CN1269938C - Refining method of reforming aromatic oil - Google Patents
Refining method of reforming aromatic oil Download PDFInfo
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- CN1269938C CN1269938C CN 200410046820 CN200410046820A CN1269938C CN 1269938 C CN1269938 C CN 1269938C CN 200410046820 CN200410046820 CN 200410046820 CN 200410046820 A CN200410046820 A CN 200410046820A CN 1269938 C CN1269938 C CN 1269938C
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Abstract
The present invention relates to a method for catalyzing, refining and reforming aromatic oil without hydrogen. The method used for catalyzing, processing and reforming aromatic oil can effectively remove trace amount of olefin in aromatic hydrocarbon without aromatic hydrocarbon loss but increase and especially, C8 aromatic hydrocarbon is increased obviously under the conditions of reaction temperature at 100 to 300 DEG C, reaction pressure at 1.0 to 2.0MPa and airspeed of 0.5 to 40 hr<-1>. Therefore, the method satisfies the refining requirements of reforming aromatic oil, has catalysts which can be regenerated and repeatedly used, and greatly reduces production cost.
Description
1, technical field
The present invention relates to a kind of process for purification of the aromatic hydrocarbon oil of reforming.
2, background technology
Petroleum naphtha is rich in aromatic hydrocarbons and solvent oil in the generation oil of catalytic reforming reaction, also contain a spot of alkene simultaneously.For the reformer of producing aromatic hydrocarbons and solvent oil, produce qualified aromatic hydrocarbons and solvent oil, all be faced with the alkene problem in the oil that generates that how to remove.At present, industrially remove that alkene has two kinds of methods in the aromatic hydrocarbon oil.A kind of is hydrofining technology, promptly utilize platinum or palladium to be loaded on the aluminum oxide as catalyzer, carry out " back end hydrogenation " in the reforming reactor back thus process is to realize making the saturated purpose that removes alkene that reaches of alkene, typical catalyzer has CN85100760A, CN85100215A, CN1448474A patent report, the industrial existing MH-508 noble metal catalyst that has Shanxi coal to develop that uses.Experiment shows: adopt " back end hydrogenation " technology effect for single benzene close-cut fraction relatively good, but for containing C simultaneously
8A～C
10 +The wide fraction product of A, the hydrogenation reaction degree of depth is difficult to take into account comprehensively, can cause aromatic hydrocarbons to lose more significantly, and catalyzer price height, also needs to consume hydrogen, and production cost is higher.Another kind method is to adopt carclazyte to make with extra care to remove alkene.Carclazyte through acidic treatment, mainly be by the condensation reaction that coincides of absorption or partially alkylated and alkene, thereby reach the purpose that removes the alkene in the aromatic hydrocarbon oil, though clay treatment process has obtained the wide industrial application, but it is relatively poor to remove the alkene effect, and because service temperature is higher, gum level uprises color burn in the feasible generation oil; In actual process, the carclazyte life cycle is short, consumption is big simultaneously, and the carclazyte behind the inactivation can not be regenerated, the general carclazyte that just need more renew in 2～3 months, and frequent replacing has increased the aromatic hydrocarbons loss and workload, a large amount of useless carclazytes need be piled and bury processing.
3, summary of the invention
At the deficiencies in the prior art, the invention provides a kind of under conditions of non-hydrogen the method for catalytic refining aromatic hydrocarbon oil, adopt this method can reduce alkene in the aromatic hydrocarbon oil, implement device long-term operation effectively.
The present invention is achieved in that aromatic hydrocarbon oil through beds, and the deolefination reaction takes place under conditions of non-hydrogen, and reaction conditions is: 100～300 ℃ of temperature of reaction, reaction pressure 1.0～2.0MPa, air speed 0.5～40hr
-1, preferably temperature of reaction is 160～200 ℃, air speed 0.5～15hr
-1
Catalyzer of the present invention is a carrier with aluminum oxide or kaolin, and beta-molecular sieve is an active component.
The aromatic hydrocarbon oil of indication of the present invention is meant that reformer generates oil, also can be among benzene,toluene,xylene, the heavy aromatics any one or two or more.
Adopt the method for this invention, have the following advantages:
This method can be removed the trace amounts of olefin in the aromatic hydrocarbons effectively, and aromatic hydrocarbons does not lose on the contrary to be increased, and particularly C8 aromatic hydrocarbons increases significantly, and the repeated use of regenerating of this catalyzer, can reduce production costs greatly.
4, embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
The aromatic hydrocarbon oil non-hydrogen catalytic refining of on the 10ml evaluating apparatus, reforming test, investigate catalytic refining ability under the differential responses temperature, catalyzer adopts kaolin, aluminium stone and beta molecular sieve through extrusion, drying and roasting preparation (down together), stock oil adopts reformation heavy aromatics oil, 149～221 ℃ of boiling ranges, bromine index is 548.63mgBr/100ml, aromaticity content is 94.18%, colloid 78mg/100ml, the colloid detection method is GB/T888019 (down together), reaction conditions is: reaction pressure 1.0Mpa, reaction velocity are 25hr
-1, test-results sees Table 1.
Catalytic refining effect under table 1 differing temps
| Temperature of reaction, ℃ | 100 | 160 | 180 | 200 | 300 |
| Bromine index, mgBr/100ml | 400 | 50 | 30 | 10 | 10 |
| Colloid, mg/100ml | 1 | 1 | 1 | 1 | 1 |
Embodiment 2
On the 10ml evaluating apparatus, carry out the test of aromatic hydrocarbon oil non-hydrogen catalytic refining, investigate catalytic refining ability under the differential responses pressure, stock oil adopts the reformer heavy aromatics, 149～221 ℃ of boiling ranges, bromine index is 548.63mgBr/100ml, reaction conditions is: 160 ℃ of temperature of reaction, reaction velocity are 25hr
-1, test-results sees Table 2.
Catalytic refining effect under table 2 different pressures
| Reaction pressure, MPa | 1.0 | 2.0 |
| Bromine index, mgBr/100ml | 50 | 50 |
| Colloid, mg/100ml | 1 | 1 |
Embodiment 3
On the 10ml evaluating apparatus, carry out the test of aromatic hydrocarbon oil non-hydrogen catalytic refining, investigate catalytic refining ability under the differential responses air speed, stock oil adopts the reformer heavy aromatics, 149～221 ℃ of boiling ranges, bromine index is a 548.63mgBr/100ml oil, reaction conditions is: 180 ℃ of temperature of reaction, and reaction pressure 1.0Mpa, test-results sees Table 3.
Catalytic refining effect under the different air speeds of table 3
| Air speed hr -1 | 0.5 | 1 | 3 | 15 | 25 | 40 |
| Bromine index, mgBr/100ml | ＜10 | ＜10 | 20 | 30 | 50 | 100 |
| Colloid, mg/100ml | 1 | 1 | 1 | 1 | 1 | 1 |
Embodiment 4
Carry out the test of aromatic hydrocarbon oil non-hydrogen catalytic refining on the 10ml evaluating apparatus, stock oil adopts reformer to generate oil, 58～141 ℃ of boiling ranges, bromine index is a 3450mgBr/100ml oil, reaction conditions is: 160 ℃ of temperature of reaction, reaction pressure 1.0Mpa, reaction velocity are 25hr
-1, the treated oil bromine index is a 347mgBr/100ml oil.
Embodiment 5
On the 10ml evaluating apparatus, carry out aromatic hydrocarbon oil non-hydrogen catalytic refining stability and accelerate test, stock oil adopts reformer heavy aromatics oil, and bromine index is a 548.63mgBr/100ml oil, and reaction conditions is: 180 ℃ of temperature of reaction, reaction pressure 1.0Mpa, reaction velocity are 25hr
-1, test-results sees Table 4, table 5.Colorimetric is taked to adopt GB 8035-87 method to measure then oil sample distillation cutting initial boiling point to 160 ℃ cut, and stock oil, treated oil are formed the employing gas chromatographic analysis.
Table 4 reformed oil catalytic refining is accelerated test-results
| Runtime hour | Bromine index mgBr/100ml | Colloid mg/100ml | Colourity number |
| 3 | 57 | 1 | ＜1# |
| 6 | 31 | 1 | ＜1# |
| 9 | 43 | 1 | ＜1# |
| 12 | 71 | 1 | ＜1# |
| 15 | 124 | 1 | ＜1# |
| 18 | 182 | 1 | ＜1# |
Table 5 stock oil, treated oil are formed
| The aromatic hydrocarbons carbon number | C8％ | C9％ | C10％ | C11％ | Total fragrant number % |
| Stock oil | 36.57 | 45.18 | 11.76 | 0.67 | 94.18 |
| Treated oil | 37.65 | 44.68 | 11.35 | 0.68 | 94.49 |
| Amplification % | 1.08 | -0.5 | -0.41 | 0.01 | 0.31 |
Claims (4)
1, a kind of under conditions of non-hydrogen the method for catalytic refining aromatic hydrocarbon oil, it is characterized in that aromatic hydrocarbon oil is through beds, the deolefination reaction takes place under conditions of non-hydrogen, reaction conditions is: 100～300 ℃ of temperature of reaction, reaction pressure 0.5～2.0Mpa, air speed 0.5～40hr-1, the catalyzer of employing is a carrier with aluminum oxide or kaolin, beta-molecular sieve is an active component.
2, method according to claim 1 is characterized in that 160～200 ℃ of temperature of reaction, reaction pressure 1.0～2.0Mpa, air speed 0.5～15hr-1.
3, method according to claim 1 is characterized in that the aromatic hydrocarbon oil of indication is meant reformed oil.
4, according to claim 1 or 3 described methods, the aromatic hydrocarbon oil that it is characterized in that indication is meant among benzene,toluene,xylene, the heavy aromatics any one or two or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410046820 CN1269938C (en) | 2004-10-01 | 2004-10-01 | Refining method of reforming aromatic oil |
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| CN 200410046820 CN1269938C (en) | 2004-10-01 | 2004-10-01 | Refining method of reforming aromatic oil |
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| CN1618932A CN1618932A (en) | 2005-05-25 |
| CN1269938C true CN1269938C (en) | 2006-08-16 |
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| CN 200410046820 Expired - Fee Related CN1269938C (en) | 2004-10-01 | 2004-10-01 | Refining method of reforming aromatic oil |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993714B (en) * | 2009-08-31 | 2014-05-28 | 中国石油化工股份有限公司 | Method for removing olefin of reformate in non-hydrogenation manner |
| CN102728394A (en) * | 2011-04-13 | 2012-10-17 | 南京亚东奥土矿业有限公司 | Preparation method and application of acid modified attapulgite clay catalyst |
| CN103012034B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Method for removing micro-quantity alkene in aromatic hydrocarbon |
| CN103012037B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Method for removing trace olefin from aromatic hydrocarbon |
| CN103012036B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Aromatic hydrocarbon purifying method |
| CN103012035B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Method for removing trace hydrocarbon out of aromatic hydrocarbon by utilizing HMCM-41 type mesoporous molecular sieve |
| CN102992932B (en) * | 2012-11-28 | 2015-01-28 | 浙江工业大学 | Method for removing olefin in aromatic hydrocarbon by M-SBA-15 type mesoporous molecular sieve |
| CN103041841B (en) * | 2012-12-28 | 2017-11-17 | 北京石油化工学院 | A kind of aromatic hydrocarbons non-hydrogen olefinic hydrocarbon expelling catalyzer and preparation method thereof |
| CN105541539B (en) * | 2015-12-10 | 2018-06-26 | 中国海洋石油总公司 | A kind of method that reformed oil xylene fraction non-hydrogen deolefination refines |
| CN107760357A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | Low accessory substance reforms oil-off olefin technique |
| CN107474871A (en) * | 2017-09-18 | 2017-12-15 | 张冰童 | A kind of method and catalyst of catalytic reforming generation oil-off olefin |
| CN112391195B (en) * | 2019-08-16 | 2022-04-05 | 中国石油化工股份有限公司 | Method for removing olefin from aromatic hydrocarbon raw material |
| CN112657545B (en) * | 2019-10-15 | 2022-09-06 | 中国石油化工股份有限公司 | Olefin removal catalyst and preparation method and application thereof |
| CN114891534B (en) * | 2022-06-01 | 2024-01-12 | 浙江工业大学 | Refining method of reformed aromatic hydrocarbon |
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