CN1027739C - Hydrocarbon cracking catalyzer composite containing vanadium fixing agent - Google Patents
Hydrocarbon cracking catalyzer composite containing vanadium fixing agent Download PDFInfo
- Publication number
- CN1027739C CN1027739C CN 91103763 CN91103763A CN1027739C CN 1027739 C CN1027739 C CN 1027739C CN 91103763 CN91103763 CN 91103763 CN 91103763 A CN91103763 A CN 91103763A CN 1027739 C CN1027739 C CN 1027739C
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- China
- Prior art keywords
- vanadium
- fixing agent
- zeolite
- heavy
- cracking catalyst
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Abstract
The present invention relates to a hydrocarbon cracking catalyst composition containing granules of a vanadium fixing agent, which is prepared from 95 to 60 wt% (preferably 90 to 70 wt%) of semisynthetic or completely synthetic cracking catalyst granules and 5 to 40 wt% (preferably 10 to 30 wt%) of granules of a vanadium fixing agent, wherein the vanadium fixing agent is prepared from 0.1 to 20 wt% (preferably 1 to 10 wt%) (by using the weight of the vanadium fixing agent as the reference) of alkaline earth metal elements and/or rare earth metal elements and a surplus amount of aluminum oxide. The catalyst composition has favorable vanadium pollution resisting capability.
Description
The present invention relates to a kind of vanadium fixing agent particulate hydrocarbon cracking catalyzer composite that contains.
In the catalytic cracking of hydrocarbon process, organic vanadium compounds and organic nickel compound in the stock oil can be deposited on the catalyzer, when these catalyzer are transported to RS Regenerator Section regeneration, in the presence of high temperature and water vapor, organic vanadium compounds can change into vanadic acid and move in catalyzer zeolite structured, destroy its skeleton structure, cause catalyst activity reduction.In order to address the above problem, be reported in the stanniferous liquid passivator of adding in the stock oil, deposit to (Oil﹠amp on the catalyzer to stop the organic vanadium compounds in the stock oil; Gas J., 1984,82(29), 127); Among USP 4228036 and the USP 4222896 is to use Al
2O
3-AlPO
4-SiO
2Or MgO-Al
2O
3-AlPO
4As the matrix of catalyzer to improve the anti-vanadium ability of catalyzer; Also have in addition among the CN 85109687A phosphorus-containing alumina particle and zeolite mixed with carrier and prepare catalyzer; Catalyzer adopts kaolin and white clouds masonry carrier among the USP 4707461; Use aluminum oxide and rare earth oxide as carrier among the EP 350280; Adopt aforesaid method can passivating vanadium to the pollution of catalyzer, but when deposited a large amount of vanadium on the catalyzer, its inhibition effect is limited.The method of the high metal content stock oil of a kind of cracking has been proposed among the USP 4650564, wherein adopted the catalyst composition (both ratios are 50: 50～90: 10) that contains cracking catalyst and aluminum oxide thinner, this method can be according to the difference increase and decrease thinner of content of vanadium in the stock oil, compare with the front several method, comparatively flexible in the use.
On the prior art basis, the object of the present invention is to provide a kind of cracking catalyst composition with good inhibition pollution of vanadium performance.
Cracking catalyst composition provided by the invention is by 95～60 heavy %, preferably the semi-synthetic or complete synthesis cracking catalyst particle of 90～70 heavy % and 5～40 weighs %, the vanadium fixing agent granulometric composition of 10～30 heavy % preferably, wherein vanadium fixing agent is by 0.1～20 heavy %, and preferably 1～10 heavy %(is a benchmark with vanadium fixing agent weight) alkali earth metal and/or thulium and surplus aluminum oxide form.
Described semi-synthetic or complete synthesis cracking catalyst is existing semi-synthetic or complete synthesis cracking catalyst; Semi-synthetic cracking catalyst can contain the zeolite activity component, one or more are selected from inorganic oxide in silicon oxide, aluminum oxide, magnesium oxide, silica-alumina, aluminum phosphate and the pure aluminium silicate and one or more and are selected from clay and/or crosslinked laminated clay in kaolin, halloysite, polynite and the sepiolite; Complete synthesis cracking catalyst can contain the zeolite activity component, one or more are selected from the inorganic oxide in silicon oxide, aluminum oxide, magnesium oxide, silica-alumina, aluminum phosphate and the pure aluminium silicate.
Said zeolite is X type zeolite, y-type zeolite, zeolite L, ZSM zeolite, mordenite, aluminum phosphate zeolite, silicon aluminium phosphate zeolite, y-type zeolite preferably, or the above-mentioned zeolite of handling through physics or chemical process, or the mixture of more than one above-mentioned zeolites, preferably be selected from the above-mentioned zeolite of the ion-exchange in hydrogen, ammonium and/or the rare earth plasma through one or more.
Cracking catalyst composition provided by the invention can be made by following method: the conventional preparation method by semi-synthetic or complete synthesis cracking catalyst prepares semi-synthetic or complete synthesis cracking catalyst particle earlier, pickling process routinely again, load 0.1～20 heavy % on alumina particle, preferably 1～10 heavy %(is a benchmark with vanadium fixing agent weight) alkali earth metal and/or thulium, 80～200 ℃ of dryings 2～24 hours, 300～800 ℃ of roastings 1～10 hour promptly get the vanadium fixing agent particle; By 95～60: 5～40, preferably 90～70: 10～30 ratio (weight ratio) mixes granules of catalyst and vanadium fixing agent particle, gets final product.
The preferably saturated pickling process of said pickling process.The size of said alumina particle and distribution and cracking catalyst particle are complementary.
Cracking catalyst composition of the present invention has good anti-vanadium ability, when content of vanadium is higher on the catalyzer, still can keep higher transformation efficiency and yield of gasoline, and the preparation method is simple, and raw material is easy to get.In the presence of high temperature and water vapor, vanadium fixing agent in the catalyst composition of the present invention can form a kind of solid metal salt with vanadium, vanadium is fixed, reduce it to zeolite structured destruction, thereby catalyst composition of the present invention allows higher vanadium capacity, is applicable to the catalytic cracking process of high vanadium raw materials oil, residual oil and heavy oil.
Below will the present invention is described further by embodiment.
Example 1
Get 100 gram γ-Al
2O
3(making in 2 hours through 550 ℃ of roastings) and calcium chloride solution (10.64 gram CaCl by pseudo-boehmite *
22H
2O is dissolved in 45 ml waters) mix, in 120 ℃ dry 4 hours down, 600 ℃ of roastings 1 hour promptly get calcic 2.07 weight % and surplus γ-Al
2O
3Vanadium fixing agent.
In 80: 20 ratios (weight ratio), ZCM-7 cracking catalyst (contain extremely steady y-type zeolite of rare earth, Qilu Petrochemical company catalyst plant is produced) is mixed with above-mentioned vanadium fixing agent, promptly get cracking catalyst composition provided by the invention, be designated as A.
* Shandong Aluminum Plant produces.
Example 2-3
Get 100 gram γ-Al
2O
3With 16 ml concns be that rare earth chloride (chemical plant, the Baotou) solution of 275 grams per liters mixes, in 100 ℃ dry 6 hours down, 600 ℃ of roastings 1 hour promptly get and contain rare earth 1.24 heavy % and surplus γ-Al
2O
3Vanadium fixing agent.
In 80: 20 ratios (weight ratio), (with the rare earth Y type zeolite is the semi-synthetic cracking catalyst of active ingredient with ZCM-7 cracking catalyst and CRC-1 catalyzer respectively, Qilu Petrochemical company catalyst plant is produced) mix with above-mentioned vanadium fixing agent, promptly get cracking catalyst composition provided by the invention, respectively be designated as B and C.
Example 4-5
18 gram re chlorides (concentration is 275 grams per liters) and 21 gram calcium chloride solutions (concentration is 33 heavy %) are mixed, add 50 gram γ-Al
2O
3, stir, in 110 ℃ dry 4 hours down, 600 ℃ of roastings 1 hour promptly get the vanadium fixing agent that contains rare earth 0.62 heavy % and calcium 4.86 heavy % and surplus aluminum oxide.
In the ratio (weight ratio) of 90: 10 and 80: 20, ZCM-7 cracking catalyst and above-mentioned vanadium fixing agent are mixed respectively, promptly get cracking catalyst composition provided by the invention, respectively be designated as D and E.
Example 6
Get 2.75 gram γ-Al
2O
3With 10 ml concns be that the magnesium chloride solution of 46.0 grams per liters mixes, in 120 ℃ dry 5 hours down, 550 ℃ of roastings 4 hours promptly get the vanadium fixing agent that contains magnesium 4.12 heavy % and surplus aluminum oxide.
In 85: 15 ratios (weight ratio), ZCM-7 cracking catalyst and above-mentioned vanadium fixing agent are mixed, promptly get cracking catalyst composition provided by the invention, be designated as F.
Example 7
Get 50 gram γ-Al
2O
3The calcium chloride solutions that add 32.8 gram concentration and be 33 heavy % mix, in 100 ℃ dry 4 hours down, 600 ℃ of roastings 1 hour promptly get the vanadium fixing agent that calcic 7.84 weighs % and surplus aluminum oxide.
In 90: 10 ratios (weight ratio), ZCM-7 cracking catalyst and above-mentioned vanadium fixing agent are mixed, promptly get cracking catalyst composition provided by the invention, be designated as G.
Example 8
Get 50 gram γ-Al
2O
3With 23 ml concns be that the re chloride of 275 grams per liters mixes, in 100 ℃ dry 6 hours down, 600 ℃ of roastings 1 hour promptly get the vanadium fixing agent that contains rare earth 3.59 heavy % and surplus aluminum oxide.
In 90: 10 ratios (weight ratio), ZCM-7 cracking catalyst and above-mentioned vanadium fixing agent are mixed, promptly get cracking catalyst composition provided by the invention, be designated as H.
Comparative Examples 1
With γ-Al
2O
3Be vanadium fixing agent,, ZCM-7 cracking catalyst and vanadium fixing agent mixed, promptly get and contrast cracking catalyst composition, be designated as contrast-1 in 80: 20 ratios (weight ratio).
Example 9
1. with reference to Mitchell's method (Ind.Eng.Chem., Prod.Res.Dev., 19,209,1980) with vanadium on the catalyst contamination: in 600 ℃ of following calcined catalysts 1 hour, with an amount of naphthenic acid vanadium solution impregnated catalyst, 100 ℃ dry 24 hours down, 600 ℃ of roastings 6 hours are to remove the whole organism on the catalyzer.
2, pollute catalyst A, B and contrast-1 as stated above, making its content of vanadium is that 0.3 heavy %(is benchmark with the catalyst weight); At 800 ℃, under the 100% water vapor condition, catalyzer was carried out burin-in process after 4 hours, evaluate catalysts reactivity worth on micro-reactor, reaction raw materials oil are 923 wax oils (proportion 0.8652, carbon residue 0.04 heavy %, 227～475 ℃ of boiling range scopes), reaction conditions is: 500 ℃ of temperature, agent-oil ratio 5, weight space velocity 16 hours
-1, catalyzer 4 grams.Reaction result sees Table 1.
Table 1
Catalyzer contrast-1 A B
Transformation efficiency, heavy % 64.67 68.52 68.95
Thing gas 19.21 18.33 16.88
Material
Coke 2.99 2.63 2.62
Flat
C
5～204℃ 42.47 47.56 49.46
Weighing apparatus,
204～303℃ 18.16 17.96 17.50
Heavy
% ＞330℃ 17.17 13.52 13.56
As seen from Table 1, under the identical situation of pollution of vanadium amount, compare with the comparative catalyst, high about 4 units of the transformation efficiency of catalyst A and B, gas recovery ratio is lower slightly, high 5～7 units of yield of gasoline; Illustrate that catalyst composition provided by the invention has good anti-vanadium ability.
Example 10
Pressing the method for example 9 pollutes and aging catalyst C, D, CRC-1 and ZCM-7, evaluate catalysts reactivity worth on micro-reactor, reaction raw materials oil are 641 solar oils (boiling range is 235～337 ℃), and reaction conditions is: 460 ℃ of temperature, agent-oil ratio 3.2, weight space velocity 16 hours
-1, 70 seconds reaction times, catalyzer loading amount 5.0 grams.Reaction result be the micro-activity of catalyzer C than high 5 units of CRC-1 catalyzer, the micro-activity of catalyzer D is than high 7 units of ZCM-7 catalyzer, visible catalyst composition provided by the invention has good anti-vanadium ability.
Example 11
Press the method for example 9 and pollute catalyzer E, F and ZCM-7, at 760 ℃, under the 100% water vapor condition, catalyzer was carried out burin-in process after 4 hours, evaluate catalysts reactivity worth on micro-reactor, reaction raw materials oil are 923 wax oils, and reaction conditions is: 500 ℃ of temperature, agent-oil ratio 6, weight space velocity 16 hours
-1, catalyzer 5 grams.Reaction result sees Table 2.
Table 2
Catalyzer E F ZCM-7
Content of vanadium, heavy % 0.5 0.5 0.5
Transformation efficiency, heavy % 72.14 72.90 66.24
Yield of gasoline, heavy % 48.09 49.45 44.49
Hydrogen/methane 0.38 0.40 0.45
Coke/transformation efficiency 0.048 0.046 0.048
As seen from Table 2, under the identical situation of pollution of vanadium amount, compare with the catalyzer that does not contain vanadium fixing agent, transformation efficiency and the yield of gasoline of catalyzer E and F are higher, illustrate that catalyst composition provided by the invention has good anti-vanadium ability.
Example 12
Press the method for example 9 and pollute and aging catalyst G, H and ZCM-7, making its content of vanadium is 0.24 heavy %, evaluate catalysts reactivity worth on micro-reactor, appreciation condition is identical with example 9.Reaction result sees Table 3.
Table 3
Catalyzer G H ZCM-7
Agent-oil ratio 666
Transformation efficiency, heavy % 75.60 65.80 63.40
Thing gas 20.55 17.40 16.91
Material
Coke 2.16 2.24 1.93
Flat
C
5～204℃ 52.89 46.16 44.57
Weighing apparatus,
204～303℃ 15.23 19.80 19.09
Heavy
% ＞330℃ 9.18 14.40 17.50
As seen from Table 3, under the identical situation of pollution of vanadium amount, compare with the catalyzer that does not contain vanadium fixing agent, transformation efficiency and the yield of gasoline of catalyzer G and H are higher, illustrate that catalyst composition provided by the invention has good anti-vanadium ability.
Example 13
Press the method for example 9 and pollute catalyzer H, at 760 ℃, normal pressure, 100% water vapor aging 4 hours down, evaluate catalysts reactivity worth on micro-reactor, appreciation condition is identical with example 9, and reaction result sees Table 4.
Table 4
Content of vanadium, heavy % 0 0.24 0.46 0.78
Agent-oil ratio 3666
Transformation efficiency, heavy % 76.28 77.34 73.92 51.24
Thing gas 17.03 21.08 18.14 13.43
Material
Coke 2.29 3.60 3.99 3.71
Flat
C
5～204℃ 56.97 52.65 51.79 34.10
Weighing apparatus,
204～330℃ 14.10 14.83 16.09 21.85
Heavy
% ＞330℃ 9.62 7.83 9.98 26.91
As seen from Table 4, catalyzer H is when the pollution of vanadium amount is 0.46 weight %, transformation efficiency is 73.92 weight %, and yield of gasoline can reach more than 50, when the pollution of vanadium amount is increased to 0.78 weight %, transformation efficiency still can be maintained to 51.24 heavy %, illustrates that catalyst composition provided by the invention has good anti-vanadium ability.
Claims (6)
1, hydrocarbon cracking catalyzer composite, it is characterized in that by the semi-synthetic or complete synthesis cracking catalyst particle of the heavy % of 95-60 and the vanadium fixing agent granulometric composition of the heavy % of 5-40, wherein vanadium fixing agent is made up of the alkali earth metal of the heavy % of 0.1-20 (is benchmark with vanadium fixing agent weight) or thulium and surplus aluminum oxide, described semi-synthetic cracking catalyst contains the zeolite activity component, one or more are selected from silicon oxide, aluminum oxide, magnesium oxide, silica-alumina, inorganic oxide in aluminum phosphate and the pure aluminium silicate, and one or more are selected from kaolin, halloysite, clay in polynite and the sepiolite and/or crosslinked laminated clay, described complete synthesis cracking catalyst contains the zeolite activity component, one or more are selected from silicon oxide, aluminum oxide, magnesium oxide, silica-alumina, inorganic oxide in aluminum phosphate or the pure aluminium silicate
Described cracking catalyst composition can be made by following method: the conventional preparation method by semi-synthetic or complete synthesis cracking catalyst prepares semi-synthetic or complete synthesis cracking catalyst particle earlier, pickling process routinely again, alkali earth metal or the thulium of the heavy % of load 0.1-20 (is benchmark with vanadium fixing agent weight) on alumina particle, 80-200 ℃ dry 2-24 hour, 300-800 ℃ roasting 1-10 hour, promptly get the vanadium fixing agent particle; Ratio (weight ratio) in 95-60: 5-40 mixes granules of catalyst and vanadium fixing agent particle, gets final product.
2, according to the described composition of claim 1, it is characterized in that described cracking catalyst particulate content is the heavy % of 90-70, the content of vanadium fixing agent is the heavy % of 10-30.
3,, it is characterized in that it is benchmark with vanadium fixing agent weight that described vanadium fixing agent contains the heavy %(of 1-10 according to the described composition of claim 1) alkali earth metal or the vanadium fixing agent particle of thulium and surplus aluminum oxide.
4,, it is characterized in that described zeolite is X type zeolite, y-type zeolite, zeolite L, ZSM zeolite, mordenite, aluminum phosphate zeolite, silicon aluminium phosphate zeolite according to the described composition of claim 1.
5,, it is characterized in that described alkali earth metal is calcium or magnesium according to the described composition of claim 1.
6,, it is characterized in that described zeolite is a y-type zeolite according to the described composition of claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103763 CN1027739C (en) | 1991-06-11 | 1991-06-11 | Hydrocarbon cracking catalyzer composite containing vanadium fixing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91103763 CN1027739C (en) | 1991-06-11 | 1991-06-11 | Hydrocarbon cracking catalyzer composite containing vanadium fixing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1067670A CN1067670A (en) | 1993-01-06 |
| CN1027739C true CN1027739C (en) | 1995-03-01 |
Family
ID=4906250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91103763 Expired - Lifetime CN1027739C (en) | 1991-06-11 | 1991-06-11 | Hydrocarbon cracking catalyzer composite containing vanadium fixing agent |
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| Country | Link |
|---|---|
| CN (1) | CN1027739C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074688C (en) * | 1998-02-20 | 2001-11-14 | 中国石化兰州炼油化工总厂 | Hydrocarbon cracking zeolite catalyst for catching vanadium and preparation thereof |
| CN100478420C (en) * | 2004-09-15 | 2009-04-15 | 中国石油化工股份有限公司 | Catalytic cracking aid and its preparing method |
| CN102228838B (en) * | 2011-04-21 | 2012-12-12 | 卓润生 | Silicon-carrier lanthanum carbonate catalytic cracking microspherical vanadium-resistant aid and preparation method thereof |
| CN102228839B (en) * | 2011-05-03 | 2012-12-12 | 卓润生 | Silicon-aluminum dual binding agent vanadium-resisting additive and preparation method thereof |
| CN103372423B (en) * | 2012-04-28 | 2015-04-29 | 中国石油化工股份有限公司 | Contact cracking catalyst of inferior heavy oil and preparation method of contact cracking catalyst |
| CN106378205A (en) * | 2016-08-12 | 2017-02-08 | 青岛惠城环保科技股份有限公司 | Preparation method for metal capturing agent |
-
1991
- 1991-06-11 CN CN 91103763 patent/CN1027739C/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| CN1067670A (en) | 1993-01-06 |
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Expiration termination date: 20110611 Granted publication date: 19950301 |