CN104437595B - Methanol aromatic hydrocarbons fluid catalyst and preparation method thereof - Google Patents
Methanol aromatic hydrocarbons fluid catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104437595B CN104437595B CN201310435120.XA CN201310435120A CN104437595B CN 104437595 B CN104437595 B CN 104437595B CN 201310435120 A CN201310435120 A CN 201310435120A CN 104437595 B CN104437595 B CN 104437595B
- Authority
- CN
- China
- Prior art keywords
- aromatic hydrocarbons
- methanol
- binding agent
- catalyst
- fluid catalyst
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of fluid catalyst of methanol aromatic hydrocarbons containing Zn and preparation method thereof, mainly solves the existing methanol arenes catalytic agent containing Zn and is being calcined the technical problem with Zn loss of elements in hydrothermal treatment process.The present invention by using including following components by weight percentage：1）10.0 ~ 40.0% binding agent；2）20.0 ~ 55.0% aluminosilicate matrix；3）20.0 ~ 70.0% molecular sieves of HZSM 5；4）0.1 ~ 10% ZnO, wherein binding agent are selected from the technical scheme of silicon containing species, preferably solve the problem, in the industrialized production available for methanol aromatic hydrocarbons.
Description
Technical field
The present invention relates to a kind of methanol aromatic hydrocarbons fluid catalyst containing Zn and preparation method thereof.
Background technology
Based on Organic Chemicals, the aromatic hydrocarbons in China more than 85% is produced by petroleum path.On the one hand, I
State's oil and natural gas resource is very short, causes the production cost of aromatic hydrocarbons increasingly to rise；On the other hand, coal resources in China phase
To abundant, the production capacity of a large amount of coal-based methanols is look for outlet.Therefore, methanol aromatic hydrocarbons is a very promising technology road
Line.
Methanol aromatic hydrocarbons is a typical acid catalyzed reaction, and catalyst used is typically by with aromatization activity
Metal（Ag, Ga, Zn etc.）It is supported on acidic molecular sieve and is made.Because the stronger acidity of ZSM-5 molecular sieve, excellent hydro-thermal are steady
Qualitative and most important duct shape selectivity, makes ZSM-5 molecular sieve be widely used in aromatization.And Zn makees
For metal cheap and easy to get, and the high selectivity that is shown in aromatization of the ZSM-5 molecular sieves that are modified of Zn and introduce
Gaze at.Many research reports show that Zn is in aromatization, by strengthening dehydrogenation functionality and occurring with the acid site of molecular sieve
Synergy, so as to improve the aromatization activity of ZSM-5 molecular sieve and selectivity.
It is more normal using polymeric aluminum chloride as binding agent in existing semi-synthetic fluid catalyst technology of preparing
See, its preparation flow is simple, and operation is easy, slurries short preparation period, and solid content is high.And the stability of polymeric aluminum chloride is also very
It is good, it is easy to slurries to deposit for a long time.But contain substantial amounts of chlorine element in polymeric aluminum chloride, produced in catalyst roasting process
Substantial amounts of hydrogen chloride gas, easily cause to equipment corrosion and environmental pollution, this requires that equipment has antiseptic property, and this gives work
Industry production brings certain technical difficulty.In addition, Lin Jie et al. [petroleum journals（PETROLEUM PROCESSING）2000 volume 16
5 phase p：36-40] research also found, when catalyst is using Al2O3 as binding agent, in high-temperature roasting and hydrothermal treatment process
In, Zn constituent elements can be migrated, and be in originally on acidic zeolite position, and the Zn to act synergistically can be formed with molecular sieve from molecular sieve
On moved on Al2O3, cause the aromatization catalyst activity containing Zn to decline.And made with polymeric aluminum chloride or other aluminium bases
The methanol arenes catalytic agent prepared for binding agent, inevitable there is also the problem of Zn losses.
Patent CN1240814 reports a kind of manufacture method of catalyst and cracking of hydrocarbon, before spray drying forming
Ludox or Silica hydrogel are added into the catalyst slurry containing polymeric aluminum chloride, carclazyte and Y type molecular sieve, is then sprayed
Dry, washing, obtain finished catalyst after drying, reduce the discharge of hydrogen chloride gas.
Patent CN1417297 reports a kind of semi-synthetic Hydrocarban coversion catalysts of the silicon substrate containing rare earth, be characterized in by containing
The silica sol binders of rare earth salts, natural aluminium silicate clay and catalyst made of artificial synthesized molecular sieve, improve heavy oil
Cracking activity and preventing from heavy metal pollution ability.
Patent CN 1552801 reports a kind of catalytic cracking catalyst and preparation method thereof, and it is by clay, Ludox, plan
Boehmite, molecular sieve and hybrid metal composition.It uses the compound binding agent that Ludox and part boehmite are combined,
The macromolecular cleavage ability of catalyst is not only enhanced, while ensures that it has good anti-wear performance again.
Patent US3957689 reports a kind of catalytic cracking catalyst.Using sulfuric acid/aluminum sulfate cushioning liquid adjustment silicic acid
Then the pH value of sodium adds clay, molecular sieve, catalyst is made by spray drying to relatively low scope.Gained catalyst has
Higher reactivity and higher anti-wear performance.
Patent US4987110, which is reported, a kind of has stronger anti-wear performance and the catalytic cracking catalyst compared with high selectivity.
And the binding agent that it is used is Ludox and polymeric aluminum chloride compound binding agent.
The content of the invention
One of technical problems to be solved by the invention are that the Zn constituent elements in the fluid catalyst of methanol aromatic hydrocarbons are being urged
A kind of technical problem being easily lost in agent roasting and hydrothermal treatment process, there is provided methanol aromatic hydrocarbons fluidized bed catalytic containing Zn
Agent, the catalyst have the advantages of Zn is not easily runed off.
The two of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem corresponding catalysis
Agent preparation method.
The three of the technical problems to be solved by the invention are to provide a kind of catalyst corresponding with solving technical problem one
Purposes.
In order to solve technical problem one, the technical solution adopted by the present invention is as follows：A kind of methanol aromatic hydrocarbons fluidisation containing Zn
Bed catalyst, by weight percentage comprising following components：
1）10.0 ~ 40.0% binding agent；
2）20.0 ~ 55.0% aluminosilicate matrix；
3）20.0 ~ 70.0% HZSM-5 molecular sieves；
4）0.1 ~ 10% ZnO；
Wherein binding agent is selected from silicon-containing material.
In above-mentioned technical proposal, preferable technical scheme is that binding agent is in Ludox, waterglass or sodium metasilicate
It is at least one.And the pH value of inorganic acid adjustment binding agent is needed to use in use in the range of 1.5 ~ 5.0.Described
Inorganic acid can be the one or more in sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.Described alumino-silicate be selected from kaolin, angstrom
At least one of Lip river stone, diatomite, bentonite or sepiolite.Described ZSM-5 molecular sieve is artificial synthesized ZSM-5 points
Son sieve exchanges by ammonium, the H type ZSM-5 molecular sieves that roasting obtains afterwards, and its sial atomic ratio Si/Al is 10 ~ 100, preferably
Si/Al be 10 ~ 50.ZnO in above-mentioned technical proposal is is supported on ZSM-5 molecular sieve using infusion process, the choosing of its presoma
From at least one of zinc chloride, zinc nitrate, zinc sulfate or zinc acetate.
To solve technical problem two, the technical solution adopted by the present invention is as follows：The methanol aromatic hydrocarbons fluid catalyst
Preparation method, include following steps：
1）The ZSM-5 molecular sieve of a certain amount of H types is weighed, loads a certain amount of ZnO over a molecular sieve using infusion process, then
By 80 ~ 120 DEG C of dry 8 ~ 24h, 500 ~ 650 DEG C of 2 ~ 8h of roasting are standby；
2）Weigh a certain amount of binding agent and mixed with water and be made into slurries, and the pH value range of slurries is adjusted by adding inorganic acid
To between 1.5 ~ 5.0；
3）Alumino-silicate is added 2）In the slurries of preparation, and it is beaten 10 ~ 60min；
4）By 1）The ZnHZSM-5 molecular sieves of middle preparation are added in slurries, continue 10 ~ 60min of mashing；
5）Slurries are prepared into micro-spherical catalyst using the method for spray drying, and pass through drying, 500 ~ 650 DEG C of roastings
Methanol aromatic hydrocarbons fluid catalyst is made in 2 ~ 8h.
In above-mentioned technical proposal, preferable technical scheme is, the pH value range of the binding agent is adjusted to 2.0 with inorganic acid
Between ~ 5.0, wherein inorganic acid is selected from least one of sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.Rate-determining steps 3）Middle slurry
Grain graininess is 1-20 μm.
Methanol aromatic hydrocarbons fluid catalyst provided by the invention, due to using based binder, therefore is avoided
Al is introduced in forming process2O3, it is therefore prevented that Zn constituent elements migrate in catalyst roasting and hydrothermal treatment process from molecular sieve surface
To Al2O3The problem of.Simultaneously as before binding agent use, by adjusting the pH value of binding agent, the steady of binding agent is improved
It is qualitative, the aggregation of silica itself is avoided, ensure that catalyst has stronger anti-wear performance.Meanwhile with using hydroxy chloride
The method that change aluminium prepares catalyst as binding agent is compared, and the present invention avoid or reduces the discharge of hydrogen chloride gas, is reduced
Environmental pollution and the corrosion to equipment, achieve preferable technique effect.
Below by specific embodiment, the present invention is further elaborated.But the present invention is not limited in these embodiments.
Embodiment
【Embodiment 1】
The ZSM-5 molecular sieve that 1500g silica alumina ratios Si/Al is 30 is weighed, is mixed with 6000g concentration for 5% aqueous ammonium nitrate solution
Close.The heating stirring 2h under the conditions of 90 DEG C, filtering, washing.Repeat said process and filter cake is placed in 120 DEG C of oven dryings afterwards twice
12h, then 550 DEG C of obtained H types of roasting 4h ZSM-5 molecular sieve.
HZSM-5 molecular sieves made from the 800g above methods are taken, with 1200g zinc nitrates（ZnO mass concentrations are 3.3%）It is water-soluble
Liquid mixes, and the HZSM-5 molecular sieves containing Zn are made by drying, 550 DEG C of roasting 4h after fully mixing.
Take 100g Guangzhou Ludox（SiO2 mass concentrations 40%, ammonium is steady）, the sulfuric acid that 11g concentration is 5% is added, adjusts pH value
To 2.0.The slurries that 500g water mixes with 100g kaolin are added, 20min is mixed using colloid mill strongly.Add 100g
The HZSM-5 molecular sieves containing Zn of above-mentioned preparation, continue to mix 20min strongly with colloid mill.By the slurries mixed using spraying
Dry method is prepared into micro-spherical catalyst, and methanol aromatic hydrocarbons fluid bed is made in 100 DEG C of dry 16h, 600 DEG C of roasting 4h
Catalyst A.
【Embodiment 2】
Take 10.0g concentrated nitric acids, add 40g water dilute after with 200g waterglass（SiO2 concentration 20%）Mixing, obtaining pH value is
2.2 mixed liquor.Take 100g diatomite to be added after being mixed with 200g water in waterglass, 15min is mixed using colloid mill strongly.Take
The HZSM-5 molecular sieves containing Zn prepared in 100g embodiments 1, are added in mixed serum, continue glue mill 30min.It will mix
Slurries micro-spherical catalyst is prepared into using the method for spray drying, and in 120 DEG C of drys 12h, 580 DEG C are calcined 6h.It will urge
Agent is washed, and removes Na ions, and methanol aromatic hydrocarbons fluid catalyst B is obtained after drying.
【Embodiment 3】
Take 80g Guangzhou Ludox（SiO2 mass concentrations 40%, ammonium is steady）, the dense phosphorus of 15g is added dropwise to after adding the dilution of 320g water
Acid.Then weigh 100g bentonites to add in Ludox, 30min is mixed using colloid mill strongly, added in 90g embodiments 1
The HZSM-5 molecular sieves containing Zn prepared, are added in mixed serum, continue glue mill 30min.By the slurries mixed using spray
The method that mist is dried is prepared into micro-spherical catalyst, and methanol aromatic hydrocarbons fluidisation is made in 110 DEG C of dry 18h, 620 DEG C of roasting 4h
Bed catalyst C.
【Embodiment 4】
80g sodium metasilicate is taken, is dissolved in 160g water, the sulfuric acid that 280g concentration is 15% is added inward, is added after well mixed
80g kaolin, 10min is mixed using colloid mill strongly.The HZSM-5 molecular sieves containing Zn prepared are added in 70g embodiments 1,
It is added in mixed serum, continues glue mill 30min.The slurries mixed are prepared into microspheroidal using the method for spray drying to urge
Agent, and methanol aromatic hydrocarbons fluid catalyst D is made in 100 DEG C of dry 18h, 650 DEG C of roasting 4h.
【Embodiment 5 ~ 7】
The HZSM-5 molecular sieves prepared in 100g embodiments 1 are taken, using zinc nitrate solution as maceration extract loading ZnO.Make respectively
Into the ZSM-5 molecular sieve containing Zn that ZnO content is 1.0%, 3.0%, 8.0%.
According to the method for embodiment 1, it is respectively adopted in the ZSM-5 molecular sieve alternate embodiment 1 of above-mentioned different ZnO contents
ZnO content is 5.0% ZSM-5 molecular sieve, is prepared into methanol aromatic hydrocarbons fluid catalyst E, F and G.
【Embodiment 8】
The ZSM-5 molecular sieve that 600g silica alumina ratios Si/Al is 60 is weighed, is mixed with 3000g concentration for 10 aqueous ammonium chloride solution
Close.Heating stirring 1.5h under the conditions of 90 DEG C, filtering, washing.Repeat said process and filter cake is placed in 120 DEG C of oven dryings afterwards twice
10h, then 540 DEG C of obtained H types of roasting 6h ZSM-5 molecular sieve.
The HZSM-5 molecular sieves for taking the 600g above methods to prepare, with 360g solution of zinc sulfate（ZnO mass concentrations are 5.2%）
Mixing, after drying, 530 DEG C of roasting 5h obtain the ZSM-5 molecular sieve containing Zn.
Take 220g Guangzhou Ludox（SiO2 mass concentrations 40%, ammonium is steady）, mixed with the dilute sulfuric acid that 700g concentration is 0.1%,
Then add 240g kaolin and be mixed into slurries, 20min is mixed using colloid mill strongly.Add the preparation of the 200g above methods
HZSM-5 molecular sieves containing Zn, continue to mix 50min strongly with colloid mill.Method by the slurries mixed using spray drying
Micro-spherical catalyst is prepared into, and methanol aromatic hydrocarbons fluid catalyst H is made in 120 DEG C of dry 8h, 640 DEG C of roasting 4h.
【Embodiment 9】
The catalyst H prepared in 150g embodiments 8 is taken, is placed in fixed fluidized-bed reactor.Water pump is used with 2.5g/
Min speed is toward water flowing in reactor.Enter before reactor, water need to be gasified by preheating device.The temperature that catalyst contacts with water
Spend for 550 DEG C, time of contact 8h.Then stop water flowing, catalyst is dried, obtains methanol aromatic hydrocarbons fluid catalyst I.
【Comparative example 1】
Take 420g Alumina gels（Al2O3 mass concentrations are 21%）, the slurries that 480g water is mixed into 240g kaolin are added,
20min is mixed using colloid mill strongly.The HZSM-5 molecular sieves containing Zn prepared are added in 200g embodiments 8, continue to use glue
The strong mixing 50min of body mill.The slurries mixed are prepared into micro-spherical catalyst using the method for spray drying, and 120
DEG C 8h is dried, methanol aromatic hydrocarbons fluid catalyst J are made in 640 DEG C of roasting 4h.
【Comparative example 2】
The catalyst J prepared in 150g comparative examples 1 is taken, is placed in fixed fluidized-bed reactor.Water pump is used with 2.5g/
Min speed is toward water flowing in reactor.Enter before reactor, water need to be gasified by preheating device.The temperature that catalyst contacts with water
Spend for 550 DEG C, time of contact 8h.Then stop water flowing, catalyst is dried, obtains methanol aromatic hydrocarbons fluid catalyst K.
The prepared catalyst of this experiment carries out performance evaluation on fixed fluidized-bed reactor, and experiment condition is reaction temperature
430 DEG C of degree, mass space velocity=1.0h-1, normal pressure, the reaction time is the methanol aromatic hydrocarbons reaction of each catalyst under 1h reaction condition
The results are shown in Table 1, and wherein BTX is represented and represented benzene, toluene and dimethylbenzene respectively.
Table 1
| Embodiment | Catalyst | Aromatics quality yield/% | BTX mass yields/% |
| Embodiment 1 | A | 59.7 | 48.2 |
| Embodiment 2 | B | 58.7 | 48.0 |
| Embodiment 3 | C | 56.3 | 45.7 |
| Embodiment 4 | D | 56.7 | 46.2 |
| Embodiment 5 | E | 52.4 | 43.0 |
| Embodiment 6 | F | 55.2 | 44.9 |
| Embodiment 7 | G | 61.7 | 48.9 |
| Embodiment 8 | H | 53.6 | 40.2 |
| Embodiment 9 | I | 47.4 | 36.5 |
| Comparative example 1 | J | 50.5 | 39.1 |
| Comparative example 2 | K | 45.4 | 35.9 |
Claims (7)
- A kind of 1. methanol aromatic hydrocarbons fluid catalyst containing Zn, by weight percentage comprising following components：1）10.0 ~ 40.0% binding agent；2）20.0 ~ 55.0% aluminosilicate matrix；3）20.0 ~ 70.0% HZSM-5 molecular sieves；4）ZnO, ZnO content are 8.0% of the HZSM-5 molecular sieves containing Zn；Wherein binding agent is selected from least one of waterglass or sodium metasilicate；The pH value of binding agent is being adjusted to 1.5-5.0 by the binding agent using preceding with inorganic acid；Sial atomic ratio Si/Al is 10-50 in the HZSM-5 molecular sieves；The preparation method of the methanol aromatic hydrocarbons fluid catalyst, includes following steps：1）The ZSM-5 molecular sieve of a certain amount of H types is weighed, a certain amount of ZnO is loaded over a molecular sieve using infusion process, then passes through 80 ~ 120 DEG C of dry 8 ~ 24h, 500 ~ 650 DEG C of 2 ~ 8h of roasting are standby；2）Weigh a certain amount of binding agent and mixed with water and be made into slurries, and the pH value range for adjusting by adding inorganic acid slurries arrives Between 1.5 ~ 5.0；3）Aluminosilicate matrix is added 2）In the slurries of preparation, and it is beaten l0 ~ 60min；4）By 1）The load Zn of middle preparation HZSM-5 molecular sieves are added in slurries, continue 10 ~ 60min of mashing；5）Slurries are prepared into micro-spherical catalyst using the method for spray drying, and pass through drying, 500 ~ 650 DEG C of 2 ~ 8h of roasting Obtained methanol aromatic hydrocarbons fluid catalyst.
- 2. methanol aromatic hydrocarbons fluid catalyst according to claim 1, it is characterised in that described aluminosilicate matrix choosing From at least one of kaolin, galapectite, diatomite, bentonite or sepiolite.
- 3. methanol aromatic hydrocarbons fluid catalyst according to claim 1, it is characterised in that the presoma of the ZnO is selected from chlorine Change at least one of zinc, zinc nitrate, zinc sulfate or zinc acetate.
- 4. methanol aromatic hydrocarbons fluid catalyst according to claim 1, it is characterised in that adjust the bonding with inorganic acid The pH value range of agent is between 2.0 ~ 5.0, and wherein inorganic acid is selected from least one of sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
- 5. methanol aromatic hydrocarbons fluid catalyst according to claim 4, it is characterised in that rate-determining steps 3）Of middle slurry Grain granularity is 1-20 μm.
- 6. a kind of method of methanol aromatic hydrocarbons, it is 300 ~ 600 DEG C in reaction temperature using methanol as raw material, reaction pressure 0.01 ~ 1MPa, methanol weight air speed are 0.1 ~ 8h-1, under conditions of water/methanol weight ratio is 0 ~ 5, raw material passes through beds and power Any one catalyst contacts during profit requires 1 ~ 4, product of the reaction generation based on aromatic hydrocarbons.
- 7. the method for methanol aromatic hydrocarbons according to claim 6, it is 350 ~ 550 DEG C in reaction temperature using methanol as raw material, 0.1 ~ 1MPa of reaction pressure, methanol weight air speed are 0.2 ~ 6h-1, under conditions of water/methanol weight ratio is 0.5 ~ 4, raw material passes through Beds, product of the reaction generation based on aromatic hydrocarbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310435120.XA CN104437595B (en) | 2013-09-24 | 2013-09-24 | Methanol aromatic hydrocarbons fluid catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310435120.XA CN104437595B (en) | 2013-09-24 | 2013-09-24 | Methanol aromatic hydrocarbons fluid catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104437595A CN104437595A (en) | 2015-03-25 |
| CN104437595B true CN104437595B (en) | 2018-01-09 |
Family
ID=52884804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310435120.XA Active CN104437595B (en) | 2013-09-24 | 2013-09-24 | Methanol aromatic hydrocarbons fluid catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104437595B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106607076B (en) * | 2015-10-21 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon from methanol and preparation method thereof |
| CN106607079A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Methanol-to-aromatic hydrocarbon catalyst and uses tehreof |
| JP6574059B2 (en) * | 2016-04-28 | 2019-09-11 | 旭化成株式会社 | Method for producing aromatic hydrocarbon-containing compound |
| CN107010639B (en) * | 2017-04-11 | 2019-10-11 | 四川润和催化新材料股份有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve and preparation method thereof and the method for being used to prepare MTA catalyst |
| 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 |
| 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 |
| CN109701598B (en) * | 2017-10-26 | 2022-04-05 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon from methanol and application thereof |
| CN109701599B (en) * | 2017-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic hydrocarbon from methanol and application method thereof |
| CN116328752A (en) * | 2022-12-13 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application of catalyst in preparation of propylene carbonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612585A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of gasoline reforming catalyst and its production and application |
| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928483A (en) * | 1974-09-23 | 1975-12-23 | Mobil Oil Corp | Production of gasoline hydrocarbons |
| CN102372535B (en) * | 2010-08-23 | 2014-05-28 | 中国石油化工股份有限公司 | Method for preparing aromatic hydrocarbon through methanol transformation |
| CN101954291B (en) * | 2010-09-26 | 2012-07-04 | 华中科技大学 | Zinc isomorphism-substituted nano molecular sieve catalyst and preparation method and application thereof |
-
2013
- 2013-09-24 CN CN201310435120.XA patent/CN104437595B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101612585A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of gasoline reforming catalyst and its production and application |
| CN103055928A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing arene via direct methanol conversion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104437595A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104437595B (en) | Methanol aromatic hydrocarbons fluid catalyst and preparation method thereof | |
| CN101032694B (en) | Catalyst composition for treating heavy feedstocks | |
| CN105688977B (en) | A kind of catalytic cracking catalyst preparation method containing boehmite | |
| CN101491772B (en) | Catalyst for naphtha catalytic cracking | |
| CN107971015A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN104437594B (en) | Low abrasion methanol aromatic hydrocarbons fluid catalyst and preparation method thereof | |
| CN103406140B (en) | Catalyst for converting aromatic hydrocarbon from alcohol ether, and preparation method and application method thereof | |
| CN104557416B (en) | The method that aromatic hydrocarbons is produced by raw material of oxygenatedchemicals | |
| CN104549470B (en) | In-situ reaction zeolite base oxygenatedchemicals aromatized catalyst and preparation method thereof | |
| CN103657711B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN103664440A (en) | Method for producing arene through conversion of methyl alcohol | |
| CN101279284B (en) | Catalyst for preparing ethylene propylene from catalytic pyrolysis | |
| CN103657712A (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN103657701B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN111686785A (en) | Heavy oil catalytic cracking catalyst and preparation method thereof | |
| CN102430422B (en) | Catalytic cracking catalyst for producing low-carbon olefin and application thereof | |
| CN103657702B (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN1311907C (en) | Cracking catalyst for petroleum hydrocarbon, and preparation method | |
| CN103785472A (en) | Catalyst used for preparation of olefins through catalytic cracking, and preparation method and application thereof | |
| CN104437596B (en) | Methanol arenes catalytic agent and preparation method thereof | |
| CN104549408B (en) | Symbiosis aromatization of methanol catalyst in situ of MCM 22/ZSM 5 and preparation method thereof | |
| JP5954970B2 (en) | Hydrocarbon catalytic cracking catalyst and process for producing the same | |
| CN106607078B (en) | The catalyst of oxygenatedchemicals paraxylene and propylene, preparation method and applications | |
| CN104557427B (en) | The method of oxygenatedchemicals aromatic hydrocarbons | |
| CN104923282B (en) | A kind of super stabilizing processing method of high rare-earth content in-situ crystallization catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |