CN104710265B - A kind of method preparing xylol and propylene - Google Patents
A kind of method preparing xylol and propylene Download PDFInfo
- Publication number
- CN104710265B CN104710265B CN201310684321.3A CN201310684321A CN104710265B CN 104710265 B CN104710265 B CN 104710265B CN 201310684321 A CN201310684321 A CN 201310684321A CN 104710265 B CN104710265 B CN 104710265B
- Authority
- CN
- China
- Prior art keywords
- xylol
- product
- propylene
- component
- reaction zone
- 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
-
- 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
-
- 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 present invention provides a kind of method preparing xylol and propylene, the method by toluene with methanol or/and dimethyl ether alkylated reaction, two courses of reaction of ethylene aromatization couple.And prepared by toluene and methanol or/and dimethyl ether alkylation in xylol byproduct of reaction rich in ethylene less than C2Component freshening carries out shape-selective aromatization, thus high selectivity production of para-xylene and propylene.
Description
Technical field
The invention belongs to chemical field, a kind of high selectivity production of para-xylene and the method for propylene are provided especially.
Background technology
Xylol (PX) and propylene are all important basic chemical raw materials.At present, xylol is mainly combined through aromatic hydrocarbons
Device obtains.Due to xylol at the content of three isomers by thermodynamic control, xylol is in xylene isomer
Only accounting for about 23%, the boiling point difference of particularly three isomers of dimethylbenzene is the least, uses common distillation technique can not obtain height
Purity para-xylene, and the adsorptive separation technology of costliness must be used.So in whole PX production process at Matter Transfer
Reason amount is big, and equipment is huge, and operating cost is high.Propylene is mainly derived from petroleum refinery and naphtha steam cracking produces ethylene
Side-product, or produce with the propane that natural gas processing is prepared for raw material.Xylol is mainly for the production of polyester, propylene
Mainly for the preparation of the 1,3-propylene glycol needed for polypropylene, acrylonitrile and production polyester.Along with the fast development of global economy,
Xylol and the demand also cumulative year after year of propylene as chemical industry base stock.
In recent years, the most many patents disclose xylol and produce new way, and wherein toluene methylation can produce
High selective xylol.USP3,965,207 disclose use ZSM-5 molecular sieve does the reaction of catalyst toluene methylation,
Under 600 DEG C of reaction temperatures, the highest selectivity of xylol is about 90%；USP3,965,208 uses the element modified ZSM-5 of VA to divide
Son sieve makees catalyst, it is suppressed that the generation of meta-xylene, mainly generates xylol and o-Dimethylbenzene, 600 DEG C of reaction temperatures
The highest selectivity of lower xylol is about 90%；The ZSM-5 molecular sieve of USP4,250,345 use phosphorus and the modification of magnesium dual element is
Catalyst, under 450 DEG C of reaction temperatures, the best selective of xylol has reached 98%；USP4,670,616 uses borosilicic acid
Molecules of salt sieve and silicon oxide or aluminium oxide are prepared as catalyst, and Selectivity for paraxylene is 50-60%；USP4,276,438、4,
278,827 molecular sieve (the SiO using special construction2/Al2O312) and with the modification such as copper, silver, gold or germanium, stannum, lead, can obtain
High selective p dialkyl benzene；USP4,444,989 use the pure silicon molecular sieve of crystal type, and make arsenic, phosphorus, magnesium, boron and tellurium
Compound is modified, and improves the selectivity of xylol；USP4,491,678 use crystal type borosilicate and IIA and
IIIA element and silicon and phosphorus are that common constituent can be greatly improved the selectivity of xylol and can improve the life-span of catalyst.
USP5,034,362 uses SiO2/Al2O3ZSM-5 and ZSM-11 of 12 is catalyst, and carries out under the conditions of higher than 650 DEG C
Roasting, can improve the selectivity of p dialkyl benzene.USP5,563,310 uses the acidic molecular sieve containing IVB element and uses VIB
Metal be modified catalyst, the selectivity of p dialkyl benzene of alkylation of toluene methanol reaction can be improved；USP6,504,
072 uses the preferred ZSM-5 of mesoporous molecular sieve, and processes under the steam higher than 950 DEG C, then changes with phosphorous oxides
Property, it is proposed that the impact on Selectivity for paraxylene of the spreading effect of catalyst micropore；USP6,613,708 uses organic metal
Catalyst is modified by compound, can be greatly improved the selectivity of p dialkyl benzene.
Chinese patent ZL200610011662.4, ZL200710176269.5, ZL200710176274.6,
ZL200710179408.X, ZL200710179409.4 and ZL200710179410.7 disclose a class methylbenzene methanol system to diformazan
The method of benzene co-producing light olefins, it is indicated that while methylbenzene methanol converts and prepares high selectivity xylol on a catalyst
Can with coproduction high-selective ethylene and propylene, in product xylol xylene isomer selectivity can reach 99wt% with
On, ethylene and propylene are at C1-C5In lower carbon number hydrocarbons, selectivity can reach more than 90wt%.But the drawback of the method is intended to obtain height
The ethylene product of purity have to pass through cold separation technology, and investment and energy consumption are the biggest, directly affects the economy of this process
Property.
Summary of the invention
It is an object of the invention to provide a kind of toluene with methanol or/and dimethyl ether reacts the side of xylol processed and propylene
Method, the method by toluene with methanol or/and dimethyl ether alkylated reaction, two courses of reaction of ethylene aromatization couple, and
Prepared by toluene and methanol or/and dimethyl ether alkylation in xylol byproduct of reaction rich in ethylene less than C2(C2 -) component
Freshening carries out shape-selective aromatization, thus high selectivity production of para-xylene and propylene.
For achieving the above object, a kind of method that the present invention provides is, by toluene with methanol or/and dimethyl ether alkylation is anti-
Answer, two courses of reaction of ethylene aromatization couple, high selectivity production of para-xylene and propylene.First raw material toluene and first
Alcohol is or/and dimethyl ether contacts with catalyst at response system, and the product that reaction generates enters piece-rate system and separates；Separated system
After separation, obtain C6Above component (C6 +), C4-C5Component, C3Component and rich in ethylene less than or equal to C2Component (C2 -), wherein,
C rich in ethylene2 -Component Returning reacting system, C6 +Component is through further isolated xylol, C3Component separates further
Obtaining propylene, reaction process is as shown in Figure 1.Wherein, described response system is the combination of two or more reaction zone.Each reaction zone
Can be a reactor, it is also possible to be the serial or parallel connection of multiple reactor.Described reactor is fixed bed, fluid bed or shifting
In movable bed any one or the most several.
In a preferred embodiment, response system is made up of two reaction zones, and the first reaction zone primary response is toluene
With methanol or/and dimethyl ether alkylated reaction, second reaction zone primary response is that ethylene (the first reaction zone by-product) aromatisation is anti-
Should.Raw material toluene is with methanol or/and dimethyl ether is contacted with catalyst I by the first reaction zone, and the product A of generation enters segregative line
System separates；After separated system separates, obtain C6 +Component, C4-C5Component, C3Component and rich in ethylene less than or equal to C2Component,
Wherein, rich in the C of ethylene2 -Component returns second reaction zone and catalyst II haptoreaction, generates product B, product B and product A
Enter piece-rate system after mixing to separate；After separated system separates, rich in the C of ethylene2 -Component continues to return second reaction zone ginseng
Add reaction, C6 +Component is through further isolated xylol, C3Component further isolated propylene.Reaction process such as Fig. 2
Shown in.
In a preferred embodiment, response system is made up of two reaction zones, and the first reaction zone primary response is toluene
With methanol or/and dimethyl ether alkylated reaction, second reaction zone primary response is that ethylene (the first reaction zone by-product) aromatisation is anti-
Should.First toluene is with methanol or/and dimethyl ether contacts with catalyst I in the first reaction zone, generates product A, product A and enters separation
System separates；By from piece-rate system rich in the C of ethylene2 -Component is passed through second reaction zone and reacts generation product on catalyst II
B, product B enter back into the first reaction zone and enter the first reaction zone toluene together with methanol or/and dimethyl ether form selected methylation
Generate product C, product C and enter piece-rate system separation；After separated system separates, obtain C6 +Component, C4-C5Component, C3Component and
Rich in ethylene less than or equal to C2Component, wherein, rich in the C of ethylene2 -Component returns second reaction zone, C6 +Component is through dividing further
From obtaining xylol, C3Component further isolated propylene.Reaction process is as shown in Figure 3.
Containing ZSM-5 zeolite molecular sieve in described catalyst I and catalyst II.Wherein, described catalyst I is ZSM-5 boiling
Stone molecular sieve hydrothermal treatment, silicone-based compound modification of surfaces are acid and pore structure obtains.Described catalyst II is ZSM-5
Zeolite molecular sieve is modified again through silicone-based compound modification of surfaces is acid and pore structure obtains through zinc compound.
The concrete preparation process of catalyst I is as follows:
(1) by ZSM-5 zeolite molecular screen primary powder through NH4 +Ion exchange, roasting are prepared as acid HZSM-5 zeolite molecules
Sieve.
(2) HZSM-5 zeolite molecular sieve is carried out hydrothermal treatment consists, obtain modified zeolite molecular sieve.The side of being preferable to carry out
In formula, hydrothermal conditions be under saturated vapor atmosphere 500-700 DEG C process 3-6 hour
(3) use Siloxane based agents that modified zeolite molecular sieve carries out surface modification, further modulation molecular sieve appearance
Face acidity and pore structure, obtain catalyst I.
The concrete preparation process of catalyst II is as follows:
(1) by ZSM-5 zeolite molecular screen primary powder through NH4 +Ion exchange, roasting are prepared as acid HZSM-5 zeolite molecules
Sieve.
(2) use zinc compound that HZSM-5 zeolite molecular sieve is modified, obtain zinc modification zeolite molecular sieve.
(3) Siloxane based agents is used zinc modification zeolite molecular sieve to carry out surface modification, outside further modulation molecular sieve
Surface acidity and pore structure, obtain catalyst II.
In a preferred embodiment, catalyst I is after silicone-based compound is modified, and the loading of Si is catalyst
The 1-10wt% of gross weight；Catalyst II is modified through zinc compound, and the loading of Zn is the 0.1-10wt% of total catalyst weight；
After silicone-based compound is modified, the loading of Si is the 1-10wt% of total catalyst weight；
In a preferred embodiment, the silicone-based compound used is shown below:
R in formula1、R2、R3And R4It it is the alkyl of 1-10 carbon atom.
In a preferred embodiment, the silicone-based compound used is tetraethyl orthosilicate.
In a preferred embodiment, described first reaction zone and second reaction zone all can use fixed bed reaction work
Skill, can be combined employing fluid bed or moving bed reaction technique simultaneously with regenerator.Described first reaction zone and second reaction zone
A reactor or the serial or parallel connection of multiple reactor can be respectively.
Toluene and methanol or/and dimethyl ether alkylation, ethylene aromatisation reaction temperature in the range of 300-600 DEG C
To realize, general toluene and methanol are or/and the preferred reaction temperature of dimethyl ether alkylation is 450-550 DEG C, and ethylene aromatisation is excellent
Reaction temperature is selected to be 400-500 DEG C.Toluene and methanol are or/and the air speed of dimethyl ether alkylated reaction is generally 0.1-10h-1, excellent
Elect 1-5h as-1。
According to general knowledge known in this field, toluene with methanol or/and in dimethyl ether alkylated reaction, toluene with methanol or/and
Dimethyl ether feed molecules arbitrarily selects than in the range of 0.1-10, it is generally preferable to for 0.2-5；In ethylene aromatization, ethylene
The air speed of reaction is generally 0.1-10h-1, preferably 1-5h-1。
It addition, those skilled in the art are according to needs of production, have the ability and motivation is by technical side of the present invention
Case is combined with common knowledge, by modulation reaction temperature and toluene and methanol or/and dimethyl ether charge ratio, ethylene recycle ratio etc. are anti-
Answer condition, it is achieved control xylol and the ratio of propylene in product within the specific limits.
In the present invention, described C2 -Component refers to the carbon number component less than or equal to 2 in molecular formula, including ethylene, ethane, first
Alkane, CO, CO2And H2Deng.
In the present invention, described C3Component refers to the compound equal to 3 of carbon number in molecular formula, including propylene, propane, third
Ketone, propanol, propionic aldehyde and isopropanol etc..
In the present invention, described C4-C5Component refers to the carbon number component equal to 4,5 in molecular formula, including iso-butane, isobutyl
Alkene, butane, 1-butylene, 2-butylene, isopentane, neopentane, pentane, 1-amylene, 2-penta be dilute and ketone, ether, the derivant etc. of aldehyde.
In the present invention, described C6 +Component refers to the component more than or equal to 6 of carbon number in molecular formula, including xylol and
Other fragrant hydrocarbons and their derivates, fat hydrocarbons and their derivates etc..
The invention have the benefit that by by C rich in ethylene in product2 -Component freshening generation aromatization enters one
Step generates aromatic hydrocarbons particularly para-xylene product, and final high selectivity xylol and the propylene of obtaining, one side avoids ethylene
The high expense that product separates, on the other hand can increase production the para-xylene product with the bigger market demand further, thus
The economy of this technology can be effectively improved.
Accompanying drawing explanation
Fig. 1 reacting flow chart of the present invention；
The first preferred reacting flow chart of Fig. 2 present invention；
The preferred reacting flow chart of Fig. 3 the second of the present invention.
Detailed description of the invention
Below by embodiment in detail the present invention is described in detail, but the invention is not limited in these embodiments.
Gas chromatograph on-line analysis product forms, and analysis condition is:
Chromatograph model: Varian CP3800
Chromatographic column: 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
Prepared by embodiment 1(catalyst I)
By 500g ZSM-5 zeolite molecular screen primary powder (SiO2/Al2O3=68) (Fushun Petrochemical Company catalyst plant) is at 550 DEG C
Template agent removing is removed in lower roasting, swaps 4 times with 0.5 molar equivalent ammonium nitrate solution, solid-like after exchange in 80 DEG C of water-baths
Product are dried in 120 DEG C of air, roasting 4 hours in 550 DEG C of air, obtain HZSM-5 zeolite molecular sieve.
By hydrothermal treatment consists, HZSM-5 zeolite molecular sieve is modified: take HZSM-5 molecular sieve 200g and be placed in quartz reaction
In device, being passed through water after being warming up to 650 DEG C, discharge is 5ml/min, and constant temperature processes 4 hours, obtains hydrothermal modification HZSM-5 zeolite
Molecular sieve.Use silicone agent tetraethyl orthosilicate that hydrothermal modification HZSM-5 zeolite molecular sieve is carried out surface modification.Step is:
The HZSM-5 zeolite molecular sieve of hydrothermal modification is put into steeped overnight in 300 grams of tetraethyl orthosilicates, pours out solid sample after liquid
120 DEG C of air are dried, roasting 4 hours in 550 DEG C of air, Si-HZSM-5 catalyst after being modified, named TMPC-
01。
Prepared by embodiment 2(catalyst II)
(1) by 500g ZSM-5 zeolite molecular screen primary powder (SiO2/Al2O3=38) (Catalyst Factory, Nankai Univ) is at 550 DEG C
Template agent removing is removed in lower roasting, swaps 4 times with 0.5 molar equivalent ammonium nitrate solution, solid-like after exchange in 80 DEG C of water-baths
Product are dried in 120 DEG C of air, roasting 4 hours at 550 DEG C, obtain HZSM-5 zeolite molecular sieve.
(2) HZSM-5 zeolite molecular sieve 200g prepared by step (1) is taken, with the zinc nitrate [Zn of 8% mass concentration
(NO3)2·6H2O] solution normal temperature dipping 4 hours, after pouring out supernatant liquid, solid sample is dried in 120 DEG C of air, 550 DEG C of skies
Roasting 6 hours in gas, obtain zinc modification Zn-HZSM-5 zeolite molecular sieve.Elementary analysis Zn content is 2.45wt%.
(3) the Zn-HZSM-5 zeolite molecular sieve 24 using tetraethyl orthosilicate (TEOS) normal temperature dipping step (2) to obtain is little
Time, after pouring out supernatant liquid solid sample dry in 120 DEG C of air, roasting 6 hours in 550 DEG C of air, obtain zinc and silane
Change modified HZSM-5 catalyst, named TMPC-02.
Comparative example 1(is without C2 -The reaction of component freshening)
By the TMPC-01 catalyst tablet forming of preparation in embodiment 1 catalyst sample that crushing and screening is 40-60 mesh
Product, take in 10 grams of catalyst loading reactors and carry out methylbenzene methanol conversion reaction, and toluene and methanol molecular proportion is respectively 2/1 and 1/
1, after one of them ratio conditioned response completes, it is passed through nitrogen purging online, then switches to air and make catalyst at 550 DEG C
Under the conditions of regenerate 5 hours, nitrogen purges and is cooled to reaction temperature and carries out the methylbenzene methanol conversion reaction of another ratio.Other are anti-
The condition is answered to be: toluene mass space velocity is 2h-1, reaction temperature is 480 DEG C.Use gas chromatograph on-line analysis product composition, go
Except the products distribution after generation water is as shown in table 1.
When fed toluene/methanol molecules is than respectively 2/1 and 1/1, in hydrocarbon product, xylol is at xylene isomerization
Selectivity in body is respectively 99.20wt%, 99.18wt%；Product C2 -The selectivity of component is respectively 6.28wt%, 9.10wt%.
The products distribution after generating water removed by table 1
* wt%, product quality is distributed.
Response system shown in embodiment 3(Fig. 2)
By the TMPC-02 catalyst difference compression molding of the TMPC-01 of preparation in embodiment 1 and preparation in embodiment 2 also
Crushing and screening is the catalyst sample of 40-60 mesh, respectively takes 10 grams of catalyst and loads the two reaction zones of fixed bed reactors.First
Reaction zone carries out methylbenzene methanol conversion reaction, and second reaction zone carries out ethylene aromatization, according to the first reaction in comparative example 1
C in district's alkylation of toluene methanol distribution of reaction products2 -Component composition preparation enters second reaction zone rich in ethylene raw and carries out virtue
Structureization is reacted.
Reaction condition: the first reaction zone toluene mass space velocity is 2h-1, reaction temperature is 480 DEG C；Second reaction zone reaction temperature
Degree is 450 DEG C.Use gas chromatograph on-line analysis reaction zone mix products composition, remove the hydrocarbon product distribution after generating water
As shown in table 2, then remove C2 -After freshening component, hydrocarbon products distribution is as shown in table 3.
When fed toluene/methanol molecules is than respectively 2/1,1/1, remove C2 -Propylene Selectivity in hydrocarbon product after component
Being respectively 3.90wt%, 6.60wt%, Selectivity for paraxylene is respectively 87.49wt%, 81.76wt%；Propylene and xylol are total
Selectivity is respectively 91.40wt%, 88.37wt%.Xylol selectivity in xylene isomer be respectively 98.57wt%,
98.21wt%。
The hydrocarbon product distribution after generating water removed by table 2
C removed by table 32 -Hydrocarbon products distribution after freshening component
Response system shown in embodiment 4(Fig. 3)
By the TMPC-02 catalyst difference compression molding of the TMPC-01 of preparation in embodiment 1 and preparation in embodiment 2 also
Crushing and screening is the catalyst sample of 40-60 mesh, respectively takes 10 grams of catalyst and loads the two reaction zones of fixed bed reactors.First
Reaction zone carries out toluene and dimethyl ether conversion reaction, and second reaction zone carries out ethylene aromatization, according in comparative example 1 first
C in the alkylation of toluene methanol distribution of reaction products of reaction zone2 -Component composition preparation enters second reaction zone rich in ethylene raw and enters
Row aromatization, product enters back into the first reaction zone and is alkylated reaction as aroamtic hydrocarbon raw material and dimethyl ether.
Reaction condition: the first reaction zone toluene mass space velocity is 2h-1, reaction temperature is 500 DEG C；Second reaction zone reaction temperature
Degree is 480 DEG C.Use gas chromatograph on-line analysis reaction zone product composition, remove the hydrocarbon product after generating water and be distributed such as table
Shown in 4, then remove C2 -After freshening component, hydrocarbon products distribution is as shown in table 5.
When fed toluene/dimethyl ether molecular proportion is respectively 4/1,2/1, remove C2 -Propylene in hydrocarbon product after freshening component
Selectivity is respectively 3.77wt%, 6.44wt%, and Selectivity for paraxylene is respectively 87.80wt%, 81.97wt%；Propylene and to two
Toluene overall selectivity is respectively 91.57wt%, 88.41wt%.Xylol selectivity in xylene isomer is respectively
98.71wt%、98.30wt%。
The hydrocarbon product distribution after generating water removed by table 4
C removed by table 52 -Hydrocarbon products distribution after freshening component
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this.All according to the present invention
The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.
Claims (7)
1. the method preparing xylol and propylene, it is characterised in that first raw material toluene and methanol are or/and dimethyl ether exists
Response system and catalyst haptoreaction, the product of generation enters piece-rate system and separates；After separated system separates, rich in ethylene
C2 -Component Returning reacting system, C6 +Component is through further isolated xylol, C3Component further isolated propylene；
Described response system is made up of two reaction zones；First toluene and methanol are or/and dimethyl ether is in the first reaction zone and catalysis
Agent I contact form selected methylation generates product A, product A and enters piece-rate system separation；By from piece-rate system rich in the C of ethylene2 -Group
Divide to be passed through after second reaction zone contacts generation product B, product B and the product A mixing of shape-selective aromatisation with catalyst II to enter and separate
System separates；After separated system separates, rich in the C of ethylene2 -Component returns second reaction zone, C6 +Component is through separating further
Obtain xylol, C3Component further isolated propylene；
Wherein, described catalyst I be ZSM-5 zeolite molecular sieve hydrothermal treatment, silicone-based compound modification of surfaces acid and
Pore structure obtains；Described catalyst II is ZSM-5 zeolite molecular sieve to be repaiied through silicone-based compound through zinc compound is modified again
Decorations surface acidity and pore structure obtain.
2. the method preparing xylol and propylene, it is characterised in that first raw material toluene and methanol are or/and dimethyl ether exists
Response system and catalyst haptoreaction, the product of generation enters piece-rate system and separates；After separated system separates, rich in ethylene
C2 -Component Returning reacting system, C6 +Component is through further isolated xylol, C3Component further isolated propylene；
Described response system is made up of two reaction zones；First toluene and methanol are or/and dimethyl ether is in the first reaction zone and catalysis
Agent I contact form selected methylation generates product A, product A and enters piece-rate system separation；By from piece-rate system rich in the C of ethylene2 -Group
Point it is passed through second reaction zone to contact shape-selective aromatisation generation product B, product B with catalyst II and enter back into the first reaction zone and entrance
The toluene of the first reaction zone together with methanol or/and dimethyl ether form selected methylation generate product C, product C enter piece-rate system divide
From；After separated system separates, rich in the C of ethylene2 -Component returns second reaction zone, C6 +Component is through further isolated pair
Dimethylbenzene, C3Component further isolated propylene；
Wherein, described catalyst I be ZSM-5 zeolite molecular sieve hydrothermal treatment, silicone-based compound modification of surfaces acid and
Pore structure obtains；Described catalyst II is ZSM-5 zeolite molecular sieve to be repaiied through silicone-based compound through zinc compound is modified again
Decorations surface acidity and pore structure obtain.
3. the method preparing xylol and propylene described in claim 1 or 2, wherein, the condition of described hydrothermal treatment consists is:
Under saturated vapor atmosphere, 500-700 DEG C processes 3-6 hour.
4. the method preparing xylol and propylene described in claim 1 or 2, wherein, described silicone-based compound is tied
Structure formula is shown below:
In formula, R1、R2、R3And R4Alkyl for 1-10 carbon atom.
5. according to the method preparing xylol and propylene described in claim 4, wherein, described silicone-based compound is positive silicon
Acetoacetic ester.
6. the method preparing xylol and propylene described in claim 1 or 2, wherein, the first reaction zone or the second reaction
District is respectively a reactor or the serial or parallel connection of multiple reactor；Connect between first reaction zone and second reaction zone or also
Connection.
7. the method preparing xylol and propylene described in claim 1 or 2, wherein, described response system by fixed bed,
Any one reactor or any several reactors in series in fluid bed or moving bed or compose in parallel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310684321.3A CN104710265B (en) | 2013-12-13 | 2013-12-13 | A kind of method preparing xylol and propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310684321.3A CN104710265B (en) | 2013-12-13 | 2013-12-13 | A kind of method preparing xylol and propylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104710265A CN104710265A (en) | 2015-06-17 |
| CN104710265B true CN104710265B (en) | 2016-12-07 |
Family
ID=53410062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310684321.3A Active CN104710265B (en) | 2013-12-13 | 2013-12-13 | A kind of method preparing xylol and propylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104710265B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214714B (en) * | 2015-10-30 | 2018-04-10 | 陕西煤化工技术工程中心有限公司 | A kind of benzene and methanol alkylation produce paraxylene catalyst and preparation method thereof |
| US10961168B2 (en) * | 2016-09-22 | 2021-03-30 | Exxonmobil Chemical Patents Inc. | Use of light gas by-products in the production of paraxylene by the methylation of toluene and or benzene |
| CN106631676B (en) * | 2016-12-09 | 2019-10-22 | 中国科学院大连化学物理研究所 | Alkylation of toluene prepares the moving bed process of paraxylene co-producing light olefins |
| CN108794288B (en) * | 2017-04-27 | 2020-08-07 | 中国科学院大连化学物理研究所 | Method for preparing low-carbon olefin and co-producing p-xylene |
| CN109847792B (en) * | 2017-11-30 | 2020-08-11 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst modification device and method |
| CN110586174A (en) * | 2019-08-23 | 2019-12-20 | 西北大学 | Catalyst capable of improving selectivity of p-xylene in xylene and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4491678A (en) * | 1982-10-19 | 1985-01-01 | Idemitsu Kosan Company Limited | Process for the production of para-xylene |
| CN101607858A (en) * | 2009-07-24 | 2009-12-23 | 中国海洋石油总公司 | The method of a kind of methyl alcohol/dimethyl ether production aromatic hydrocarbons and propylene simultaneously |
| CN102464549A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for producing propylene and p-xylene |
-
2013
- 2013-12-13 CN CN201310684321.3A patent/CN104710265B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4491678A (en) * | 1982-10-19 | 1985-01-01 | Idemitsu Kosan Company Limited | Process for the production of para-xylene |
| CN101607858A (en) * | 2009-07-24 | 2009-12-23 | 中国海洋石油总公司 | The method of a kind of methyl alcohol/dimethyl ether production aromatic hydrocarbons and propylene simultaneously |
| CN102464549A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for producing propylene and p-xylene |
Non-Patent Citations (1)
| Title |
|---|
| ZSM-5分子筛择形功能的化学修饰及其对二甲苯催化合成的研究;朱志荣;《中国优秀博硕士学位论文全文数据库（博士） 工程科技Ⅰ辑》;20070415(第4期);第B014-76页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104710265A (en) | 2015-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104710265B (en) | A kind of method preparing xylol and propylene | |
| US10894752B2 (en) | Catalyst and method for aromatization of C3-C4 gases, light hydrocarbon fractions and aliphatic alcohols, as well as mixtures thereof | |
| CN101417236B (en) | Fluid bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin | |
| CN101417235B (en) | Movable bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin | |
| CN101456784B (en) | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent | |
| CN101945702A (en) | Process for the conversion of ethane to aromatic hydrocarbons | |
| CN101456786B (en) | Method for preparing p-xylene and co-producing light olefins by toluene and methylating reagent | |
| CN101945840A (en) | Process for the conversion of ethane to aromatic hydrocarbons | |
| CN101417233A (en) | Fixed bed catalyst for alkylation of toluene and methanol to produce paraxylene and low-carbon olefin and use thereof | |
| JP6408611B2 (en) | Process for producing p-xylene and propylene from methanol and / or dimethyl ether | |
| CN106215970A (en) | The modification processing method of HZSM 5 molecular sieve catalyst and application | |
| CN104710267B (en) | A kind of methanol or/and the method for dimethyl ether paraxylene and propylene | |
| CN104710266B (en) | A kind of methanol is or/and the method for dimethyl ether xylol co-producing light olefins | |
| CN101456785B (en) | Method for producing p-xylene and co-producing light olefins with high selectivity | |
| JP6408612B2 (en) | A method for producing p-xylene with high selectivity and co-producing propylene | |
| CN106588528A (en) | Moving bed method for preparing paraxylene co-production low-carbon olefin through methyl alcohol and/or dimethyl ether | |
| CN106140272A (en) | A kind of aromatizing catalyst for light hydrocarbon and preparation method thereof | |
| CN105294374B (en) | A kind of methanol and/or dimethyl ether for paraxylene and propylene method | |
| CN105272798B (en) | A kind of method of high selectivity production of para-xylene propylene simultaneously | |
| KR101827449B1 (en) | Surface modified zeolite catalyst for manufacturing propylene from ethylene and preparation method thereof | |
| CN104710268B (en) | Method for preparing p-xylene and co-producing low-carbon olefin through benzene and methanol or/and dimethyl ether | |
| CN109776246A (en) | Methanol and/or dimethyl ether for paraxylene co-producing light olefins moving bed process method | |
| CN109824468A (en) | Alkylation of toluene prepares the moving bed process method of paraxylene co-producing light olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |