CN108031487A - A kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline - Google Patents
A kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline Download PDFInfo
- Publication number
- CN108031487A CN108031487A CN201711171439.0A CN201711171439A CN108031487A CN 108031487 A CN108031487 A CN 108031487A CN 201711171439 A CN201711171439 A CN 201711171439A CN 108031487 A CN108031487 A CN 108031487A
- Authority
- CN
- China
- Prior art keywords
- preparation
- small
- catalyst
- gasoline
- sulfur
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline, step are as follows：(1) clay is beaten, and sequentially adds rare earth compound, vanadium-containing compound, when stirring 13 is small, filtering；(2) gained filter cake in step (1) is dried, roasted, 600 800 DEG C of temperature, when the time 0.5 2 is small；(3) by roasting material reslurry, grinding in (2), its average grain diameter≤5 μm is made；(4) boehmite is beaten, and adds zinc compound, is 2.5 4 with phosphoric acid to pH, 30 DEG C of controlling reaction temperature ＜, 10 30min of aging；(5) by (3) (4) slurries mix stirring 0.5 1 it is small when, sequentially add Aluminum sol, REY molecular sieves, be acidified；(6) by (5) acidified slurries mist projection granulating, the catalyst is made after roasting, washing, drying.The catalyst prepared with the method for the present invention, sulfur content in gasoline reduce 55.7%, 60.7% and 67.8% respectively, and positive effect, realizes the purpose of the present invention.
Description
Technical field
The present invention relates to a kind of preparation method for the catalytic cracking catalyst that content of sulfur in gasoline is reduced in catalytic cracking process.
Background technology
China's FCC gasoline accounts for more than the 70% of gasoline product total amount, and 90% sulphur comes from FCC gasoline in product oil, with
The execution of new unleaded gas standard, sulfur reduction becomes key.
At present, reducing content of sulfur in gasoline has a FCC feedstock pretreatment, during FCC using suitable catalyst or auxiliary agent,
The methods of FCC gasoline product post-processes.It is wherein simple and convenient using sulfur-lowing catalyst, it is not necessary to which that additional investment establishes device, no
Influence product distribution and quality, economical and effective.Presently mainly add the elements such as vanadium, zinc.
CN1597850A, which describes the introducing Zn-ef ficiency in NaY modifying process, can reduce content of sulfur in gasoline to a certain degree, but
Activated centre aluminium oxide is easily lost in.
US5376608 is to load zinc oxide on the alumina support, forms gahnite, but results of industrial application is not
Substantially.
CN1974726 describes to contain in terms of vanadic anhydride in the particle shape vanadium oxide of 0.3-3wt% in microballoon,
And add that antimony is in combination, but the toxicity of antimony is too big.
The vanadium that US6482315 loads 5-10wt% on inorganic oxide can reduce more than S35 %, but vanadium is unlocked,
Vanadic acid is formed under thermal and hydric environment, saboteur's sieve, reduces catalyst activity.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of catalytic cracking catalyst for reducing content of sulfur in gasoline
Preparation method：
A kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline, it is characterised in that preparation process is as follows：
(1) clay is beaten, and sequentially adds rare earth compound, vanadium-containing compound, when stirring 1-3 is small, filtering；
(2) gained filter cake in step (1) is dried, roasted, 600-800 DEG C of temperature, when time 0.5-2 is small；
(3) by roasting material reslurry, grinding in (2), its average grain diameter≤5 μm is made；
(4) boehmite is beaten, and is added zinc compound, is 2.5-4, controlling reaction temperature ＜ with phosphoric acid to pH
30 DEG C, aging 10-30min；
(5) by (3) (4) slurries mix stirring 0.5-1 it is small when, sequentially add Aluminum sol, REY molecular sieves, be acidified；
(6) by (5) acidified slurries mist projection granulating, the catalyst is made after roasting, washing, drying.
One or more of the clay in kaolin, galapectite, sepiolite in step (1).
Rare earth compound in step (1) is selected from LaCl3、CeCl2、YCl3、La2(CO3)2One or both of, add
Ratio is with RE2O3Meter accounts for the 1-5% of total catalyst weight.
One or more of the vanadium-containing compound in ammonium metavanadate, vanadic sulfate, vanadyl oxalate in step (1), add
Enter ratio with V2O5Meter accounts for the 1-5% of total catalyst weight.
One or more of the zinc compound in zinc nitrate, zinc chloride, zinc sulfate in step (4), additional proportion
The 0.5-3% of total catalyst weight is accounted in terms of ZnO.
The additional proportion of boehmite in step (4) is with Al2O3Meter accounts for the 10-20% of total catalyst weight.
Aluminum sol additional proportion in step (5) is with Al2O3Meter accounts for the 6-10% of total catalyst weight.
REY additional proportions in step (5) are the 30-40wt% for accounting for total catalyst weight.
The catalytic cracking catalyst for the reduction content of sulfur in gasoline that the above method is prepared.
Embodiment
Analysis test assessment method used in the embodiment of the present invention and comparative example：
(1) chemical composition：Xray fluorescence spectrometer
(2) surface is compared：Nitrogen adsorption instrument
(3) performance evaluation：Evaluated using FFB small fixed flowing beds evaluating apparatus and urged using what the silica-alumina material was prepared into
The reactivity worth of fluidized cracking catalysts, catalyst inventory 180g, heavy oil air speed 20h-1。
Raw materials used specification in the embodiment of the present invention and comparative example：
(1) zinc nitrate：It is commercially available,
(2) rare earth chloride：It is commercially available,
(3) vanadyl oxalate：It is commercially available,
(4) vanadic sulfate：It is commercially available,
(5) 85% phosphoric acid：It is commercially available,
(5) REY molecular sieves：Qingdao Hui Cheng environmental protection Science and Technology Co., Ltd. produces, RE2O3=14wt%,
(5) it is commercially available to prepare the Aluminum sol used in catalyst, boehmite, kaolin.
The present invention is further illustrated for the following examples, but does not therefore limit the present invention.
Embodiment 1：
(1) 3.76 kilograms of kaolin are beaten, sequentially add 1.36 kilograms of re chlorides (with RE2O3Count 22wt%),
1.5L vanadyl oxalate solutions are (with V2O5Count 200g/L), when stirring 2 is small, filtering,
(2) gained filter cake in step (1) is dried, roasted, 600 DEG C of temperature, when the time 0.5 is small,
(3) by roasting material reslurry, grinding in (2), average grain diameter≤5 μm are made,
(4) 2.77 kilograms of boehmites are beaten, add 500ml zinc nitrate solutions (200g/L in terms of ZnO), use phosphoric acid
It is 2.5 to be acidified to pH,
(5) by (3) (4) slurries mix stirring 0.5 it is small when, sequentially add 3.63 kilograms of Aluminum sols, 3.89 kilograms
REY molecular sieves,
(6) it is spray-dried, the catalyst is made, marked as JL-1.
Embodiment 2：
(1) 3.41 kilograms of kaolin are beaten, sequentially add 1.82 kilograms of re chlorides (with RE2O3Count 22wt%),
2.0L vanadyl oxalate solutions are (with V2O5Count 200g/L), when stirring 2 is small, filtering,
(2) gained filter cake in step (1) is dried, roasted, 600 DEG C of temperature, when the time 0.5 is small,
(3) by roasting material reslurry, grinding in (2), average grain diameter≤5 μm are made,
(4) 2.77 kilograms of boehmites are beaten, add 1000ml zinc nitrate solutions (200g/L in terms of ZnO), use phosphorus
It is 2.5 that acid, which is acidified to pH,
(5) by (3) (4) slurries mix stirring 0.5 it is small when, sequentially add 3.63 kilograms of Aluminum sols, 3.89 kilograms
REY molecular sieves,
(6) it is spray-dried, the catalyst is made, marked as JL-2.
Embodiment 3：
(1) 3.06 kilograms of kaolin are beaten, sequentially add 2.27 kilograms of re chlorides (with RE2O3Count 22wt%),
2.5L vanadyl oxalate solutions are (with V2O5Count 200g/L), when stirring 2 is small, filtering,
(2) gained filter cake in step (1) is dried, roasted, 600 DEG C of temperature, when the time 0.5 is small,
(3) by roasting material reslurry, grinding in (2), average grain diameter≤5 μm are made,
(4) 2.77 kilograms of boehmites are beaten, add 1500ml zinc nitrate solutions (200g/L in terms of ZnO), use phosphorus
It is 2.5 that acid, which is acidified to pH,
(5) by (3) (4) slurries mix stirring 0.5 it is small when, sequentially add 3.63 kilograms of Aluminum sols, 3.89 kilograms
REY molecular sieves,
(6) it is spray-dried, the catalyst is made, marked as JL-3.
The analysis result of catalyst is as follows in example:
The analysis result of 1 catalyst of table
Catalyst aging：The catalyst of preparation is spare after hydro-thermal process 17h under 800 DEG C, 100% water vapor conditions.
Evaluating catalyst：The evaluation of catalyst carries out evaluation progress on FFB is fixed fluidized bed.Feedstock oil chooses certain refinery
Mixed material oil, feedstock property is shown in Table 2, and contrast medium is AIC-950 (production of Qingdao Hui Cheng environmental protection Science and Technology Co., Ltd.),
Reaction temperature is 510 DEG C, oil ratio 5.0, catalyst inventory 180g, air speed 20h-1, evaluation result is shown in Table 3.
2. raw material oil nature of table.
Table 3.FFB small fixed flowing bed evaluation results.
As can be seen from Table 3, the catalyst prepared with the method for the present invention, sulfur content in gasoline reduce 55.7% respectively,
60.7% and 67.8%, positive effect, realizes the purpose of the present invention.
Although the above-mentioned embodiment to the present invention is described, not to the limit of the scope of the present invention
System, those skilled in the art should understand that, on the basis of technical scheme, those skilled in the art need not pay
Go out various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (8)
1. a kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline, it is characterised in that preparation process is as follows：
(1) clay is beaten, and sequentially adds rare earth compound, vanadium-containing compound, when stirring 1-3 is small, filtering；
(2) gained filter cake in step (1) is dried, roasted, 600-800 DEG C of temperature, when time 0.5-2 is small；
(3) by roasting material reslurry, grinding in (2), its average grain diameter≤5 μm is made；
(4) boehmite is beaten, and is added zinc compound, is 2.5-4, controlling reaction temperature ＜ 30 with phosphoric acid to pH
DEG C, aging 10-30min；
(5) by (3) (4) slurries mix stirring 0.5-1 it is small when, sequentially add Aluminum sol, REY molecular sieves, be acidified；
(6) by (5) acidified slurries mist projection granulating, the catalyst is made after roasting, washing, drying.
2. preparation method according to claim 1, it is characterised in that clay in step (1) be selected from kaolin, galapectite,
One or more in sepiolite.
3. preparation method according to claim 1, it is characterised in that the rare earth compound in step (1) is selected from LaCl3、
CeCl2、YCl3、La2(CO3)2One or both of, additional proportion is with RE2O3Meter accounts for the 1-5% of total catalyst weight.
4. preparation method according to claim 1, it is characterised in that the vanadium-containing compound in step (1) is selected from metavanadic acid
One or more in ammonium, vanadic sulfate, vanadyl oxalate, additional proportion is with V2O5Meter accounts for the 1-5% of total catalyst weight.
5. preparation method according to claim 1, it is characterised in that zinc compound in step (4) be selected from zinc nitrate,
One or more in zinc chloride, zinc sulfate, additional proportion account for the 0.5-3% of total catalyst weight in terms of ZnO.
6. preparation method according to claim 1, it is characterised in that the additional proportion of the boehmite in step (4) with
Al2O3Meter accounts for the 10-20% of total catalyst weight.
7. preparation method according to claim 1, it is characterised in that the Aluminum sol additional proportion in step (5) is with Al2O3Meter
Account for the 6-10% of total catalyst weight.
8. preparation method according to claim 1, it is characterised in that the REY additional proportions in step (5) are to account for catalyst
The 30-40wt% of gross weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711171439.0A CN108031487A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711171439.0A CN108031487A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108031487A true CN108031487A (en) | 2018-05-15 |
Family
ID=62093212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711171439.0A Pending CN108031487A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108031487A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108176A (en) * | 2019-06-21 | 2020-12-22 | 中国石油天然气股份有限公司 | Preparation method of catalyst for reducing sulfur content of catalytically cracked gasoline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485132A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and and the preparation thereof |
| JP2007160250A (en) * | 2005-12-15 | 2007-06-28 | Petroleum Energy Center | Method of manufacturing catalyst, catalytic cracking catalyst and method of producing low-sulfur catalytically-cracked gasoline |
| CN101822996A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Catalyst compound capable of reducing gasoline sulfur content and preparation method thereof |
| CN106925336A (en) * | 2017-05-08 | 2017-07-07 | 青岛惠城环保科技股份有限公司 | A kind of Resid Fcc Catalyst and preparation method thereof |
-
2017
- 2017-11-22 CN CN201711171439.0A patent/CN108031487A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1485132A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Sulfur transfer catalyst and and the preparation thereof |
| JP2007160250A (en) * | 2005-12-15 | 2007-06-28 | Petroleum Energy Center | Method of manufacturing catalyst, catalytic cracking catalyst and method of producing low-sulfur catalytically-cracked gasoline |
| CN101822996A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Catalyst compound capable of reducing gasoline sulfur content and preparation method thereof |
| CN106925336A (en) * | 2017-05-08 | 2017-07-07 | 青岛惠城环保科技股份有限公司 | A kind of Resid Fcc Catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 中国石油化工信息学会石油炼制分会编.: "《2001年石油炼制技术大会论文集》", 31 October 2001, 北京：中国石化出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112108176A (en) * | 2019-06-21 | 2020-12-22 | 中国石油天然气股份有限公司 | Preparation method of catalyst for reducing sulfur content of catalytically cracked gasoline |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104114273B (en) | Silica containing alumina support, catalyst prepared therefrom and its application method | |
| CN1957070A (en) | Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons | |
| CN104549475B (en) | Preparation method of FCC gasoline desulfurization agent composition | |
| CN101619231B (en) | Fuel oil adsorption desulfurization adsorbent and method for preparing same | |
| CN103028432B (en) | A kind of wear-resistant catalyst for heavy oil catalytic cracking for reducing content of sulfur in gasoline and preparation method thereof | |
| CN109304210A (en) | A kind of catalytic cracking catalyst preparation method of cracking wax tailings high-yield diesel oil | |
| CN107970961B (en) | Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method | |
| CN108031487A (en) | A kind of preparation method for the catalytic cracking catalyst for reducing content of sulfur in gasoline | |
| CN101670295B (en) | Preparation method of cracking catalyst | |
| CN109789392A (en) | Peptization for can fluidized catalyst aluminium oxide method | |
| CN105618116B (en) | A kind of preparation method of hydrocracking catalyst | |
| CN103789013A (en) | Metal chelating agent, preparation method and application thereof, and catalytic cracking method | |
| JP2007054753A (en) | Fluid catalytic cracking catalyst, its production method and production method of low-sulfur catalytic cracked gasoline | |
| CN105728031A (en) | Anti-heavy-metal catalytic cracking catalyst and preparation method | |
| CN106890675B (en) | Preparation method of rare earth-containing catalytic cracking catalyst | |
| CN114425399A (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| CN105854929B (en) | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN109692697B (en) | Macroporous kaolinite and preparation and application thereof | |
| CN1879960A (en) | Heavy metal resistant catalytic cracking adjuvant and process for preparing same | |
| CN109465005B (en) | Sulfur transfer catalyst and preparation method thereof | |
| CN106925336A (en) | A kind of Resid Fcc Catalyst and preparation method thereof | |
| CN114345292A (en) | Sulfur transfer agent with strong base site and preparation method thereof | |
| CN109894121B (en) | Preparation method of catalyst for preparing 1, 3-butadiene from butylene | |
| CN1312255C (en) | Process for preparing cracking catalyst for hydrocarbons containing molecular sieves | |
| CN109692676B (en) | Macroporous kaolinite and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180515 |
|
| WD01 | Invention patent application deemed withdrawn after publication |