CN1958739A - Aromatization catalyst, preparation method, and application - Google Patents
Aromatization catalyst, preparation method, and application Download PDFInfo
- Publication number
- CN1958739A CN1958739A CN 200510114493 CN200510114493A CN1958739A CN 1958739 A CN1958739 A CN 1958739A CN 200510114493 CN200510114493 CN 200510114493 CN 200510114493 A CN200510114493 A CN 200510114493A CN 1958739 A CN1958739 A CN 1958739A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- quality
- complex carrier
- family element
- zeolite
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention discloses an aromatization catalyst for C4-C12 hydrocarbons. The catalyst comprises oxide of VA group element 0.1-10.0 wt. % and composite carrier. The composite carrier is composed of MCM-22 zeolite 10-90 wt. % and Al2O3 10-90 wt. %. The catalyst can comprise a second modifying component Zn or Ga. The catalyst can be used for aromatization reaction with high aromatic hydrocarbon yield, and the gaseous products contain large amounts of ethylene and propylene.
Description
Technical field
The present invention is a kind of aromatized catalyst and method for making and application, specifically, is a kind of aromatizing catalyst for light hydrocarbon and preparation method, and uses this catalyzer to carry out light-hydrocarbon aromatized method.
Background technology
At present, the used active ingredient ZSM-5 zeolite of light dydrocarbon aromatization reaction catalyzer has aromizing performance preferably, and rich hydrogen producing when producing aromatic hydrocarbons is than non-zeolite catalysts, as Bi
2O
3-Al
2O
3, its stability also is greatly improved.Therefore, the application of this catalyzer in light-hydrocarbon aromatized technology more and more is subject to people's attention.But catalyzer still exists coking deactivation very fast, and one way running period short (generally having only several to tens hours) needs problems such as frequent regeneration.In order to realize the operation of continous-stable, the Cyclar process using moving-bed cyclic regeneration technology of UOP and the exploitation of BP company, cost of investment is higher.Simultaneously, the output of dry gas (being mainly methane and ethane) is big in the light-hydrocarbon aromatized product that use ZSM-5 zeolite catalyst obtains, and utility value is lower, has influenced the economy of this process.For this reason, people explore and use the active ingredient of other zeolite as aromatized catalyst.
CN1504409A discloses a kind of ZSM-35/MCM-22 cocrystallization molecular sieve and preparation method thereof, and this molecular sieve mixes with aluminum oxide, and the catalyzer that makes of carrying metal is used for the aromizing and the isomerization of catalytically cracked gasoline again.250 ℃, 0.8MPa, charging air speed 3.0 hours
-1, hydrogen/oil volume is than being to react under 200 the condition, the olefin(e) centent of reaction back catalytically cracked gasoline reduces 11.63%, aromaticity content increases by 11.88%.
It is the catalyst activity component that Song Yueqin etc. (" petrochemical complex " 2004 the 33rd volumes supplementary issue P405～407) in " research of liquefied gas low temperature aromizing performance on MCM-22 and ZSM-23 molecular sieve " literary composition adopt Hydrogen MCM-22 and ZSM-23 molecular sieve respectively, with the liquefied gas is that raw material carries out aromatization, the result shows that MCM-22 has better low temperature butylene aromizing performance than ZSM-23, and helps the generation of macromole aromatic hydrocarbons.350 ℃, 0.5MPa, weight space velocity 2 hours
-1Condition under, be that 50% liquefied gas is that raw material carries out aromatization with butylene concentration, aromatics yield is not more than 30% in the product.
USP4,982,033 disclose and a kind of light aliphatic hydrocarbon have been converted into the process of aromatic hydrocarbons, are the catalyst activity component with the MCM-22 zeolite, with C
2～C
12Aliphatic hydrocarbon is converted into aromatic hydrocarbons, and optionally produces low-carbon alkene.538 ℃ is that raw material reacts with the reforming raffinate oil, aromatics yield less than 20%, propene yield about 7%.
N.Kumar etc. disclose a kind of MCM-22 zeolite of Ga/Zn modification in " Applied Catalyst A:Genaral " 1996 the 147th volumes the 1st phase P175～187, this modified zeolite has higher aromatization activity and arenes selectivity to butane.
Summary of the invention
The purpose of this invention is to provide a kind of aromatizing catalyst for light hydrocarbon and preparation method thereof, this catalyzer method for making is simple, and the dry gas amount is low in the reaction product, can obtain more ethene and propylene, and the aromatics yield height.
Another object of the present invention provides uses catalyzer of the present invention to carry out light-hydrocarbon aromatized method.
C provided by the invention
4～C
12Hydrocarbon aromatization catalyst comprises the oxide compound and the complex carrier of the VA family element of 0.1～10.0 quality %, and described complex carrier is made up of the MCM-22 zeolite of 10～90 quality % and the aluminum oxide of 10～90 quality %.
It is active ingredient that catalyzer of the present invention adopts the MCM-22 zeolite, and with VA family element it is carried out modification, and the catalyzer that makes has higher ethene and propene yield under higher aromatics yield, thereby has improved the utility value of light dydrocarbon aromatization reaction.Above-mentioned catalyzer adds second kind of modifying element zinc or gallium, can further improve its aromizing performance.
Embodiment
The present invention to the MCM-22 zeolite be active ingredient catalyzer with VA family element modified, in this modified catalyst, add second modified metal zinc or the gallium again, when the output of ethene and propylene improves in making light-hydrocarbon aromatized product, further improved aromatics yield.
Except that VA family element oxide, also can further contain the oxide compound of zinc or gallium in the catalyzer of the present invention, its content is 0.1～5.0 quality %.
Preferred 0.5～7.0 quality % of the content of VA family element oxide in the catalyzer of the present invention, when containing the oxide compound of zinc or gallium, preferred 0.5～3.0 quality % of the content of zinc or gallium oxide.
Complex carrier in the described catalyzer preferably is made up of the MCM-22 zeolite of 30～80 quality % and the aluminum oxide of 20～70 quality %.The mol ratio of the silica of the MCM-22 zeolite in the complex carrier is 10～100, and is preferred 20～40, the preferred gama-alumina of the aluminum oxide in the carrier.
The preferred phosphorus of VA family element, antimony or the bismuth that are used for modification in the described catalyzer.Be suitable for the preferred C of hydro carbons that catalyzer of the present invention carries out aromizing
4～C
8Straight chain hydrocarbon or cyclic hydrocarbon.
Preparation of catalysts method of the present invention comprises HMCM-22 zeolite and hydrated aluminum oxide mixing aftershaping are made complex carrier, then with the soluble compound solution impregnation complex carrier that contains VA family element, dry roasting.After comparatively preferably will complex carrier drying with the soluble compound solution impregnation that contains VA family element, again with the soluble salt solution impregnation of zinc or gallium, dry roasting.Gu liquid during dipping/than being 0.6～1.5 milliliter/gram, dipping temperature is 20～40 ℃.The preferred pseudo-boehmite of described hydrated aluminum oxide.
The preferred extruded moulding of the forming method of described complex carrier, the extrusion method is: with the HMCM-22 zeolite with after hydrated aluminum oxide mixes, the dilute nitric acid solution that adds suitable quantity of water and concentration and be 1～3 quality % is mediated to even, extruded moulding then, 100～120 ℃ of dryings, 500～700 ℃ of roastings promptly get complex carrier.Preferred 2～8 hours of the time of described drying and roasting.
Be to improve selectivity of catalyst of the present invention, stability and regenerability, preferably with gained complex carrier after the roasting at 400～700 ℃, be preferably 500～600 ℃ and carry out hydrothermal treatment consists, the mass space velocity that water contacts with carrier during processing is 0.5～2.5 hour
-1, preferred 1～8 hour of hydrothermal treatment consists time.And then, make catalyzer in the complex carrier after preferred VA family element and zinc or the gallium introducing hydrothermal treatment consists with VA family element.
The soluble compound of the described VA of preparation steeping fluid family element is selected from the nitrate or the acetate of phosphoric acid salt, phosphite, phosphoric acid, phosphorous acid, metaphosphoric acid, tetra-sodium, phosphorus trichloride, antimony or bismuth among the above-mentioned preparation method.The soluble salt of described zinc or gallium is selected from its nitrate, acetate or vitriol.
C provided by the invention
4～C
12The aromatization of hydrocarbons method comprises described hydro carbons at 400～600 ℃, preferred 540～580 ℃, under 0.1～1.0MPa, the preferred 0.1～0.5MPa condition with catalyzer contact reacts of the present invention.The suitable lighter hydrocarbons charging mass space velocity of reaction is 0.2～12.0 hour
-1, preferred 0.7～2.0 hour
-1Described aromatization reactor can adopt reactors such as fixed bed, moving-bed, riser tube.
Suitable the inventive method is carried out the preferred C of hydro carbons of aromizing
4～C
8Straight chain hydrocarbon or cyclic hydrocarbon, hydro carbons preferably is selected from liquefied petroleum gas (LPG), mixed C
4, low-pressure gas, petroleum naphtha, condensate oil or pyrolysis gasoline.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare catalyzer of the present invention.
(1) preparation complex carrier: get SiO
2/ Al
2O
3Mol ratio is 30 HMCM-22 zeolite powder 65 grams, 35 gram pseudo-boehmite powder (the PURAL SB that German sasol company produces) mix, adding 45 ml waters and 2 ml concns is the salpeter solution mixing of 1.0 quality %, mix and pinch even back extruded moulding, 110 ℃ of dryings 4 hours, 550 ℃ of roastings 4 hours were carried out hydrothermal treatment consists 4 hours in 500 ℃ then, and the feedwater quality air speed is 1.5 hours
-1, make complex carrier.
(2) preparation catalyzer
Getting (1) step carrier that makes 100 grams, is that the phosphoric acid solution of 10 mg/ml flooded 1 hour with 100 ml concns, 110 ℃ of dryings 4 hours, and 550 ℃ of roastings 4 hours make catalyst B, and its composition sees Table 1.
Example 2
Method by example 1 prepares catalyzer, and different is that the used phosphoric acid concentration of (2) step impregnated carrier is 80 mg/ml, and the composition of the catalyzer C that makes sees Table 1.
Example 3
Method by example 1 prepares catalyzer, is the solution replacement phosphoric acid of 20 mg/ml nitric acid antimony with concentration in different is (2) step, and the composition that makes catalyzer D sees Table 1.
Example 4
Method by example 1 prepares catalyzer, is the solution replacement phosphoric acid of 20 mg/ml bismuth acetates with concentration in different is (2) step, and the composition that makes catalyzer E sees Table 1.
Example 5
Method by example 1 prepares catalyzer, and different is that the used HMCM-22 zeolite powder of preparation carrier is 40 grams in (1) step, and the pseudo-boehmite powder is 60 grams, and the composition of the catalyzer F that makes sees Table 1.
Example 6
Method by example 1 prepares catalyzer, and different is is the phosphoric acid solution impregnated carrier of 10 mg/ml with 100 ml concns earlier in (2) step, and 110 ℃ of dryings are the Zn (NO of 40 mg/ml with 100 ml concns again after 4 hours
3)
2Solution impregnation 1 hour, 110 ℃ of dryings are 4 hours then, 550 ℃ of roastings 4 hours, the composition of the catalyzer G that makes sees Table 1.
Example 7
Method by example 1 prepares catalyzer, and different is is the phosphoric acid solution impregnated carrier of 10 mg/ml with 100 ml concns earlier in (2) step, and 110 ℃ of dryings are the Ga of 20 mg/ml with 100 ml concns again after 4 hours
2(SO
4)
3Solution impregnation 1 hour, 110 ℃ of dryings are 4 hours then, 550 ℃ of roastings 4 hours, the composition of the catalyzer H that makes sees Table 1.
Example 8
Method by example 1 prepares catalyzer, and different is that the used HMCM-22 zeolite powder of preparation carrier is 40 grams in (1) step, and the pseudo-boehmite powder is 60 grams; (2) be the phosphoric acid solution impregnated carrier of 10 mg/ml with 100 ml concns earlier in the step, 110 ℃ of dryings are the Zn (NO of 40 mg/ml with 100 ml concns again after 4 hours
3)
2Solution impregnation 1 hour, 110 ℃ of dryings are 4 hours then, 550 ℃ of roastings 4 hours, the composition of the catalyst I that makes sees Table 1.
Comparative Examples 1
Complex carrier with example 1 (1) step preparation is catalyzer K, and its composition sees Table 1.
Comparative Examples 2
Method by example 1 prepares catalyzer, and different is that carrier is the Zn (NO of 40 mg/ml with 100 ml concns in (2) step
3)
2Solution impregnation 1 hour, 110 ℃ of dryings are 4 hours then, 550 ℃ of roastings 4 hours, the composition of the catalyzer M that makes sees Table 1.
Comparative Examples 3
Method by example 1 prepares catalyzer, and different is that carrier is the Ga of 20 mg/ml with 100 ml concns in (2) step
2(SO
4)
3Solution impregnation 1 hour, 110 ℃ of dryings are 4 hours then, 550 ℃ of roastings 4 hours, the composition of the catalyst n that makes sees Table 1.
Example 9
With mixed C
4Be raw material, the reactivity worth of catalyzer of the present invention is estimated.The evaluation response condition is: 550 ℃, 0.3MPa, raw materials quality air speed 1.0 hours
-1, the reaction times is 30 hours.Mixed C
4Composition sees Table 2, and evaluation result sees Table 3.
As shown in Table 3, with the catalyst B～F of the VA element P of family, Sb or Bi modification, than unmodified MCM-22 catalyzer K, ethene, productivity of propylene in light-hydrocarbon aromatized increase among the present invention.In addition, on the family element modified basis of VA, add catalyzer G～I of the present invention that modified metal zinc or gallium make again, than simple comparative catalyst M, N with zinc or gallium modification, in the higher ethene of maintenance, productivity of propylene, aromatics yield increases to some extent, and hydrogen yield also increases.
Example 10
The test of catalyzer aromatization.
With the petroleum naphtha was raw material, and its composition sees Table 4,550 ℃, 0.3MPa, naphtha feed mass space velocity 1.0 hours
-1Reaction conditions under catalyzer G is carried out light dydrocarbon aromatization reaction test, the reaction times is 30 hours, the results are shown in Table 5.
As shown in Table 5, the catalyzer of the present invention that makes with phosphorus and zinc modification MCM-22 is used for the naphtha aromtization reaction, when aromatics yield reached 30.02 quality %, ethene, propene yield were also higher, illustrated that catalyzer of the present invention is equally applicable to have the aromizing of higher carbon number light hydrocarbon feedstocks.
Table 1
| Instance number | The catalyzer numbering | Carrier is formed, quality % | Catalyzer is formed, quality % | |||
| MCM-22 | Aluminum oxide | Carrier | VA family element oxide | The Zn/Ga oxide compound | ||
| 1 | B | 70 | 30 | 99.28 | P 2O 5 0.72 | - |
| 2 | C | 70 | 30 | 94.20 | P 2O 5 5.80 | - |
| 3 | D | 70 | 30 | 98.95 | Sb 2O 5 1.05 | - |
| 4 | E | 70 | 30 | 98.70 | Bi 2O 5 1.30 | - |
| 5 | F | 44 | 56 | 99.28 | P 2O 5 0.72 | - |
| 6 | G | 70 | 30 | 97.57 | P 2O 5 0.72 | ZnO 1.71 |
| 7 | H | 70 | 30 | 98.40 | P 2O 5 0.72 | Ga 2O 3 0.88 |
| 8 | I | 44 | 56 | 97.57 | P 2O 5 0.72 | ZnO 1.71 |
| Comparative Examples 1 | K | 70 | 30 | 100.00 | - | - |
| Comparative Examples 2 | M | 70 | 30 | 98.29 | - | ZnO 1.71 |
| Comparative Examples 3 | N | 70 | 30 | 99.12 | - | Ga 2O 3 0.88 |
Table 2
| Mixed c 4 fraction hydrocarbon content | Quality % |
| Propane propylene butane butene-1 isobutene butene-2 pentane 1,3-butadiene amylene | 0.88 0.27 25.04 15.91 24.72 32.14 0.24 0.41 0.39 |
| Add up to | 100.00 |
Table 3
| The catalyzer numbering | B | C | D | E | F | G | H | I | K | M | N | |
| Butene conversion, quality % | 90.15 | 88.14 | 89.24 | 90.22 | 87.64 | 89.49 | 92.12 | 88.26 | 90.77 | 89.25 | 91.02 | |
| Product yield, quality % | H 2 C 2 ＝ C 3 ＝Gas liquid aromatic hydrocarbons | 0.23 3.87 10.24 6.30 93.70 22.28 | 0.21 3.71 11.26 6.32 93.68 22.83 | 0.34 3.69 11.13 6.49 93.51 22.31 | 0.37 3.82 10.98 6.12 93.88 22.67 | 0.19 3.80 9.69 5.98 94.02 21.50 | 0.82 3.40 10.91 8.04 91.96 24.46 | 1.10 3.62 11.13 7.64 92.36 24.89 | 0.30 3.87 10.30 6.56 93.44 22.67 | 0.42 3.33 8.25 5.87 94.13 22.98 | 0.48 2.68 7.69 7.66 92.34 21.67 | 0.54 2.71 8.02 7.01 92.99 21.81 |
Table 4
| The petroleum naphtha hydrocarbon content, quality % | Alkane | Naphthenic hydrocarbon | Aromatic hydrocarbons | Add up to |
| C 5 C 6 C 7 C 8 C 9 C 10 C 11 | 0.37 10.10 12.18 12.72 10.82 4.64 0.27 | 0.49 7.00 12.65 10.62 9.48 1.72 0.00 | 0.00 0.32 1.22 2.72 2.51 0.17 0.00 | 0.86 17.42 26.05 26.06 22.81 6.53 0.27 |
| Amount to | 51.10 | 41.96 | 6.94 | 100.00 |
Table 5
| Reaction product | Yield, quality % |
| H 2 C 2 ＝ C 3 ＝Gas liquid aromatic hydrocarbons | 0.50 2.55 6.29 6.22 93.78 30.02 |
Claims (16)
1, a kind of C
4～C
12Hydrocarbon aromatization catalyst comprises the oxide compound and the complex carrier of the VA family element of 0.1～10.0 quality %, and described complex carrier is made up of the MCM-22 zeolite of 10～90 quality % and the aluminum oxide of 10～90 quality %.
2,, it is characterized in that also containing in the described catalyzer zinc of 0.1～5.0 quality % or the oxide compound of gallium according to the described catalyzer of claim 1.
3, according to the described catalyzer of claim 1, the content that it is characterized in that the oxide compound of VA family element in the described catalyzer is 0.5～7.0 quality %.
4, according to the described catalyzer of claim 2, the content that it is characterized in that zinc or gallium oxide is 0.5～3.0 quality %.
5,, it is characterized in that described complex carrier is made up of the MCM-22 zeolite of 30～80 quality % and the aluminum oxide of 20～70 quality % according to claim 1 or 2 described catalyzer.
6,, it is characterized in that described VA family element is phosphorus, antimony or bismuth according to claim 1 or 2 described catalyzer.
7, according to claim 1 or 2 described catalyzer, the mol ratio that it is characterized in that silica in the described MCM-22 zeolite is 10～100.
8, according to claim 1 or 2 described catalyzer, it is characterized in that described aluminum oxide is a gama-alumina, described hydro carbons is C
4～C
8Straight chain hydrocarbon or cyclic hydrocarbon.
9, the described Preparation of catalysts method of a kind of claim 1 comprises HMCM-22 zeolite and hydrated aluminum oxide mixing aftershaping are made complex carrier, then with the soluble compound solution impregnation complex carrier that contains VA family element, dry roasting.
10, in accordance with the method for claim 9, it is characterized in that with after the complex carrier drying of soluble compound solution impregnation that contains VA family element, again with the soluble salt solution impregnation of zinc or gallium, dry roasting.
11, according to claim 9 or 10 described methods, it is characterized in that the complex carrier after the roasting is carried out hydrothermal treatment consists at 400～700 ℃, the mass space velocity that water contacts with carrier during processing is 0.5～2.5 hour-1.
12,, it is characterized in that the soluble compound of VA family element is selected from the nitrate or the acetate of phosphoric acid salt, phosphite, phosphoric acid, phosphorous acid, metaphosphoric acid, tetra-sodium, phosphorus trichloride, antimony or bismuth according to claim 9 or 10 described methods.
13, in accordance with the method for claim 10, the soluble salt that it is characterized in that described zinc or gallium is selected from its nitrate, acetate or vitriol.
14, a kind of C
4～C
12The aromatization of hydrocarbons method, comprise with described hydro carbons under 400～600 ℃, 0.1～1.0MPa condition with the described catalyzer contact reacts of claim 1.
15, in accordance with the method for claim 14, it is characterized in that described hydro carbons is C
4～C
8Straight chain hydrocarbon or cyclic hydrocarbon.
16, in accordance with the method for claim 14, it is characterized in that described hydro carbons is selected from liquefied petroleum gas (LPG), mixed C
4, low-pressure gas, petroleum naphtha, condensate oil or pyrolysis gasoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101144932A CN100395314C (en) | 2005-10-31 | 2005-10-31 | Aromatization catalyst, preparation method, and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101144932A CN100395314C (en) | 2005-10-31 | 2005-10-31 | Aromatization catalyst, preparation method, and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1958739A true CN1958739A (en) | 2007-05-09 |
| CN100395314C CN100395314C (en) | 2008-06-18 |
Family
ID=38070597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101144932A Active CN100395314C (en) | 2005-10-31 | 2005-10-31 | Aromatization catalyst, preparation method, and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100395314C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596461B (en) * | 2008-06-02 | 2011-07-20 | 中国石油化工股份有限公司 | Light-hydrocarbon aromatized catalyst and preparation method thereof |
| CN102233274A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof |
| CN101538184B (en) * | 2008-03-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for aromatizing light hydrocarbons |
| CN102950017A (en) * | 2011-08-26 | 2013-03-06 | 中国石油化工股份有限公司 | Catalyst for producing gasoline by refinery dry gas and preparation method thereof |
| CN107573966A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | A kind of method that high octane gasoline component is produced by F- T synthesis naphtha |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4982033A (en) * | 1988-10-06 | 1991-01-01 | Mobil Oil Corp. | Process for converting light aliphatics to aromatics |
| CN1100124C (en) * | 2000-08-30 | 2003-01-29 | 中国石油化工股份有限公司 | Aromatizing catalyst for light hydrocarbon and its preparing process |
| CN1254435C (en) * | 2002-11-29 | 2006-05-03 | 中国石油天然气股份有限公司 | ZSM-35/MCM-22 cocrystallization molecular sieve and preparation method thereof |
-
2005
- 2005-10-31 CN CNB2005101144932A patent/CN100395314C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538184B (en) * | 2008-03-20 | 2012-07-25 | 中国石油化工股份有限公司 | Method for aromatizing light hydrocarbons |
| CN101596461B (en) * | 2008-06-02 | 2011-07-20 | 中国石油化工股份有限公司 | Light-hydrocarbon aromatized catalyst and preparation method thereof |
| CN102233274A (en) * | 2010-04-28 | 2011-11-09 | 中国石油化工股份有限公司 | Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof |
| CN102950017A (en) * | 2011-08-26 | 2013-03-06 | 中国石油化工股份有限公司 | Catalyst for producing gasoline by refinery dry gas and preparation method thereof |
| CN102950017B (en) * | 2011-08-26 | 2016-03-02 | 中国石油化工股份有限公司 | Oil refinery dry gas is utilized to produce the Catalysts and its preparation method of gasoline |
| CN107573966A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | A kind of method that high octane gasoline component is produced by F- T synthesis naphtha |
| CN107573966B (en) * | 2016-07-05 | 2020-03-24 | 中国石油化工股份有限公司 | Method for producing high-octane gasoline component from Fischer-Tropsch synthesis naphtha |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100395314C (en) | 2008-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1217892C (en) | Process for producing aromatic hydrocarbon compounds and liquefied petroleum gas from hydrocarbon feedstock | |
| CN1915923A (en) | Method for preparing propylene through catalytic cracking C4-C12 olefin | |
| CN1990104A (en) | Molecular sieve catalyst, preparing method and use thereof | |
| CN1955255A (en) | Petroleum hydrocarbon catalytic pyrolysis catalyst and its application | |
| CN1958739A (en) | Aromatization catalyst, preparation method, and application | |
| CN103058814B (en) | Method for producing aromatic hydrocarbon and olefin from liquefied gas | |
| CN1087654C (en) | Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof | |
| CN1940023A (en) | Deep pyrolytic catalyst of heavy oil | |
| CN1218783C (en) | Catalyzer for preparing olefine in low carbon number through catalytic cracking and its preparing method and application | |
| CN1261535C (en) | Method for preparing gasoline with low content of olefin by modifying direct distillation gasoline | |
| CN1915931A (en) | Method for producing propylene from methanol or dimethyl ether | |
| CN1915934A (en) | Method for producing propylene | |
| CN1915937A (en) | Method for producing propylene, ethene in hihg yield | |
| CN100368359C (en) | Production system for increasing production of propylene | |
| CN1234806C (en) | Catalytic pyrolysis process for producing petroleum hydrocarbon of ethylene and propylene | |
| CN104109071B (en) | The method of cracked C 5 fraction propylene | |
| CN101033166A (en) | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above | |
| CN1915935A (en) | Method for raising selectivity of propylene | |
| CN1205154C (en) | Method of increasing propylene product and reducing olefine content in gasoline using C4 distillation | |
| CN1915924A (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN1189433C (en) | Method for preparing ethene and propylene | |
| CN112642466B (en) | Butane aromatization catalyst and preparation method and application thereof | |
| CN1212372C (en) | Catalytic conversion method using C4 fraction to increase small molecule olefine hydrocarbon yield | |
| CN112646598A (en) | Method for converting low-carbon alkane into aromatic hydrocarbon | |
| CN1464035A (en) | Process for producing gasoline from low-carbon hydrocarbon containing olefin as raw material |
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 |