CN102069008B - Catalyst for removing olefin in reformed arene and preparation method thereof - Google Patents
Catalyst for removing olefin in reformed arene and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for removing olefin in reformed arene. The catalyst comprises the following components in percentage by weight: 20-80 percent of MCM series molecular sieve and 20-80 percent of modified REY molecular sieve, wherein the REY molecular sieves are DOSY or CDY; the DOSY is the REY of phosphorus-containing amorphous silicon oxide, in the 31P MAS NMS spectrum of the DOSY, the chemical shift is the sum of the peak areas of a -15+/-2ppm peak and a -23+/-2ppm peak, and the specific value of the peak area sum to a total peak area is larger than 85 percent; the CDY is an REY, and metered by rare earth oxide, the content of rare earth is 12-22 weight percent; and rare earth ions are all in a molecular sieve cellule, and non-framework aluminum does not exist. The catalyst is used for removing olefin in reformed generated oil and has better olefin removal activity and stability.
Description
Technical field
The present invention is a kind of Catalysts and its preparation method that removes alkene in the reformed arene, specifically, is a kind of olefinic hydrocarbon expelling catalyzer that contains molecular sieve and preparation method thereof.
Background technology
Catalytic reforming generates in the oil and is rich in aromatic hydrocarbons, also contains a small amount of alkene.Produce qualified aromatic hydrocarbons, must remove alkene wherein, otherwise the bromine index of aromatic hydrocarbon product, corrosion and pickling color are defective.Alkene also can be influential to the performance of equipment, adsorbent and the catalyst in downstream.In addition, alkene easily forms colloid and other byproduct, pollutes the heat-transfer area of operating equipment, thereby reduces its service efficiency.Therefore, the technology that removes of trace amounts of olefin has important practical significance in the exploitation reformation BTX aromatics.
Alkene in the reformed oil generally removes with following methods: reformed oil makes alkene change into alkane by selective hydrogenation; Reformed oil behind the hydrogenation is through Aromatics Extractive Project, with behind the hydrogenation of olefins in raffinating oil as solvent naphtha, the BTX aromatics that extracting obtains is removed alkene through bleaching earth adsorption, carries out rectifying again.In addition, in employing the reformed oil fractionation is cut into benzene, toluene and C
8 +In BTX aromatics and the technique, before each cut enters rectifying column, with carclazyte trace amounts of olefin absorption is wherein removed.
At present, most commercial plants employing activation granular carclazytes remove the alkene in the reformation BTX aromatics, under the non-hydrogen reaction condition, and reactor parallel connection or serial operation.General raw material all needed through clay treatment before entering benzene,toluene,xylene (or circulation dimethylbenzene of isomerization unit) tower.Granular carclazyte has preferably effect to the alkene removing from benzene to the dimethylbenzene cut, and shortcoming is that inactivation is fast, and life cycle is short, and the general carclazyte that just need to more renew in 2～3 months, frequent have increased loss and the workload of aromatic hydrocarbons.In addition, can not effective regeneration behind the carclazyte inactivation, therefore a large amount of useless carclazytes needs landfill disposal, both has been unfavorable for environmental protection, needs again a large amount of extra landfill expenses.
Remove that the another kind of method of alkene is to carry out Hydrobon in the reformation BTX aromatics.Industrial normal use non-precious metal catalyst such as Co-Mo or Ni-Mo/Al
2O
3Remove alkene.USP6500996B
1The method of a kind of BTX of purification is disclosed, first reformate is contacted with hydrotreating catalyst, make the alkadienes that wherein contains be converted into oligomer, again oligomer is separated, and then the reformate of hydrotreatment contacted with molecular sieve, wherein alkene is converted into alkylaromatic hydrocarbon.Described molecular screening is from REY, MCM-22, MCM-36, MCM-49, MCM-56 or β zeolite, and described hydrotreating catalyst is nickel-molybdenum/aluminium oxide catalyst.
CN02109413.6 discloses a kind of reformed oil selective hydrogenation and olefin hydrocarbon removal catalyst, and take aluminium oxide as carrier, Pt or Pd are active constituent, and K, Na or Mg are auxiliary agent.High pressure (1.8～2.8MPa), face hydrogen (H
2/ HC volume ratio=100～500), high (volume space velocity 2.0～4.0h during liquid of air speed
-1) condition under, the bromine index of reformed arene that can bromine index is higher is down to below the 100mgBr/100g.Catalyst contains noble metal component, and is relatively good for removing in the benzene effect of alkene, but to C
6～C
8Aromatic hydrocarbon product, the hydrogenation reaction degree of depth is difficult to take into account comprehensively, aromatic hydrocarbons loss is more remarkable.In addition, because reaction pressure and temperature are relatively high, also need to face hydrogen, therefore having relatively high expectations to equipment.Catalyst also needs sulfuration when going into operation, and operating process is more loaded down with trivial details.
CN200510114239.2 discloses treating adsorbent of a kind of white spirit and preparation method thereof, uses nitrate solution dipping X zeolite to make adsorbent, and described nitrate is selected from copper nitrate or zinc nitrate.This adsorbent is used for petroleum solvent oil-off olefin and aromatic hydrocarbons, and the arene engaging scraping rate can reach more than 90%, and bromine index can be down to below 300～400mgBr/100g.
CN200410046820.0 discloses a kind of preparation method of reforming aromatic oil, take aluminium oxide or kaolin as carrier, beta-molecular sieve is that active constituent makes catalyst, makes aromatic naphtha through beds, at non-hydrogen, 100～300 ℃, 0.5～2.0MPa, air speed 0.5～40hr
-1Condition under the deolefination reaction occurs, can reduce bromine index and the colloid of reforming aromatic oil, and not lose the aromatic hydrocarbons in the reformate.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst and preparation method who removes alkene in the reformed arene, this catalyst has preferably deolefination activity and stable.
The catalyst that removes alkene in the reformed arene provided by the invention, comprise the MCM Series Molecules sieve of 20～80 quality % and the modification REY molecular sieve of 20～80 quality, described modification REY molecular sieve is DOSY or CDY, and described DOSY is phosphorous and REY amorphous silicon oxide, its
31In the P MAS NMR spectrum, chemical shift is that the ratio of peak area sum and total peak area at-15 ± 2ppm peak and-23 ± 2ppm peak is greater than 85%, described CDY is a kind of REY, wherein take the content of rare earth of rare earth oxide as 12～22 % by weight, rare earth ion all is positioned at the little cage of molecular sieve, and does not have non-framework aluminum.
The present invention is with REY molecular sieve and the compound catalyst of making of MCM Series Molecules sieve of modification, in the reaction of reformed arene deolefination than the clay catalyst of industrial use, has good reactivity worth, and can regenerate, catalyst has long service life, operation cycle that can extension fixture.
The specific embodiment
The present invention is with REY molecular sieve and the compound catalyst of making of MCM Series Molecules sieve of modification, both compound not only has good adsorption function to alkene, but also have suitable acidity, make alkene generation polymerization and alkylated reaction, thereby further reduce olefin(e) centent.In composite molecular screen, add the better acidity of modulation molecular sieve of sepiolite, catalyst is had better fall the alkene effect.
Catalyst of the present invention preferably includes the MCM Series Molecules sieve of 30～80 quality % and the modified Y molecular sieve of 20～70 quality %.
Performance for the performance molecular sieve preferably adds binding agent in composite molecular screen, preferred binding agent is aluminium oxide and/or sepiolite.In the situation that add binding agent, catalyst of the present invention preferably includes the MCM Series Molecules sieve of 40～80 quality %, the modified Y molecular sieve of 20～60 quality % and aluminium oxide and/or the sepiolite of 10～50 quality %, more preferably comprises the MCM Series Molecules sieve of 40～60 quality %, the modified Y molecular sieve of 20～50 quality % and aluminium oxide and/or the sepiolite of 10～40 quality %.When described binding agent was aluminium oxide and sepiolite, the mass ratio of sepiolite and aluminium oxide was 0.1～10: 1, preferred 0.5～5.0: 1.
The detailed preparation method of described DOSY and CDY is respectively referring to CN1660496A and CN1733362A.The silica/alumina molar ratio of DOSY and CDY molecular sieve is 0.5～100, preferred 2～50.
Described MCM Series Molecules sieves preferred MCM-22, MCM-36, MCM-49 or MCM-56.The silica/alumina molar ratio of used MCM Series Molecules sieve is 20～100, preferred 30～60.
The sodium content of the used molecular sieve of catalyst of the present invention should be not more than 1.0 quality %, preferably is not more than 0.5 quality %, and the degree of crystallinity of molecular sieve should be not less than 90%.
The sepiolite that adds in the catalyst of the present invention is a kind of rich fibrous magnesium silicate clay mineral, belongs to phyllosilicate, forms by silicon-oxy tetrahedron with by the magnesium ion of octahedral coordination, has the transiens architectural feature of chain and stratiform.This structure is so that the sepiolite particle has micro-fiber structure.Because the special tectonic that sepiolite has makes it keep a series of brilliant roads, thereby has great specific area and extremely strong adsorptivity, decolourising property and dispersiveness, thermal stability is high, and resistance to elevated temperatures can reach 1500～1700 ℃.
The preparation method of catalyst of the present invention comprises MCM Series Molecules sieve and modified Y molecular sieve is fully mixed rear addings sesbania powder and dilute acid soln kneading, or adding carboxymethyl cellulose or methocel solution kneading, extruded moulding then, drying, roasting.
The molecular sieve molded need adds extrusion aid in the said method, and described extrusion aid can be sesbania powder and dilute acid soln, also can be carboxymethyl cellulose or methocel solution.The preferred nitric acid of described acid, acetic acid, citric acid or any both or three's mixture in them.
If prepare the catalyst of salic and/or sepiolite, then need aluminium hydrate powder and/or sepiolite are added mixing in MCM Series Molecules sieve and the modified Y molecular sieve, and then kneading, extruded moulding.
When using sesbania powder and dilute acid soln moulding, the mass ratio of other solid matter is 0.01～0.2 in used sesbania powder and the mixed system: 1, preferred 0.01～0.1: 1, and the mass ratio of solid matter is 0.01～0.5 in dilute acid soln and the mixed system: 1, preferred 0.1～0.3: 1.
When using cmc soln or methocel solution moulding, the mass ratio of solid matter is 0.01～0.5 in used cmc soln or methocel solution and the mixed system: 1, preferred 0.5～0.4: 1.
Baking temperature described in the said method is 30～150 ℃, preferred 60～120 ℃, and sintering temperature is 400～750 ℃, preferred 450～650 ℃.
Catalyst of the present invention is applicable to remove the alkene in the reformed arene, deolefination carries out under conditions of non-hydrogen, reaction temperature is 70～300 ℃, preferred 100～200 ℃, pressure 0.1～5.0MPa, preferred 1.0～2.5MPa, and the liquid quality air speed of reaction is 0.1～200 o'clock
-1, preferred 0.5～50 o'clock
-1
The activity of olefinic hydrocarbon expelling catalyzer quantizes such as bromine valency or bromine index BI with olefin conversion or bromine number.The assay method of bromine valency or bromine index is undertaken by GB SH/T 0630-1996 (2006) method.Olefin conversion is higher, and perhaps bromine valency or bromine index are lower, illustrates that catalyst activity is better.The height of catalyst stability is by the speed that olefin conversion reduces or bromine number raises under the condition of certain reaction, perhaps will keep identical bromine number under certain reaction pressure and air speed, and the speed that reaction temperature improves is weighed.Selectively the referring to of catalyst do not have aromatic hydrocarbons loss or the aromatic hydrocarbons extent of damage lower in the deolefination course of reaction.The molecular sieve that catalyst of the present invention uses and aluminium oxide and/or sepiolite all have preferably hydrothermal stability, so the catalyst use of can repeatedly regenerating.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare catalyst of the present invention.
(catalyst branch company in Chang Ling produces, and contains Al to get 50 gram DOSY molecular sieves
2O
321.3 quality %, SiO
257.3 quality %, lanthana 4.5 quality %, cerium oxide 8.5 quality %, Na
2O 0.06 quality %) (the remarkable Chemical Industry Science Co., Ltd in Shanghai produces, and silica/alumina molar ratio is 45, Na with 50 gram MCM-22 molecular sieves
2O content is 0.08 quality %) fully mix, according to the mixed molecular sieve powder: sesbania powder: nitric acid: acetic acid: citric acid: water=50: 1: 2: 3: 3: 40 quality is more even than kneading, then extrusion, pelletizing, 120 ℃ of dryings 12 hours, 550 ℃ of roastings made bar shaped catalyst DOC-1 in 4 hours, wherein contain DOSY molecular sieve 50 quality %, MCM-22 molecular sieve 50 quality %.
Example 2
Press the method Kaolinite Preparation of Catalyst of example 1, different is that the carboxymethylcellulose sodium solution of mixed molecular sieve powder and 5 quality % is more even than kneading by 5: 3 quality, then extrusion, pelletizing, 120 ℃ of dryings 12 hours, 550 ℃ of roastings made bar shaped catalyst DOC-2 in 4 hours, wherein contain DOSY molecular sieve 50 quality %, MCM-22 molecular sieve 50 quality %.
Example 3
Press the method Kaolinite Preparation of Catalyst of example 1, different is that 30 gram DOSY molecular sieves are mixed with 70 gram MCM-22 molecular sieves, contains DOSY molecular sieve 30 quality % among the catalyst DOC-3 that makes, MCM-22 molecular sieve 70 quality %.
Example 4
Press the method Kaolinite Preparation of Catalyst of example 1, different is that (catalyst branch company in Chang Ling produces, and wherein contains Al with CDY
2O
321.7 quality %, SiO
258.0 quality %, lanthana 10.9 quality %, Na
2O 0.08 quality %) replaces DOSY, contain CDY molecular sieve 50 quality % among the catalyst DOC-4 that makes, MCM-22 molecular sieve 50 quality %.
Example 5
Press the method Kaolinite Preparation of Catalyst of example 1, different is that (the remarkable Chemical Industry Science Co., Ltd in Shanghai produces, and silica/alumina molar ratio is 30, contains Na with the MCM-56 molecular sieve
2O 0.04 quality %) replaces the MCM-22 molecular sieve, contain DOSY molecular sieve 50 quality % among the catalyst DOC-5 that makes, MCM-56 molecular sieve 50 quality %.
Example 6
Press the method Kaolinite Preparation of Catalyst of example 1, different is to add 50 gram aluminium hydrate powders (Sasol company productions in mixed molecular sieve, trade mark SB), contain the DOSY molecular sieve of 36.4 quality %, the MCM-22 molecular sieve of 36.4 quality % and the aluminium oxide of 27.2 quality % among the catalyst DOC-6 that makes.
Example 7
Press the method Kaolinite Preparation of Catalyst of example 1, different is adds 20 gram sepiolites in the mixed molecular sieve (Hunan swan goose sepiolite Co., Ltd produces, and wherein contains MgO 22.4 quality %, SiO
264.2 quality %, Al
2O
36.84 quality %) and 10 gram SB powder, contain the DOSY molecular sieve of 39.2 quality %, the MCM-22 molecular sieve of 39.2 quality %, the sepiolite of 15.7 quality % and the aluminium oxide of 5.9 quality % among the catalyst DOC-7 that makes.
Example 8
Press the method Kaolinite Preparation of Catalyst of example 1, different is to add 30 gram sepiolites in mixed molecular sieve, contains the DOSY molecular sieve of 38.5 quality %, the MCM-22 molecular sieve of 38.5 quality % and the sepiolite of 23 quality % among the catalyst DOC-8 that makes.
Example 9
Press the method Kaolinite Preparation of Catalyst of example 8, different is that the sepiolite that adds is 50 grams, contains the DOSY molecular sieve of 33.3 quality %, the MCM-22 molecular sieve of 33.3 quality % and the sepiolite of 33.4 quality % among the catalyst DOC-9 that makes.
Comparative Examples 1
Press the method Kaolinite Preparation of Catalyst of example 1, different is not add the DOSY molecular sieve, makes catalyst DB-1.
Comparative Examples 2
Press the method Kaolinite Preparation of Catalyst of example 1, different is not add the MCM-22 molecular sieve, makes catalyst DB-2.
Comparative Examples 3
Press the method Kaolinite Preparation of Catalyst of example 1, different is only to use CDY molecular sieve extruded moulding, makes catalyst DB-3.
Example 7～18
Following instance is estimated the deolefination performance of catalyst of the present invention.
On the 10mL reaction unit, the reformed oil of gram is estimated catalyst as raw material take bromine index as 2.6mgBr/100, and appreciation condition is: 170 ℃, when 1.5MPa, charging mass space velocity 12
-1, the results are shown in Table 1.
As shown in Table 1, catalyst of the present invention is than the comparative catalyst, and the bromine index of product is lower, and catalyst deactivation rate is slower, illustrates that catalyst of the present invention has higher activity and stable.
Example 19～30
On the 10mL reaction unit, the C of gram take bromine index as 440mgBr/100
8 +BTX aromatics is that raw material is estimated catalyst, and appreciation condition is: 200 ℃, when 1.5MPa, charging mass space velocity 20
-1, the results are shown in Table 2.
As shown in Table 2, catalyst of the present invention is than the comparative catalyst, and the bromine index increase of product is slower, illustrates that the deactivation rate of catalyst of the present invention is slower, has higher activity and stable.
Table 1
Table 2
Claims (10)
1. catalyst that removes alkene in the reformed arene, comprise the MCM Series Molecules sieve of 20～80 quality % and the modification REY molecular sieve of 20～80 quality %, described modification REY molecular sieve is DOSY or CDY, and described DOSY is phosphorous and REY amorphous silicon oxide, its
31In the P MAS NMR spectrum, chemical shift is that the ratio of peak area sum and total peak area at-15 ± 2ppm peak and-23 ± 2ppm peak is greater than 85%, described CDY is a kind of REY, wherein take the content of rare earth of rare earth oxide as 12～22 % by weight, rare earth ion all is positioned at the little cage of molecular sieve, and does not have non-framework aluminum.
2. according to catalyst claimed in claim 1, it is characterized in that described catalyst comprises the MCM Series Molecules sieve of 30～80 quality % and the modification REY molecular sieve of 20～70 quality %.
3. according to catalyst claimed in claim 1, it is characterized in that described catalyst comprises the MCM Series Molecules sieve of 30～60 quality %, the modification REY molecular sieve of 30～60 quality % and aluminium oxide and/or the sepiolite of 10～40 quality %.
4. according to catalyst claimed in claim 3, it is characterized in that the mass ratio of sepiolite and aluminium oxide is 0.1～10: 1 in the described catalyst.
5. according to described any one catalyst of claim 1～4, it is characterized in that described MCM Series Molecules screening is from MCM-22, MCM-36, MCM-49 or MCM-56.
6. the preparation method of the described catalyst of claim 1, comprise MCM Series Molecules sieve and modification REY molecular sieve are fully mixed rear adding sesbania powder and dilute acid soln kneading, or add carboxymethyl cellulose or methocel solution kneading, extruded moulding then, dry, roasting.
7. in accordance with the method for claim 6, it is characterized in that described acid is selected from nitric acid, acetic acid, citric acid or any both or three's mixture in them.
8. in accordance with the method for claim 6, it is characterized in that aluminium hydrate powder and/or sepiolite are added mixing in MCM Series Molecules sieve and the modification REY molecular sieve.
9. in accordance with the method for claim 6, the mass ratio that it is characterized in that other solid matter in described sesbania powder and the mixed system is 0.01～0.1: 1, and the mass ratio of solid matter is 0.1～0.5: 1 in dilute acid soln and the mixed system.
10. the mass ratio that in accordance with the method for claim 6, it is characterized in that solid matter in described cmc soln and the mixed system is 0.1～0.5: 1.
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| CN103007996B (en) * | 2011-09-28 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst for removing olefin in reformed oil and preparation method of catalyst |
| 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 |
| CN110813370B (en) * | 2019-10-29 | 2022-05-24 | 浙江工业大学 | Method for refining aromatic hydrocarbon by utilizing microporous mesoporous core-shell structure composite molecular sieve |
| CN114425427B (en) * | 2020-10-10 | 2023-08-04 | 中国石油化工股份有限公司 | Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030166453A1 (en) * | 2002-02-25 | 2003-09-04 | Kuvettu Mohan Prabhu | Stabilized dual zeolite single particle catalyst composition and a process thereof |
| CN1660496A (en) * | 2004-02-27 | 2005-08-31 | 中国石油化工股份有限公司 | REY molecular sieve containing phosphor and amorphous silica, preparation method and application |
| CN1733362A (en) * | 2004-08-13 | 2006-02-15 | 中国石油化工股份有限公司 | Rare earth Y molecular screen and process for preparing the same |
| CN101138740A (en) * | 2006-09-05 | 2008-03-12 | 北京盛大京泰化学研究所 | Cracking catalyst containing nanometer rare-earth oxide and method of preparing the same |
| CN101429452A (en) * | 2007-11-08 | 2009-05-13 | 中国石油天然气股份有限公司 | Method for producing high-octane gasoline |
-
2009
- 2009-11-19 CN CN 200910222394 patent/CN102069008B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030166453A1 (en) * | 2002-02-25 | 2003-09-04 | Kuvettu Mohan Prabhu | Stabilized dual zeolite single particle catalyst composition and a process thereof |
| CN1660496A (en) * | 2004-02-27 | 2005-08-31 | 中国石油化工股份有限公司 | REY molecular sieve containing phosphor and amorphous silica, preparation method and application |
| CN1733362A (en) * | 2004-08-13 | 2006-02-15 | 中国石油化工股份有限公司 | Rare earth Y molecular screen and process for preparing the same |
| CN101138740A (en) * | 2006-09-05 | 2008-03-12 | 北京盛大京泰化学研究所 | Cracking catalyst containing nanometer rare-earth oxide and method of preparing the same |
| CN101429452A (en) * | 2007-11-08 | 2009-05-13 | 中国石油天然气股份有限公司 | Method for producing high-octane gasoline |
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