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CN1297018A - Catalytic cracking catalyst for preparing light oil with high yield and its preparing process - Google Patents

Catalytic cracking catalyst for preparing light oil with high yield and its preparing process Download PDF

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CN1297018A
CN1297018A CN 99123717 CN99123717A CN1297018A CN 1297018 A CN1297018 A CN 1297018A CN 99123717 CN99123717 CN 99123717 CN 99123717 A CN99123717 A CN 99123717A CN 1297018 A CN1297018 A CN 1297018A
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earth metal
molecular sieve
alkaline
carrier
described catalyzer
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CN1157465C (en
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杨建�
范中碧
周素静
邱中红
张万虹
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

A catalytic cracking catalyst is composed of carrier (50-95 wt.%) and molecular sieve containing alkali-earth metal (5-50 wt.%), and is prepared through mixing the compound containing alkali-earth metal with molecular sieve in the presence of water, drying, calcining to obtain said molecular sieve, dispersing it in carrier slurry, and drying shaping. Its advantages are high yield of light oil, high diesel oil/gasoline ratio, and low formation of gas and coke.

Description

A kind of catalytic cracking catalyst of light oil with high yield and preparation thereof
The invention relates to a kind of catalytic cracking of petroleum hydrocarbon Catalysts and its preparation method.More particularly, the invention relates to a kind of Catalysts and its preparation method molecular sieve, that be used for catalytic cracking of petroleum hydrocarbon that contains.
Along with the increase of market to the lightweight oil demand, and catalytically cracked stock heavy, poor qualityization increasingly, people require cracking catalyst possess simultaneously preventing from heavy metal pollution, can pressure fuel macromole, reduce the function of secondary reaction, to reach light oil with high yield (gasoline and diesel oil), to reduce the purpose of coke and dry gas.
EP256 discloses a kind of catalyzer that is used for cracking of oil in 771, and its usefulness that consists of the heavy % of 40-90 is the SiO that makes of glue method altogether 2-MgO matrix, the zeolite of the heavy % of 5-40, the Al of the heavy % of 0-40 2O 3Clay with the heavy % of 0-50.This catalyzer has the SiO of ratio 2-Al 2O 3For the cracking catalyst of matrix is high gasoline and diesel yield and high-wearing feature energy,, emphasize in the literary composition that magnesium can not be existing by detected magnesian state for having this performance.
USP4,784,750 disclosed catalytic cracking processs relate to a kind of catalyzer, and Y zeolite with specific physico-chemical parameter that this catalyzer is obtained through hydro-thermal and acid treatment by the heavy % of 5-50 and the heavy % of 50-95 are selected from SiO 2Al 2O 3, SiO-MgO and clay matrix constitute.This catalyzer has cracking activity and gasoline selective preferably.
USP3, reported in 781,199 adopt stabilization anti-ammonia Y zeolite be used for hydrocracking catalyst after the nitrogenous hydrocarbon feed hydrofining.This Preparation of catalysts method is: earlier with the NaY molecular sieve through the roasting of ammonium salt exchange-roasting-exchange again-again make stabilization Y zeolite, then with Al 2O 3, MgO, SiO 2Mix Deng inorganic oxide or its mixture.
EP40276 discloses a kind of low tart alkali metal containing prepare zeolite method, be that the forming composition of zeolite or zeolite and substrate material is handled to the temperature range of salts solution boiling point in pH7-12, room temperature with excessive alkali metal cation medium (for example salts solution), the ZSM class zeolite catalyst of the alkali metal containing that makes with this method has obtained the acid active of expection when being used for the isomerization reaction of naphthenic hydrocarbon.
In sum, do not see in the prior art to have and alkaline-earth metal is introduced molecular sieve make catalyzer in order to improve the report of middle distillate oil yield.
The objective of the invention is on the basis of above-mentioned prior art, to provide a kind of novel cracking catalyst to improve in the product the particularly yield of diesel oil of lightweight oil, reduce the growing amount of coke and dry gas simultaneously.
We find, alkaline-earth metal is directly introduced the strong acid center that molecular sieve can significantly reduce molecular sieve, and keep the weak acid center of the overwhelming majority.The cracking catalyst made from the molecular sieve that contains alkaline-earth metal can weaken the secondary cracking reaction of oil product molecule, thereby improves the middle distillate oil yield of product, reduces the growing amount of gas and coke simultaneously.
Catalyzer provided by the invention is by being that the molecular sieve of alkaline including earth metal of 5-50% of benchmark and the carrier of 50-95% are formed with the catalyst weight.
Wherein said molecular sieve is a multiple molecular sieve commonly used in the catalytic cracking catalyst, comprise X type, Y type, ZSM type molecular sieve, and they handle the modified product that obtains through ion-exchange or various physical chemistry method, as USY, REY, REHY, HZSM-5, RE-ZSM-5 etc.
Said alkaline-earth metal is Be, Mg, Ca, Sr, Ba, preferred Mg and Ca.
The content of alkaline-earth metal in molecular sieve in alkaline earth metal oxide, is advisable with the 0.1-25% that accounts for molecular sieve weight.
Wherein said carrier is various carriers commonly used in the catalytic cracking catalyst, as SiO 2Al 2O 3, Al 2O 3-clay etc.
Preparation of catalysts step provided by the invention is as follows:
1. make the alkaline including earth metal molecular sieve according to one of following method:
Method one is dispersed in dissolving or the alkaline including earth metal compound after abundant wet-milling in the molecular sieve pulp, adds or does not add ammoniacal liquor, mixes after drying, roasting;
Method two will be dispersed in through the molecular sieve after the abundant wet-milling in the solution of alkaline including earth metal compound, add ammoniacal liquor and will mix after-filtration, washing, drying, roasting.
2. the molecular sieve of alkaline including earth metal is dispersed in the carrier pulp drying and moulding according to the weight ratio of molecular sieve: carrier=5-50: 50-95.
Among the preparation method provided by the invention, said alkaline-earth metal is Be, Mg, Ca, Sr, Ba, preferred Mg and Ca.Said alkaline including earth metal compound is selected from oxide compound, muriate, vitriol or the nitrate of above-mentioned alkaline-earth metal.The consumption of alkaline earth metal compound is advisable in the 0.1-25% that the alkaline-earth metal in the alkaline including earth metal molecular sieve (with oxide compound) accounts for molecular sieve weight.
Said molecular sieve is various molecular sieves commonly used in the catalytic cracking catalyst, comprise X type, Y type, ZSM type molecular sieve, and they handle the modified product that obtains through ion-exchange or various physical chemistry method, as USY, REY, REHY, HZSM-5, RE-ZSM-5 etc.
The roasting of said alkaline including earth metal molecular sieve is carried out finishing in 2-5 hour under 500-650 ℃.
Said carrier is various carriers commonly used in the catalytic cracking catalyst, as SiO 2Al 2O 3, Al 2O 3-clay etc.
Among the present invention because alkaline-earth metal has been introduced molecular sieve, strong acid center in the molecular sieve is suppressed, thereby can weaken the secondary cracking reaction of oil product molecule effectively with its catalyzer as active ingredient, and then improved the especially yield of diesel oil of lightweight oil, improve the diesel and gasoline ratio in the product, reduced the productive rate of gas and coke.This catalyzer is applicable to the catalytic cracking or the hydrocracking of the hydro carbons that comprises heavy oil.
Following example will give further instruction to the present invention, but the scope of protecting not thereby limiting the invention.
Example 1
The explanation of this example prepares the alkaline including earth metal super-stable Y molecular sieves with magnesium chloride.
Get MgCl 26H 2O 33 grams (Beijing dicyclo chemical reagent factory, content is not less than 97.0%) add deionized water 30 grams, obtain MgCl 2Solution.
(USY, lattice constant are 24.47A, and degree of crystallinity is 77%, RE to get super-stable Y molecular sieves 2O 3Content 0.67%, Na 2O content 1.4%) 100 grams (800 ℃/1hr calcination base) add deionized water 180 gram wet-millings, get molecular sieve pulp.
With above-mentioned MgCl 2Solution is dispersed in the molecular sieve pulp, and the gained mixed serum is placed 120 ℃ baking oven inner drying, and roasting 5hr in 500 ℃ High Temperature Furnaces Heating Apparatus promptly gets magniferous super-stable Y molecular sieves sample again.Brief note is sample a.
Analytical results shows that Mg content in this sample (in magnesium oxide) is 6.1 heavy %.
Example 2
The explanation of this example prepares alkaline including earth metal rare earth hydrogen Y zeolite with sal epsom.
Get MgSO 47H 2O 64 grams (Red Star chemical plant, Beijing, content is not less than 98.0%) add deionized water 400 grams, obtain MgSO 4Solution.
(REHY, lattice constant are 24.69A, and degree of crystallinity is 61%, RE with 100 gram (calcination base) rare earth hydrogen Y zeolites 2O 3Content 12.3%, Na 2O content 4.4%) add the water wet-milling, under fully stirring, it is added above-mentioned MgSO then 4In the solution, and add ammoniacal liquor (Beijing Yili Fine Chemicals Co., Ltd., NH 3Content is the heavy % of 25-28) 87 milliliters.
The gained mixed serum is filtered, and wash with 1500 ml deionized water.The gained wet cake is placed 120 ℃ baking oven inner drying, and roasting 5hr in 500 ℃ High Temperature Furnaces Heating Apparatus promptly gets magniferous rare earth hydrogen Y zeolite sample again.Brief note is sample b.
Analytical results shows that Mg content in this sample (in magnesium oxide) is 7.9 heavy %.
Example 3
The explanation of this example prepares alkaline including earth metal ZSM type molecular sieve with magnesium chloride.
Get MgCl 26H 2O 81 grams add deionized water 73 grams, obtain MgCl 2Solution.
(silica alumina ratio is 61, Na to get the ZSM-5 molecular sieve 2O content 0.035%) 100 grams (base burns) add deionized water 150 gram wet-millings, get molecular sieve pulp.
With above-mentioned MgCl 2Solution is dispersed in the molecular sieve pulp, and the gained mixed serum is placed 120 ℃ baking oven inner drying, and roasting 5hr in 500 ℃ High Temperature Furnaces Heating Apparatus promptly gets magniferous type ZSM 5 molecular sieve sample again.Brief note is sample c.
Analytical results shows that Mg content in this sample (in magnesium oxide) is 13.8 heavy %.
Example 4
The explanation of this example prepares the alkaline including earth metal super-stable Y molecular sieves with magnesium oxide.
Get magnesium oxide (Dunhuang Chenical Plant, Shanghai, minimum content is not less than 98.0%) 33 grams (base burns), add deionized water 50 gram wet-millings and become slurries.
Get super-stable Y molecular sieves (specification is with example 1) 100 grams, add deionized water 180 gram wet-millings, get molecular sieve pulp.
Above-mentioned magnesium oxide slurries are dispersed in the molecular sieve pulp, the gained mixed serum is placed 120 ℃ baking oven inner drying, roasting 2hr in 650 ℃ High Temperature Furnaces Heating Apparatus promptly gets magniferous super-stable Y molecular sieves sample again.Brief note is sample d.
Analytical results shows that Mg content in this sample (in magnesium oxide) is 24.8 heavy %.
Example 5
The explanation of this example prepares the alkaline including earth metal super-stable Y molecular sieves with magnesium chloride.
Get MgCl 26H 2O (specification is with example 1) 2.6 grams add deionized water 120 grams, obtain MgCl 2Solution.
Get super-stable Y molecular sieves (specification is with example 1) 100 grams, add deionized water 180 gram wet-millings, get molecular sieve pulp.
With above-mentioned MgCl 2Solution is dispersed in the molecular sieve pulp, and adds 1 milliliter of ammoniacal liquor (specification is with example 2).The gained mixed serum is placed 120 ℃ baking oven inner drying, and roasting 5hr in 500 ℃ High Temperature Furnaces Heating Apparatus promptly gets magniferous super-stable Y molecular sieves sample again.Brief note is sample e.
Analytical results shows that Mg content in this sample (in magnesium oxide) is 0.5 heavy %.
Example 6
This example explanation, magnesium introduced molecular sieve after, the strong acid center of molecular sieve has obtained inhibition, and has kept a large amount of weak acid centers.
With ammonia adsorption-desorption method, the acidity of test molecule sieve on SORPTOMATIC-1900 adsorption-desorption instrument.Test process is: sample is earlier through roasting and vacuum outgas, again in 175 ℃ of absorption down, and desorption under same temperature then, and by the absorption and the desorption rate of mass spectrum record ammonia.
Not have the acid site of desorption of ammonia be strong acid center in definition in this test, desorption the acid site of ammonia be the weak acid center.Test result is as shown in table 1.Table 1
Figure 9912371700101
Example 7
The explanation of this example prepares the alkaline including earth metal super-stable Y molecular sieves with nitrocalcite.
Get Ca (NO 3) 24H 2O (Red Star chemical plant, Beijing, content is not less than 99.0%) 45 grams add deionized water 600 grams, obtain Ca (NO 3) 2Solution.
With 100 gram (calcination base) super-stable Y molecular sieves (specification is with example 1) wet-millings, under fully stirring, it is added above-mentioned Ca (NO then 3) 2In the solution, and add 54 milliliters of ammoniacal liquor.The gained mixed serum is filtered, and wash with 1500 ml deionized water.The gained wet cake is placed 120 ℃ baking oven inner drying, and roasting 5hr in 500 ℃ High Temperature Furnaces Heating Apparatus promptly gets calcareous super-stable Y molecular sieves sample again.Brief note is sample f.
Analytical results shows that calcium contents in this sample (in calcium oxide) is 6.7 heavy %.
Example 8
This example explanation calcic molecular sieve to contain the magnesium molecular sieve similar performance arranged, i.e. the introducing of calcium has suppressed the strong acid center of molecular sieve, and has kept a large amount of weak acid centers.
The acid test method is with example 6.
Test result sees Table 2.Table 2
Example number The molecular sieve numbering Acid mmol/g Acidity change %
Strong acid Weak acid Strong acid Weak acid
Raw material 7 USY f 0.74 0.32 2.60 2.31 Benchmark-56.8 Benchmark-11.2
Example 9-11
The explanation of this example is provided by the invention to be the Preparation of catalysts of active ingredient with the alkaline including earth metal molecular sieve.
Get molecular sieve a, each 30 gram (burn base) of b and f add 233 grams respectively after the wet-milling, solid content be 30%, be the semi-synthetic carrier (Al of binding agent with the pseudo-boehmite 2O 3/ carclazyte=23/47) in, stir, drying and moulding obtains catalyst sample A respectively then, B and F.
Comparative Examples 1-2
Prepare catalyzer as active ingredient according to method and the carrier consumption of example 9-11 with super-stable Y molecular sieves (specification is with example 1), rare earth hydrogen Y zeolite (specification is with example 2), obtain comparison catalyst sample A ' and B '.
Example 12
This example explanation, provided by the invention is that the catalyzer of active ingredient has higher lightweight oil (gasoline+diesel oil) yield with the alkaline including earth metal super-stable Y molecular sieves; Higher diesel and gasoline ratio and lower gas and coke production rate.
With catalyst sample A provided by the invention, F and comparative catalyst's sample A ' wore out 4 hours under the 100% water vapor condition at 800 ℃, estimated on MAT-11 type heavy oil microreactor.Stock oil is 923 triumph wax oils, 483 ℃ of temperature of reaction, agent-oil ratio 4.Evaluation result is listed in table 3.Table 3
Example 13
This example explanation, provided by the invention is that the catalyzer of active ingredient has higher lightweight oil (gasoline+diesel oil) yield with alkaline including earth metal rare earth hydrogen Y zeolite; Higher diesel and gasoline ratio; Lower gas and coke production rate.
Except that agent-oil ratio is 3, under the identical condition of pre-treatment and reaction conditions and example 12, catalyst sample B and B ' are estimated, the results are shown in table 4.
Table 4
Figure 9912371700122

Claims (10)

1. catalytic cracking catalyst is characterized in that being made up of the molecular sieve of the alkaline including earth metal of carrier that accounts for catalyst weight 50-95% and 5-50%.
2. according to the described catalyzer of claim 1, it is characterized in that wherein said carrier is selected from SiO 2Al 2O 3Or Al 2O 3-clay.
3. according to the described catalyzer of claim 1, it is characterized in that wherein said alkaline-earth metal is selected from one of Be, Mg, Ca, Sr and Ba.
4. according to the described catalyzer of claim 3, it is characterized in that wherein said alkaline-earth metal is selected from Mg or Ca.
5. according to the described catalyzer of one of claim 1,3 or 4, it is characterized in that the content of said alkaline-earth metal wherein accounts for the 0.1-25% of molecular sieve weight.
6. according to the described catalyzer of claim 1, it is characterized in that wherein said molecular screening is from one of X type, Y type or ZSM type.
7. according to the described catalyzer of claim 6, it is characterized in that wherein said molecular screening is from one of USY, REY, REHY, H-ZSM-5 or RE-ZSM-5.
8. claim 1 Preparation of catalysts method is characterized in that comprising the steps:
(1) make the alkaline including earth metal molecular sieve according to one of following method:
Method one, will dissolve or the alkaline including earth metal compound after abundant wet-milling is dispersed in the molecular sieve pulp, and add or do not add ammoniacal liquor, mix after drying, roasting;
Method two, will be dispersed in through the molecular sieve after the abundant wet-milling in the solution of alkaline including earth metal compound, and add ammoniacal liquor and mix after-filtration, washing, drying, roasting;
(2) molecular sieve of alkaline including earth metal is dispersed in the carrier pulp drying and moulding according to the weight ratio of molecular sieve: carrier=5-50: 50-95.
9. according to the described preparation method of claim 8, it is characterized in that wherein said alkaline earth metal compound is selected from the oxide compound of alkaline-earth metal, muriate, vitriol or nitrate.
10. according to the described preparation method of claim 8, the roasting that it is characterized in that wherein said alkaline including earth metal molecular sieve is to carry out under 500-650 ℃ 2-5 hour.
CNB99123717XA 1999-11-17 1999-11-17 Catalytic cracking catalyst for preparing light oil with high yield and its preparing process Expired - Lifetime CN1157465C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100336889C (en) * 2002-10-07 2007-09-12 大卫·B·巴舍利克 Preparation method of fluid catalytic cracking catalyst component mixture for fluid catalytic cracking device
CN100357398C (en) * 2003-06-30 2007-12-26 中国石油化工股份有限公司 Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof
CN1978593B (en) * 2005-11-30 2010-12-01 中国石油化工股份有限公司 Cracking catalyst
CN102652038A (en) * 2009-12-16 2012-08-29 环球油品公司 OCP catalyst with improved steam tolerance
WO2014040365A1 (en) 2012-09-14 2014-03-20 中国石油化工股份有限公司 Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor
EP2792408A4 (en) * 2011-12-15 2015-08-19 Petrochina Co Ltd Magnesium modified ultra-stable rare earth y-type molecular sieve and preparation method therefor
EP2792641A4 (en) * 2011-12-15 2015-08-19 Petrochina Co Ltd Ultra-stable rare earth y-type molecular sieve and preparation method therefor
US9630171B2 (en) 2012-06-27 2017-04-25 China Petroleum & Chemical Corporation Catalyst containing a modified Y-type zeolite and a preparation process thereof
CN108201898A (en) * 2016-12-20 2018-06-26 中国石油天然气股份有限公司 Method for modifying Y-type molecular sieve
CN110193375A (en) * 2018-02-26 2019-09-03 中国石油天然气股份有限公司 Preparation method of magnesium salt precipitation modified Y-type molecular sieve

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100336889C (en) * 2002-10-07 2007-09-12 大卫·B·巴舍利克 Preparation method of fluid catalytic cracking catalyst component mixture for fluid catalytic cracking device
CN100357398C (en) * 2003-06-30 2007-12-26 中国石油化工股份有限公司 Cracking catalyst for hydrocarbon containing molecular sieve and preparation process thereof
CN1978593B (en) * 2005-11-30 2010-12-01 中国石油化工股份有限公司 Cracking catalyst
CN102652038A (en) * 2009-12-16 2012-08-29 环球油品公司 OCP catalyst with improved steam tolerance
EP2792641A4 (en) * 2011-12-15 2015-08-19 Petrochina Co Ltd Ultra-stable rare earth y-type molecular sieve and preparation method therefor
EP2792408A4 (en) * 2011-12-15 2015-08-19 Petrochina Co Ltd Magnesium modified ultra-stable rare earth y-type molecular sieve and preparation method therefor
US9789475B2 (en) 2011-12-15 2017-10-17 Petrochina Company Limited Ultra-stable rare earth Y-type molecular sieve and preparation method therefor
US9840422B2 (en) 2011-12-15 2017-12-12 Petrochina Company Limited Magnesium modified ultra-stable rare earth Y-type molecular sieve and preparation method therefor
US9630171B2 (en) 2012-06-27 2017-04-25 China Petroleum & Chemical Corporation Catalyst containing a modified Y-type zeolite and a preparation process thereof
WO2014040365A1 (en) 2012-09-14 2014-03-20 中国石油化工股份有限公司 Catalytic cracking catalyst of rare earth-containing y-type molecular sieve and preparation method therefor
US9656255B2 (en) 2012-09-14 2017-05-23 China Petroleum & Chemical Corporation Catalytic cracking catalyst having a rare earth-containing Y zeolite and a preparation process thereof
CN108201898A (en) * 2016-12-20 2018-06-26 中国石油天然气股份有限公司 Method for modifying Y-type molecular sieve
CN110193375A (en) * 2018-02-26 2019-09-03 中国石油天然气股份有限公司 Preparation method of magnesium salt precipitation modified Y-type molecular sieve

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