CN105016954A - Method for preparing propylene and aromatic hydrocarbon from methyl alcohol or/and dimethyl ether - Google Patents
Method for preparing propylene and aromatic hydrocarbon from methyl alcohol or/and dimethyl ether Download PDFInfo
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- CN105016954A CN105016954A CN201410171979.9A CN201410171979A CN105016954A CN 105016954 A CN105016954 A CN 105016954A CN 201410171979 A CN201410171979 A CN 201410171979A CN 105016954 A CN105016954 A CN 105016954A
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- methyl alcohol
- propylene
- dimethyl ether
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention relates to a method for preparing propylene and aromatic hydrocarbon from methyl alcohol or/and dimethyl ether, belonging to the field of chemistry and chemical engineering. The method is carried out according to the following steps: firstly, enabling methyl alcohol or/and dimethyl ether to contact with a catalyst in a reaction system to prepare low-carbon olefin; separating the generated product in a separating system; enabling an ethylene-rich C2<-> component and an olefin-rich C4<+> component obtained through the separating system to return to the reaction system and contact with the catalyst to carry out an aromatization reaction to prepare aromatic hydrocarbon; further separating a C3 component to obtain propylene. According to the method disclosed by the invention, high separation cost for an ethylene product is avoided on one hand, and on the other hand, the efficiency of the aromatic hydrocarbon can be effectively improved by adopting olefin aromatization, and thus the economy of preparing petroleum chemicals from methyl alcohol or/and dimethyl ether can be effectively improved.
Description
Technical field
The invention belongs to chemical field, particularly a kind of methyl alcohol is or/and the method for propylene and aromatic hydrocarbons is prepared in dme reaction.
Background technology
Alkene and aromatic hydrocarbons are all important basic chemical raw materials, are commonly referred to as triolefin triphen, and triolefin comprises ethene, propylene and divinyl, and triphen comprises benzene,toluene,xylene, are called for short BTX.At present, alkene and aromatic hydrocarbons are mainly derived from petroleum resources, along with the fast development of global economy, as the demand also cumulative year after year of the triolefin triphen of chemical industry basic raw material, but the worsening shortages of petroleum resources makes imbalance between supply and demand more and more outstanding, the triolefin triphen production technology therefore developing non-oil resource will be the effective way of resolving contradiction.
Methanol-to-olefins and preparing propylene from methanol are the new ways that Non oil-based route produces ethene, propylene.Within 1976, Mobil Oil company has carried out the reaction that methyl alcohol is converted into hydrocarbon polymer on ZSM-5 molecular sieve catalyzer.USP4,035, disclose the process that methyl alcohol transforms gasoline on ZSM-5 molecular sieve catalyzer in 430; USP4,542, disclose the technology of methyl alcohol preparing low-carbon olefins on ZSM-5 molecular sieve catalyzer in 252; USP3,911,041, USP4,049,573, USP4, disclose in 100,219, JP60-126233, JP61-97231 and JP62-70324 use phosphorus, magnesium, silicon or alkali metal modification ZSM-5 molecular sieve catalyzer by the reaction of preparing low carbon olefinic hydrocarbon with methanol; USP5,367, disclosing Dalian Chemical Physics Research Institute in 100 uses the ZSM-5 molecular sieve catalyzer of phosphorus and lanthanum modification by the reaction of methyl alcohol or dme preparing low-carbon olefins, and its ethene and propylene overall selectivity are only about 65wt%, and ethene, propylene and butylene overall selectivity are greater than 85wt%.USP4 in 1984,440, disclose an eka-silicon phosphorus aluminium SAPO Zeolite synthesis method in 871, wherein SAPO-34 molecular sieve is owing to having suitable small structure and the surface acidity of medium tenacity, presents excellent catalytic performance in methanol to olefins reaction.1988, the application (Applied Catalysis, Vol.40, No1-2,1988, p316) of Dalian Chemistry and Physics Institute reported first SAPO-34 molecular sieve in methanol conversion ethene, propylene reaction.Within 2009, adopt Dalian Chemistry and Physics Institute technology to drive successfully with 1,800,000 tons, the Shenhua packet header preparing low carbon olefinic hydrocarbon with methanol industrialized unit that SAPO-34 molecular sieve is catalyzer, indicate that Non oil-based route olefin producing technologies obtains important breakthrough.
Methanol is the new way that Non oil-based route produces aromatic hydrocarbons for aromatic hydrocarbons.Chinese patent application CN101244969 discloses a kind of C
1-C
2the fluidizer of hydro carbons or aromatization of methanol and catalyst regeneration, utilizes this device and catalyzer, can regulate the coking state of the catalyzer in aromatization reactor at any time, thus reaches continuous high-efficient conversion C
1-C
2hydro carbons or methyl alcohol highly selective generate the object of aromatic hydrocarbons.Chinese patent CN1880288 discloses a kind of process of methanol conversion for preparing arene, and in ZSM-5 Type Zeolites agent, methanol oxidation is converted into the product based on aromatic hydrocarbons, and the overall selectivity with aromatic hydrocarbons is high, and technological operation is advantage flexibly.US Patent No. 4615995 discloses a kind of ZSM-5 molecular sieve catalyzer having supported Zn and Mn, for preparing olefin through methanol conversion and aromatic hydrocarbons, can be changed the ratio of low-carbon alkene/aromatic hydroxy compound in product by the content of Zn and Mn in regulating catalyst.But because Methanol aromatic hydrocarbons carbon base absorption rate is lower and the price factor of aromatic hydrocarbons seriously hinders the industrial application of Methanol aromatic hydrocarbons technology.
On the other hand, although preparing low carbon olefinic hydrocarbon with methanol obtains industrial application, having to pass through low temperature separation process, thus making plant energy consumption increase to obtain polymer grade ethylene product, economic benefit reduces.If the ethylene product that methanol-to-olefins obtains directly is carried out aromizing preparing aromatic hydrocarbon without low temperature separation process, not only solve the energy consumption problem of low temperature separation process, and can realize by the object of methyl alcohol through ethylene making aromatic hydrocarbons, methyl alcohol carbon back utilization ratio also can obtain and significantly improve.
Summary of the invention
The object of this invention is to provide a kind of methyl alcohol or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, the method by methyl alcohol or/and the reaction of dme preparing low-carbon olefins, light dydrocarbon aromatization reaction two reaction process couplings, finally obtain propylene and aromatic product.
For achieving the above object, a kind of methyl alcohol of the present invention, or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, carries out according to following steps:
(1) first methyl alcohol is or/and dme contacts preparing low-carbon olefins at the reaction zone A of reactive system with catalyst I, and temperature of reaction is at 300-600o, and reaction feed mass space velocity counts 0.1-10h with methyl alcohol
-1;
(2) product generated enters separation system A and is separated, and obtains the C being rich in ethene
2 -component, be rich in the C of alkene
4 +component and C
3component, by C
3component is separated further and obtains propylene;
(3) C of ethene is rich in
2 -component and the C being rich in alkene
4 +the reaction zone B of component Returning reacting system contacts with catalyst I I and carries out aromatization preparing aromatic hydrocarbon, and temperature of reaction is 300-600o, and reaction feed mass space velocity counts 0.1-10h with amount of alkene
-1; The product generated enters separation system B and is separated, and obtains lighter hydrocarbons C
1-C
5component and aromatic hydrocarbons;
Described reactive system is by any one reactor in fixed bed, fluidized-bed or moving-bed or any several reactors in series or compose in parallel.
Described reaction zone A or reaction zone B is respectively the serial or parallel connection of a reactor or multiple reactor.
Described catalyst I is phosphor-silicon-aluminum molecular sieve catalyzer, and catalyst I I is metal-modified silicoaluminophosphate molecular sieve catalyst.
Described phosphor-silicon-aluminum molecular sieve catalyzer is SAPO-34 and SAPO-18 molecular sieve catalyst, preferred SAPO-34 molecular sieve catalyst.
Described metal-modified silicoaluminophosphate molecular sieve catalyst is metal modified HZSM-5-5 or HZSM-11 molecular sieve catalyst, preferred HZSM-5 molecular sieve catalyst.Prepare according to following steps:
(1) by former for ZSM-5 molecular sieve powder, at 550 DEG C, template is removed in roasting, exchange is carried out 4 times with the ammonium nitrate solution of volumetric molar concentration 0.3M in 80 DEG C of water-baths, after exchanging, solid sample is dried in 120 DEG C of air, at 550 DEG C, roasting 3 hours, obtains HZSM-5 or HZSM-11 zeolite molecular sieve respectively;
(2) the metal-nitrate solutions normal temperature dipping 4 hours of HZSM-5 6% mass concentration prepared by step (1) is got, incline and solid sample 120 DEG C oven dry after supernatant liquid, roasting 6 hours in 550 DEG C of air, obtains modified metal-HZSM-5 molecular sieve catalyst.
Described modified metal be gallium, silver and zinc any one, preferred gallium; The quality loading of gallium is 0.1-10%, and the quality loading of preferred gallium is 0.1-5%.
In described step (1), methyl alcohol is or/and it is 350-500 DEG C that dme preparing low-carbon olefins reacts preferred temperature of reaction, and reaction feed mass space velocity counts 0.5-8h with methyl alcohol
-1.
In described step (3), preferred light dydrocarbon aromatization reaction temperature is 400-500 DEG C, and reaction feed mass space velocity counts 0.1-4h with amount of alkene
-1.
In the present invention, described C
2 -component refers to that in molecular formula, carbonatoms is less than or equal to the component of 2, comprises ethene, ethane, methane, CO, CO
2and H
2deng.
In the present invention, described C
3component refers to the compound that in molecular formula, carbonatoms equals 3, comprises propylene, propane.
In the present invention, described C
4 +component refers to that in molecular formula, carbonatoms is more than or equal to 4 components, comprises the rare and C of butane, 1-butylene, 2-butylene, Trimethylmethane, iso-butylene, iso-pentane, neopentane, pentane, 1-amylene, 2-penta
6chain hydrocarbon etc.
Beneficial effect of the present invention is: methyl alcohol, or/and dme low-carbon alkene such as highly selective preparing ethylene and propylene on aperture SAPO-34 molecular sieve catalyst, then will be rich in the C of ethene in product
2 -component and the C being rich in alkene
4 +component carries out aromatization preparing aromatic hydrocarbon, final acquisition propylene and aromatic hydrocarbon product.Avoid the high expense that ethylene product is separated on the one hand, adopt alkene aromizing effectively can improve aromatics yield on the other hand, thus effectively can improve methyl alcohol or/and dme produces the economy of petroleum chemicals.
Accompanying drawing explanation
Fig. 1 reacting flow chart of the present invention.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
Following examples adopt gas chromatograph on-line analysis product composition, and analysis condition is: chromatogram model Varian CP3800, chromatographic column: CP PoraPLOT Q-HT, CP Wax52CB capillary chromatographic column, carrier gas: helium, 5ml/min; Post case temperature: 60-220 DEG C, temperature programming, 15 DEG C/min, injector temperature: 260 DEG C; Detector: flame ionization ditector (FID), detector temperature: 300 DEG C.
The present invention adopts following preferred embodiment, and reactive system is made up of two reaction zones, and reaction zone A main reaction is methyl alcohol or/and the reaction of dme preparing low-carbon olefins, and reaction zone B main reaction is ethene and C
4alkene (reaction zone A by product) aromatization.Material benzenemethanol is or/and dme contacts the product A generating and be rich in low-carbon alkene with catalyst I at reaction zone A; Product A enters the C obtaining being rich in ethene after separation system A is separated
2 -component and the C being rich in alkene
4 +component enters into reaction zone B and contacts with catalyst I I and carry out aromatization and generate product B, is rich in the C of propylene
3component is separated further and obtains propylene; Product B enters after separation system B is separated and obtains lighter hydrocarbons C
1-C
5component and aromatic hydrocarbons.Described reaction zone A and reaction zone B can be respectively the serial or parallel connection of a reactor or multiple reactor, and reacting flow chart as shown in Figure 1
In a preferred embodiment, described reaction zone A and reaction zone B all can use fixed bed reaction technique, can be combined simultaneously adopt fluidized-bed or moving bed reaction technique with revivifier.
In the present invention, catalyst I is prepared and is adopted the method for embodiment 3 in patent CN101121529A to prepare SAPO-34 molecular sieve, and 350 DEG C of roastings 2 hours, 450 DEG C of roastings 1 hour, 550 DEG C of roastings 4 hours, obtained SAPO-34 molecular sieve catalyst, called after SP-34.
In the present invention, catalyst I I preparation is carried out according to following steps:
(1) by 500g ZSM-5 zeolite molecular screen primary powder (SiO
2/ Al
2o
3=50) template is removed in (Catalyst Factory, Nankai Univ) roasting at 550 DEG C, exchange is carried out 4 times with 0.3 molar equivalent ammonium nitrate solution in 80 DEG C of water-baths, after exchanging, solid sample is dried in 120 DEG C of air, at 550 DEG C, roasting 3 hours, obtains HZSM-5 zeolite molecular sieve respectively.
(2) gallium nitrate [Ga (NO of HZSM-5 6% mass concentration prepared by step (1) is got
3)
3] solution normal temperature dipping 4 hours, incline and solid sample 120 DEG C oven dry after supernatant liquid, roasting 6 hours in 550 DEG C of air, obtains gallium modification Ga-HZSM-5 molecular sieve catalyst, called after Ga-HZ-5.Ultimate analysis Ga loading is 2.26wt%.
Embodiment 1
By SP-34 catalyst tablet forming and crushing and screening is 40-60 object catalyst sample, get 10 grams of catalyzer and load in the fixed-bed reactor of reaction zone A and carry out methyl alcohol or dimethyl ether conversion reaction respectively, methyl alcohol and dme mass space velocity are 2h
-1, temperature of reaction is 420 DEG C.Adopt gas chromatograph on-line analysis product composition, the products distribution removed after generating water is as shown in table 1.
In the hydrocarbon product that methyl alcohol or dimethyl ether conversion are obtained by reacting on SP-34 catalyzer, Propylene Selectivity is respectively 45.12wt%, 46.01wt%; C
2 -and C
4 +selectivity is respectively 54.88wt%, 53.99wt%, wherein C
2 =+ C
4 =+ C
5 =olefine selective is respectively 49.76wt%, 50.00wt%.
Table 1 methanol/dimethyl ether preparing low-carbon olefins reaction result
* wt%, quality product distributes.
By Ga-HZ-5 catalyst tablet forming and crushing and screening is 40-60 object catalyst sample, get 10 grams of catalyzer and load in the fixed reactor of reaction zone B.By C in the reaction of methanol conversion products distribution
2 -component and C
4 +composition, the reaction zone B of Returning reacting system contacts with catalyst I I and carries out aromatization preparing aromatic hydrocarbon, and feedstock quality air speed is with C
2 =+ C
4 =+ C
5 =alkene counts 1h
-1, temperature of reaction is 450 DEG C.The product obtained enters after separation system B is separated and obtains lighter hydrocarbons C
1-C
5component and aromatic hydrocarbons;
Adopt gas chromatograph on-line analysis product composition, product slates is as shown in table 2.
C in hydro carbons gross product
1-C
5lighter hydrocarbons selectivity is 20.94wt%, and total arenes selectivity is 79.06wt%.
The light-hydrocarbon aromatized products distribution of table 2
* wt%, quality product distributes.
By methyl alcohol or/and dimethyl ether for olefin product distribution and light-hydrocarbon aromatized products distribution in proportion normalization method can obtain methyl alcohol or/and dimethyl ether distributes for propylene and aromatic product, as shown in table 3.
In the hydrocarbon product that methyl alcohol or dimethyl ether conversion are obtained by reacting, Propylene Selectivity is respectively 45.78wt%, 46.66wt%; Arenes selectivity is respectively 42.85wt%, 42.17wt%.
Table 3 methyl alcohol is or/and dimethyl ether is for propylene and aromatic product distribution
| Raw material | Methyl alcohol | Dme |
| Feed time (hour) | 1 | 1 |
| Methanol/dimethyl ether conversion rate (%) | 100 | 100 |
| Propylene (wt%) | 45.78 | 46.66 |
| Aromatic hydrocarbons (wt%) | 42.85 | 42.17 |
| Products distribution (wt%) * | ||
| CH 4 | 1.77 | 1.75 |
| C 2H 4 | 0.67 | 0.66 |
| C 2H 6 | 0.57 | 0.56 |
| C 3H 6 | 45.78 | 46.66 |
| C 3H 8 | 5.39 | 5.29 |
| C 4 | 2.48 | 2.44 |
| C 5 | 0.47 | 0.46 |
| Benzene | 5.25 | 5.16 |
| Toluene | 16.14 | 15.88 |
| Ethylbenzene | 0.39 | 0.38 |
| Dimethylbenzene | 13.89 | 13.67 |
| ≧C 9 | 7.18 | 7.07 |
| Add up to | 100.00 | 100.00 |
* wt%, quality product distributes.
Embodiment 2
By SP-34 catalyst tablet forming and crushing and screening is 40-60 object catalyst sample, get 10 grams of catalyzer and load in the fixed-bed reactor of reaction zone A and carry out methyl alcohol or dimethyl ether conversion reaction respectively, methyl alcohol or dme mass space velocity are 0.5h
-1, temperature of reaction is 350 DEG C.In the hydrocarbon product be obtained by reacting, Propylene Selectivity is respectively 47.28wt%, 48.23wt%; C
2 -and C
4 +selectivity is respectively 52.72wt%, 51.77wt%, wherein C
2 =+ C
4 =+ C
5 =olefine selective is respectively 47.61wt%, 47.92wt%.
By Ga-HZ-5 catalyst tablet forming and crushing and screening is 40-60 object catalyst sample, get 10 grams of catalyzer and load in the fixed reactor of reaction zone B.By C in the reaction of methanol conversion products distribution
2 -component and C
4 +composition, the reaction zone B of Returning reacting system contacts with catalyst I I and carries out aromatization preparing aromatic hydrocarbon, and feedstock quality air speed is with C
2 =+ C
4 =+ C
5 =alkene counts 0.2h
-1, temperature of reaction is 500 DEG C.The product obtained enters after separation system B is separated and obtains lighter hydrocarbons C
1-C
5component and aromatic hydrocarbons.C in hydro carbons gross product
1-C
5lighter hydrocarbons selectivity is 18.52wt%, and total arenes selectivity is 81.48wt%.
By methyl alcohol or/and dimethyl ether for olefin product distribution and light-hydrocarbon aromatized products distribution in proportion normalization method can obtain methyl alcohol or/and dimethyl ether distributes for propylene and aromatic product, in the hydrocarbon product that methyl alcohol or dimethyl ether conversion are obtained by reacting, Propylene Selectivity is respectively 47.63wt%, 48.76wt%; Arenes selectivity is respectively 42.96wt%, 42.18wt%.
Embodiment 3
By SP-34 catalyst tablet forming and crushing and screening is 40-60 object catalyst sample, get 10 grams of catalyzer and load in the fixed-bed reactor of reaction zone A and carry out methyl alcohol or dimethyl ether conversion reaction respectively, methyl alcohol and dme mass space velocity are 8h
-1, temperature of reaction is 500 DEG C.In the hydrocarbon product be obtained by reacting, Propylene Selectivity is respectively 42.65wt%, 43.14wt%; C
2 -and C
4 +selectivity is respectively 57.35wt%, 56.86wt%, wherein C
2 =+ C
4 =+ C
5 =olefine selective is respectively 51.68wt%, 52.57wt%.
By Ga-HZ-5 catalyst tablet forming and crushing and screening is 40-60 object catalyst sample, get 10 grams of catalyzer and load in the fixed reactor of reaction zone B.By C in the reaction of methanol conversion products distribution
2 -component and C
4 +composition, the reaction zone B of Returning reacting system contacts with catalyst I I and carries out aromatization preparing aromatic hydrocarbon, and feedstock quality air speed is with C
2 =+ C
4 =+ C
5 =alkene counts 4h
-1, temperature of reaction is 400 DEG C.The product obtained enters after separation system B is separated and obtains lighter hydrocarbons C
1-C
5component and aromatic hydrocarbons.C in hydro carbons gross product
1-C
5lighter hydrocarbons selectivity is 22.48wt%, and total arenes selectivity is 77.52wt%.
By methyl alcohol or/and dimethyl ether for olefin product distribution and light-hydrocarbon aromatized products distribution in proportion normalization method can obtain methyl alcohol or/and dimethyl ether distributes for propylene and aromatic product, in the hydrocarbon product that methyl alcohol or dimethyl ether conversion are obtained by reacting, Propylene Selectivity is respectively 43.82wt%, 44.63wt%; Arenes selectivity is respectively 44.46wt%, 44.08wt%.
Claims (9)
1. methyl alcohol is or/and dimethyl ether is for a method for propylene and aromatic hydrocarbons, it is characterized in that carrying out according to following steps:
(1) first methyl alcohol is or/and dme contacts preparing low-carbon olefins at the reaction zone A of reactive system with catalyst I, and temperature of reaction is at 300-600o, and reaction feed mass space velocity counts 0.1-10h with methyl alcohol
-1;
(2) product generated enters separation system A and is separated, and obtains the C being rich in ethene
2 -component, be rich in the C of alkene
4 +component and C
3component, by C
3component is separated further and obtains propylene;
(3) C of ethene is rich in
2 -component and the C being rich in alkene
4 +the reaction zone B of component Returning reacting system contacts with catalyst I I and carries out aromatization preparing aromatic hydrocarbon, and temperature of reaction is 300-600 DEG C, and reaction feed mass space velocity counts 0.1-10h with amount of alkene
-1; The product obtained enters separation system B and is separated, and obtains lighter hydrocarbons C
1-C
5component and aromatic hydrocarbons.
2. according to methyl alcohol described in claim 1 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, it is characterized in that described reactive system is by any one reactor in fixed bed, fluidized-bed or moving-bed or any several reactors in series or compose in parallel.
3. according to methyl alcohol described in claim 1 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, it is characterized in that described reaction zone A or reaction zone B is respectively the serial or parallel connection of a reactor or multiple reactor.
4. according to methyl alcohol described in claim 1 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, it is characterized in that described catalyst I is phosphor-silicon-aluminum molecular sieve catalyzer, catalyst I I is metal-modified silicoaluminophosphate molecular sieve catalyst.
5. according to methyl alcohol described in claim 4 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, it is characterized in that described phosphor-silicon-aluminum molecular sieve catalyzer is SAPO-34 and SAPO-18 molecular sieve catalyst, preferred SAPO-34 molecular sieve catalyst.
6. according to methyl alcohol described in claim 4 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, it is characterized in that described metal-modified silicoaluminophosphate molecular sieve catalyst is metal modified HZSM-5-5 or HZSM-11 molecular sieve catalyst, preferred HZSM-5 molecular sieve catalyst; Prepare according to following steps:
(1) template is removed in the roasting at 550 DEG C of former for ZSM-5 molecular sieve powder, exchange is carried out 4 times with the ammonium nitrate solution of volumetric molar concentration 0.3M in 80 DEG C of water-baths, after exchanging, solid sample is dried in 120 DEG C of air, and at 550 DEG C, roasting 3 hours, obtains HZSM-5 molecular sieve;
(2) the metal-nitrate solutions normal temperature dipping 4 hours of HZSM-5 molecular sieve 6% mass concentration prepared by step (1) is got, incline and solid sample 120 DEG C oven dry after supernatant liquid, roasting 6 hours in 550 DEG C of air, obtains modified metal-HZSM-5 molecular sieve catalyst.
7. according to methyl alcohol described in claim 6 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, wherein, described modified metal be gallium, silver and zinc any one, preferred gallium; The quality loading of gallium is 0.1-10%, and the quality loading of preferred gallium is 0.1-5%.
8. according to methyl alcohol described in claim 1 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, it is characterized in that in described step (1), methyl alcohol is or/and it is 350-500 DEG C that dme preparing low-carbon olefins reacts preferred temperature of reaction, reaction feed mass space velocity counts 0.5-8h with methyl alcohol
-1.
9. according to methyl alcohol described in claim 1 or/and dimethyl ether is for the method for propylene and aromatic hydrocarbons, it is characterized in that in described step (3), preferred light dydrocarbon aromatization reaction temperature is 400-500 DEG C, reaction feed mass space velocity counts 0.1-4h with amount of alkene
-1.
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| CN105772065A (en) * | 2016-04-13 | 2016-07-20 | 贵州大学 | Modified ZSM-5 molecular sieve based catalyst and preparing method thereof |
| CN105854931A (en) * | 2016-04-13 | 2016-08-17 | 贵州大学 | Preparation method of modified SAPO-34 molecular sieve catalyst |
| CN107970985A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of aromatisation auxiliary agent and preparation method thereof |
| CN108947756A (en) * | 2017-05-22 | 2018-12-07 | 中国科学院大连化学物理研究所 | The method of methanol or dimethyl ether in high selectivity propylene co-production gasoline and multi-methyl benzene product |
| CN111530497A (en) * | 2020-04-16 | 2020-08-14 | 西北大学 | Catalyst capable of improving MTA reaction stability and preparation method and application method thereof |
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| CN105772063A (en) * | 2016-04-13 | 2016-07-20 | 贵州大学 | Modified ZSM-5 molecular sieve based catalyst and preparing method thereof |
| CN105772065A (en) * | 2016-04-13 | 2016-07-20 | 贵州大学 | Modified ZSM-5 molecular sieve based catalyst and preparing method thereof |
| CN105854931A (en) * | 2016-04-13 | 2016-08-17 | 贵州大学 | Preparation method of modified SAPO-34 molecular sieve catalyst |
| CN105772065B (en) * | 2016-04-13 | 2018-01-30 | 贵州大学 | A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof |
| CN105772063B (en) * | 2016-04-13 | 2018-01-30 | 贵州大学 | A kind of molecular sieve catalyst of modified ZSM-5 5 and preparation method thereof |
| CN105854931B (en) * | 2016-04-13 | 2018-01-30 | 贵州大学 | A kind of preparation method of the molecular sieve catalysts of modified SAPO 34 |
| CN107970985A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of aromatisation auxiliary agent and preparation method thereof |
| CN108947756A (en) * | 2017-05-22 | 2018-12-07 | 中国科学院大连化学物理研究所 | The method of methanol or dimethyl ether in high selectivity propylene co-production gasoline and multi-methyl benzene product |
| CN108947756B (en) * | 2017-05-22 | 2020-11-13 | 中国科学院大连化学物理研究所 | Method for preparing propylene and co-producing gasoline and polymethyl benzene products by methanol or dimethyl ether with high selectivity |
| CN111530497A (en) * | 2020-04-16 | 2020-08-14 | 西北大学 | Catalyst capable of improving MTA reaction stability and preparation method and application method thereof |
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