CN1007426B - Method of production of aromatic hydrocarbons - Google Patents
Method of production of aromatic hydrocarbonsInfo
- Publication number
- CN1007426B CN1007426B CN 85104308 CN85104308A CN1007426B CN 1007426 B CN1007426 B CN 1007426B CN 85104308 CN85104308 CN 85104308 CN 85104308 A CN85104308 A CN 85104308A CN 1007426 B CN1007426 B CN 1007426B
- Authority
- CN
- China
- Prior art keywords
- weight
- gallium
- aluminate
- silico
- hydrocarbon
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing aromatic hydrocarbons by mixing hydrocarbon raw materials containing C3/C4 with C2 hydrocarbons, particularly to with ethane. The mixed hydrocarbon raw materials contact a catalyst containing aluminosilicate at a temperature lower than 580 DEG C. In the catalyst, the molar ratio of silicon oxide to aluminum oxide is ate least 5:1. The product is very high in the content of the aromatic hydrocarbons, and can be used for gasoline admixtures.
Description
The invention relates to the method for producing aromatic hydrocarbons, its raw material is to be mixed with C
2Hydrocarbon particularly is mixed with the C of ethane
3(or) C
4The hydro carbons of hydrocarbon.
Up to now, by the route of synthesis of open chain hydrocarbon production aromatic hydrocarbons, be with the hydrocarbon feed that contains three carbon atoms at least, perhaps with containing C
2Hydrocarbon carries out as the raw material of main ingredient.The raw material that contains 3 or more carbon atoms at first carries out two polymerizations, and the product of dimerization at high temperature carries out cyclisation with various catalyzer more then.This class technological process has been appeared in the newspapers and has been led, for example our English Patent NOS.1507778 and 1561590.As introducing among we the disclosed european patent application specification sheets NO.0050021, major ingredient is C on the other hand
2Hydrocarbon raw material can be converted into aromatic hydrocarbons more than 580 ℃.The aromatic hydrocarbons of Sheng Chaning wherein also has some to can be used as useful gasoline blending compound usually also with a spot of open chain hydro carbons in this way.
Have now found that, the ethane that contains in the raw material for
3/ C
4The selectivity that hydrocarbon reaction generates aromatic hydrocarbons can produce suitable favorable influence, and the temperature of its temperature when being lower than the independent aromizing of ethane.
Therefore, the present invention is a kind of method of producing aromatic hydrocarbons, is included under the temperature that is lower than 580 ℃, makes and contains 50%(weight at least) C
3(or) C
4Aromatic hydrocarbons and 10～50%(weight) ethane and a kind of catalyst composition carry out contact reacts, this catalyzer is the silico-aluminate that the mol ratio that contains silicon oxide and aluminum oxide was at least 5: 1.
This silico-aluminate contains greater than the mol ratio of the silicon oxide more than 5: 1 to aluminum oxide, and the most suitable is 20: 1 to 150: 1.This is exponential type (MFI) zeolite that a class has suitable solution stream, and its general formula is M
2/ nOAl
2O
3YSiO
2ZH
2O, M is a positively charged ion in the formula, is n valency positive charge ion, and y is the integer greater than 5, and Z is the integer from zero to 40.Positively charged ion M is alkalimetal ion preferably, alkaline-earth metal ions or proton.MFI type zeolite belongs to a kind of known zeolites structure-type zeolite, delivers (" zeolite structure type atlas " author Meier, W by the International Zeolite Association structure council, M and Olsen, D.H.(1978), polycrystal book service place provides, Pennsylvania, America, the Pittsburgh).The specific examples of this class zeolite is ZSM class, especially ZSM-5.These zeolites are produced by following raw materials according usually: silicon oxide, aluminum oxide, alkaline earth metal hydroxides and nitrogenous alkali, and as ammonia or alkanolamine, for example diethanolamine.The zeolite of producing with this quadrat method is at our disclosed European patent, by the agency of among the application specification Nos.002899 and 0002900.
This silico-aluminate (synthesis type or Hydrogen) can be used for hydrocarbon conversion process.Yet, be loaded with as the silico-aluminate of the catalyst component of metal oxide or metal ion and so on more favourable.Wherein, the compound of gallium and gallium ion are worth recommending especially.Have suitable life-span and active year gallium catalyzer in order to produce, the synthetic zeolite need pass through a series of treatment step:
(a) use diluted acid, promptly nitric acid washs the synthetic zeolite;
(b) acid treatment in (a), washed zeolite are carried out drying treatment;
(c) at high temperature, be higher than 500 ℃ of following calcination exsiccant zeolites;
(d), the zeolite of calcination is carried hold gallium compound or gallium ion with known dipping technique or ion exchange technique;
(e) make zeolite and the porous matrix that carries gallium with a kind of tackiness agent, for example silicon oxide or aluminum oxide are glued together.
Catalyzer with this quadrat method preparation has high initial activity, but owing to produce the high speed deposition of carbon thereupon, activity reduces rapidly.Have been found that if make the catalyst member inactivation, just can significantly reduce carbon distribution, and less to activity influence.Can make the controlled inactivation of catalyzer by the method for doing calcination with the method or the high temperature of steam treatment catalyzer.
Can use steam pure or dilution during steam treatment, preferably 10～40%(volume), treatment temp is higher than 400 ℃, preferably 500～650 ℃.Another kind method is in the temperature more than 600 ℃, preferably does calcination for 700～900 ℃.These treatment processs, different according to the difference of zeolite preparation method, can save initial calcination step (c), but except initial scorching hot, also to carry out calcination usually.
Through washing, dry and synthetic zeolite that calcination is handled, the cationic exchange of warp and gallium ion or with the dipping method of gallium compound makes and holds gallium its year again.
When the positively charged ion of silico-aluminate and gallium ion exchanged, gallium ion was the aqueous solution with gallium salt, and as gallium nitrate, the aqueous solution form of gallium chloride or gallium sulfate provides.Adopt common ion exchange technique, carry out the exsiccant method subsequently again, prepare this catalyzer.For example, the aqueous solution that can make the such gallium compound of gallium nitrate at room temperature or under the high temperature (being reflow method) contact with silico-aluminate.The silico-aluminate that exchanged is used the decant method again, separates with filter method more subsequently, with the deionized water washing for several times, carries out drying at last again.Before in the aqueous solution that silico-aluminate is added to gallium compound, silico-aluminate can be handled according to the european patent application specification sheets NO0024930 that we have delivered.
It is common dipping method that another kind of zeolite carries the gallium method, it is gallium compound, be submerged in as gallium oxide on the surface of silico-aluminate, perhaps be incorporated in the hole in the zeolite crystal, for gallium compound this can make catalyzer with the hydrocarbon raw material contact reacts before during activation treatment, improve gallium oxide content.Suitable gallium compound is a gallium nitrate.
Dipping can carry out like this: prepare a kind of solution of gallium compound earlier, be advisable with the aqueous solution, for example the saltpetre aqueous solution under agitation joins common silico-aluminate in this aqueous solution again, forms mashed prod, then carries out drying under vacuum, high temperature.
Utilize the compound of gallium, for example gallium nitrate makes its ionization in the aqueous solution, and when preparing catalyst component, some gallium ion can exchange with the positively charged ion of silico-aluminate, even also is like this when utilizing the method for dipping silico-aluminate.
No matter adopt which kind of Preparation of Catalyst or activatory method, the content of gallium can change in the catalyst component, for example, can account for 0.05～10%(weight of silico-aluminate total amount in the catalyst component)
Contain C in the mixing raw material
3(or) C
4Hydrocarbon, with this hydrocarbon as the principal reaction thing.C
3And C
4The specific examples of hydrocarbon has propane, propylene, normal butane, Trimethylmethane, n-butene and iso-butylene.Wherein propane and butane are best, in the suitable hydrocarbon feed, and C
3/ C
4Hydrocarbon should be higher than 50% by weight, preferably more than 70%.
Desire to change into the mixing raw material of aromatic hydrocarbons or gasoline blending compound, ethane content wherein should be lower than 45%(weight), be preferably in 15～45%(weight)
Can or utilize C from the outside
3/ C
4The circulation products that the raw material aromizing is produced joins C with ethane
3/ C
4Go in the component, in continuous processing, the technology of cycle ethane is useful especially, after beginning inductive phase, can produce the ethane of q.s, removes excessive ethane simultaneously and pays a methane that produces, thereby reach a kind of steady state.
This technology is a kind of gas phase process process, in the temperature more than 450 ℃, is preferably 475～570 ℃ temperature, mixing raw material change into aromatic hydrocarbons and (or) contain the aromatic hydrocarbons of gasoline fusion group.
The pressure of reaction is 1～20 crust, is preferably 2～10 crust.
Be 1～50 second the duration of contact of mixing raw material and catalyst component, is preferably 5～20 seconds.The LHSV(liquid hourly space velocity degree of reactant) is 0.5～8, is preferably 2～4.
It is good that this mixing raw material gained result who contains ethane of the present invention can get being combined as of result than single raw material.In addition, be added with ethane and also have a benefit, can without nitrogen dilute raw material (be this effect be not depend merely on reduce reactant and the product dividing potential drop caused).
Following embodiment can further specify method of the present invention.
Embodiment 1
The detailed description of catalyzer
The diethanolamine method that the european patent application specification sheets Nos.002899 and 002900 that utilizes us to deliver is introduced prepares zeolite, SiO
2To Al
2O
3Mol ratio be 39.6: 1.
Through rare nitric acid washing, vacuum-drying is then 550 ℃ of following calcinations 60 hours again for Zhi Bei zeolite like this.The zeolite of calcination refluxes with gallium nitrate solution again, filters washing and dry.Use the Ludox AS40(registered trademark of capacity then) carry out bondingly, obtain a kind of particle that contains 2.5% tackiness agent.As described in we disclosed European patent No.0024930, the adherent catalyzer carry hold gallium oxide before, in 550 ℃ air, use the 19%(volume) steam treatment 2 hours.
Under the absolute pressure of 535 ℃ temperature and 6 crust, make and contain 54%(weight) propane, 4.5%(weight) butane and 41.5%(weight) mixture of ethane is by a gallium/zeolite catalyst, contains 0.6%(weight on this catalyzer) gallium.Be about 14 seconds the duration of contact of calculating under reaction conditions.Total time is 98 hours in air-flow, is divided into several stages Collection and analysis liquid sample and gaseous products around here.The average yield of these several sections tests is 28.5% liquid (weight), wherein contains the aromatic hydrocarbons greater than 95%, and the propane of recovery and butane are respectively 7.8% and 0.3%.Total concentration of ethane in product is higher than charging.Therefore, liquid can be considered to because the result that the butane of 46.2% propane and 4.2% transforms, and this shows that selectivity is a 56.5%(weight)
Compare therewith, under same catalyzer and reaction conditions, after 97 hours, for containing 91.7%(weight) propane and 7.5%(weight) the available liquid yield of charging of butane is 37.2%(weight), the propane and the butane that reclaim are respectively 20.0% and 0.2%, but selectivity is a 47.0%(weight).
Under similarity condition, with the independent charging of ethane, the yield of liquid is 2.5%.Therefore, above-mentioned parallel feeding can expect and obtain 24.7% liquid, and what these liquid were generated by ethane is 1.0%, and what transformed by 50.4% propane and butane is 23.7%, and selectivity is 47%, and this is starkly lower than actual result.
Embodiment 2, the additive contrast of ethane and nitrogen
Use 5 examples 1 same incoming mixture and reaction conditions, after test in two hours, the weight of resulting liquid is equivalent to 46.3% of propane and butane in the raw material, contains the C of trace amounts of olefin
3And C
4The yield of hydrocarbon is equivalent to 20.6% of charging.Therefore, its selectivity to liquid is a 58.3%(weight).
At this moment, replace ethane in the charging with nitrogen, after two hour other test period, the liquid that obtains is equivalent to 39.4% of propane and butane in the charging, and C
3And C
4Yield be 17.0%, so its selectivity to liquid is a 47.5%(weight).
Claims (9)
1, a kind of method of producing aromatic hydrocarbons is characterized in that, is contacted with catalyzer by the blended hydrocarbon feed being lower than under 580 ℃ the condition, and hydrocarbon feed contains the C of 50% (weight) at least
3(or) C
4Hydrocarbon, and the ethane of 10～50% (weight) contain silico-aluminate in the catalyzer, wherein silicon oxide was at least 5: 1 the mol ratio of aluminum oxide.
2, be synthesis type or Hydrogen or be loaded with metallic compound or metal ion according to the silico-aluminate that the process of claim 1 wherein.
3, according to the method for claim 2, wherein metal in the metallic compound or metal ion are galliums.
4, according to containing weight in the hydrocarbon feed that the process of claim 1 wherein greater than 50%() C
3(or) C
4Hydrocarbon and less than 15～45%(weight) ethane.
5, according to the method for claim 3, wherein be loaded with on the silico-aluminate of gallium, silicon oxide is 20: 1 to 150: 1 to the mol ratio of aluminum oxide.
6, according to any one method in the claim 3 to 5, wherein the content of gallium is 0.05～10%(weight of silico-aluminate total amount in the above-mentioned composition in the catalyst composition).
7, according to any one method in the claim 1 to 5, wherein the blended hydrocarbon feed be converted into aromatic hydrocarbon and (or) the gasoline blending compound is to be to carry out under 475 ℃ to 575 ℃ in gas phase, temperature.
8, according to any one method in the claim 1 to 5, wherein the conversion of total hydrocarbon feed is to carry out under the condition of 1 to 20 crust in absolute pressure.
9, according to any one method in the claim 1 to 5, catalyst composition wherein is with before total hydrocarbon feed contacts, and the inactivation of part has been carried out in the processing of doing calcination with steam or high temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104308 CN1007426B (en) | 1983-12-24 | 1985-06-07 | Method of production of aromatic hydrocarbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB838334486A GB8334486D0 (en) | 1983-12-24 | 1983-12-24 | Aromatic hydrocarbons |
| CN 85104308 CN1007426B (en) | 1983-12-24 | 1985-06-07 | Method of production of aromatic hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104308A CN85104308A (en) | 1986-12-03 |
| CN1007426B true CN1007426B (en) | 1990-04-04 |
Family
ID=25741731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85104308 Expired CN1007426B (en) | 1983-12-24 | 1985-06-07 | Method of production of aromatic hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007426B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361959B (en) * | 2009-03-27 | 2014-07-30 | 吉坤日矿日石能源株式会社 | Method for producing aromatic hydrocarbons |
| US20130131414A1 (en) * | 2009-11-02 | 2013-05-23 | Mahesh Venkataraman Iyer | Process for the conversion of propane and butane to aromatic hydrocarbons |
| US8835706B2 (en) | 2009-11-02 | 2014-09-16 | Shell Oil Company | Process for the conversion of mixed lower alkanes to aromatic hydrocarbons |
-
1985
- 1985-06-07 CN CN 85104308 patent/CN1007426B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104308A (en) | 1986-12-03 |
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