CN105080593B - For dimethyl ether and the method for modifying of the molecular sieve catalysts of benzene alkylation reaction ZSM 11 - Google Patents
For dimethyl ether and the method for modifying of the molecular sieve catalysts of benzene alkylation reaction ZSM 11 Download PDFInfo
- Publication number
- CN105080593B CN105080593B CN201410200846.XA CN201410200846A CN105080593B CN 105080593 B CN105080593 B CN 105080593B CN 201410200846 A CN201410200846 A CN 201410200846A CN 105080593 B CN105080593 B CN 105080593B
- Authority
- CN
- China
- Prior art keywords
- zsm
- dimethyl ether
- molecular sieve
- catalyst
- sieve catalysts
- 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
Abstract
It is a kind of to be used for the method for modifying of dimethyl ether and the molecular sieve catalysts of benzene alkylation reaction ZSM 11, category molecular sieve catalyst field.Comprise the following steps that：By the molecular sieves of Na types ZSM 11, with certain liquid-solid ratio and alkali and organic surface active agent mixed solution heating stirring 0.1~1 hour at 65~85 DEG C, wash to drying and roasting after neutrality, then with 0.5~1.0mol/L ammonium nitrate solution in 70~90 DEG C of exchanges, dry roasting, is made H type molecular sieves.The molecular sieve catalysts of surfactant alkali process ZSM 11 of the present invention, compared with conventional alkali process or molecular sieve catalysts of ZSM 11 without alkali process, the stability of dimethyl ether and benzene conversion ratio can be further enhanced on catalyst.
Description
Technical field
The invention belongs to molecular sieve catalyst field, and in particular to one kind is used for dimethyl ether and benzene alkylation reaction ZSM-11
The method of modifying of molecular sieve catalyst.
Background technology
Aromatic hydrocarbons is the important foundation raw material of petrochemical industry, in total about 8,000,000 kinds known organic compound, aromatization
Compound account for about 30%.Using natural gas (main component methane) or petroleum refinery's dry gas (mainly containing methane, ethane, ethene) with
It is that academic circles at present and industrial quarters are more popular that oil liquefied gas or methanol (dimethyl ether), which carry out anaerobic aromatization and prepares aromatic hydrocarbons,
Research topic.
Shanxi coalification patent CN1880288A in use methanol, dimethyl ether for raw material, modified ZSM-5 is catalyst,
It is the product based on aromatic hydrocarbons by methanol, dimethyl ether conversion, separates gas-phase product lower carbon number hydrocarbons and liquid product through refrigerated separation, liquid
Phase product obtains aromatic hydrocarbons and non-aromatics, the further aromatisation of low-carbon hydro carbons through extract and separate.But during alkane aromatization,
Hydrogen has a strong impact on the aromatisation yield and selectivity of alkane, therefore the gas-phase product of methanol, dimethyl ether aromatisation is directly entered
Enter the technique not optimum process that low-carbon aromatizing reaction of hydrocarbons carries out aromatization.
Patent CN201010111821.4 discloses dimethyl ether aromatisation compared with aromatization of methanol process, with following excellent
Gesture：
1) dimethyl ether can be dehydrated by aromatization of methanol and be prepared, and sterling is obtained after being then separated from water.In aromatization
In device, generate the water of every mole of aromatic hydrocarbons by-product reduces 30-50% than direct methyl ether aromatization process.The process is incited somebody to action equivalent in advance
Portion of water is separated out, so that the chance that aromatized catalyst contacts water is reduced, can be by the life-span of catalyst at high temperature
Improve 1-3 times.
2) dimethyl ether is first dehydrated again the process of aromatisation by methanol, first using dehydrating agent, is reused aromatized catalyst, is made
Obtain the consumption reduction by 30% of aromatized catalyst.It is acid because the water adsorbed in dimethyl ether aromatization process on catalyst is reduced
Increase, aromatics yield 5-15% high than aromatization of methanol.Make the time contracting that gas is purged in catalyst regeneration reactor simultaneously
It is short, 20 DEG C of regeneration temperature can be properly increased so that the heat increase by 5% that regenerated catalyst can be taken back for aromatization.
During water partial pressure reduction, also cause the size of aromatization reactor to reduce 20%, the reduction of the cost of aromatization reactor.
3) dimethyl ether is gaseous state, and the solubility in water is less than methanol, can so reduce when being subsequently separated from water
Complexity.
4) fluidized-bed reactor is used, is fed with methanol, if degree of superheat is not enough, partially liq can cause fluid bed
The easy hardened or difficult fluidisation of small particle catalyst.And dimethyl ether is gaseous feed, then this shortcoming is prevented effectively from, fluid bed can be caused
Operation become more steadily with easily.
Kecskem é ti etc. [A.Sz é chenyi, F.Solymosi, Catalysis Letters127 (2008) 13-19]
Report Mo2Dimethyl ether aromatization on C/ZSM-5 catalyst, when being reacted at 450 DEG C, Mo2C load capacity is 10%
Total arenes selectivity is that 42.5%, C8 selectivity is 22.3% on catalyst.Sun Changyong [Fang Yiwen, Song Yibing, grandson's length are brave etc.,
It is catalyzed journal, 2010,31 (3)：264] the acid enhancing of report H-ZSM-5 molecular sieve catalysts and increasing for acid site are conducive to
Dimethyl ether aromatisation.When adding 2%Zn in H-ZSM-5 catalyst, total arenes yield is from 50.0% when being reacted at 360 DEG C
Increase to 66.2%, C8 aromatics yields increases to 39.0% from 28.6%.When reaction temperature is increased to 480 DEG C, total arenes yield
Increase to 78.0%.Its economic value produces gasoline or methane aromatizing production benzene far above MTG methods.
Chinese patent CN201010111821.4 discloses continuously aromatizing dimethyl ether and catalyst regeneration method and device.
This is a typical process patent, and using specific catalyst, in certain reactor, (fixed bed, moving bed is combined with fluid bed
Continuous aromatization is carried out in device to regenerate with catalyst.Using the device and catalyst and method, pure diformazan can be handled
Ether or the mixed material containing dimethyl ether, the activity with the catalyst in regulation aromatization reactor reach that continuous high-efficient turns
Change dimethyl ether and high selectivity generates the purpose of aromatic hydrocarbons.Chinese patent CN201010146915.5 discloses a kind of methanol or dimethyl ether
The system and technique CN201010111821.4 and 201010146915.5 of preparing aromatic hydrocarbon by converting are typical process patent, and
Non-catalytic patent).Material benzenemethanol or dimethyl ether are reacted in aromatization reactor first, and reacted product is through separation
Afterwards, H2, methane, mixing C8 aromatic hydrocarbons and part C9+ hydro carbons is as output of products system, and C2+ non-aromatics and except mixing C8 aromatic hydrocarbons and
Part C9Aromatic hydrocarbons outside+hydro carbons then returns to respective reaction device as circulation logistics and carries out further aromatization.Using this
Technique, by being separated and being recycled the product in methanol or dimethyl ether aromatization process, not only improves material aromatic hydrocarbons
Yield and selectivity, and technique is flexibly, can convert target product according to the demand in market.
Chinese patent CN201110070849.2 discloses a kind of benzene and the catalyst of methanol alkylation and its preparation and application；
Described catalyst is with H type MCM-56 zeolites and γ-or η-Al2O3For complex carrier, load molybdenum, nickel, magnesium, lanthanum, boron or its oxidation
One or more of compositions in thing, in terms of vehicle weight 100%, H types MCM-56 zeolites account for 50-80%, Al in carrier2O3Account for 20-
50%, molybdenum, nickel, magnesium, lanthanum, the metal of boron or its oxide loaded is the 3-20% of vehicle weight；The catalyst has more
High benzene and the activity of conversion of methanol, and with higher dimethylbenzene selective, the conversion ratio of benzene reach more than 50%, toluene and
The selectivity of dimethylbenzene takes full advantage of benzene and methanol resource more than 90%, and the relative reduction life of toluene and dimethylbenzene
Produce cost.
A kind of method that Chinese patent CN200910075173.9 discloses benzene and methanol alkylation preparing methylbenzene and dimethylbenzene, it is former
Expect benzene, the benzene and methanol that rectifying is reclaimed are fed together, and the amount of toluene and dimethylbenzene is adjusted by the ratio of benzene feed and methanol, are had
There is the characteristics of catalyst choice is high.The catalyst used is Beta, Y, modenite, ZSM-5 and ZSM-22, ZSM-11 molecule
Sieve.
A kind of method that Chinese patent CN201110100011.3 discloses benzene and methanol or dimethyl ether dimethylbenzene.Benzene and first
Alcohol is raw material, 300-500 DEG C of reaction temperature, reaction pressure 0.5-3MPa, feed space velocity 0.8-3h-1, raw material contacts with solid acid
(containing one or more free molecular sieves, solidification inorganic acid, heteropoly acid, solid super-strong acid isoreactivity component) is alkylated
React and obtain dimethylbenzene, preferably solve petroleum resources and be limited, benzene and methanol production capacity surplus, benzene can not or be difficult to be made two
The problem of toluene, methanol or dimethyl ether are directly translated into dimethylbenzene route selection and the too low material consumption of yield, high energy consumption.
A kind of method that Chinese patent CN201110100004.3 discloses benzene and methanol or dimethyl ether grade oil toluene.Should
Invention is by using a kind of solid acid catalyst of modification, using benzene and methanol or dimethyl ether as raw material, in reaction temperature 250-600
DEG C, reaction pressure 0.05-5.0MPa, raw material weight air speed 0.3-1h-1Under the conditions of, make raw material catalyst (be selected from ZSM-5,
ZSM-12, modenite, USY, beta-molecular sieve, UZM molecular sieves, at least one of EU-1 molecular sieves or MCM-41 molecular sieves contain
Have in Mg, Ga, Ba, Zn, Ga, Mo, Ni, Co, W, Cu, Fe, Zr, Ti, Pt, Pd, Sn, Pb, La or Ce metallic element at least
One kind, containing selected from least one of P, S, Cl, B nonmetalloid) on occur alkylated reaction and obtain toluene.
Sz é chenyi etc. [A.Sz é chenyi, F.Solymosi, Catalysis Letters127 (2008) 13-19] are reported
The road dimethyl ether and benzene coreaction under the conditions of 200-500 DEG C, reaction respectively pure and carried out on modified zsm-5 zeolite,
It was found that temperature is more than 350 DEG C, the yield that toluene, dimethylbenzene and C9 aromatic hydrocarbons are significantly increased after benzene is added.When with Mo2C and ZnO
After decorating molecule sieve, reactivity worth further gets a promotion.
Microporous mesoporous composite molecular screen has micropore and mesoporous dual model pore size distribution, combines the duct advantage of mesoporous material
With the highly acid and high hydrothermal stability of micro porous molecular sieve, two kinds of material advantage complementations, synergy can be made.It is microporous mesoporous compound
The gradient distribution of molecular sieve bore diameter is reasonably combined with acidity, will produce beneficial cooperative effect, and have in terms of absorption and catalysis
Wide application prospect.Alkali process is the effective ways for manufacturing microporous mesoporous composite molecular screen.Li Yu rather wait [Y.Li, S.Liu,
S.Xie, L.Xu, Appl.Catal.A360 (2009) 8-16] to report the Zn/ZSM-5 through alkali treatment modifying microporous mesoporous compound
Molecular sieve catalyst shows superior reaction stability during 1- hexene aromatizations.Sadowska etc. [K.Sadowska,
A.Wach,Z.Olejniczak,P.J.Datka,Microporous and Mesoporous
Materials167 (2013) 82-88.] research discovery is compared with soda ash processing, and the addition of surfactant can produce more points
Narrow mesoporous of cloth.Yoo etc. [W.C.Yoo, X.Zhang, M.Tsapatsis, A.Stein,
Micropor.Mesopor.Mater.149 (2012) 147-157] find compared with common alkali process, surfactant alkali process
Obtained ZSM-5 molecular sieve has higher crystallinity and more excellent pore structure property.Schmidt etc. [F.Schmidt,
M.R.Lohe,B.Büchner,F.Giordanino,F.Bonino,S.Kaskel,Micropor.Mesopor.Mater.165
(2013) 148-157] to find after surfactant alkali process that ZSM-5 molecular sieve is shown in methanol converts hydrocarbon reaction processed stronger
Stability.[K.Sadowska, K.G the ó ra-Marek, J.Datka, Vibrational such as Sadowska
Spectroscopy63 (2012) 418-425.] report compared with soda ash solution, surfactant and aqueous slkali are jointly processed by
Due to mesoporous effective generation after ZSM-5 molecular sieve, hence it is evident that improve sour position accessibility.
It is above-mentioned that plurality of advantages is shown to molecular sieve progress alkali process rear catalyst, but it is only limitted to ZSM-5 molecular sieve system
Research, to ZSM-11 carry out alkali process not yet report.Although ZSM-5 and ZSM-11 are ZSM Series Molecules sieve, but the former belongs to
(it is made up of in MFI topological structures the linear pattern duct and sinusoidal duct that intersect), the latter is that MEL topological structures are (cross one another
Straight hole road), be present some differences in skeleton structure, be mainly reflected on the crosspoint in duct.Tinkling of pieces of jade etc. [L.Zhang, H.Liu,
X.Li, S.Xie, Y.Wang, W.Xin, S.Liu, L.Xu, Fuel Process.Technol.91 (2010) 449-455] find
Compared with similar acidity with the ZSM-5 molecular sieve of particle size, ZSM-11 is shown more in 1- hexene aromatization reactions
High aromatics yield.On this basis, we apply for alkali plus surfactant processing ZSM-11 molecular sieve catalysts and for two
The patent of methyl ether and benzene alkylation reaction.
The content of the invention
It is an object of the invention to provide a kind of changing for dimethyl ether and benzene alkylation reaction ZSM-11 molecular sieve catalysts
Property method, the process employs the ZSM-11 molecular sieve catalysts that alkali plus surfactant are handled with certain liquid-solid ratio, with routine
Alkali process or compared with the ZSM-11 molecular sieve catalysts without alkali process, the stability of dimethyl ether and benzene conversion ratio on catalyst
It can be further enhanced.
The present invention is a kind of for dimethyl ether and the method for modifying of benzene alkylation reaction ZSM-11 molecular sieve catalysts, specific step
It is rapid as follows：
It is a kind of to be used for the method for modifying of dimethyl ether and benzene alkylation reaction ZSM-11 molecular sieve catalysts, it is characterised in that to press
Carried out according to following steps：By Na- type ZSM-11 molecular sieves, existed with certain liquid-solid ratio with alkali and organic surface active agent mixed solution
Heating stirring 0.1~1 hour at 65~85 DEG C, washing is to neutral and then drying and roasting, then with 0.5~1.0mol/L nitric acid
H- type molecular sieves are made in 70~90 DEG C of exchanges, dry roasting in ammonium salt solution.
The liquid-solid ratio is that mixed solution ml/ molecular screen primary powders g is 20~40ml mixed solutions/g molecular sieves.
Described alkaline concentration is 0.1~1.0mol/L.
The alkali is 80~2 with surfactant molar concentration rate:1.
The aqueous slkali is one or both of sodium hydroxide and potassium hydroxide solution；Organic surface active agent is 16
One kind or many in alkyl trimethyl ammonium bromide (CTAB), polyquaternium -6 (PDADMAC) or TBAH (TBAOH)
Kind.
The drying temperature is 90~130 DEG C, and drying time is 1~12 hour.
The sintering temperature is 450~600 DEG C, and roasting time is 2~8 hours.
Na in the molecular sieve catalyst of modified ZSM-5-11 prepared by the present invention2O content is less than or equal to 0.05wt%.
The ZSM-11 molecular sieve catalysts of belt surface activating agent alkali process are used for the present invention into dimethyl ether and benzene alkylation is anti-
Should, compared with conventional alkali process or Zn/ZSM-11 molecular sieve catalysts without alkali process, dimethyl ether and benzene conversion on catalyst
The stability of rate can be further enhanced.
Brief description of the drawings
Fig. 1 is used for raw material in dimethyl ether and benzene alkylation reaction for catalyst prepared by the present invention to be changed with the reaction time
Figure, wherein (1) be dimethyl ether with reaction time variation diagram, (2) be benzene with reaction time variation diagram, reaction condition：Benzene/dimethyl ether
(mol ratio)=2/1, P=0.1MPa, T=450 DEG C, WHSV (dimethyl ether)=8h-1；
Embodiment
Chemical reagent used of the invention is purchased in market, and XRF detections INSTRUMENT MODEL used is in the embodiment of the present invention：
The MagiX X-ray type luminoscopes of Philips companies production
Following examples will be further described to the present invention, but not thereby limiting the invention.
Comparative example 1
8g Na type ZSM-11 molecular sieves are exchanged into three times (1 hour/time), washing three in 0.8mol/L ammonium nitrate solution
Catalyst Cat-A is made after being calcined 4 hours at 510 DEG C in secondary (1 hour/time), 110 DEG C of dryings 10 hours.Wherein ammonium nitrate is handed over
It is 85 DEG C to change with washing temperature.Gained catalyst Cat-A detects through XRF, the Na in the catalyst2O is less than 0.05wt%.
Comparative example 2
By 8g Na type ZSM-11 molecular sieves in 280ml concentration is 0.5mol/L sodium hydroxide solution at 75 DEG C it is sharp
Handled 0.2 hour with heating water bath, filter and wash to neutrality, 110 DEG C of drying 3 hours, 550 DEG C of roastings 6 hours.Will be obtained
Molecular sieve exchange three times (1 hour/time) with 0.8mol/L ammonium nitrate solution, wash three times (1 hour/time), 110 DEG C of dryings
10 hours, catalyst Cat-B is made after being calcined 4 hours at 540 DEG C.Wherein ammonium nitrate is exchanged and washing temperature is 80 DEG C.Institute
Obtain catalyst to detect through XRF, the Na in the catalyst2O is less than 0.05wt%.
Embodiment 1
The potassium hydroxide and concentration for being 0.3mol/L in 160ml concentration by 8g Na- type ZSM-11 molecular sieves are 0.01mol/
In L CTAB mixed solutions, handled 0.7 hour using heating water bath at 65 DEG C, filter and wash to neutrality, 100 DEG C of dryings 5
Hour, 450 DEG C are calcined 8 hours.Obtained molecular sieve is exchanged into three times (1 hour/time) with 0.5mol/L ammonium nitrate solution,
Three times (1 hour/time) is washed, 100 DEG C of drying 4 hours obtain catalyst Cat-C after being calcined 3 hours at 510 DEG C.Wherein nitric acid
Ammonium is exchanged and washing temperature is 90 DEG C.Gained catalyst detects through XRF, the Na in the catalyst2O is less than 0.05wt%.
Embodiment 2
The sodium hydroxide and concentration for being 0.4mol/L in 320ml concentration by 8g Na- type ZSM-11 molecular sieves be
In 0.005mol/L PDADMAC mixed solutions, handled 0.3 hour using heating water bath at 80 DEG C, filter and wash into
Property, 120 DEG C of dryings 6 hours, 580 DEG C are calcined 3 hours.Obtained molecular sieve is exchanged three with 0.6mol/L ammonium nitrate solution
Secondary (1 hour/time), washes three times (1 hour/time), 120 DEG C of drying 5 hours, obtained catalyst after being calcined 2 hours at 580 DEG C
Cat-D.Wherein ammonium nitrate is exchanged and washing temperature is 85 DEG C.Gained catalyst detects through XRF, the Na in the catalyst2O is less than
0.05wt%.
Embodiment 3
The potassium hydroxide and concentration for being 0.6mol/L in 240ml concentration by 8g Na- type ZSM-11 molecular sieves are 0.01mol/
In L TBAOH and 0.05mol/L CTAB mixed solutions, handled 0.5 hour using heating water bath at 70 DEG C, filter and wash
Wash to neutrality, 90 DEG C of dryings 4 hours, 550 DEG C are calcined 6 hours.By obtained molecular sieve 0.9mol/L ammonium nitrate solution
Three times (1 hour/time) is exchanged, three times (1 hour/time) is washed, 90 DEG C of drying 12 hours are obtained after being calcined 6 hours at 500 DEG C
Catalyst Cat-E.Wherein ammonium nitrate is exchanged and washing temperature is 70 DEG C.Gained catalyst is detected through XRF, in the catalyst
Na2O is less than 0.05wt%.
Embodiment 4
The sodium hydroxide and concentration for being 1.0mol/L in 200ml concentration by 8g Na- type ZSM-11 molecular sieves are 0.02mol/
In L CTAB mixed solutions, handled 0.1 hour using heating water bath at 85 DEG C, filter and wash to neutrality, 130 DEG C of dryings 2
Hour, 550 DEG C are calcined 7 hours.Obtained molecular sieve is exchanged into three times (1 hour/time) with 0.7mol/L ammonium nitrate solution,
Wash three times (1 hour/time), 130 DEG C of drying 5 hours, 5 hours rear catalyst Cat-F of roasting at 510 DEG C.Wherein ammonium nitrate
Exchange and washing temperature is 80 DEG C.Gained catalyst detects through XRF, the Na in the catalyst2O is less than 0.05wt%.
Comparative example 1~2 and the reaction evaluating of embodiment 1~4：
Reactivity worth is evaluated to be carried out on fixed-bed reactor, and 1.0g catalyst is placed in into stainless steel reactor (internal diameter
12mm, length 32cm) middle part flat-temperature zone.Procatalyst is reacted in N2(200ml/min) atmosphere pre-processes 1h in 500 DEG C of original positions,
Then adjust to given temperature, raw material is dimethyl ether and benzene, and reaction condition is：0.1MPa, 450 DEG C, dimethyl ether weight space velocity 8h-1, dimethyl ether/benzene mole ratio=1/2, nitrogen flow rate=200mL/min.Product from charging to 1 hour is given up, afterwards with certain
Time interval sampling analysis, be sampled as every time 2 hours accumulation sample.The product of generation is gas through gas-liquid separator separates
With liquid, gas and product liquid are constituted with Agilent7890A chromatographic system analysis, and product liquid uses PONA capillaries
Post (50m × 0.2mm × 0.5um), hydrogen flame ionization detector.Analysis result is normalized, and obtains dry gas, liquefied gas and liquid production
Thing is constituted.The percentage that the present invention is used is weight percentage.
Alkali adds dimethyl ether and benzene conversion ratio on the modified ZSM-11 molecular sieve catalysts of surfactant processing with the time
Change is as shown in Figure 1.As can be seen from Figure, raw material (dimethyl ether and benzene) initial conversion is all very on all catalyst
Similar, with the extension in reaction time, the difference of feed stock conversion becomes larger.With conventional alkali process or undressed ZSM-
11 molecular sieve catalysts (Cat-A, Cat-B) are compared, ZSM-11 molecular sieve catalysts through surfactant alkali process (Cat-C,
Cat-D, Cat-E, Cat-F) on dimethyl ether and benzene conversion ratio stability can be further enhanced.
Claims (4)
1. it is a kind of for dimethyl ether and the method for modifying of benzene alkylation reaction ZSM-11 molecular sieve catalysts, it is characterised in that according to
Following steps are carried out：By Na- type ZSM-11 molecular sieves, with certain liquid-solid ratio and alkali and organic surface active agent mixed solution 65
~85 oHeating stirring 0.1 ~ 1 hour under C, washing is to neutral and then drying and roasting, then with 0.5 ~ 1.0 mol/L ammonium nitrate
Solution is in 70 ~ 90oC is exchanged, and H- type molecular sieves are made in dry roasting,
The liquid-solid ratio is that mixed solution ml/ molecular screen primary powders g is 20 ~ 40ml mixed solutions/g molecular sieves；
The alkali is 80 ~ 2 with surfactant molar concentration rate:1；
The aqueous slkali is one or both of sodium hydroxide and potassium hydroxide solution；Organic surface active agent is cetyl
One or more in trimethylammonium bromide, polyquaternium -6 or TBAH.
2. a kind of modification for dimethyl ether and benzene alkylation reaction ZSM-11 molecular sieve catalysts according to claim 1
Method, it is characterised in that described alkaline concentration is 0.1 ~ 1.0 mol/L.
3. a kind of modification for dimethyl ether and benzene alkylation reaction ZSM-11 molecular sieve catalysts according to claim 1
Method, it is characterised in that the drying temperature is 90 ~ 130oC, drying time is 1 ~ 12 hour.
4. a kind of modification for dimethyl ether and benzene alkylation reaction ZSM-11 molecular sieve catalysts according to claim 1
Method, it is characterised in that the sintering temperature is 450 ~ 600oC, roasting time is 2 ~ 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410200846.XA CN105080593B (en) | 2014-05-12 | 2014-05-12 | For dimethyl ether and the method for modifying of the molecular sieve catalysts of benzene alkylation reaction ZSM 11 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410200846.XA CN105080593B (en) | 2014-05-12 | 2014-05-12 | For dimethyl ether and the method for modifying of the molecular sieve catalysts of benzene alkylation reaction ZSM 11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105080593A CN105080593A (en) | 2015-11-25 |
| CN105080593B true CN105080593B (en) | 2017-08-29 |
Family
ID=54562458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410200846.XA Active CN105080593B (en) | 2014-05-12 | 2014-05-12 | For dimethyl ether and the method for modifying of the molecular sieve catalysts of benzene alkylation reaction ZSM 11 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105080593B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963638B (en) * | 2016-10-20 | 2019-09-24 | 中国科学院大连化学物理研究所 | Preparation method for dimethyl ether and benzene alkylation reaction ZSM-11 molecular sieve catalyst |
| CN110756218A (en) * | 2019-09-12 | 2020-02-07 | 大连龙缘化学有限公司 | Synthetic method and application of catalyst for producing durene |
| CN113372308B (en) * | 2021-05-10 | 2022-06-10 | 浙江糖能科技有限公司 | Preparation method of bis- (5-formylfurfuryl) ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671690A (en) * | 2011-12-14 | 2012-09-19 | 河南科技大学 | Catalyst for preparing dimethyl ether by methanol and preparation method thereof |
| CN102807230A (en) * | 2012-07-27 | 2012-12-05 | 中国科学院大连化学物理研究所 | Method for preparing hierarchical porous MCM-22 molecular sieves |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6843977B2 (en) * | 2000-05-25 | 2005-01-18 | Board Of Trustees Of Michigan State University | Ultrastable porous aluminosilicate structures and compositions derived therefrom |
-
2014
- 2014-05-12 CN CN201410200846.XA patent/CN105080593B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671690A (en) * | 2011-12-14 | 2012-09-19 | 河南科技大学 | Catalyst for preparing dimethyl ether by methanol and preparation method thereof |
| CN102807230A (en) * | 2012-07-27 | 2012-12-05 | 中国科学院大连化学物理研究所 | Method for preparing hierarchical porous MCM-22 molecular sieves |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105080593A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104370676B (en) | A kind of take C 4 olefin as the method for raw material production propylene by-product ethene | |
| Wu et al. | Ethylene formation from ethanol dehydration using ZSM-5 catalyst | |
| CN105622306B (en) | The method that aromatic hydrocarbons is produced using oxygenatedchemicals as raw material | |
| CN104230615B (en) | The method of biomass derivatives γ-valerolactone catalytic cracking aromatic hydrocarbons and cyclopentenone | |
| CN103664482B (en) | A kind of reaction process using moving bed technique oxygenatedchemicals to be converted into aromatic hydrocarbons | |
| CN101157593B (en) | Method for producing light olefins by methanol or/and dimethyl ether | |
| CN104624224B (en) | A kind of method of modifying of the molecular sieve catalysts of Zn/ZSM 11 | |
| CN102040448B (en) | Method for preparing propylene by catalyzing methanol/dimethyl ether with composite molecular sieve with core-shell structure | |
| CN106140266B (en) | A kind of metal-modified ZSM-5 molecular sieve catalyst and its preparation method and application | |
| Feng et al. | Highly effective F-modified HZSM-5 catalysts for the cracking of naphtha to produce light olefins | |
| CN101780417A (en) | Catalyst for preparing paraxylene and low-carbon olefin by methyl alcohol conversion, preparation method and application thereof | |
| CN106215970B (en) | The modification processing method of HZSM-5 molecular sieve catalyst and application | |
| Qu et al. | Advances in zeolite-supported metal catalysts for propane dehydrogenation | |
| CN105080593B (en) | For dimethyl ether and the method for modifying of the molecular sieve catalysts of benzene alkylation reaction ZSM 11 | |
| CN105016954B (en) | A kind of methanol or/and dimethyl ether for propylene and aromatic hydrocarbons method | |
| Singh et al. | Renewable aromatics from tree-borne oils over zeolite catalysts promoted by transition metals | |
| Luk et al. | Impact of carrier acidity on the conversion of syngas to higher alcohols over zeolite-supported copper-iron catalysts | |
| Jiao et al. | Methanol-to-olefins over FeHZSM-5: Further transformation of products | |
| CN102553632B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof and application | |
| CN103055930A (en) | Low carbon alkane dehydrogenation catalyst and preparation method | |
| CN101279280B (en) | Catalyst for preparing propylene transformed from methanol | |
| Liu et al. | Ethanol conversion to selective high-value hydrocarbons over Ni/HZSM-5 zeolite catalyst | |
| Nawaz et al. | Pt− Sn-Based SAPO-34 Supported Novel Catalyst for n-Butane Dehydrogenation | |
| CN107398294B (en) | Preparation method and application of modified binder-free ZSM-11 molecular sieve catalyst | |
| Ma et al. | Recent developments in the field of dehydration of bio-renewable glycerol to acrolein over molecular sieve catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |