CN104801332B - A kind of methanol aromatic hydrocarbons process catalyst preparation method - Google Patents
A kind of methanol aromatic hydrocarbons process catalyst preparation method Download PDFInfo
- Publication number
- CN104801332B CN104801332B CN201410035193.4A CN201410035193A CN104801332B CN 104801332 B CN104801332 B CN 104801332B CN 201410035193 A CN201410035193 A CN 201410035193A CN 104801332 B CN104801332 B CN 104801332B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- methanol
- zsm
- catalyst
- acid
- 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.)
- Expired - Fee Related
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
Abstract
The present invention provides a kind of preparation method of methanol arenes catalytic agent, and the method for preparing catalyst comprises the following steps：(a) molecular sieves of Hydrogen ZSM 5 are provided；(b) molecular sieves of Hydrogen ZSM 5 of the step (a) are modified using acid solution, by separating, wash, are dried and are obtained the modified molecular sieves of Hydrogen ZSM 5 after being calcined；(c) solution containing metallic cobalt is impregnated on the molecular sieves of Hydrogen ZSM 5 of the modification of the step (b), described methanol arenes catalytic agent is obtained after drying and roasting.The present invention also provides described methanol arenes catalytic agent and application thereof.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, is used for urging by methanol-fueled CLC aromatic hydrocarbons more particularly to a kind of
Agent and preparation method thereof.
Background technology
Produced with large petrochemical industry that the aromatic hydrocarbons of benzene,toluene,xylene (being referred to as BTX) for representative is a kind of high added value
Product, it all has and had been widely used in chemical industry, medicine and other fields.With the scarcity of petroleum resources, the price of aromatic hydrocarbons also occupies height not
Under.Aromatic hydrocarbons is converted into from resourceful methanol, is a very valuable alternative route, has caused increasingly extensive
Concern.
Preparing gasoline by methanol technique is originated from by methanol preparing aromatic hydrocarbon earliest, the technique is succeeded in developing first by Mobil companies
, and realized and industrialize in New Zealand in 1979.
CN201010261674.9 reports a kind of method for preparing catalyst of methanol preparing aromatic hydrocarbon, point that this method uses
Son sieve carrier is one or several kinds of in ZSM-5, ZSM-11 and beta-molecular sieve, obtained aromatics yield modified using La and P etc.
About 60wt%, and the yield of the BTX is 24-35%.
CN1880288A discloses a kind of small-grain ZSM-5 catalyst of load gallium and lanthanum, and proposes the pair of reaction
The two-stage method reaction process of the further aromatisation of Product olefins.The yield of aromatic hydrocarbons reaches more than 65wt%.
CN200910135643.6 discloses a kind of method for preparing catalyst of aromatization of methanol, using various concentrations
Ga, Zn, Cu, Cr, Ag are carried on ZSM-5 molecular sieve, in pressure 2.3Mpa, 400 DEG C, raw material liq air speed 4.0h-1React bar
Under part, the yield of aromatic hydrocarbons is 60-65wt%.
In summary, CN1880288A, CN200910135643.6 refer to how to improve aromatics yield to 60~65%,
But it is the failure to improve BTX；And CN201010261674.9 aromatics yield is 60wt%, and BTX also improves compared to prior art
And it is 24-35% to reach yield, but the content of the BTX still has much room for improvement.
Therefore, this area, which lacks, can improve aromatics yield and the methanol preparing aromatic hydrocarbon catalyst of BTX contents and its preparation
Method.
The content of the invention
The first object of the present invention, which is to obtain, can improve aromatics yield and the methanol preparing aromatic hydrocarbon catalyst of BTX contents
And preparation method thereof.
The second object of the present invention is to obtain the side that can improve aromatics yield and the methanol preparing aromatic hydrocarbon of BTX contents
Method.
The third object of the present invention is to obtain the methanol preparing aromatic hydrocarbon catalysis that can improve aromatics yield and BTX contents
Agent.
The fourth object of the present invention is to obtain the methanol preparing aromatic hydrocarbon catalysis that can improve aromatics yield and BTX contents
The purposes of agent.
In the first aspect of the present invention, there is provided a kind of preparation method of methanol arenes catalytic agent, the catalyst system
Preparation Method comprises the following steps：
(a) Hydrogen ZSM-5 molecular sieve is provided；
(b) the Hydrogen ZSM-5 molecular sieve of the step (a) is modified using acid solution, by separating, washing, drying,
With modified Hydrogen ZSM-5 molecular sieve is obtained after roasting；
(c) on the Hydrogen ZSM-5 molecular sieve of modification that the solution containing metallic cobalt is impregnated to the step (b), through drying and
Described methanol arenes catalytic agent is obtained after roasting.
In the specific embodiment of the present invention, the silica alumina ratio (SiO of the Hydrogen ZSM-5 molecular sieve2/Al2O3) be
20-200, preferably 30-150, the silica alumina ratio calculate for mol ratio.
In the specific embodiment of the present invention, the acid solution can be nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, vinegar
Acid, the one or several kinds of citric acid.
In the specific embodiment of the present invention, the concentration of the acid solution is 0.05-1mol/L.
In the specific embodiment of the present invention, in step (b), when modified the Hydrogen ZSM-5 of the step (a) with
The mixing temperature of acid solution is 20-100 DEG C；Incorporation time is 1-24h.
In the specific embodiment of the present invention, in step (c), the solution containing metallic cobalt is impregnated into the step
Suddenly the dipping temperature on the modified hydrogen ZSM-5 of (c) is 20-100 DEG C；Dip time is 1-24h.
In the specific embodiment of the present invention, the metal cobalt source can be cobalt nitrate, cobaltous sulfate, cobalt chloride,
The one or several kinds of cobalt acetate etc..
In the specific embodiment of the present invention, the content of metallic cobalt is the 0.1-10% of total catalyst weight, preferably
For 0.1-8%.
In the specific embodiment of the present invention, the sintering temperature of the ZSM-5 molecular sieve is 300-800 DEG C, excellent
Elect 400-600 DEG C as.
The second aspect of the present invention provides a kind of method of methanol aromatic hydrocarbons, and methods described includes：Institute of the present invention be present
In the case of the catalyst stated, methanol is contacted with gas phase with catalyst, so as to react hydrocarbon compound of the generation containing aromatic hydrocarbons.
In the specific embodiment of the present invention, preferably carry out under the following conditions：Reaction temperature is 300-550
DEG C, more preferably 350-500 DEG C；Reaction pressure is 0.1-5MPa, more preferably 0.1-2Mpa；Methanol feed liquid air speed is
0.1-20h-1, more preferably 0.1-10h-1, most preferably 0.1-5h-1。
The third aspect of the present invention provides the methanol arenes catalytic agent that a kind of method of the present invention obtains.
It is anti-in methanol aromatic hydrocarbons that the fourth aspect of the present invention provides a kind of methanol arenes catalytic agent as described in the present invention
Application in answering.
Embodiment
The present inventor, by improving preparation technology, obtains a kind of raising methanol system virtue by in-depth study extensively
Catalyst of hydrocarbon activity and preparation method thereof, can especially improve yield and BTX contents that methanol prepares aromatic hydrocarbons.It is complete on this basis
Into the present invention.
The technical concept of the present invention is：
The method for preparing catalyst of methanol aromatic hydrocarbons is all more complicated at present, is typically all supported on ZSM- using various metals
On 5 molecular sieves, and it is less for the study on the modification of ZSM-5 molecular sieve itself.The present invention proposes a kind of effective ZSM-5 molecular sieve
Method of modifying, then load single metallic cobalt on the ZSM-5 molecular sieve being modified, realize the simplification of catalyst preparation,
And improve the activity of the methanol aromatic hydrocarbons of catalyst.
The technological means or obtained effect of the present invention includes：
Preparation method provided by the invention is first modified using certain density acid solution to ZSM-5 molecular sieve, then
By ZSM-5 molecular sieve drying, roasting；Above-mentioned modified ZSM-5 is impregnated with the solution containing metallic cobalt again, by drying, roasting
The steps such as burning complete preparation process.
Catalyst powder prepared by preparation method provided by the invention can further use extruded moulding or spray
Mist is molded, therefore goes for fixed bed or fluidized-bed process, and method for preparing catalyst has good versatility.
It is described in detail to various aspects of the present invention below：
In the present invention, term " containing " or " comprising " represent that various composition can be applied to the mixture or group of the present invention together
In compound.Therefore, term " mainly by ... form " and " consist of " are included in term " containing " or " comprising ".
The preparation method of catalyst
The present invention provides a kind of preparation method of methanol arenes catalytic agent, and the method for preparing catalyst includes following step
Suddenly：
(a) Hydrogen ZSM-5 molecular sieve is provided；
(b) the Hydrogen ZSM-5 molecular sieve of the step (a) is modified using acid solution, by separating, washing, drying,
With modified Hydrogen ZSM-5 molecular sieve is obtained after roasting；
(c) on the Hydrogen ZSM-5 molecular sieve of modification that the solution containing metallic cobalt is impregnated to the step (b), through drying and
Described methanol arenes catalytic agent is obtained after roasting.
" the Hydrogen ZSM-5 molecular sieve " is commercially available, can also be led to commercially available or oneself synthesis sodium form
Pernitric acid ammonium ion exchanges to obtain.It can be that NaZSM-5 originals powder removes template through high-temperature roasting to be somebody's turn to do " Hydrogen ZSM-5 molecular sieve "
Afterwards, obtained after carrying out ion exchange in the solution such as ammonium nitrate through drying, being calcined.
Specific such as (but not limited to)：Weigh a certain amount of NaZSM-5 molecular screen primary powders (Catalyst Factory, Nankai Univ,
Silica alumina ratio SiO2/Al2O3=38), roasting removes template at 550 DEG C, and 1mol/L ammonium nitrate solution is used in 80 DEG C of water-baths
Exchange 2 times, 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 sieves of Hydrogen.
In the specific embodiment of the present invention, the silica alumina ratio (SiO of the Hydrogen ZSM-5 molecular sieve2/Al2O3) be
20-200, preferably 30-150.The silica alumina ratio calculates for mol ratio.
In a detailed embodiment, by the ZSM-5 molecular sieve of the Hydrogen and certain density acid solution in a constant temperature
Degree is lower to be mixed, and is then separated ZSM-5 molecular sieve and is washed, dries, is calcined；Finally the solution containing metallic cobalt is impregnated into again
On ZSM-5 molecular sieve, and final catalyst is obtained through drying, roasting.
In the specific embodiment of the present invention, the acid solution can be nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, lemon
The one or several kinds of acid.It these are only citing, acid solution not limited to this of the invention or other soluble inorganic acids
Solution or organic acid soln, as long as not producing limitation to the goal of the invention of the present invention.Preferably, the acid solution is that strong acid is molten
Liquid, such as hydrochloric acid, sulfuric acid, nitric acid etc., it can easily ionize out hydrogen ion, and to facilitate dealuminzation, therefore effect is preferable.Its
Secondary, the acid solution is alternatively weak acid, such as acetic acid, citric acid etc..
In the specific embodiment of the present invention, the concentration of the acid solution is 0.05-1mol/L.The acid solution
Concentration can further be adjusted according to actual conditions, this is within the scope of the present invention.Preferably, the acid is molten
When liquid is strong acid, the concentration of strong acid solution is 0.05-1mol/L.The concentration selection of acid solution is also critically important, works as acid solutions
When too big, because of excessive dealuminzation catalyst backbone can be caused to cave in；When concentration is too small, modified effect can not be had because too dilute
Fruit.Certainly, the acid solution can also be weak acid.
In the specific embodiment of the present invention, in step (b), when modified the Hydrogen ZSM-5 of the step (a) with
The mixing temperature of acid solution is 20-100 DEG C, preferably 30-80 DEG C, more preferably 40-60 DEG C；Incorporation time is 1-24h, preferably 2-10
Hour.The selection of mixing temperature is critically important when modified, and the too high then dealuminzation of temperature is serious, causes catalyst backbone to cave in, temperature is too
Low then effect is bad.In addition, the selection of incorporation time is also critically important when modified.Study and find through the present inventor, in too strong acid
The heart easily causes product and cracked, and causes that accessory substance alkane is more, and hydrogen transfer reaction is violent；And it is easier to accumulate on acid site
Carbon.These too strong acid sites are taken off, leave stronger acid site, then are advantageous to the formation of aromatic hydrocarbons.Moreover, the present inventor
It was found that there is a reasonable time scope at a suitable temperature, too strong acid site can be taken off in this time range
Fall, so as to dredge duct.Then dealuminzation is serious for overlong time, time too short effect unobvious.
In the specific embodiment of the present invention, in step (c), the solution containing metallic cobalt is impregnated into the step
Suddenly the temperature on the modified hydrogen ZSM-5 of (c) is 20-100 DEG C；Dip time is 1-24h, to ensure dipping effect, during dipping
Between can not be too short, at least 1-12 hour.
In the specific embodiment of the present invention, the metal cobalt source can be cobalt nitrate, cobaltous sulfate, cobalt chloride,
The one or several kinds of cobalt acetate etc..
In the specific embodiment of the present invention, the content of metallic cobalt is the 0.1-10% of total catalyst weight, preferably
For 0.1-8%.In the dipping process, it may occur that the ion exchange of part, but the mainly deposition of cobalt salt.
In the specific embodiment of the present invention, in order to improve activity, the sintering temperature of the ZSM-5 molecular sieve is
300-800 DEG C, preferably 400-600 DEG C.Roasting after dipping is necessary step, and in the roasting process, cobalt salt becomes oxygen
Change cobalt state.
The invention provides a kind of methanol arenes catalytic agent preparation method of ZSM-5 molecular sieve structure containing metallic cobalt.
Then metallic cobalt is supported on and changed first to use acid solution modified zsm-5 zeolite by method for preparing catalyst provided by the invention again
Property the ZSM-5 molecular sieve crossed on, catalyst prepared by this method, which is used for the reaction of methanol aromatic hydrocarbons, can significantly improve virtue in product
The content of hydrocarbon content, particularly BTX.
Specifically, a certain amount of NaZSM-5 molecular screen primary powders (Catalyst Factory, Nankai Univ, silica alumina ratio SiO are weighed2/
Al2O3=38), roasting removes template at 550 DEG C, is exchanged 2 times, exchanged with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths
Molecular sieve afterwards is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.Or bought from market
The Hydrogen ZSM-5 molecular sieve.
By the ZSM-5 molecular sieve of the Hydrogen and certain density acid solution, preferred concentration is that 0.05-1mol/L strong acid is molten
Liquid at a certain temperature, such as at 20-100 DEG C mixes, and incorporation time 1-24h, then ZSM-5 molecular sieve is separated and washed
Wash, dry, be calcined；Finally the solution containing metallic cobalt is impregnated on ZSM-5 molecular sieve again, and obtained most through drying, roasting
Whole catalyst, sintering temperature are 300-800 DEG C, preferably 400-600 DEG C.
The present invention also provides the methanol arenes catalytic agent that a kind of described method obtains.
The method of methanol aromatic hydrocarbons
A kind of method of methanol aromatic hydrocarbons, methods described include：In the case of catalyst of the present invention, methanol with
Gas phase contacts with catalyst, so as to react generation aromatic hydrocarbons and other hydro carbons.Water is not added with methanol or adds seldom water.
Methods described has no particular limits to type of reactor and reaction condition, such as uses fixed bed or fluidized-bed reaction
Device etc..
In the specific embodiment of the present invention, preferably carry out under the following conditions：Reaction temperature is 300-550
DEG C, more preferably 350-500 DEG C；Reaction pressure is 0.1-5MPa, more preferably 0.1-2Mpa；Methanol feed liquid air speed is
0.1-20h-1, more preferably 0.1-10h-1, most preferably 0.1-5h-1.The reaction condition can be improved further containing for BTX
Amount.
Preferred embodiment
The invention discloses a kind of preparation method of methanol arenes catalytic agent, the method for preparing catalyst are specific such as
Under：
The ZSM-5 molecular sieve of Hydrogen is mixed at a certain temperature with certain density acid solution, then by ZSM-5 molecules
Sieve separation is simultaneously washed, dries, is calcined；Finally the solution containing metallic cobalt is impregnated on ZSM-5 molecular sieve again, and through drying, roasting
Burn and obtain final catalyst.
Described ZSM-5 molecular sieve requirement is Hydrogen, silica alumina ratio (SiO2/Al2O3) it is 20-200, preferably 30-150.
The acid solution can be the one or several kinds in nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid etc..Preferably nitre
The strong acid such as 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 temperature that cobalt-carrying solution is impregnated on ZSM-5 is 20-100 DEG C；Dip time is 1-24h.Metal cobalt source can be
The one or several kinds of cobalt nitrate, cobaltous sulfate, cobalt chloride, cobalt acetate etc..The content of metallic cobalt is the 0.1- of total catalyst weight
10%, preferably 0.1-8%.
In catalyst preparation process, the sintering temperature of ZSM-5 molecular sieve is 300-800 DEG C, preferably 400-600 DEG C.
In the case where foregoing catalyst be present, methanol is contacted with gas phase with catalyst, so as to react generation virtue
Hydrocarbon and other hydro carbons.Methods described has no particular limits to type of reactor and reaction condition, such as uses fixed bed or fluidisation
Bed reactor etc., is preferably carried out under the following conditions：Reaction temperature is 300-550 DEG C；Reaction pressure is 0.1-5MPa；Methanol enters
Feed liquid body air speed is 0.1-20h-1。
Unless specific instructions, various raw materials of the invention can be by being commercially available；Or the routine side according to this area
Method is prepared.Unless otherwise defined or described herein, all specialties used herein are ripe with art technology with scientific words
It is identical to practice meaning known to personnel.In addition any method similar or impartial to described content and material all can be applied to this
In inventive method.
Other aspects of the present invention are apparent to those skilled in the art due to this disclosure
's.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally marked according to country
Quasi- measure.If without corresponding national standard, built according to general international standard, normal condition or according to manufacturer
The condition of view is carried out.Unless otherwise indicated, otherwise all number is parts by weight, and all percentage is weight percentage, institute
The polymer molecular weight stated is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and the skilled people of art technology
Meaning known to member is identical.In addition any method similar or impartial to described content and material all can be applied to the present invention
In method.
Embodiment 1
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Catalyst Factory, Nankai Univ, silica alumina ratio SiO2/Al2O3=38), exist
Roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, the molecular sieve after exchange
Dried in 120 DEG C of air, 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
20 grams of above-mentioned HZSM-5 molecular sieves are weighed, are put at 50 DEG C in 200ml0.3mol/L hydrochloric acid solution, stirring is mixed
Close 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.2g cobalt nitrates are weighed, 30ml water, is well mixed, then the ZSM-5 after roasting is put into 40 DEG C of cobalt nitrate molten
12h is impregnated in liquid.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter) it is 1.2wt%.
Methanol aromatic hydrocarbons reacts：
It is 20-40 mesh by the catalyst breakage screening after roasting.
8 grams of Catalyst packings are weighed to enter in the stainless steel fixed bed reactors that internal diameter is 12mm, at reaction conditions, Xiang Qi
In be passed through methanol vapor, to be reacted.Specifically reaction condition is：Reaction temperature：420 DEG C, pressure：0.5Mpa, the liquid of methanol
Body air speed：2.0h-1.Methanol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 300 DEG C, in the preheating
Cause methanol liquid to gasify to form steam in device, be then incubated into reactor and react.Product makes under conditions of insulation
On-line analysis is carried out with gas-chromatography, gas-chromatography uses PLOT Q capillary columns and hydrogen flame detector.
Embodiment 2
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Catalyst Factory, Nankai Univ, silica alumina ratio SiO2/Al2O3=38), exist
Roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, the molecular sieve after exchange
Dried in 120 DEG C of air, 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
20 grams of above-mentioned HZSM-5 molecular sieves are weighed, are put at 60 DEG C in 200ml0.3mol/L citric acid solution, are stirred
Mix 6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.5g cobalt nitrates are weighed, 30ml water, is well mixed, the ZSM-5 after roasting is then put into 20 DEG C of cobalt nitrate solutions
Middle dipping 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter, accounts for total amount) it is 1.8wt%.
The reaction of methanol aromatic hydrocarbons and analysis condition are the same as embodiment 1.
Embodiment 3
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO2/Al2O3=
50), roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, after exchange
Molecular sieve is dried in 120 air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
20 grams of above-mentioned HZSM-5 molecular sieves are weighed, are put at 55 DEG C in 200ml0.2mol/L hydrochloric acid solution, stirring is mixed
Close 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.8g cobaltous sulfates are weighed, 30ml water, is well mixed, then the ZSM-5 after roasting is put into 30 DEG C of cobaltous sulfate molten
15h is impregnated in liquid.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter, accounts for total amount) it is 2.1wt%.
The reaction of methanol aromatic hydrocarbons and analysis condition are the same as embodiment 1.
Embodiment 4
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO2/Al2O3=
50), roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, after exchange
Molecular sieve is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
20 grams of above-mentioned HZSM-5 molecular sieves are weighed, are put at 50 DEG C in 200ml0.1mol/L salpeter solution, stirring is mixed
Close 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.7g cobalt nitrates are weighed, 30ml water, is well mixed, then the ZSM-5 after roasting is put into 20 DEG C of cobalt nitrate molten
12h is impregnated in liquid.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter, accounts for total amount) it is 1.9wt%.
The reaction of methanol aromatic hydrocarbons and analysis condition are the same as embodiment 1.
Embodiment 5
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO2/Al2O3=
50), roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, after exchange
Molecular sieve is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
20 grams of above-mentioned HZSM-5 molecular sieves are weighed, are put at 20 DEG C in 200ml0.2mol/L sulfuric acid solution, stirring is mixed
Close 6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.5g cobaltous sulfates are weighed, 30ml water, is well mixed, the ZSM-5 after roasting is then put into 25 DEG C of cobalt sulfate solutions
Middle dipping 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter, accounts for total amount) it is 2.0wt%.
The reaction of methanol aromatic hydrocarbons and analysis condition are the same as embodiment 1.
Embodiment 6
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO2/Al2O3=
50), roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, after exchange
Molecular sieve is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
20 grams of above-mentioned HZSM-5 molecular sieves are weighed, are put at 30 DEG C in 200ml0.1mol/L sulfuric acid solution, stirring is mixed
Close 6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.5g cobalt chlorides are weighed, 30ml water, is well mixed, the ZSM-5 after roasting is then put into 40 DEG C of cobalt chloride solutions
Middle dipping 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter, accounts for total amount) it is 2.2wt%.
The reaction of methanol aromatic hydrocarbons and analysis condition are the same as embodiment 1.
Embodiment 7
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Catalyst Factory, Nankai Univ, silica alumina ratio SiO2/Al2O3=38), exist
Roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, the molecular sieve after exchange
Dried in 120 DEG C of air, 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
20 grams of above-mentioned HZSM-5 molecular sieves are weighed, are put at 30 DEG C in 200ml0.3mol/L phosphoric acid solution, stirring is mixed
Close 4h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.5g cobalt chlorides are weighed, 30ml water, is well mixed, the ZSM-5 after roasting is then put into 25 DEG C of cobalt chloride solutions
Middle dipping 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter, accounts for total amount) it is 2.1wt%.
The reaction of methanol aromatic hydrocarbons and analysis condition are the same as embodiment 1.
Embodiment 8
Hydrogen type catalyst used is commercial HZSM-5 molecular sieves (the silica alumina ratio SiO from the purchase of Tianjin Nankai university2/Al2O3=
38).20 grams of above-mentioned HZSM-5 molecular sieves are weighed, is put into 200ml0.1mol/L phosphoric acid solution, is stirred at 40 DEG C
6h.Then filter, wash, 120 DEG C of dryings, 550 DEG C of roasting 6h；
1.5g cobalt chlorides are weighed, 30ml water, is well mixed, the ZSM-5 after roasting is then put into 40 DEG C of cobalt chloride solutions
Middle dipping 10h.Then 120 DEG C of dryings, 550 DEG C of roasting 6h.
In finished catalyst, the content that metal Co is determined through ICP (presses Co2O3Meter, accounts for total amount) it is 1.9wt%.
Comparative example 1
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Catalyst Factory, Nankai Univ, silica alumina ratio SiO2/Al2O3=38), exist
Roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, the molecular sieve after exchange
Dried in 120 DEG C of air, 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
It is 20-40 mesh by the HZSM-5 molecular sieve catalysts crushing and screening after above-mentioned roasting.
8 grams of Catalyst packings are weighed to enter in the stainless steel fixed bed reactors that internal diameter is 12mm, at reaction conditions, Xiang Qi
In be passed through methanol vapor, to be reacted.Specifically reaction condition is：Reaction temperature：420 DEG C, pressure：0.5Mpa, the liquid of methanol
Body air speed：2.0h-1.Methanol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 300 DEG C, in the preheating
Cause methanol liquid to gasify to form steam in device, be then incubated into reactor and react.Product makes under conditions of insulation
On-line analysis is carried out with gas-chromatography, gas-chromatography uses PLOT Q capillary columns and hydrogen flame detector.
Comparative example 2
Weigh a certain amount of NaZSM-5 molecular screen primary powders (Shanghai Fuxu Molecular Sieve Co., Ltd., silica alumina ratio SiO2/Al2O3=
50), roasting removes template at 550 DEG C, is exchanged 2 times with 1mol/L ammonium nitrate solution in 80 DEG C of water-baths, after exchange
Molecular sieve is dried in 120 DEG C of air, and 550 DEG C of roasting 6h obtain the HZSM-5 molecular sieves of Hydrogen.
It is 20-40 mesh by the HZSM-5 molecular sieve catalysts crushing and screening after above-mentioned roasting.
8 grams of Catalyst packings are weighed to enter in the stainless steel fixed bed reactors that internal diameter is 12mm, at reaction conditions, Xiang Qi
In be passed through methanol vapor, to be reacted.Specifically reaction condition is：Reaction temperature：420 DEG C, pressure：0.5Mpa, the liquid of methanol
Body air speed：2.0h-1.Methanol enters preheater by constant-flux pump in liquid form, and the temperature of preheater is 300 DEG C, in the preheating
Cause methanol liquid to gasify to form steam in device, be then incubated into reactor and react.Product makes under conditions of insulation
On-line analysis is carried out with gas-chromatography, gas-chromatography uses PLOT Q capillary columns and hydrogen flame detector.
As a result collect and be listed in the table below.
Table 1
* note：Aromatics yield is based on total hydrocarbons product
Conclusion
It was found from above-described embodiment, the catalyst of methanol aromatic hydrocarbons of the invention obtains higher aromatics yield, more has
Value is that of obtaining higher BTX contents, and value of the aromatic hydrocarbons as alternative route is prepared so as to greatly improve methanol.
In addition, when it is 35~40 that the silica alumina ratio of the present invention, which reaches mol ratio, best effect can be arrived, its aromatics yield is not
Less than 65%, even up to more than 70%, BTX yields are not less than 43%, even up to more than 50%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not limited to the substantial technological content model of the present invention
Enclose, substantial technological content of the invention is broadly to be defined in the right of application, any technology that other people complete
Entity or method, if with the right of application defined in it is identical, also or a kind of equivalent change, will
It is considered as being covered by among the right.
All it is incorporated as referring in this application in all documents that the present invention refers to, it is independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above of the present invention has been read, those skilled in the art can be right
The present invention makes various changes or modifications, and these equivalent form of values equally fall within the application appended claims limited range.
Claims (19)
1. a kind of preparation method of methanol arenes catalytic agent, the method for preparing catalyst comprise the following steps：
(a) Hydrogen ZSM-5 molecular sieve is provided；
(b) the Hydrogen ZSM-5 molecular sieve of the step (a) is modified using acid solution, by separating, washing, drying and roasting
Modified Hydrogen ZSM-5 molecular sieve is obtained after burning；The Hydrogen ZSM-5 molecular sieve of the step (a) and acid solution is mixed when modified
It is 20-60 DEG C to close temperature；Incorporation time is 4-10h；
(c) solution containing metallic cobalt is immersed on the Hydrogen ZSM-5 molecular sieve of the modification of the step (b), through drying and roasting
Described methanol arenes catalytic agent is obtained after burning.
2. the method as described in claim 1, it is characterised in that the silica alumina ratio (SiO of the Hydrogen ZSM-5 molecular sieve2/Al2O3)
For 20-200, the silica alumina ratio is calculated with mol ratio.
3. method as claimed in claim 2, it is characterised in that the silica alumina ratio (SiO of the Hydrogen ZSM-5 molecular sieve2/Al2O3)
For 30-150.
4. the method as described in claim 1, it is characterised in that the acid is nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, lemon
One or several kinds in acid.
5. the method as described in claim 1, it is characterised in that the concentration of the acid solution is 0.05-1mol/L.
6. the method as described in claim 1, it is characterised in that in step (c), the solution containing metallic cobalt is impregnated into described
Temperature on the modified hydrogen ZSM-5 molecular sieve of step (b) is 20-100 DEG C；Dip time is 1-24h.
7. the method as described in claim 1, it is characterised in that the metal cobalt source of the solution containing metallic cobalt be cobalt nitrate,
One or several kinds in cobaltous sulfate, cobalt chloride, cobalt acetate.
8. the method as described in claim 1, it is characterised in that the content of metallic cobalt is total catalyst weight in the catalyst
0.1-10%.
9. method as claimed in claim 8, it is characterised in that the content of metallic cobalt is total catalyst weight in the catalyst
0.1-8%.
10. the method as described in claim 1, it is characterised in that the sintering temperature of the ZSM-5 molecular sieve is 300- after dipping
800℃。
11. method as claimed in claim 10, it is characterised in that the sintering temperature of the ZSM-5 molecular sieve is after dipping
400-600℃。
12. a kind of method of methanol aromatic hydrocarbons, methods described include：Exist as described in any one of claim 1-11
In the case of the catalyst that method is prepared, methanol is contacted with gas phase with catalyst, so as to react generation containing aromatic hydrocarbons
Hydrocarbon compound.
13. method as claimed in claim 12, it is characterised in that preferably carry out under the following conditions：Reaction temperature is 300-
550℃；Reaction pressure is 0.1-5MPa；Methanol feed liquid air speed is 0.1-20h-1。
14. method as claimed in claim 13, it is characterised in that reaction temperature is 350-500 DEG C.
15. method as claimed in claim 13, it is characterised in that reaction pressure 0.1-2MPa.
16. method as claimed in claim 13, it is characterised in that methanol feed liquid air speed is 0.1-10h-1。
17. method as claimed in claim 13, it is characterised in that methanol feed liquid air speed is 0.1-5h-1。
A kind of 18. methanol arenes catalytic agent that the method as described in claim 1 obtains；Metallic cobalt contains in the catalyst
Amount presses Co2O3It is calculated as more than the 0.1% of total catalyst weight and no more than 2.0%.
A kind of 19. application of methanol arenes catalytic agent as claimed in claim 18 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 CN104801332A (en) | 2015-07-29 |
| CN104801332B true 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) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 (2)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103537315B (en) * | 2012-07-12 | 2015-11-25 | 中国石油化工股份有限公司 | Methanol arenes catalytic agent and preparation method thereof |
-
2014
- 2014-01-24 CN CN201410035193.4A patent/CN104801332B/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| Hierarchical H-ZSM-5-supported cobalt for the direct synthesis of gasoline-range hydrocarbons from syngas: Advantages, limitations, and mechanistic insight;Sina Sartipi,et al;《Journal of Catalysis》;20130614;第305卷;文章第180页2.1节、2.2.1节，第184页Table 2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104801332A (en) | 2015-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104801332B (en) | A kind of methanol aromatic hydrocarbons process catalyst preparation method | |
| CN106423263B (en) | A kind of synthesis of the catalyst and low-carbon alkene of hydrogenation of carbon dioxide producing light olefins | |
| CN101204664B (en) | Multiphase catalytic oxidation cyclohexane catalyst for cyclohexanone and cyclohexanol and preparation method thereof | |
| CN106140266B (en) | A kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation method and application | |
| EP3356035A1 (en) | Process for producing aromatics from a heavy hydrocarbon feed | |
| 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 | |
| CN106890668A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN105983435B (en) | A kind of isomerization of butene catalyst and its preparation method and application | |
| CN110075908A (en) | A kind of catalyst and preparation method thereof for synthesis gas one-step synthesis aromatic hydrocarbons | |
| CN110075911A (en) | One kind being used for C10+Heavy arene hydrogenation takes off the catalyst and preparation method thereof of alkyl | |
| CN106890671A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN103752306B (en) | Preparation method of a kind of prepared from benzene and hydrogen thiacyclohexane catalyst and products thereof and application | |
| CN105195172B (en) | A kind of in-situ synthetic method of aromatizing catalyst for light hydrocarbon | |
| CN106890665B (en) | Catalyst for producing methyl acetate by dimethyl ether carbonylation and application thereof | |
| CN102895990A (en) | Light hydrocarbon aromatization catalyst and preparation method thereof | |
| CN111514926A (en) | Molecular sieve catalyst, and preparation method and application thereof | |
| CN102211036B (en) | A kind of modified molecular sieve catalyst and its precursor and preparation method thereof | |
| CN105498829B (en) | A kind of aromatization of methanol catalyst and its preparation method and application | |
| CN110314696B (en) | Composite catalyst, preparation method thereof and preparation method of ethylene | |
| CN101444732B (en) | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof | |
| CN109876849B (en) | 1, 4-naphthoquinone catalyst prepared by liquid-phase oxidation of naphthalene and preparation method and application thereof | |
| CN107282090B (en) | The catalyst that ethane is reacted with benzene | |
| CN113289677B (en) | Complex phase metal catalyst for preparing aromatic hydrocarbon from synthesis gas and preparation method thereof | |
| CN111036284A (en) | Catalyst, preparation method thereof and method for preparing low-carbon olefin from synthesis gas | |
| CN105983434A (en) | Preparation method and use of binder-free ZSM-11 molecular sieve-based catalyst |
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 |
Granted publication date: 20171219 Termination date: 20210124 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |