CN102199069A - Method for preparing aromatic hydrocarbons by methanol-containing raw materials - Google Patents
Method for preparing aromatic hydrocarbons by methanol-containing raw materials Download PDFInfo
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Abstract
A method for preparing aromatic hydrocarbons by methanol-containing raw materials. The methanol-containing raw materials comprise methanol and distilled gasoline. The method comprises that the methanol-containing raw materials and catalysts undergo a reaction under conditions of preparing aromatic hydrocarbons by methanol. The method provided by the invention solves the problems that in the prior arts, heat in a reactor is removed through an intermediate cooler and a multitubular reactor is utilized for heat removal or cold product gas is transmitted back to a raw material inlet to remove heat or a diluting material is added to control reaction heat. The method has the advantages of simple processes, and simple and convenient operation.
Description
Technical field
The present invention relates to a kind of method by the feedstock production aromatic hydrocarbons that contains methyl alcohol.
Background technology
Aromatic hydrocarbons is important petrochemicals, has higher added value.The aromatic hydrocarbons of China is mainly derived from petroleum resources, and the present situation of China's oil shortage of resources has determined the scarcity of aromatic hydrocarbon resource.From the direct preparing aromatic hydrocarbon by converting of resourceful methyl alcohol, for the shortage of alleviating aromatic hydrocarbons, improve the added value of Downstream Products of Methanol, prolong Coal Chemical Industry and gas chemical industry's industrial chain, have significant values.Adopting methyl alcohol to prepare aromatic hydrocarbons is the new way that non-petroleum path is produced aromatic hydrocarbons.
1976, Mobil Oil company carried out methyl alcohol is converted into hydrocarbon polymer on the ZSM-5 molecular sieve catalyst reaction.US4035430 discloses a kind of methyl alcohol transforms gasoline on the ZSM-5 molecular sieve catalyst process.CN101244969A discloses the devices and methods therefor of a kind of continuous aromatization and catalyst regeneration, this method is 450-800 ℃ in temperature, pressure is to carry out under the 0.1-2MPa, and adopts the fluidized-bed reaction-regenerating unit of a complete and continuous aromizing and catalyst regeneration.Because molecular sieve (silicon, the structural compounds of aluminium and phosphorus etc.) intensity is low, can not satisfy the wearing and tearing under the fast conveying of high gas in transport pipe in violent gas-solid turbulence wearing and tearing in the fluidized-bed and frequent reaction and the regenerative process.So catalyst attrition is big.Fluidized-bed reaction-the regenerating unit investment is big, operation easier is big.And for example, CN1880288A discloses the technology that a kind of methanol conversion prepares aromatic hydrocarbons, and this method comprises the steps: that (1) is raw material with methyl alcohol, with the ZSM-5 molecular sieve is catalyzer, at working pressure is 0.1-5MPa, and service temperature is 300-460 ℃, and the raw material liq air speed is 0.1-6.0h
-1Under the condition, be converted into product based on aromatic hydrocarbons through one section catalytic reaction; (2) product based on aromatic hydrocarbons passes through refrigerated separation, with gas-phase product lower carbon number hydrocarbons and liquid product C
5 +Hydrocarbon separates; (3) liquid product C
5 +Hydrocarbon obtains aromatic hydrocarbons and non-aromatics through extracting and separating.Because the reaction of adopting methyl alcohol to prepare aromatic hydrocarbons is a strong exothermal reaction, in reaction process, heat is difficult to be removed, and therefore, reaction is difficult to reach balance and can causes the reactor temperature runaway and make catalyst deactivation.In addition, still be not suitable for the industrialized unit report of fixed bed at present.
Summary of the invention
Goal of the invention of the present invention is to overcome being prepared by methyl alcohol in the reaction process of aromatic hydrocarbons of prior art, heat is difficult to be removed, make reaction be difficult to reach balance, can cause the reactor temperature runaway and make the defective of catalyst deactivation, provide a kind of and can control reaction process heat well, and make the higher employing methyl alcohol of productive rate of aromatic hydrocarbons prepare the method for aromatic hydrocarbons.
The invention provides a kind of method by the feedstock production aromatic hydrocarbons that contains methyl alcohol, wherein, the described raw material that contains methyl alcohol comprises methyl alcohol and straight-run spirit, and this method is included under the methyl alcohol system aromatic hydrocarbons condition, with described raw material and the catalyzer contact reacts that contains methyl alcohol.
The present inventor finds, when adopting methyl alcohol and straight-run spirit as reaction raw materials, the process (reaction → alkene of methyl alcohol+water → aromatic hydrocarbons) of utilizing methyl alcohol to prepare aromatic hydrocarbons is a strong exothermal reaction, and utilize straight-run spirit generation cracking, the process that series reaction such as aromizing generate aromatic hydrocarbons is the strong process that absorbs heat, by making two reaction process at a reactor, as carrying out thermal coupling in the fixed-bed reactor, the reaction heat effect of the two is cancelled out each other, reduced the heat effect of total reaction, and can control reaction process heat well, can prevent the temperature runaway and the catalyst deactivation that use methyl alcohol to prepare reactor in the aromatic hydrocarbons process merely well, and can effectively improve the productive rate of aromatic hydrocarbons, as, the transformation efficiency of methyl alcohol and straight-run spirit greater than 80 weight %, aromatic hydrocarbons (benzene in the product, toluene and dimethylbenzene) content greater than 60 weight %.Adopt method of the present invention to solve simultaneously needing to adopt side cooler in the prior art is the problem of the catalyzer heat removal in the reactor, and need to adopt the shell and tube reactor heat-obtaining or return the feed(raw material)inlet and come heat-obtaining or control the problem of reaction process heat by increasing diluted material by introducing cold product gas, have that flow process is simple, advantages of simple operation.
Embodiment
According to method provided by the invention, the described raw material that contains methyl alcohol comprises methyl alcohol and straight-run spirit, and this method is included under the condition of methyl alcohol system aromatic hydrocarbons, with described raw material and the catalyzer contact reacts that contains methyl alcohol.
According to the present invention, described method can be to carry out under the condition of conventional methyl alcohol system aromatic hydrocarbons, the condition of described methyl alcohol system aromatic hydrocarbons comprises temperature of reaction and reaction pressure, the selectable range broad of described temperature of reaction and reaction pressure, under the preferable case, described temperature of reaction can be 300-600 ℃, more preferably 350-500 ℃; Reaction pressure can be 0.1-2MPa, is preferably 0.1-1.2MPa.
According to the present invention, wherein, the material feeding weight space velocity that contains methyl alcohol can be 0.1-20h
-1, be preferably 1-10h
-1Contain the material feeding weight space velocity of methyl alcohol in above-mentioned scope by control, can guarantee that methyl alcohol and straight-run spirit fully react on the one hand, obtain aromatic hydrocarbons with high yield, can also effectively prevent to react overtemperature on the other hand, thereby prevent coking and improve its transformation efficiency.
Obviously, in theory, as long as except containing methyl alcohol, also contain a small amount of straight-run spirit in the raw material, the heat that the reaction of methyl alcohol system aromatic hydrocarbons is emitted is utilized by the reaction of straight-run spirit system aromatic hydrocarbons, compare with the methanol feedstock that does not contain straight-run spirit, just can control reaction process heat better, can advantageously prevent the temperature runaway and the catalyst deactivation that use methyl alcohol to prepare reactor in the aromatic hydrocarbons process merely, and can relatively effectively improve the transformation efficiency of aromatic hydrocarbons, therefore, among the present invention, the two the selectable range broad of charge proportion of methyl alcohol and straight-run spirit.But, in order in thermopositive reaction and thermo-negative reaction, to obtain balance well, the methyl alcohol system of making aromatic hydrocarbons temperature of reaction is in controlled range, the present inventor furthers investigate the charge proportion of the two, found that, when the mass ratio of described methyl alcohol and straight-run spirit is 0.1-10, during in particular for 1-5, after reaction starts, do not need extra heat supply is carried out in reaction, the heat that promptly utilizes two reactions itself to emit and absorb, control reaction temperature well, therefore, under the preferable case, the mass ratio of described methyl alcohol and straight-run spirit is 0.1-10, more preferably 1-5.
Described methyl alcohol can use with the form of aqueous methanol, and the mass concentration of methyl alcohol can be 50-100%.When described methyl alcohol used with the form of aqueous methanol, the amount of described methyl alcohol was all with methyl alcohol CH
3The amount meter of OH.Described straight-run spirit refers to the petroleum naphtha that obtained by crude oil atmospheric distillation, and the boiling range scope of described straight-run spirit is generally 30-200 ℃, is preferably 40-170 ℃.
According to the present invention, described catalyzer can be used in catalyzer of the present invention for various, for example, described catalyzer can be preferably ZSM-5 and/or ZSM-11 zeolite molecular sieve for Si-Al zeolite molecular sieve with MFI structure and/or the Si-Al zeolite molecular sieve with MEL structure.
More preferably under the situation, in order to improve the arenes selectivity of catalyzer methanol conversion reaction, the modulation acidic zeolite, catalyzer of the present invention is the Si-Al zeolite molecular sieve of the metal-modified MFI structure of process and/or the Si-Al zeolite molecular sieve with MEL structure, promptly, described catalyzer contains the Si-Al zeolite molecular sieve with MFI structure and/or the Si-Al zeolite molecular sieve with MEL structure and loads on this and has the Si-Al zeolite molecular sieve of MFI structure and/or have metal component on the Si-Al zeolite molecular sieve of MEL structure, and the metal in the described metal component can be selected from Mn, Co, Ni, Cu, Zn, Mo, in Ga and the rare earth metal one or more; Wherein, rare earth metal is preferably the soluble salt of lanthanum; Non-rare earth metal is preferably one or more among Mn, Zn and the Mo; The content of metal can be the 0.1-15 weight % of total catalyst weight in the described metal component.
The content of described metal component middle-weight rare earths metal is the 0.1-10 weight % of total catalyst weight, and the content of non-rare earth metal is the 0.1-10 weight % of total catalyst weight.
According to the present invention, the preparation method of the Si-Al zeolite molecular sieve of metal-modified MFI structure of process and/or MEL structure comprises the steps:
(1) the former powder of zeolite molecular sieve is carried out NH
4+Ion-exchange, roasting are prepared into acidic zeolite;
(2) use non-rare earth metal solution of solubility and/or soluble ree metal salt solution that acidic zeolite is flooded, as long as the concentration of metal-salt satisfies the content requirement of metal component in the catalyzer in non-rare earth metal salt solutions of the time of dipping and solubility and/or the soluble ree metal salt solution; Obtain non-rare earth metal and/or rare-earth metal modified zeolite molecular sieve after drying and the roasting;
(3) modified catalyst compressing tablet, the drying and moulding that step (2) is prepared.
Wherein, in step (1), the former powder of zeolite molecular sieve is carried out NH
4+The method of ion-exchange can be the method for this area routine, for example, exchanges with ammonium nitrate solution; The temperature of described roasting can be 450-650 ℃.In step (2), described non-rare earth metal soluble salt can be a soluble metal nitrate for described soluble metallic salt, and the exsiccant temperature can be 50-150 ℃, and the exsiccant time was generally 1-15 hour; The temperature of roasting can be 450-650 ℃, and the time of roasting can be 1-10 hour.In step (3), the method and the condition of catalyzer being carried out drying, compression molding are conventionally known to one of skill in the art, as, the exsiccant temperature can be 50-150 ℃.
The process that employing of the present invention contains the feedstock production aromatic hydrocarbons of methyl alcohol can be carried out in existing various reactors, is specially adapted to adopt fixed-bed reactor.
To further describe in detail the present invention by specific embodiment below.In the catalyzer content of metal by x ray fluorescence spectrometry (Yang Cuiding etc., petrochemical industry chemical analysis method (the RIPP test method, Science Press, 1990, P380) record.And in the following embodiments, the boiling range scope of described straight-run spirit is 30-200 ℃.
To further describe in detail the present invention by specific embodiment below.
Embodiment 1
Present embodiment is used to illustrate the preparation of fixed bed catalyst
(1) with the 500 gram former powder of ZSM-5 zeolite molecular sieve (Catalyst Factory, Nankai Univ) SiO
2/ Al
2O
3=50 (mol ratios) are removed template 550 ℃ of following roastings, exchange 4 times with 0.5 molar equivalent ammonium nitrate solution in 80 ℃ of water-baths, and exchange is then dried in 120 ℃ of air, and 550 ℃ of following roastings 3 hours obtain the HZSM-5 zeolite molecular sieve.
(2) with 20 gram HZSM-5 zeolite molecular sieve compression moldings of step (1) preparation, obtaining 40-60 order sample behind crushing and screening, be divided into two parts, under normal temperature (25 ℃), is respectively the zinc nitrate Zn (NO of 3 weight % and 9 weight % with concentration
3)
2Solution impregnation 4 hours, at 120 ℃ down after the oven dry, and roasting 6 hours in 550 ℃ of air, obtain non-rare-earth metal modified catalyzer;
(3) with concentration be the La (NO of 10 weight %
3)
3Aqueous solution impregnation steps (2) obtains non-rare-earth metal modified catalyzer 12 hours, after oven dry under 120 ℃, 550 ℃ of following roastings 3 hours, obtains the Zn-La-HZSM-5 zeolite molecular sieve.Two catalyzer are distinguished called after MTA-111 and MTA-112.(charge capacity of Zn is 1 weight % among the MTA-111, the charge capacity 3 weight % of La; The charge capacity of Zn is 3 weight % among the MTA-112, the charge capacity 3 weight % of La)
Embodiment 2
Present embodiment is used to illustrate the preparation of fixed bed catalyst
(1) with the 500 gram former powder of ZSM-5 zeolite molecular sieve (Catalyst Factory, Nankai Univ) SiO
2/ Al
2O
3=50 (mol ratios) are removed template 550 ℃ of following roastings, exchange 4 times with 0.5 molar equivalent ammonium nitrate solution in 80 ℃ of water-baths, and exchange is then dried in 120 ℃ of air, and 550 ℃ of following roastings 3 hours obtain the HZSM-5 zeolite molecular sieve.
(2) with 20 gram HZSM-5 zeolite molecular sieve compression moldings of step (1) preparation, obtaining 40-60 order sample behind crushing and screening, be divided into two parts, under normal temperature (25 ℃), is respectively the nitric acid molybdenum Mo (NO of 3.7 weight % and 11.1 weight % with concentration
3)
3Solution normal temperature dipping 4 hours, after oven dry under 120 ℃, roasting is 6 hours in 550 ℃ of air, obtains non-rare-earth metal modified catalyzer;
(3) with concentration be the La (NO of 10 weight %
3)
3Aqueous solution impregnation steps (2) obtains non-rare-earth metal modified catalyzer 12 hours, after oven dry under 120 ℃, 550 ℃ of following roastings 3 hours, obtains the Mo-La-HZSM-5 zeolite molecular sieve.Two catalyzer are distinguished called after MTA-113 and MTA-114.(charge capacity of Mo is 1 weight % among the MTA-113, and the charge capacity of La is 3 weight %, and the charge capacity of Mo is 3 weight % among the MTA-114, and the charge capacity of La is 3 weight %)
Embodiment 3
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
With the catalyzer MTA-111 of embodiment 1 preparation and MTA-112 as catalysts, 5 gram catalyzer are respectively charged in the fixed-bed reactor, in 550 ℃ of air atmospheres, handled 1 hour, under nitrogen atmosphere, cool to 450 ℃ of temperature of reaction, 500 ℃ the time, remove nitrogen, methyl alcohol and straight-run spirit are pumped into reactor and catalyzer contact reacts (weight ratio of methyl alcohol and straight-run spirit is 10: 1) by fresh feed pump.Raw material feed weight air speed is 2h
-1, the controlling reactor internal pressure is 0.15MPa.Reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 1.
Table 1
| Catalyzer | MTA-111 | MTA-112 |
| Temperature of reaction ℃ | 450 | 500 |
| Feed time (minute) | 30 | 30 |
| Transformation efficiency (weight %) | 92.34 | 91.28 |
| Aromatics yield in the product (weight %) | 64.11 | 63.03 |
Embodiment 4
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
Catalyzer MTA-113 with embodiment 2 preparations, MTA-114 is as catalysts, 5 gram catalyzer are respectively charged into fixed-bed reactor, in 550 ℃ of air atmospheres, handled 1 hour, under nitrogen atmosphere, cool to 400 ℃ of temperature of reaction respectively, 500 ℃ the time, remove nitrogen, pump into reactor and catalyzer contact reacts (weight ratio of methyl alcohol and straight-run spirit is 10: 3) by fresh feed pump.Raw material feed weight air speed is 2h
-1, the control reaction pressure is 0.1MPa.Reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 2.
Table 2
| Catalyzer | MTA-113 | MTA-114 |
| Temperature of reaction | 400 | 500 |
| Feed time (minute) | 30 | 30 |
| Transformation efficiency (weight %) | 93.89 | 92.23 |
| Aromatics yield in the product (weight %) | 65.23 | 63.71 |
Embodiment 5
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
With the catalyzer MTA-113 of embodiment 2 preparation and MTA-114 as catalysts, 5 gram catalyzer are respectively charged into fixed-bed reactor, in 550 ℃ of air atmospheres, handled 1 hour, when under nitrogen atmosphere, cooling to 450 ℃ of temperature of reaction, remove nitrogen, pump into reactor and catalyzer contact reacts (weight ratio of methyl alcohol and straight-run spirit is 10: 5) by fresh feed pump.The material feeding weight space velocity is 2h
-1, the control reaction pressure is 0.2MPa.Reaction product adopts the on-line analysis of Varian3800 gas-chromatography.Reaction result is as shown in table 3.
Table 3
| Catalyzer | MTA-113 | MTA-114 |
| Temperature of reaction | 450 | 450 |
| Feed time (minute) | 30 | 30 |
| Transformation efficiency (weight %) | 93.33 | 94.02 |
| Aromatics yield in the product (weight %) | 65.37 | 66.29 |
Embodiment 6
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
Method according to embodiment 3 prepares aromatic hydrocarbons, and different is, catalyst system therefor has the Zn-HZSM-5 zeolite molecular sieve of 3 weight %Zn for the only load according to the method preparation of embodiment 1, and temperature of reaction is 450 ℃, and the material feeding weight space velocity is 8h
-1, the control reaction pressure is 1MPa.Reaction result is as shown in table 4.
Table 4
| Catalyzer | ?Zn-HZSM-5 |
| Temperature of reaction | ?450 |
| Feed time (minute) | ?30 |
| Transformation efficiency (weight %) | ?81.59 |
| Aromatics yield in the product (weight %) | ?62.33 |
Embodiment 7
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
Method according to embodiment 3 prepares aromatic hydrocarbons, and different is that the weight ratio of methyl alcohol and straight-run spirit is 10: 2.Reaction result is as shown in table 5.
Table 5
| Catalyzer | MTA-111 | MTA-112 |
| Temperature of reaction | 450 | 500 |
| Feed time (minute) | 30 | 30 |
| Transformation efficiency (weight %) | 92.89 | 92.22 |
| Aromatics yield in the product (weight %) | 64.59 | 64.09 |
Embodiment 8
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
Method according to embodiment 3 prepares aromatic hydrocarbons, and different is that the weight ratio of methyl alcohol and straight-run spirit is 10: 4.Reaction result is as shown in table 6.
Table 6
| Catalyzer | MTA-111 | MTA-112 |
| Temperature of reaction | 450 | 500 |
| Feed time (minute) | 30 | 30 |
| Transformation efficiency (weight %) | 93.61 | 93.11 |
| Aromatics yield in the product (weight %) | 65.00 | 64.45 |
Embodiment 9
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
Method according to embodiment 3 prepares aromatic hydrocarbons, and different is that the weight ratio of methyl alcohol and straight-run spirit is 1: 1.Reaction result is as shown in table 7.
Table 7
| Catalyzer | MTA-111 | MTA-112 |
| Temperature of reaction | 450 | 500 |
| Feed time (minute) | 30 | 30 |
| Transformation efficiency (weight %) | 93.72 | 93.59 |
| Aromatics yield in the product (weight %) | 65.99 | 65.23 |
Embodiment 10
Present embodiment is used to illustrate the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol
Method according to embodiment 3 prepares aromatic hydrocarbons, and different is that the weight ratio of methyl alcohol and straight-run spirit is 1: 10.Reaction result is as shown in table 8.
Table 8
| Catalyzer | ?MTA-211 | MTA-212 |
| Temperature of reaction | ?450 | 500 |
| Feed time (minute) | ?30 | 30 |
| Transformation efficiency (weight %) | ?95.81 | 94.17 |
| Aromatics yield in the product (weight %) | ?62.14 | 61.58 |
From the table 1-8 the result as can be seen, adopt method of the present invention, need not a large amount of heat removals, by making methyl alcohol and straight-run spirit in a reactor, carry out thermal coupling, the reaction heat effect of the two is cancelled out each other, reduce the heat effect of total reaction, in addition, also had simple, the advantages of simple operation of flow process.
Claims (12)
1. the method by the feedstock production aromatic hydrocarbons that contains methyl alcohol is characterized in that, the described raw material that contains methyl alcohol comprises methyl alcohol and straight-run spirit, and this method is included under the condition of methyl alcohol system aromatic hydrocarbons, with described raw material and the catalyzer contact reacts that contains methyl alcohol.
2. method according to claim 1, wherein, the condition of described methyl alcohol system aromatic hydrocarbons comprises that temperature is 300-600 ℃, and pressure is 0.1-2MPa, and the feed weight air speed of methyl alcohol and straight-run spirit is 0.1-20h
-1
3. method according to claim 2, wherein, described temperature is 350-500 ℃, and pressure is 0.1-1.2MPa, and the feed weight air speed of methyl alcohol and straight-run spirit is 1-10h
-1
4. method according to claim 1 and 2, wherein, the mass ratio of described methyl alcohol and straight-run spirit is 0.1-10.
5. method according to claim 4, wherein, the mass ratio of described methyl alcohol and straight-run spirit is 1-5.
6. according to claim 1,2 or 5 described methods, wherein, described straight-run spirit refers to the petroleum naphtha that obtained by crude oil atmospheric distillation, and the boiling range scope of described straight-run spirit is 30-200 ℃.
7. method according to claim 6, wherein, the boiling range scope of described straight-run spirit is 40-170 ℃.
8. method according to claim 1, wherein, described catalyzer is the Si-Al zeolite molecular sieve that has the Si-Al zeolite molecular sieve of MFI structure and/or have the MEL structure.
9. method according to claim 1, wherein, described catalyzer contains the Si-Al zeolite molecular sieve with MFI structure and/or the Si-Al zeolite molecular sieve with MEL structure and loads on this and has the Si-Al zeolite molecular sieve of MFI structure and/or have metal component on the Si-Al zeolite molecular sieve of MEL structure, and the metal in the described metal component is selected from one or more in Mn, Co, Ni, Cu, Zn, Mo, Ga and the rare earth metal; The content of metal is the 0.1-15 weight % of total catalyst weight in the described metal component.
10. method according to claim 9, wherein, the content of metal component middle-weight rare earths metal is the 0.1-10 weight % of total catalyst weight, the content of non-rare earth metal is the 0.1-10 weight % of total catalyst weight.
11. according to Claim 8 or 9 described methods, wherein, the Si-Al zeolite molecular sieve of the described MFI of having structure and/or the Si-Al zeolite molecular sieve of MEL structure are ZSM-5 and/or ZSM-11 zeolite molecular sieve.
12. method according to claim 1, wherein, described being reflected in the fixed-bed reactor carried out.
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| CN104549440A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Adhesive-free oxy-compound aromatization catalyst and preparation method thereof |
| CN104557419A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon from methanol or dimethyl ether |
| CN107206365A (en) * | 2015-01-22 | 2017-09-26 | 托普索公司 | For converting methanol into the method for being suitable as gasoline or mixed material |
| CN108126734A (en) * | 2017-11-29 | 2018-06-08 | 华东理工大学 | Low-temp methanol prepares catalyst of aromatic hydrocarbons and preparation method thereof |
| CN109701596A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Catalyst system |
| CN109701601A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Combination catalyst system and application thereof |
| CN110872524A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Method for preparing aromatic hydrocarbon by converting ABE fermentation liquor |
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| CN104549440A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Adhesive-free oxy-compound aromatization catalyst and preparation method thereof |
| CN104557419A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon from methanol or dimethyl ether |
| CN107206365A (en) * | 2015-01-22 | 2017-09-26 | 托普索公司 | For converting methanol into the method for being suitable as gasoline or mixed material |
| CN109701596A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Catalyst system |
| CN109701601A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Combination catalyst system and application thereof |
| CN109701596B (en) * | 2017-10-26 | 2022-12-09 | 中国石油化工股份有限公司 | Catalyst system |
| CN109701601B (en) * | 2017-10-26 | 2022-12-09 | 中国石油化工股份有限公司 | Combined catalyst system and use thereof |
| CN108126734A (en) * | 2017-11-29 | 2018-06-08 | 华东理工大学 | Low-temp methanol prepares catalyst of aromatic hydrocarbons and preparation method thereof |
| CN108126734B (en) * | 2017-11-29 | 2020-12-11 | 华东理工大学 | Catalyst for preparing aromatic hydrocarbon from methanol at low temperature and preparation method thereof |
| CN110872524A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Method for preparing aromatic hydrocarbon by converting ABE fermentation liquor |
| CN110872524B (en) * | 2018-09-04 | 2021-12-17 | 中国科学院大连化学物理研究所 | Method for preparing aromatic hydrocarbon by converting ABE fermentation liquor |
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Application publication date: 20110928 |