CN101130477A - Method for producing branched-chain long-chain alkylbenzene with rudder-alkylbenzene and long chain-chain olefinic hydrocarbon - Google Patents
Method for producing branched-chain long-chain alkylbenzene with rudder-alkylbenzene and long chain-chain olefinic hydrocarbon Download PDFInfo
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- CN101130477A CN101130477A CNA2007100124131A CN200710012413A CN101130477A CN 101130477 A CN101130477 A CN 101130477A CN A2007100124131 A CNA2007100124131 A CN A2007100124131A CN 200710012413 A CN200710012413 A CN 200710012413A CN 101130477 A CN101130477 A CN 101130477A
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- olefin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a making method of long-chained alkyl benzene with branched chain through short-chained alkyl benzene and long-chained olefin, which is characterized by the following: fixing AlCl3 on the Al2O3, SiO2, Al2O3-SiO2 or siallite molecular sieve carrier; setting the length alkyl chain length of short-chained alkyl benzene as C1-C5 and long-chained olefin as C6-C20 olefin; adopting suspended bed reaction pattern to synthesize long-chained alkyl benzene with branched chain under 0. 5-5. 0Mpa at 0-200 deg. c; setting the molar rate of short-chained alkyl benzene and long-chained olefin at 20: 1-2: 1; obtaining the olefin transformation rate to 100% and the selectivity of branched chained long-chained alkyl benzene of benzene ring at long-alkyl high-carbon position more than 60%. The catalyst displays high activity, selectivity and stability.
Description
Technical field
The invention belongs to the petroleum refining process technical field, particularly a kind of with solid acid---immobilized AlCl
3Be catalyzer, adopt the suspension bed reactive mode, make the side chain long-chain alkyl benzene with the alkylbenzene and the long-chain olefin reaction that have short alkyl chain, and then to make the novel method of tertiary oil production in oil field with oil displacement surfactant.
Background technology
Along with the increase of world energy sources demand, more and more higher to the requirement of the produced quantity of oil and production efficiency, 1/3 of the general only extraction oil in-place of conventional oil production method (once with the secondary method), about 2/3 crude oil still is trapped in the oil reservoir.Tertiary oil recovery technology is a kind of method that especially effectively improves recovery ratio.In tertiary oil recovery technology, it is bigger that surfactant flooding improves the recovery ratio amplitude, uses extensivelyr, is a kind of flooding method with development potentiality.
The sulfonate type anion surfactant is widely used surfactant oil displacement.Alkylbenzene sulfonate is the main type in the sulfonate type anion surfactant.Alkylbenzene sulfonate is at HF or AlCl by aromatic hydrocarbons such as benzene,toluene,xylene, naphthalene and long-chain olefin
3Alkylated reaction takes place down and generates alkylbenzene in catalyst action, uses SO then
3Or oleum carries out sulfonation, makes with the alkali neutralization again.HF that in alkylation process, uses or AlCl
3Catalyzer is severe corrosion equipment and environment polluted in process of production, and product and catalyzer are not easily separated.
At present, the countries in the world scholar has carried out broad research to benzene on solid acid catalyst and long chain olefin alkylation reaction.
Though with the solid phosphoric acid be catalyzer aspect corrodibility and environmental pollution than HF and AlCl
3Bright apparent improvement is arranged, but because such catalyzer does not have the transalkylation function, product yield is low.The molecular sieve catalyst of succeeding in developing in recent years has mercerising, ZSM, Y, β and MCM series zeolite, it is better active, pollution-free, not only has the alkylation function, but also has the alkyl transformation function of polyalkylbenzene, but for the alkylated reaction of benzene and normal olefine, the easy inactivation of general molecular sieve, poor stability.At present, there are many R﹠D institutions carried heteropoly acid catalyst being studied that (thunder will is firm etc., chemical reaction and technology (J), 2002,18 (1): 1-11) at home.
The inactivation of solid acid catalysts such as HY, β zeolite mainly is because the alkene autohemagglutination forms burnt matter and polyalkylbenzene causes that plug-hole is caused.HY zeolite catalyst duct has only 0.76nm, burnt matter that generates in the reaction or polyalkylbenzene are easy to stop up the duct of carrier, make reaction raw materials be difficult to enter catalyzer inside, product can not spread out, make activity of such catalysts position forfeiture catalytic capability (Chen Wei etc., petrochemical complex, 1996,25:164 (3): 164-167); Zhu Haiou etc., Nanjing University, 2002,24 (2): 20-23).
People such as king's the last two have summarized benzene and long chain olefin alkylation reaction Study on Technology progress (modern chemical industry, 2002,22 (2): 11-14).The catalyzer of report has the sial of fluoridizing, molecular sieve, and heteropolyacid and ionic liquid etc., and introduced the Detal technology of the employing solid acid that UOP and Petresa company develop cooperatively, claim its total running cost to be lower than HF technology.
CN1340491 relates to the alkylation reaction method of a kind of benzene and alkene, comprises benzene and C
2-C
15Strand alkene reacts under alkylation reaction condition in the presence of-kind of solid acid catalyst, it is characterized in that in alkylated reaction raw material and/or alkene, gross weight with benzene and alkene is a benchmark, contains the organic or inorganic compound that contains the strong electronegativity element or its mixture of 10-3000ppm.
WO9626787 relates to the catalyzer that is used to prepare alkylbenzene.Active component A lX
3, be carried on clay, SiO
2-Al
2O
3Or on the metal oxide, X is Cl, Br or I.WO9111417 is with＞C
8Alkene is raw material, and benzene/alkene mol uses unformed hole and porous Lewis acid inorganic oxide catalyst than＜5, and carrier is one or more compound of the oxide compound of aluminium, silicon, germanium, titanium and zirconium.Alkylation reaction condition is: temperature of reaction-40-250 ℃, and pressure 20-25000KPa, air speed 0.01-500/h.
Jaenicke, people such as Stephan (Singapore university chemistry system) deliver is entitled as mesoporosity silicon oxide and the application (Abstracts of aluminum oxide in fine chemistry industry is synthetic, 222nd ACS National Meeting, Chicago, USA, August 26-30,2001, PETP-006Publisher:American Chemical Society, Washington D.C.).For environmental safety, " Green Chemistry " notion is proposed.Prepared the MCM-41 of different porosities; Dipping AlCl
3Or ZnCl
2, obtain the solid Lewis acid catalyst that is used for benzene alkylation of highly selective.
(J.Chem.Resear., Synopses (1997), (11), 430-431, J.Chem.Soc., Chem.Commun. (1995), (19), two kinds of catalyzer of the relevant benzene alkylation of 2037-40) delivering such as the Australia York Clark James H of university.The HMS of mesopore is loaded with AlCl
3, the porous carrier substance is loaded with AlCl
3Catalyzer.
Novel solid acid---the immobilized AlCl that provides use to have high reactivity, highly selective and high stability is provided purpose of the present invention
3The new technology of the synthetic side chain long-chain base alkane benzene of catalyzer.
Another object of the present invention is to provide a kind of novel process of easy, practical synthetic surfactant oil displacement side chain long-chain alkyl benzene, and no equipment corrosion, catalyst-free separate the synthetic side chain long-chain alkyl benzene of green catalysis process of aftertreatment with product;
A further object of the present invention is to provide the method that a kind of composite structure is clear and definite, form stable oil field surfactant oil displacement side chain long-chain alkyl benzene.
Summary of the invention
The purpose of this invention is to provide a kind of with immobilized AlCl
3Solid acid is a catalyzer, adopts the suspension bed reactive mode, is raw material by alkylbenzene that has short alkyl chain and long-chain olefin, makes the method for side chain long-chain alkyl benzene by alkylated reaction.
Technical solution of the present invention is, 0～200 ℃ of temperature of reaction, under reaction pressure 0.5～5.0MPa condition, short-chain alkyl benzene and long-chain olefin mol ratio are in 20: 1～2: 1 scopes, the volume ratio of catalyzer and raw material adopts the suspension bed reactive mode to make the side chain long-chain alkyl benzene in 0.05～0.5 scope.The catalyzer that is adopted is immobilized AlCl
3Catalyzer, wherein AlCl
3Be to realize supportedly by reacting with the carrier surface hydroxyl, muriate accounts for the 3-30% of total catalyst weight on the catalyzer.Immobilized AlCl
3The carrier of catalyzer is to have γ-Al mesoporous or the mesopore-macropore double-pore structure
2O
3, SiO
2, Al
2O
3-SiO
2And Si-Al molecular sieve.
The short alkyl chain length that described short-chain alkyl benzene is contained is C
1～C
5, can be the mixture of a kind of short-chain alkyl benzene or multiple short-chain alkyl benzene.Long-chain olefin is C
6～C
20Alkene can be pure alkene or multiple alkene mixture, has water-content≤20ppm in short alkyl chain alkylbenzene and the long-chain olefin raw material, diene content≤0.5%.
The invention has the beneficial effects as follows immobilized AlCl
3Catalyzer has stronger acidity, helps carrying out alkylated reaction manufacturing side chain long-chain alkyl benzene with the alkylbenzene and the long-chain olefin of short alkyl chain by carbonium ion intermediate mechanism; Employing has carrier mesoporous or the mesopore-macropore double-pore structure, helps the long-chain olefin polymkeric substance that side reaction generates in alkylated reaction and spreads rapidly, thereby avoid the duct to stop up, and helps the stability of solid acid catalyst; To not corrosion of conversion unit, need not behind the alkylated reaction to deviate from catalyzer through alkali cleaning, water washing process, there are not waste water, waste liquid to produce, belong to the green catalysis process.
Embodiment
Embodiment 1
Fixed bed AlCl
3The 20mL high purity of packing in producer γ-Al
2O
3(spherical d=1.8-2.0mm) is heated to 500 ℃, feeds N respectively with the flow velocity of 40ml/min and 0.8-2.0mL/h
2And CCl
4, produce AlCl
3Steam 11.1-27.8mmol/h; Fixed bed AlCl
3Pack in the immobilized reactor and have the SiO of meso-hole structure
2(40-60 order) 4.5mL (3.0g) carries out dehydration fever at 500 ℃ earlier and handles 2h; At 40mL/min N
2The AlCl that produces of following of carrier band
3Add AlCl
3In the immobilized reactor, under 300 ℃, carry out AlCl
3Immobilized reaction, reaction times 4.0h uses N then under 400 ℃
2Purge 1h, after this be cooled to normal temperature.The immobilized AlCl of gained
3Catalyzer 3.24g, wherein AlCl
x(x=2.2) account for 7.5 (m) %.
Embodiment 2
With toluene and pure laurylene is that raw material carries out alkylated reaction.In having the stainless steel autoclave reactor of magnetic agitation, 100mL adds the immobilized AlCl of 3.24g
3Catalyzer, adding cumulative volume is toluene and the C of 40mL
12 =Alkene (toluene/C
12 =Mix alkene=10: 1mol ratio), 40 ℃ of temperature of reaction, reaction pressure 1.0MPa be reaction 3h down, and experimental result shows that olefin conversion is 100%, and product is mainly the methyl dodecylbenzene.The selectivity that phenyl ring is in the company's of propping up alkylbenzene of dodecyl chain 2-, 3-, 4-, 5-, 6-position is respectively 20.3%, 16.5%, 21.2%, 23.7% and 18.3%.
Embodiment 3
Experimental technique is with embodiment 2, and difference is that aromatic hydrocarbons is ethylbenzene.Experimental result shows that olefin conversion is 100%, product is mainly right-ethyl-dodecylbenzene.The selectivity that phenyl ring is in the company's of propping up alkylbenzene of dodecyl chain 2-, 3-, 4-, 5-, 6-position is respectively 21.1%, 17.9%, 19.6%, 23.1% and 18.3%
Embodiment 4
With toluene, ethyl benzene mixtures is that raw material and pure laurylene carry out alkylated reaction.In having the stainless steel autoclave reactor of magnetic agitation, 100mL adds the immobilized AlCl of 3.24g
3Catalyzer, adding cumulative volume is toluene, ethylbenzene and the C of 40mL
12 =Alkene (aromatic hydrocarbons/C
12 =Mix alkene=10: the 1mol ratio, toluene/ethylbenzene=1: 1mol than), 40 ℃ of temperature of reaction, reaction pressure 1.0MPa be reaction 3h down, experimental result shows that olefin conversion is 100%, product is mainly right-methyl-dodecylbenzene and right-ethyl-dodecylbenzene.
Embodiment 5
With toluene and C
10 =～C
13 =Mixed olefins is that raw material carries out alkylated reaction.In having the stainless steel autoclave reactor of magnetic agitation, 100mL adds the immobilized AlCl of 3.24g
3Catalyzer, adding cumulative volume is toluene and the C of 40mL
10 =～C
13 =Mixed olefins (toluene/C
10 =～C
13 =Mix alkene=20: 1mol ratio), 80 ℃ of temperature of reaction, reaction pressure 1.0MPa be reaction 3h down, and experimental result shows that olefin conversion is 100%, and product is mainly cyclic monomer base benzene.The selectivity that phenyl ring is in the company's of propping up alkylbenzene of long alkyl chain 2-, 3-, 4-, 5-, 6-position is respectively 24.5%, 8.6%, 19.3%, 21.5% and 26.1%.
Embodiment 6
With toluene and C
14 =～C
18 =Mixed olefins is that raw material carries out alkylated reaction.In having the stainless steel autoclave reactor of magnetic agitation, 100mL adds the immobilized AlCl of 3.24g
3Catalyzer, adding cumulative volume is toluene and the C of 40mL
14 =～C
18 =Mixed olefins (toluene/C
14 =～C
18 =Mix alkene=20: 1mol ratio), 80 ℃ of temperature of reaction, reaction pressure 1.0MPa be reaction 3h down, and experimental result shows that olefin conversion is 100%, and product is mainly cyclic monomer base benzene.The selectivity that phenyl ring is in the company's of propping up alkylbenzene of long alkyl chain 2-, 3-, 4-, 5-, 6,7-position is respectively 20.4%, 13.7%, 18.6%, 24.3%, 18.25% and 4.7%.
Claims (6)
1. make the method for side chain long-chain alkyl benzene by short-chain alkyl benzene and long-chain olefin, it is characterized in that, 0～200 ℃ of temperature of reaction, under reaction pressure 0.5～5.0MPa condition, short-chain alkyl benzene and long-chain olefin mol ratio are in 20: 1～2: 1 scopes, the volume ratio of catalyzer and raw material adopts the suspension bed reactive mode to make the side chain long-chain alkyl benzene in 0.05～0.5 scope, and the catalyzer that is adopted is immobilized AlCl
3Catalyzer.
2. the method by short-chain alkyl benzene and long-chain olefin manufacturing side chain long-chain alkyl benzene according to claim 1 is characterized in that AlCl
3Be to realize supportedly by reacting with the carrier surface hydroxyl, muriate accounts for the 3-30% of total catalyst weight on the catalyzer.
3. the method by short-chain alkyl benzene and long-chain olefin manufacturing side chain long-chain alkyl benzene according to claim 1 and 2 is characterized in that, is used to prepare described immobilized AlCl
3The carrier of catalyzer is the γ-Al with mesoporous or mesoporous-macropore double-pore structure
2O
3, SiO
2, Al
2O
3-SiO
2And Si-Al molecular sieve, its specific surface area is 120～450m
2/ g, mean pore size is 5～1200nm; Granularity is 10～400 orders.
4. according to the described method of claim 1, it is characterized in that the short alkyl chain length that described short-chain alkyl benzene is contained is C by alkylbenzene that has short alkyl chain and long-chain olefin reaction manufacturing side chain long-chain alkyl benzene
1～C
5, can be the mixture of a kind of short-chain alkyl benzene or multiple short-chain alkyl benzene.
5. according to the described method of claim 1, it is characterized in that described long-chain olefin is C by alkylbenzene that has short alkyl chain and long-chain olefin reaction manufacturing side chain long-chain alkyl benzene
6～C
20Alkene can be pure alkene or multiple alkene mixture.
6. according to claim 1, the 4 or 5 described methods of making the side chain long-chain alkyl benzene by alkylbenzene that has short alkyl chain and long-chain olefin reaction, it is characterized in that, described water-content≤20ppm in short alkyl chain alkylbenzene and the long-chain olefin raw material, diene content≤0.5% of having.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100124131A CN101130477A (en) | 2007-08-06 | 2007-08-06 | Method for producing branched-chain long-chain alkylbenzene with rudder-alkylbenzene and long chain-chain olefinic hydrocarbon |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100124131A CN101130477A (en) | 2007-08-06 | 2007-08-06 | Method for producing branched-chain long-chain alkylbenzene with rudder-alkylbenzene and long chain-chain olefinic hydrocarbon |
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|---|---|
| CN101130477A true CN101130477A (en) | 2008-02-27 |
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|---|---|---|---|
| CNA2007100124131A Pending CN101130477A (en) | 2007-08-06 | 2007-08-06 | Method for producing branched-chain long-chain alkylbenzene with rudder-alkylbenzene and long chain-chain olefinic hydrocarbon |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237325A (en) * | 2015-10-08 | 2016-01-13 | 江苏汉光实业股份有限公司 | Ultrahigh-purity alkyl benzene |
| CN108569944A (en) * | 2017-03-14 | 2018-09-25 | 中国石油化工股份有限公司 | The production method of branched alkylbenzene |
| CN111514924A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for catalytic synthesis of long-chain alkyl aromatic hydrocarbon |
| CN112300769A (en) * | 2020-02-12 | 2021-02-02 | 中国石油天然气股份有限公司 | Temperature-resistant foam oil displacement agent, preparation method and application thereof |
| US11370722B2 (en) | 2020-06-22 | 2022-06-28 | Nanjing Chemistry New Energy Technology Co. Ltd. | Method for producing long-chain alkylbenzene |
-
2007
- 2007-08-06 CN CNA2007100124131A patent/CN101130477A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237325A (en) * | 2015-10-08 | 2016-01-13 | 江苏汉光实业股份有限公司 | Ultrahigh-purity alkyl benzene |
| CN108569944A (en) * | 2017-03-14 | 2018-09-25 | 中国石油化工股份有限公司 | The production method of branched alkylbenzene |
| CN108569944B (en) * | 2017-03-14 | 2021-03-30 | 中国石油化工股份有限公司 | Process for producing branched alkylbenzene |
| CN112300769A (en) * | 2020-02-12 | 2021-02-02 | 中国石油天然气股份有限公司 | Temperature-resistant foam oil displacement agent, preparation method and application thereof |
| CN112300769B (en) * | 2020-02-12 | 2022-08-02 | 中国石油天然气股份有限公司 | Temperature-resistant foam oil displacement agent, preparation method and application thereof |
| CN111514924A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for catalytic synthesis of long-chain alkyl aromatic hydrocarbon |
| US11370722B2 (en) | 2020-06-22 | 2022-06-28 | Nanjing Chemistry New Energy Technology Co. Ltd. | Method for producing long-chain alkylbenzene |
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Open date: 20080227 |