conditions: reaction temperature is 300-550 DEG C, is more preferably 350-500 DEG C; Reaction pressure is 0.1-5MPa, is more preferably 0.1-2Mpa; Methanol feed liquid air speed is 0.1-20h
-1, be more preferably 0.1-10h
-1, most preferably be 0.1-5h
-1.
The Methanol arenes catalytic agent that 12. 1 kinds of the method for claim 1 obtain.
The application of 13. 1 kinds of Methanol arenes catalytics as claimed in claim 12 agent in the reaction of Methanol aromatic hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410035193.4A CN104801332B (en) | 2014-01-24 | 2014-01-24 | A kind of methanol aromatic hydrocarbons process catalyst preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410035193.4A CN104801332B (en) | 2014-01-24 | 2014-01-24 | A kind of methanol aromatic hydrocarbons process catalyst preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104801332A true CN104801332A (en) | 2015-07-29 |
| CN104801332B CN104801332B (en) | 2017-12-19 |
Family
ID=53686776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410035193.4A Expired - Fee Related CN104801332B (en) | 2014-01-24 | 2014-01-24 | A kind of methanol aromatic hydrocarbons process catalyst preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104801332B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607080A (en) * | 2015-10-21 | 2017-05-03 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing arene through adopting methyl alcohol as raw material and preparation and application methods thereof |
| CN109701599A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The catalyst of methanol aromatic hydrocarbons and application thereof method |
| CN109701622A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The fluid catalyst of methanol aromatic hydrocarbons |
| CN109701597A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Methanol arenes catalytic agent of high hydrothermal stability and application thereof |
| CN109701598A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Methanol arenes catalytic agent and application thereof |
| CN110498425A (en) * | 2018-05-17 | 2019-11-26 | 中国科学院大连化学物理研究所 | A kind of method of selective modification zeolite molecular sieve outer surface acidity |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767038A (en) * | 2010-02-05 | 2010-07-07 | 中国海洋石油总公司 | Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application |
| CN102895990A (en) * | 2011-07-29 | 2013-01-30 | 中国石油天然气股份有限公司 | Light hydrocarbon aromatization catalyst and preparation method thereof |
| US20140018592A1 (en) * | 2012-07-12 | 2014-01-16 | Shanghai Research Institute Of Petrochemical Technology Sinopec | Molded catalyst for the conversion of methanol to aromatics and process for producing the same |
-
2014
- 2014-01-24 CN CN201410035193.4A patent/CN104801332B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767038A (en) * | 2010-02-05 | 2010-07-07 | 中国海洋石油总公司 | Catalyst for preparing paraxylene by methyl alcohol conversion, preparation method thereof and application |
| CN102895990A (en) * | 2011-07-29 | 2013-01-30 | 中国石油天然气股份有限公司 | Light hydrocarbon aromatization catalyst and preparation method thereof |
| US20140018592A1 (en) * | 2012-07-12 | 2014-01-16 | Shanghai Research Institute Of Petrochemical Technology Sinopec | Molded catalyst for the conversion of methanol to aromatics and process for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| SINA SARTIPI,ET AL: "Hierarchical H-ZSM-5-supported cobalt for the direct synthesis of gasoline-range hydrocarbons from syngas: Advantages, limitations, and mechanistic insight", 《JOURNAL OF CATALYSIS》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607080A (en) * | 2015-10-21 | 2017-05-03 | 上海碧科清洁能源技术有限公司 | Catalyst for preparing arene through adopting methyl alcohol as raw material and preparation and application methods thereof |
| CN106607080B (en) * | 2015-10-21 | 2019-01-18 | 上海碧科清洁能源技术有限公司 | It is a kind of for preparing the catalyst and its methods for making and using same of aromatic hydrocarbons using methanol as raw material |
| CN109701599A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The catalyst of methanol aromatic hydrocarbons and application thereof method |
| CN109701622A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The fluid catalyst of methanol aromatic hydrocarbons |
| CN109701597A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Methanol arenes catalytic agent of high hydrothermal stability and application thereof |
| CN109701598A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Methanol arenes catalytic agent and application thereof |
| CN109701598B (en) * | 2017-10-26 | 2022-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon from methanol and application thereof |
| CN109701599B (en) * | 2017-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon from methanol and application method thereof |
| CN109701597B (en) * | 2017-10-26 | 2022-07-12 | 中国石油化工股份有限公司 | Methanol-to-aromatic hydrocarbon catalyst with high hydrothermal stability and application thereof |
| CN109701622B (en) * | 2017-10-26 | 2022-07-12 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing aromatic hydrocarbon from methanol |
| CN110498425A (en) * | 2018-05-17 | 2019-11-26 | 中国科学院大连化学物理研究所 | A kind of method of selective modification zeolite molecular sieve outer surface acidity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104801332B (en) | 2017-12-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104801332A (en) | Preparation method of catalyst for methanol to aromatics | |
| CN104307560B (en) | Catalyst for preparing propylene byproduct high-octane gasoline by taking methanol as raw material and preparation method of catalyst | |
| CN105536863B (en) | A kind of molecular sieve catalyst and its preparation method and purposes for methanol conversion for preparing arene | |
| KR101127996B1 (en) | A microsphere catalyst used for converting oxygen compound to olefine and preparation method thereof | |
| CN104053504B (en) | For oxygenate being changed into the improvement performance of the ZSM-5 zeolite catalyst that Ga-and Zn-of aromatic hydrocarbons exchanges | |
| CN105435839B (en) | A kind of methanol arenes catalytic agent for containing two kinds of molecular sieves and preparation method | |
| CN106607080B (en) | It is a kind of for preparing the catalyst and its methods for making and using same of aromatic hydrocarbons using methanol as raw material | |
| CN105597815A (en) | ZSM-5/ZnVPI-8 composite structure molecular sieve catalyst | |
| CN105195211A (en) | Methyl alcohol and C4 hydrocarbon aromatization catalyst and aromatization method | |
| CN106311269A (en) | Iron-based catalyst prepared by sol-gel combustion method, and preparation method and applications of iron-based catalyst | |
| CN102895990A (en) | Light hydrocarbon aromatization catalyst and preparation method thereof | |
| CN102211036B (en) | A kind of modified molecular sieve catalyst and its precursor and preparation method thereof | |
| CN111203283A (en) | Supported catalyst, preparation method thereof and method for preparing olefin by oxidative coupling of methane | |
| CN105195172A (en) | In-situ synthesis method for light-hydrocarbon aromatization catalyst | |
| CN107970949B (en) | A kind of three selective hydrogenation catalyst of carbon, preparation method and method of hydrotreating | |
| CN105642342A (en) | SAPO-5/SAPO-34 composite molecular sieve, preparation method and application thereof | |
| CN106607048B (en) | The method of fixed bed production low-carbon alkene | |
| CN101444732B (en) | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof | |
| CN102600889B (en) | Light hydrocarbon aromatization catalyst and its preparation method | |
| CN101357876B (en) | Method for conveying C<+>9 heavy aromatics to light aromatics | |
| CN104174430B (en) | Alcohol ether is converted into paraxylene and C by one 2-C 3the Catalysts and its preparation method of alkene | |
| CN104907091B (en) | A kind of catalyst, its preparation method and its application for being used to prepare aromatic hydrocarbons by methanol | |
| CN104667955B (en) | A catalyst for hydrogenation modification and a preparing method thereof | |
| CN105498829B (en) | A kind of aromatization of methanol catalyst and its preparation method and application | |
| CN106215971A (en) | A kind of catalyst of two-step method preparing gasoline by methanol hydrocarbonylation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171219 Termination date: 20210124 |