CN1566269A - Cracking process of hydrocarbon oil - Google Patents

Cracking process of hydrocarbon oil Download PDF

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CN1566269A
CN1566269A CN 03147986 CN03147986A CN1566269A CN 1566269 A CN1566269 A CN 1566269A CN 03147986 CN03147986 CN 03147986 CN 03147986 A CN03147986 A CN 03147986A CN 1566269 A CN1566269 A CN 1566269A
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metal
oxide
content
zeolite
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CN1261527C (en
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刘宇键
龙军
朱玉霞
田辉平
陈振宇
郭瑶庆
张久顺
何鸣元
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a cracking process of hydrocarbon oil which comprises, under cracking condition, contacting a hydrocarbon oil with a catalyst mixture of cracking adjuvant and catalytic cracking catalyst, wherein the cracking adjuvant comprises a carrying agent and a metal constituent, at least one portion of the metal constituent exists in a deacidized valence state, it is one or several selected from the periodic table of elements, i.e., IIIA group non-aluminium metals, IVA group metals, VA group metals, IB group metals, IIB group metals, VB group metals, VIB group metals, VIIB group metals, and VIII group non-noble metals.

Description

A kind of cracking method for hydrocarbon oil
Technical field
The invention relates to a kind of cracking method of hydrocarbon ils.
Background technology
In recent years, for the consideration of environmental protection, worldwide, the requirement of oil fuel standard is improved constantly.With China is example, and State Quality Supervision Bureau had formulated " motor spirit objectionable impurities control criterion " in 1999, and according to the requirement of this standard, the sulphur content of gasoline product should be less than 800ppm.In fact, the sulphur of gasoline product more than 90% comes from FCC gasoline, and on the other hand, the proportion of middle-eastern crude in the shared crude oil in Chinese refinery with higher sulfur content is increasing, and therefore, the sulphur content that reduces in the FCC gasoline is most important to producing clean gasoline.
At present, can be by stock oil be carried out the hydrogenation pre-treatment, or FCC gasoline carried out making with extra care behind the hydrogenation reach the purpose that reduces the FCC sulfur in gasoline.Yet these two kinds of method investments are big, and the process cost height also can make the alkene partial hydrogenation in the gasoline, causes the loss of octane value.
In order to reduce the partial hydrogenation of alkene in the gasoline, reduce the loss of octane value, in recent years, U.S. Philips Petroleum Co. (Phillips Petroleum Company) has developed a series of methods that are used for removing the sorbent material of pressure gasoline and diesel oil fuel sulphur and remove sulphur in pressure gasoline and the diesel oil fuel.
CN1355727A and patent families US6 thereof, 254,766B1 discloses a kind of being used for and has removed the adsorbent composition of sulphur and remove the method for sulphur from pressure gasoline and diesel-fuel stream from pressure gasoline and diesel-fuel.This adsorbent composition is made up of zinc oxide, silicon oxide, oxidation al and ni, and described nickel exists with the reduction valence state basically, and the amount of its existence can remove sulphur from pressure gasoline or diesel-fuel under desulfurization condition.The described method that removes sulphur from pressure gasoline and diesel-fuel stream comprises makes pressure gasoline contact with described adsorbent composition with diesel-fuel stream, form the desulfurized fluid and the sulfided sorbent of pressure gasoline or diesel-fuel, isolate pressure gasoline or diesel-fuel after the desulfurization.
CN1382071A and patent families US6 thereof, 184,176B1 discloses a kind of being used for and has removed the adsorbent composition of sulphur and remove the method for sulphur from pressure gasoline and diesel-fuel stream from pressure gasoline and diesel-fuel.This adsorbent composition is made up of zinc oxide, silicon oxide, aluminum oxide and cobalt, and described cobalt exists with the reduction valence state basically, and the amount of its existence can remove sulphur from pressure gasoline or diesel-fuel under desulfurization condition.The described method that removes sulphur from pressure gasoline and diesel-fuel stream comprises makes pressure gasoline contact with described adsorbent composition with diesel-fuel stream, form the desulfurized fluid and the sulfided sorbent of pressure gasoline or diesel-fuel, isolate pressure gasoline or diesel-fuel after the desulfurization.
CN1384770A and patent families US6 thereof, 271,173B1 discloses a kind of being used for and has removed the adsorbent composition of sulphur and remove the method for sulphur from pressure gasoline and diesel-fuel stream from pressure gasoline and diesel-fuel.This adsorbent composition is made up of the promoter metals that is carried on the carrier compositions, and described carrier compositions is made up of zinc oxide, silicon oxide, aluminum oxide and calcium cpd, and described calcium cpd is calcium sulfate, calcium aluminate, calcium phosphate or Calucium Silicate powder; Described promoter metals exists with the reduction valence state basically, and the amount of reduction valence state promoter metals can remove sulphur from pressure gasoline or diesel-fuel under desulfurization condition.The described method that removes sulphur from pressure gasoline and diesel-fuel stream comprises makes pressure gasoline contact with described adsorbent composition with diesel-fuel stream, form the desulfurized fluid and the sulfided sorbent of pressure gasoline or diesel-fuel, isolate pressure gasoline or diesel-fuel after the desulfurization.
CN1382201A and patent families US6 thereof, 338,794B1 discloses a kind of being used for and has removed the adsorbent composition of sulphur and remove the method for sulphur from pressure gasoline and diesel-fuel stream from pressure gasoline and diesel-fuel.This adsorbent composition is made up of zinc titanate carrier and metal, metal oxide or metal oxide precursor promotor, described metal is cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, vanadium or two or more mixture arbitrarily wherein, described promoter metals exists with the reduction valence state basically, the amount that reduction valence state metallic promoter agent exists can remove sulphur from pressure gasoline or diesel-fuel under desulfurization condition.The described method that removes sulphur from pressure gasoline and diesel-fuel stream comprises makes pressure gasoline contact with described adsorbent composition with diesel-fuel stream, form the desulfurized fluid and the sulfided sorbent of pressure gasoline or diesel-fuel, isolate pressure gasoline or diesel-fuel after the desulfurization.
CN1382199A and patent families US6 thereof, 274,533B1 discloses a kind of being used for and has removed the adsorbent composition of sulphur and remove the method for sulphur from pressure gasoline and diesel-fuel stream from pressure gasoline and diesel-fuel.This adsorbent composition is made up of bimetal promotor and granular carrier, and described bimetal promotor is gone up substantially with the reduction valence state and existed, and the amount of its existence can remove sulphur from pressure gasoline or diesel-fuel under desulfurization condition.Described bimetal promotor is selected from any two or more mixture of cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony or vanadium.Described carrier is by forming with the zinc oxide of any suitable inorganic and organic carrier combination.Described inorganic carrier comprises silicon oxide, silica gel, aluminum oxide, clay, pure aluminium silicate, silica-alumina, titanium oxide, zirconium white, Zinc aluminate, zinc titanate, zinc silicate, calcium aluminate, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium aluminate, magnesium titanate, synthetic zeolite and natural zeolite.The described method that removes sulphur from pressure gasoline and diesel-fuel stream comprises makes pressure gasoline contact with described adsorbent composition with diesel-fuel stream, form the desulfurized fluid and the sulfided sorbent of pressure gasoline or diesel-fuel, isolate pressure gasoline or diesel-fuel after the desulfurization.
US6,346,190B1 discloses a kind of being used for and has removed the adsorbent composition of sulphur and remove the method for sulphur from pressure gasoline and diesel-fuel stream from pressure gasoline and diesel-fuel.This adsorbent composition is made up of zinc ferrite, nickel and a kind of mineral binder bond basically, and described zinc ferrite and nickel exist with the reduction valence state, and the amount of its existence can remove sulphur from pressure gasoline or diesel-fuel under desulfurization condition.Described mineral binder bond can be silicon oxide, aluminum oxide, clay, clay.With described total composition is benchmark, and the content of zinc oxide is 2-70 weight %, and the content of ferric oxide is 3-70 weight, and the content of described binding agent is 0.1-30 weight %, and the content of nickel is 1-50 weight %.
WO 02/18517A1 discloses a kind of being used for and has removed the adsorbent composition of sulphur and remove the method for sulphur from pressure gasoline and diesel-fuel stream from pressure gasoline and diesel-fuel.This adsorbent composition contains a kind of carrier component, a kind of wear-resistant component and a kind of promoter component, and described promoter component exists with the reduction valence state basically, and the amount of its existence can remove sulphur from pressure gasoline or diesel-fuel under desulfurization condition.Described carrier comprises zinc oxide and any suitable inorganic and organic carrier.Inorganic carrier comprises silicon oxide, silica gel, aluminum oxide, diatomite, pearlstone, silica-alumina, titanium oxide, zirconium white, Zinc aluminate, zinc titanate, zinc silicate, magnesium aluminate, magnesium titanate, synthetic zeolite, natural zeolite and their combination.Described wear-resistant component is selected from clay, high-alumina cement, Roman cement portland cement, calcium aluminate, Calucium Silicate powder, mica and their combination.Described clay comprises bentonite, and sodium type bentonite is through the bentonite of pickling, diatomite, potter's clay, kaolin, polynite, illite, halloysite, hectorite, sepiolite and composition thereof.Described promoter component comprises cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony or vanadium and their mixtures.Described wear-resistant components contents is 1-30 weight %, and promoter component content is 5-50 weight %.Described carrier component preferably contains zinc oxide, and the content of zinc oxide is 10-90 weight %.Described carrier component more preferably contains zinc oxide, silicon oxide and aluminum oxide, and the content of silicon oxide is 5-85 weight %, and alumina content is 0.1-30 weight %.
The disclosed sulfur method of above-mentioned Philips Petroleum Co. belongs to purified method behind pressure gasoline and the diesel oil fuel, and promptly their stock oil of handling is gasoline and diesel oil fuel.
In the FCC riser tube, by the method for catalytic cracking, it is the most attractive technological approaches economically that the sulphur original position is removed.For reaching this purpose, need in catalytic cracking process, add auxiliary agent with desulfurizing function, perhaps use the auxiliary agent that has desulfurizing function, contains the desulfurization component.
US6,036,847 and patent families EP0,798,362A2 discloses a kind of fluidized catalytic cracking of hydrocarbons method, wherein, and under the condition of described hydrocarbon feed hydrogenation outside not existing, a zone of cracking by cracking, and all particles that comprise builder granule wherein, contain another particle constantly in cracking hydrocarbon district and an auxiliary agent breeding blanket circulation in all particles, this particle has the activity of the cracking hydrocarbon ils lower than builder granule, and described activity is benchmark with the fresh granules.This particle is made up of the inorganic oxide of titanium oxide and a kind of non-oxide titanium basically.The inorganic oxide of described non-oxide titanium contains a kind of Lewis acid, this Lewis acid is selected from following element and compound composition thereof one group: nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and germanium, described Lewis acid loads on the aluminum oxide.Because use this auxiliary agent that contains titanium oxide, crackate FCC sulfur in gasoline content is reduced.
US5,376,608 disclose a kind of assistant composition with desulfidation, said composition contains (A) and is dispersed in zeolite/molecular sieve in a kind of inorganic oxide matrix, (b) contain the alumina component of Lewis acid, this alumina component contains the Lewis acid of 1-50 weight %, and described Lewis acid is selected to load on and contains nickel, copper, zinc, silver, cadmium, indium, tin, mercury, thallium, lead, bismuth, boron, aluminium (non-oxide aluminium) and the element of gallium and a group of oxide compound on the aluminum oxide.
WO 99/49001A1 discloses a kind of composition that reduces sulphur content in the hydrocarbon component, and said composition contains a kind of houghite (hydrotalcite) material, and this material can also contain a kind of FCC auxiliary agent with a kind of Lewis acid dipping in the said composition.Described Lewis acid comprises transition metal, particularly the element of zinc, copper, nickel, cobalt, iron and manganese and compound.
WO 01/21733A1 discloses a kind of in the presence of hot reclaiming aid, contains the catalyst cracking method of organosulfur compound hydrocarbon raw material, and described auxiliary agent contains a kind of component that reduces The product sulfur, this component contains a kind of oxidation state greater than zero metal component, and described metal component comprises the 3rd cycle of the periodic table of elements, VB family, VIIB family, VIII family, IIB family, the metallic compound of IVA family or complex compound, as vanadium, zinc, iron, cobalt, the metallic compound of manganese and gallium or complex compound.The component of described reduction The product sulfur comprises that pore structure contains the molecular sieve of above-mentioned metal component, also comprises being dispersed in auxiliary agent carrier optional position, as the above-mentioned metal component in the porous oxide carrier.
WO 01/21732A1 discloses a kind of method that reduces sulphur content in the cracking petroleum fraction, this method is included in the temperature of raising and a kind of auxiliary agent and a kind of auxiliary agent that reduces the product sulphur content and exists down, with the petroleum fractions catalytic cracking, obtain having liquid crackate than low sulfur content.Wherein, the auxiliary agent of described reduction product sulphur content contains a kind of non-molecular sieve carrier of vanadium that contains, and described non-molecular sieve carrier can be the organic or inorganic carrier, preferred carrier is amorphous or the para-crystal inorganic oxide, as aluminum oxide, silicon oxide, clay or their mixture.
CN1281887A discloses a kind of method that reduces catalytic cracking gasoline cut sulphur content, and this method is included in high temperature and the product desulfurizing assistant agent exists down, catalytic cracking gasoline feedstock fraction, the liquid cracked product of preparation low sulfur content.This desulfurizing assistant agent contains the porous molecular screen that metal ingredient is contained in a kind of cavernous structure inside.Described porous molecular screen can be a large pore zeolite, and promptly orifice diameter is at least the zeolite of 0.7 nanometer, as y-type zeolite, rare earth Y type zeolite (REY), ultrastable Y (USY), L zeolite, Beta zeolite, mordenite, ZSM-18 zeolite.Described molecular sieve also can be a mesopore zeolite, be orifice diameter for greater than 0.56 zeolite, as Pentasil zeolite, ZSM-5 zeolite, ZSM-22, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, MCM-56 zeolite less than 0.7 nanometer.Described molecular sieve can also be a non-zeolite molecular sieve, as the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate.Titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integratedsilicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, silico-aluminate silicoaluminophosphates (SAPO), gallium germanate (gallogermanates) and their combination.
CN1261618A discloses a kind of sulfur method of catalytic cracking gasoline cut, this method is included under the existence of high temperature, auxiliary agent and product desulfurizing assistant agent, to contain the petroleum cut catalytic cracking of organosulfur compound, produce the liquid crackate of low sulfur content.Described product desulfurizing assistant agent contains a kind of porous molecular screen, this molecular sieve contains first metal component and second metal component, first metal component is positioned at Molecular Sieve Pore inside and oxidation state greater than zero, and second metal component comprises at least a rare earth element that is positioned at Molecular Sieve Pore inside.Described first kind of metal component is selected from periodic table of elements period 4 and IIB, VB, IIIA, the metal, particularly vanadium of VIII family, zinc, iron, gallium.
In the method for reduction catalytic cracking gasoline cut sulphur content recited above used auxiliary agent in preparation process all through super-dry, roasting and/or hydrothermal treatment consists, there is not reduction process, therefore, contained metal component all exists with its highest oxidation state in these auxiliary agents.
Summary of the invention
The purpose of this invention is to provide a kind of new cracking method for hydrocarbon oil with strong sweetening power.
Method provided by the invention is included under the cracking conditions, the catalyst mixture of a kind of hydrocarbon ils with a kind of cracking additive and catalytic cracking catalyst contacted, reclaim the catalytic cracking production that sulphur content reduces, described cracking additive contains a kind of carrier and a kind of metal component, wherein, with the auxiliary agent total amount is benchmark, the content of carrier is 0.1-99.9 weight %, metal oxide in the maxivalence attitude, the content of metal component is 0.1-99.9 weight %, at least a portion of described metal component exists with the reduction valence state, it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, described carrier is selected from heat-resistant inorganic oxide, clay, molecular sieve and be suitable as in the mineral compound of carrier one or more.
Compared with prior art, method provided by the invention has strong sweetening power and heavy oil conversion performance.
Particularly the content of heat-resistant inorganic oxide is 2-68 weight % in described cracking additive, the content of clay is greater than 30 to 80 weight %, the content of molecular sieve is 0-40 weight %, metal oxide in described maxivalence attitude, when the content of metal component was 0.1-30 weight %, this method had stronger sweetening power and heavy oil conversion performance.
For example, according to method provided by the invention, adopting the content of aluminum oxide is 45.0 weight %, and kaolinic content is 49.0 weight %, with Co 2O 3Meter, cobalt contents is 5.0 weight %, the average valence of cobalt be 0 or+1.5 (average valence of cobalt is 0 or 0.5 for the ratio with the maxivalence attitude of cobalt), adopt different methods to prepare, described metal component is distributed in Industrial Catalysis cracking catalysis agent composition that above-mentioned cracking additive in the cracking additive or in the clay and the industrial trade mark be HGY-2000R (in the mixture, the content of cracking additive provided by the invention is 5.0 weight %, the content of Industrial Catalysis cracking catalyst is 95.0 weight %), in temperature of reaction is 480 ℃, and weight hourly space velocity is 16 hours -1, the agent weight of oil is 2.0 weight % than being under 6.0 the condition to sulphur content, boiling range be 329-550 ℃ decompressed wax oil carry out catalytic cracking, transformation efficiency is up to 70.9-71.8 weight %, the sulphur content in the gasoline product has only the 603.2-615 mg/litre.And adopt each component concentration identical, just the valence state of cobalt is its maxivalence attitude (+divalent), the reference cracking additive of different methods preparation and the catalytic cracking catalyst mixture of HGY-2000R, under identical condition, identical stock oil is carried out catalytic cracking, transformation efficiency has only 66.9-67.3 weight %, and the sulphur content in the gasoline product is up to the 753.8-765.2 mg/litre.
Again for example, according to method provided by the invention, adopting the content of aluminum oxide is 20.2 weight %, kaolinic content is 37.0 weight %, the MOY zeolite content is 35.0 weight %, in oxide compound, silver and molybdenum content are 7.8 weight %, the average valence of silver is 0 (average valence of silver is 0 for the ratio with the maxivalence attitude of silver), the average valence of molybdenum the is 3.3 above-mentioned cracking additive of (average valence of molybdenum is 0.55 for the ratio with the maxivalence attitude of molybdenum) and Industrial Catalysis cracking catalysis agent composition that the industrial trade mark is HGY-2000R is (in the mixture, the content of cracking additive provided by the invention is 10 weight %, the content of industrial cracking catalyst is 90 weight %), in temperature of reaction is 520 ℃, and weight hourly space velocity is 16 hours -1, the agent weight of oil is 2.0 weight % than being under 3.5 the condition to sulphur content, and boiling range is that 329-550 ℃ decompressed wax oil carries out catalytic cracking, and transformation efficiency is up to 76.3 weight %, and the sulphur content in the gasoline product has only 589.3 mg/litre.And adopt each component concentration identical, just the valence state of silver and molybdenum is the reference cracking additive of its maxivalence attitude, under identical condition, identical stock oil is carried out catalytic cracking, transformation efficiency has only 72.3 weight %, and the sulphur content in the gasoline product is up to 810.3 mg/litre.
Embodiment
According to method provided by the invention, be benchmark with the auxiliary agent total amount, the content of described carrier is preferably 20-99.5 weight %, and in the metal oxide of maxivalence attitude, the content of metal component is 0.5-80 weight %.
Described reduction valence state refers to that the average valence of described metal component is zeroth order or is higher than zeroth order and is lower than its highest oxidation state.
The maxivalence attitude of metal component described here is meant after abundant oxidation, the highest oxidation state of metal component described in the metal oxide of energy stable existence.For example, the highest oxidation state of the non-aluminum metal of periodic table of elements IIIA family is generally+3 valencys (as gallium); The highest oxidation state of IVA family metal is generally+4 valencys; The highest oxidation state of VA family metal is generally+5 valencys; The highest oxidation state of IB family metal is generally+divalent (as copper) or+1 valency (as silver); The highest oxidation state of IIB family metal is generally+divalent; The highest oxidation state of VB family metal is generally+5 valencys; The highest oxidation state of group vib metal is generally+6 valencys; The highest oxidation state of VIIB family metal is generally+4 valencys (as manganese) or+7 valencys (as rhenium); The non-noble metal highest oxidation state of VIII family is generally+3 valencys (as iron or cobalt) or+divalent (as nickel).
Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of desulfurization cracking additive matrix and/or binding agent one or more, as in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, alkaline earth metal oxide, IB family metal oxide, the IIB family metal oxide one or more.In preferred aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, magnesium oxide, calcium oxide, the zinc oxide one or more.Wherein, if the metal component that the metal in the IB family metal oxide, IIB family metal oxide wholly or in part when going back ortho states, just completely or partially becomes auxiliary agent of the present invention to be contained.
Described clay is selected from as in the clay of cracking additive active ingredient one or more, as in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite (also claiming bentonite), sodium type wilkinite, the wilkinite, potter's clay, illite, halloysite, hectorite through pickling one or more.
The mineral compound that is suitable as carrier comprises one or more in the existing various mineral compound that is suitable as carrier, as in the titanate of the silicate of the phosphoric acid salt of the aluminate of the vitriol of the titanate of the silicate of the phosphoric acid salt of the aluminate of the vitriol of alkaline-earth metal, alkaline-earth metal, alkaline-earth metal, alkaline-earth metal, alkaline-earth metal, zinc, zinc, zinc, zinc, zinc, high-alumina cement, Roman cement, portland cement, clay, the mica one or more.One or more in calcium sulfate, calcium aluminate, calcium phosphate, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium aluminate, magnesium titanate, Zinc aluminate, zinc titanate, zinc silicate, high-alumina cement, Roman cement, portland cement, clay, the mica particularly.
The various sorbent materials that are used as gasoline and diesel oil distillate desulfurization in the prior art can be used as the described cracking additive of cracking method for hydrocarbon oil provided by the invention, forming under the identical situation, the cracking additive that contains oxidation state with employing is compared, and adopts these cracking methods that contain the sorbent material of as-reduced metal component to have stronger sweetening power.These auxiliary agents are published in the patent or patent application of various countries, and representative example comprises:
(1) CN1355727A and patent families US6 thereof, 254,766B1 is disclosed to be used for removing from pressure gasoline and diesel-fuel the adsorbent composition of sulphur, this adsorbent composition is made up of zinc oxide, silicon oxide, oxidation al and ni, and described nickel is basically with the reduction valence state, and preferred zeroth order exists, the content of nickel is 5-50 weight % in the adsorbent composition, the content of zinc oxide is 10-90 weight %, and the content of silicon oxide is 5-85 weight %, and the content of aluminum oxide is 5-30 weight %.
(2) CN1382071A and patent families US6 thereof, 184,176B1 is disclosed to be used for removing from pressure gasoline and diesel-fuel the adsorbent composition of sulphur, this adsorbent composition is made up of zinc oxide, silicon oxide, aluminum oxide and cobalt, and described cobalt is basically with the reduction valence state, and preferred zeroth order exists, the content of cobalt is 5-50 weight % in the adsorbent composition, the content of zinc oxide is 10-90 weight %, and the content of silicon oxide is 5-85 weight %, and the content of aluminum oxide is 5-30 weight %.
(3) CN1384770A and patent families US6 thereof, 271,173B1 is disclosed to be used for removing from pressure gasoline and diesel-fuel the adsorbent composition of sulphur, this adsorbent composition is made up of the promoter metals that is carried on the carrier compositions, described carrier compositions is made up of zinc oxide, silicon oxide, aluminum oxide and calcium cpd, and described calcium cpd is calcium sulfate, calcium aluminate, calcium phosphate or Calucium Silicate powder; Described promoter metals is basically with the reduction valence state, preferred zeroth order exists, the content of promoter metals is 5-50 weight % in the adsorbent composition, the content of zinc oxide is 10-90 weight %, the content of silicon oxide is 5-85 weight %, the content of aluminum oxide is 5-30 weight %, and described promoter metals is cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, vanadium or two or more mixture arbitrarily wherein.
(4) CN1382201A and patent families US6 thereof, 338,794B1 is disclosed to be used for removing from pressure gasoline and diesel-fuel the adsorbent composition of sulphur, this adsorbent composition is made up of zinc titanate carrier and metal, metal oxide or metal oxide precursor promoter metals, described promoter metals is cobalt, nickel, iron, manganese, copper, molybdenum, tungsten, silver, tin, vanadium or two or more mixture arbitrarily wherein, described promoter metals exists with the reduction valence state basically, and the content of promoter metals is 5-50 weight % in the adsorbent composition.
(5) CN1382199A and patent families US6 thereof, 274,533B1 is disclosed to be used for removing from pressure gasoline and diesel-fuel the adsorbent composition of sulphur, this adsorbent composition is made up of bimetal promotor and granular carrier, described bimetal promotor is gone up substantially with the reduction valence state and is existed, described bimetal promotor is selected from cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, any two or more mixture of antimony or vanadium, described carrier is by forming with the zinc oxide of any suitable inorganic carrier combination, and described inorganic carrier comprises silicon oxide, silica gel, aluminum oxide, clay, pure aluminium silicate, silica-alumina, titanium oxide, zirconium white, Zinc aluminate, zinc titanate, zinc silicate, calcium aluminate, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium aluminate, magnesium titanate, synthetic zeolite and natural zeolite.Under the preferable case, described granular carrier is formed described bimetal promotor by zinc oxide, silicon oxide and aluminum oxide and is made up of nickel and cobalt, the content of nickel and cobalt is 5-40 weight % in the adsorbent composition, the content of zinc oxide is 10-90 weight %, the content of silicon oxide is 5-85 weight %, and the content of aluminum oxide is 5-30 weight %.
(6) US6,346,190B1 is disclosed to be used for removing from pressure gasoline and diesel-fuel the adsorbent composition of sulphur, this adsorbent composition is made up of zinc ferrite, nickel and a kind of mineral binder bond basically, described zinc ferrite and nickel exist with the reduction valence state, described mineral binder bond can be silicon oxide, aluminum oxide, clay, clay, with described total composition is benchmark, the content of zinc oxide is 2-70 weight %, the content of ferric oxide is 3-70 weight, the content of described binding agent is 0.1-30 weight %, and the content of nickel is 1-50 weight %.
(7) the disclosed adsorbent composition that is used for removing sulphur of WO 02/18517A1 from pressure gasoline and diesel-fuel, this adsorbent composition contains a kind of carrier component, a kind of wear-resistant component and a kind of promoter component, described promoter component exists with the reduction valence state basically, described carrier comprises zinc oxide and any suitable inorganic carrier, and described inorganic carrier comprises silicon oxide, silica gel, aluminum oxide, diatomite, pearlstone, silica-alumina, titanium oxide, zirconium white, Zinc aluminate, zinc titanate, zinc silicate, magnesium aluminate, magnesium titanate, synthetic zeolite, natural zeolite and their combination.Described wear-resistant component is selected from clay, high-alumina cement, Roman cement portland cement, calcium aluminate, Calucium Silicate powder, mica and their combination, described clay comprises bentonite, sodium type bentonite, through the bentonite of pickling, diatomite, potter's clay, kaolin, polynite, illite, halloysite, hectorite, sepiolite and composition thereof.Described promoter component comprises cobalt, nickel, iron, manganese, copper, zinc, molybdenum, tungsten, silver, tin, antimony or vanadium and their mixtures.Described wear-resistant components contents is 1-30 weight %, and promoter component content is 5-50 weight %, and described carrier component preferably contains zinc oxide, and the content of zinc oxide is 10-90 weight %.Described carrier component more preferably contains zinc oxide, silicon oxide and aluminum oxide, and the content of silicon oxide is 5-85 weight %, and alumina content is 0.1-30 weight %.
According to embodiment preferred of the present invention, described cracking additive contains a kind of heat-resistant inorganic oxide, clay and a kind of metal component, contain or do not contain molecular sieve, with the cracking additive total amount is benchmark, the content of heat-resistant inorganic oxide is 2-68 weight %, the content of clay is greater than 30 to 80 weight %, the content of molecular sieve is 0-40 weight %, metal oxide in described maxivalence attitude, the content of metal component is 0.1-30 weight %, described metal component exists with the reduction valence state, and it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more.The content of described heat-resistant inorganic oxide is preferably 10-60 weight %, and the content of clay is preferably 35-60 weight %, and the content of molecular sieve is preferably 0-30 weight %, and in the metal oxide of described maxivalence attitude, the content of metal component is 0.5-20 weight %.Under the preferable case, be benchmark with the total amount of described cracking additive, the total content of described clay and zeolite is 35-80 weight %, is preferably 40-75 weight %.In this cracking additive, because the mixture content of clay or clay and zeolite is higher, its proportion and catalytic cracking catalyst are very approximate, the mixing of the two is more even, use the provided by the inventionization method of this auxiliary agent to have stronger sweetening power, and, unexpectedly, also have stronger heavy oil cracking ability.
According to method provided by the invention, under the preferable case, the ratio of the average valence of described metal component and its maxivalence attitude is 0-0.95, and more preferably under the situation, this ratio is 0.1-0.7.
The method of measuring described metal component average valence is as follows:
Accurately take by weighing about 0.4 gram cracking additive, put into the sample pool of TPD/R/O analysis tester, feeding hydrogen content is the hydrogen of 5 volume % and the gas mixture of nitrogen, the flow of hydrogen is 20 ml/min, with the speed of sample pool with 10 ℃/minute, be warming up to 1000 ℃ from room temperature, the cracking additive in the sample pool is carried out temperature programmed reduction(TPR), measure before the reduction respectively and reduction back cracking additive on the TPR characteristic peak of metal component, calculate the average valence of metal component according to following formula:
β M＝β M′-2f(A 1-A)/N
Wherein: β MBe the average valence of metal component M in the cracking additive, β M' be the maxivalence attitude of metal component M in the cracking additive; The TPR characteristic peak area of metal component M in the A cracking additive that to be metal component M exist with the reduction valence state; A 1The TPR characteristic peak area of metal component M in the cracking additive that exists with highest oxidation state for metal component M; N is the content (unit is mole) of metal component M in the cracking additive; F is a correction factor, and its measuring method is as follows: accurately take by weighing the sample pool that about 6.5 milligrams of CuO put into above-mentioned TPD/R/O analysis tester, under these conditions, measure the TPR characteristic peak area K that CuO is reduced fully 2, calculate hydrogen-consuming volume (mole) K by the stoichiometric number of reduction reaction 1, f is the ratio of hydrogen-consuming volume and TPR characteristic peak area, i.e. f=K 1/ K 2, the unit of f is a mole/TPR characteristic peak area.
Because therefore the position difference of the TPR characteristic peak of each metal, even contain metal component more than 2 kinds in the cracking additive, also can determine the TPR characteristic peak of each metal component.
According to method provided by the invention, the non-aluminum metal of described IIIA family comprises gallium, indium, thallium.Described IVA family metal comprises germanium, tin, lead.Described VA family metal comprises antimony, bismuth.Described IB family metal comprises copper, silver.Described IIB family metal comprises zinc, cadmium.Described VB family metal comprises vanadium, niobium, tantalum.Described group vib metal comprises chromium, molybdenum, tungsten.Described VIIB family metal comprises manganese, technetium, rhenium.Described VIII family base metal comprises iron, cobalt, nickel.Described metal component is preferably one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel, more preferably one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.
Described metal component can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.According to specific embodiment of the present invention, described metal component particularly when described metal component is vanadium, nickel and/or iron, is present in heat-resistant inorganic oxide and/or the clay.According to another one specific embodiment of the present invention, described metal component particularly when described metal component is iron, is present in the molecular sieve.
In embodiment preferred of the present invention, described heat-resistant inorganic oxide is selected from one or more in the heat-resistant inorganic oxide that is used as existing catalytic cracking catalyst matrix and binder component, is preferably in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide one or more.In preferred aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, magnesium oxide, the calcium oxide one or more.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.
In embodiment preferred of the present invention, described clay is selected from as in the clay of cracking additive active ingredient one or more, is preferably in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.Preferred clay is a kaolin.These clays are conventionally known to one of skill in the art.
According to method provided by the invention, described molecular screening is from as the zeolite of cracking additive active ingredient and in the non-zeolite molecular sieve one or more.
Described zeolite is preferably one or more in large pore zeolite and the mesopore zeolite.Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite one or more, the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth particularly, one or more in the Beta zeolite.
Described mesopore zeolite is to have greater than the zeolite of 0.56 nanometer less than the cavernous structure of 0.7 nano-rings opening, as zeolite (as the ZSM-5 zeolite) with MFI structure, in the zeolite with MFI structure (as phosphorous and/or rare earth ZSM-5 zeolite, the zeolite that the disclosed phosphorated of CN1194181A has the MFI structure) of phosphorous and/or rare earth, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite, the MCM-56 zeolite one or more.
Described non-zeolite molecular sieve refers to that aluminium in the zeolite and/or silicon are partly or entirely by the molecular sieve of one or more replacements in other element such as phosphorus, titanium, gallium, the germanium.These examples of molecular sieve comprise that the silicate with Different Silicon aluminum ratio is (as metal silicate metallosilicate, titanosilicate titanosilicate), metal aluminate metalloaluminates (as germanium aluminate Germaniumaluminates), metal phosphate metallophosphates, aluminate or phosphate aluminophosphates, metallic aluminium phosphoric acid salt metalloaluminophosphates, the aluminosilicophosphate metal integratedsilicoaluminophosphates (MeAPSO and ELAPSO) of melts combine, silico-aluminate silicoaluminophosphates (SAPO), in the gallium germanate (gallogermanates) one or more.One or more in SAPO-17 molecular sieve, SAPO-34 molecular sieve and the SAPO-37 molecular sieve particularly.
Under the preferable case, described molecular screening is from the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, one or more in the zeolite with MFI structure of Beta zeolite, the zeolite with MFI structure, phosphorous and/or rare earth.
The described cracking additive of method provided by the invention can also contain the rare earth metal component, and described rare earth metal component exists with the form of metal and/or compound.Described rare earth metal component can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.Described rare earth metal is selected from one or more in group of the lanthanides and the actinium series rare earth metal, be preferably in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, the lutetium one or more, more preferably lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal.With the cracking additive total amount is benchmark, and in oxide compound, described rare earth metal components contents is 0-50 weight %, is preferably 0-15 weight %.
The described cracking additive of method provided by the invention can also contain phosphorus component, and described phosphorus component is with the compound of phosphorus, as the oxide compound and/or the existence of phosphatic form of phosphorus.Described phosphorus component can be present in molecular sieve, heat-resistant inorganic oxide and the clay simultaneously, also may reside in molecular sieve, heat-resistant inorganic oxide and clay any two kinds, can also be present in any one of molecular sieve, heat-resistant inorganic oxide and clay.With the cracking additive total amount is benchmark, and in element phosphor, the content of described phosphorus component is 0-15 weight %, is preferably 0-8 weight %.
In example of the present invention, when if rare earth component and/or phosphorus component are the preparation cracking additive, used molecular sieve contains itself, the content of described molecular sieve is the content that contains the molecular sieve of rare earth component and/or phosphorus component, phosphorus component and rare earth components contents are not calculated separately, do not provide separately yet.
The described cracking additive of method provided by the invention can adopt disclosed any one method preparation of prior art, as can be according to CN1355727A and patent families US6 thereof, 254,766B1, CN1382071A and patent families US6 thereof, 184,176B1, CN1384770A and patent families US6 thereof, 271,173B1, CN1382201A and patent families US6 thereof, 338,794B1, CN1382199A and patent families US6 thereof, 274,533B1, US6,346,190B1, the preparation of WO 02/18517A1 disclosed method.
The preparation method of described cracking additive also can carry out with reference to the preparation method of the described cracking additive of the following preferred embodiment of the invention.
The preparation method of the described cracking additive of the preferred embodiment of the invention comprises and will contain the metal component compound, heat-resistant inorganic oxide and clay, the composition that contains or do not contain molecular sieve contacts with a kind of atmosphere that contains reducing gas, the described temperature that contacts with the atmosphere that contains reducing gas is enough to make the average valence of described metal component to be lower than its highest oxidation state with the time that contacts, described metal is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, each components contents makes in the final auxiliary agent and contains in the composition, in the auxiliary agent total amount, the heat-resistant inorganic oxide of 2-68 weight %, clay greater than 30-80 weight %, oxide compound in maxivalence attitude metal, 0.1-30 the metal component of weight %, the molecular sieve of 0-40 weight %.
Wherein, the described atmosphere that contains reducing gas refers to pure reducing gas or contains reducing gas and inert gas atmosphere.
The example of described pure reducing gas comprises hydrogen, carbon monoxide and contains in the hydro carbons of 1-5 carbon atom one or more, preferably includes in hydrogen, carbon monoxide, methane, ethane, propane, butane and various isomer thereof, pentane and the various isomer thereof one or more.
Described rare gas element refers to not the gas with described composition or metal component compound generation chemical action, as periodic table of elements O family gas, one or more in nitrogen, the carbonic acid gas.
The described example that contains reducing gas and inert gas atmosphere comprises hydrogen, carbon monoxide, contain one or more the mixture in one or more and the rare gas element in the hydro carbons of 1-5 carbon atom, the dry gas in the refinery.
In the described atmosphere that contains reducing gas, the concentration of reducing gas is not particularly limited, as long as the amount of used reducing gas can be with described metal component reduction.Under the preferable case, in the described atmosphere that contains reducing gas, reducing gas content is at least 10 volume %, more preferably 50 volume %.
Described composition is enough to make the average valence of described metal component and the ratio of its maxivalence attitude to be reduced to 0-0.95 with a kind of atmosphere that contains reducing gas temperature that contacts and the time that contacts, and is preferably 0.1-0.7.In general, the temperature of described contact can be 100-900 ℃, is preferably 400-700 ℃, and the time of contact is 0.1 second to 10 hours, is preferably 1 second-5 hours.Described contact can be a Static Contact, and promptly in an airtight container, the atmosphere that will contain reducing gas contacts with described composition.Described contact can be dynamic contact also, is about to the described bed that contains the atmosphere of reducing gas by described composition.The pressure of described contact both can carry out under normal pressure without limits, also can carry out being higher or lower than under the normal pressure.The consumption that contains the atmosphere of reducing gas is that every gram cracking additive per hour is not less than 5 milliliters of reducing gass, and preferred every gram cracking additive per hour is not less than 10 milliliters of reducing gass, and more preferably every gram cracking additive is 100-2000 milliliter reducing gas per hour.
Each components contents preferably makes in the final cracking additive and contains in the composition, with the cracking additive total amount is benchmark, the heat-resistant inorganic oxide of 10-60 weight %, the clay of 35-60 weight %, the molecular sieve of 0-30 weight % and in the oxide compound of maxivalence attitude metal, the metal component of 0.5-20 weight %.
Described metal component compound, heat-resistant inorganic oxide and the clay of containing, the composition that contains or do not contain molecular sieve can be the existing cracking additive that contains metal component, also can be to introduce the composition that obtains behind the metal component compound in the cracking additive of metallic components not.
The existing preparation method who contains the cracking additive of metal component is conventionally known to one of skill in the art, here repeats no more.
The method of introducing the metal component compound in the cracking additive of metallic components not also be the method for routine.For example, can adopt following method in the cracking additive of metallic components not, to introduce the metal component compound, prepare described metal component compound, heat-resistant inorganic oxide and the clay of containing, contain or do not contain the composition of molecular sieve.
One of method
(1), dry or moist then with containing the solution impregnation heat-resistant inorganic oxide of described metal component compound, precursor, clay and/or the molecular sieve of heat-resistant inorganic oxide; The solution that perhaps will contain described metal component compound mixes with precursor, clay and/or the molecular sieve of heat-resistant inorganic oxide, heat-resistant inorganic oxide, and is dry or moist then; Perhaps precursor, clay and/or the molecular sieve with described metal component compound and heat-resistant inorganic oxide, heat-resistant inorganic oxide carries out physical mixed; The solution that perhaps will contain described metal component compound mixes with precursor, clay and/or the molecular sieve of heat-resistant inorganic oxide, heat-resistant inorganic oxide, the precipitation agent that adds described metal component compound, described metal component is deposited in precursor, clay and/or the molecular sieve of heat-resistant inorganic oxide, heat-resistant inorganic oxide, dry or moist; The solution that perhaps will contain described metal component compound mixes with precursor, clay and/or the molecular sieve of heat-resistant inorganic oxide, heat-resistant inorganic oxide, and the slurry preparation that obtains is become colloid; Perhaps water-fast described metal component compound is mixed with precursor, clay and/or molecular sieve and the deionized water of heat-resistant inorganic oxide, heat-resistant inorganic oxide, the slurry preparation that obtains is become colloid, dry or moist;
(2) will introduce the heat-resistant inorganic oxide of described metal component compound, precursor, clay and/or the molecular sieve of heat-resistant inorganic oxide, or described mixture, or colloid and deionized water and the not heat-resistant inorganic oxide, precursor, clay and/or the molecular sieve making beating of heat-resistant inorganic oxide of metallic components compound, being prepared into solid content is 10-60 weight %, be preferably the slurries of 10-50 weight %, the slurries that drying obtains, roasting or not roasting.
Two of method
With precursor, clay and the deionized water of heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, making beating, being prepared into solid content is 10-60 weight %, be preferably the slurries of 10-50 weight %, can also contain molecular sieve in the described slurries, the slurries that drying obtains, roasting or not roasting, then, with the solid that obtains after the solution impregnation drying that contains described metal component compound, perhaps the solution with described metal component compound mixes with dried solid, then, drying, roasting or not roasting.
Three of method
Precursor, clay, described metal component compound and deionized water making beating with heat-resistant inorganic oxide and/or heat-resistant inorganic oxide, being prepared into solid content is 10-50 weight %, be preferably the slurries of 20-50 weight %, can also contain molecular sieve in the described slurries, the slurries that drying obtains, roasting or not roasting.
If also contain rare earth metal component and/or phosphorus component in the cracking additive, can adopt top method separately or introduce rare earth metal component and/or phosphorus component when introducing above-mentioned metal component, just replace the compound of above-mentioned metal component to get final product with rare earth compound and/or phosphorus compound.Described rare earth metal component and/or phosphorus component can also be the y-type zeolite or the overstable gamma zeolite of rare earth and/or phosphorus (as contain) that commercially available molecular sieve itself is had.
Wherein, the drying behind the described introducing metal component compound and the drying means of slurries and condition are conventionally known to one of skill in the art, for example, the exsiccant method can be dry, oven dry, forced air drying, spraying drying.The method of the drying means preferably spray drying of slurries.The exsiccant temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.Roasting condition behind roasting after the described slurry dried and the impregnating metal compound also is conventionally known to one of skill in the art, in general, maturing temperature behind roasting after the described slurry dried and the impregnating metal compound is 400-700 ℃, be preferably 450-650 ℃, roasting time was at least 0.5 hour, be preferably 0.5-100 hour, more preferably 0.5-10 hour.
The precursor of described heat-resistant inorganic oxide refers in described cracking catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminum oxide can be selected from hydrated aluminum oxide (as pseudo-boehmite) and/or aluminium colloidal sol.The precursor of silicon oxide can be selected from silicon sol, one or more in silicon gel and the water glass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of silicon sol and aluminium colloidal sol, one or more in the silica-alumina gel.The precursor of other heat-resistant inorganic oxide can be selected from its oxyhydroxide, as oxyhydroxide, the boric acid of zirconium, titanium, alkaline-earth metal.
Described metal component compound can be water-soluble compound of described metal, also can be to be insoluble in water and/or water-fast compound, as the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, the non-noble metal nitrate of VIII family, muriate, oxyhydroxide, in the oxide compound one or more, particularly gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the nitrate of cobalt, muriate, oxyhydroxide, in the oxide compound one or more.
Described rare earth compound can be water-soluble compound of rare earth metal, also can be to be insoluble in water and/or water-fast compound, as in the muriate of rare earth metal, nitrate, oxyhydroxide, the oxide compound one or more.
Described phosphorus compound can be water-soluble compound of described phosphorus, also can be to be insoluble in water and/or water-fast compound, as phosphoric acid, phosphorous acid, and the oxide compound of the phosphoric acid salt of ammonium, alkali-metal phosphoric acid salt, phosphorus, in the aluminum phosphate one or more.
Catalytic cracking catalyst in the described catalyst mixture that contains cracking additive and catalytic cracking catalyst is various catalytic cracking catalysts, as the various molecular sieves that contain, heat-resistant inorganic oxide contains or argillaceous not, contain or do not contain the rare earth metal component, contain or phosphorated catalytic cracking catalyst not.In described catalytic cracking catalyst, all on the books in former various patents of delivering of the content of the kind of the kind of the kind of described molecular sieve and content, heat-resistant inorganic oxide kind and content, clay and content, rare earth metal component and content, phosphorus and the non-patent literature, also be conventionally known to one of skill in the art.As CN 1024504C, CN 1085722C, CN 1307087A, the disclosed catalytic cracking catalyst of CN 1384173A.
In the described catalyst mixture that contains cracking additive and catalytic cracking catalyst, the content range of described cracking additive is the content range of cracking additive routine, and this scope is conventionally known to one of skill in the art.In general, with the described total amount that contains the catalyst mixture of cracking additive and catalytic cracking catalyst is benchmark, and the content that described cracking additive accounts for catalyst mixture is 0.1-50 weight %, is preferably 1-40 weight %, 1-30 weight % at least more preferably, preferably 1-20 weight % at least.
Can also contain other auxiliary agent in the described catalyst mixture that contains cracking additive and catalytic cracking catalyst, as in ignition dope, sulfur transfer catalyst, the octane enhancing additive one or more.All on the books in former various patents of delivering of these auxiliary agents and the non-patent literature.As CN 1034222C, the disclosed ignition dope of CN 1072109A, CN1089362C, CN 1286134A, CN 1295877A, the disclosed sulfur transfer catalyst of CN 1334316A, CN 1020280C, the disclosed octane enhancing additive of CN 1031409C.
According to method provided by the invention, described cracking hydrocarbon oil condition is conventional catalytic cracking condition.In general, this cracking hydrocarbon oil condition comprises that temperature of reaction is 400-700 ℃, is preferably 450-600 ℃, and weight hourly space velocity is 10-120 hour -1, be preferably 10-80 hour -1, the agent weight of oil is preferably 3-15 than for 1-20.
Method provided by the invention is particularly suitable for hydrocarbon oil containing surphur is carried out catalytic cracking, reduces the sulphur content in the crackate.When described auxiliary agent is the described auxiliary agent of the preferred embodiment of the invention, method provided by the invention is carried out catalytic cracking except being particularly suitable for to hydrocarbon oil containing surphur, the sulphur content that reduces in the crackate also improves beyond the transformation efficiency of hydrocarbon ils simultaneously, also be fit to the hydrocarbon ils of sulfur-bearing is not carried out catalytic cracking, to improve the transformation efficiency of hydrocarbon ils.
Described hydrocarbon ils is selected from oil and boiling range greater than 330 ℃ various petroleum fractionss, as sulfur-bearing or not long residuum, vacuum residuum, the decompressed wax oil of sulfur-bearing, the normal pressure wax oil, straight-run gas oil, propane is light/heavily de-oiling and wax tailings and through long residuum, vacuum residuum, the decompressed wax oil of hydrotreatment, one or more in the normal pressure wax oil.
The following examples will the present invention will be further described.
Unless stated otherwise, used kaolin is that Suzhou kaolin company produces in the example, and its solid content is 76 weight %; Used pseudo-boehmite is that Shandong Zibo 501 factories produce, and its solid content is 62 weight %; Used aluminium colloidal sol is produced its Al for the Shandong catalyst plant 2O 3Content is 21 weight %; Used silicon sol is produced its SiO for the Shandong catalyst plant 2Content is 27 weight %; The compound of metal component is chemical pure.
Embodiment 1
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
With kaolin, pseudo-boehmite, concentration is the cobalt nitrate aqueous solution mixing of 30 weight %, add deionized water, mix, slowly adding concentration under stirring fast is the hydrochloric acid of 36.5 volume %, regulate the pH value to 2.0 of slurries, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain.The consumption of kaolin, pseudo-boehmite and cobalt nitrate aqueous solution makes kaolin butt weight, Al 2O 3And Co 2O 3The ratio of weight be 50.0: 45.0: 5.0.
With the slurries spraying drying under 150 ℃ temperature that obtains, 550 ℃ of following roastings 1 hour.The catalyzer 200 that obtains is restrained in the fixed bed reduction reactor of packing into, under 400 ℃ of temperature, feeding flow is the hydrogen of 1000 ml/min, make hydrogen contact 0.5 hour with described solid, the temperature of reactor is reduced to room temperature, unload the solid after the reduction, obtain cracking additive C1 of the present invention.The ratio of the composition of auxiliary agent C1 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.Auxiliary agent is formed by calculating in the table 1, and the content of metal component is in the oxide compound of described metal component highest oxidation state.
Embodiment 2
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
Method by example 1 prepares auxiliary agent, and different is, the temperature that described solid contacts with hydrogen is 700 ℃, and be 3 hours duration of contact, obtains cracking additive C2 of the present invention.The ratio of the composition of auxiliary agent C2 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.
Embodiment 3
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
Kaolin, pseudo-boehmite and deionized water are mixed, slowly adding concentration under stirring fast is the hydrochloric acid of 36.5 volume %, regulate the pH value to 2.0 of slurries, it is 25 weight % that the add-on of deionized water makes the solid content of the slurries that obtain, and it is 50.0: 45.0 that the add-on of kaolin, pseudo-boehmite makes the weight ratio of kaolin and aluminum oxide.The slurries that spraying drying obtains under 150 ℃ temperature are the solid behind the cobalt nitrate aqueous solution impregnation drying of 10 weight % with concentration, and 550 ℃ of roastings, the consumption of cobalt nitrate aqueous solution makes Co then 2O 3With the weight ratio of kaolin and aluminum oxide be 5.0: 95.0.At 800 ℃, wore out 6 hours then with 100% water vapour.Solid after aging 200 is restrained in the fixed bed reduction reactor of packing into, under 400 ℃ of temperature, feeding flow is the hydrogen of 1000 ml/min, make hydrogen contact 0.5 hour with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain cracking additive C3 of the present invention.The ratio of the composition of C3 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.
Embodiment 4
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
With 3.19 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of Cobaltous nitrate hexahydrate aqueous solution dipping of 40 weight %, and 120 ℃ of oven dry obtain containing Co 2O 39.09 the kaolin of weight %.
Method by example 1 prepares auxiliary agent, and different is with containing Co 2O 39.09 the kaolin of weight % replaces example 1 described kaolin, does not add Xiao Suangu, obtains cracking additive C4 of the present invention.The ratio of the composition of auxiliary agent C4 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 1.
Comparative Examples 1
The explanation of this Comparative Examples contains reference auxiliary agent of highest oxidation state metal component and preparation method thereof.
Method by example 1 prepares auxiliary agent, and different is that the process that in fixed-bed reactor solid is not contacted with hydrogen obtains reference auxiliary agent CB1.The composition of CB1 is listed in the table 1.
Comparative Examples 2
The explanation of this Comparative Examples contains reference auxiliary agent of highest oxidation state metal component and preparation method thereof.
Method by example 3 prepares auxiliary agent, and different is that the process that in fixed-bed reactor solid is not contacted with hydrogen obtains reference auxiliary agent CB2.The composition of CB2 is listed in the table 1.
Table 1
Example number ??1 ??2 ??3 ??4 Comparative Examples 1 Comparative Examples 2
The auxiliary agent numbering ??C1 ??C2 ??C3 ??C4 ??CB1 ??CB2
The molecular sieve kind ??- ??- ??- ??- ??- ??-
Molecular sieve content, weight % ??- ??- ??- ??- ??- ??-
The heat-resistant inorganic oxide kind ??Al 2O 3 ??Al 2O 3 ??Al 2O 3 ??Al 2O 3 ??Al 2O 3 ??Al 2O 3
Heat-resistant inorganic oxide content, weight % ??45.0 ??45.0 ??45.0 ??45.0 ??45.0 ??45.0
Clay types Kaolin Kaolin Kaolin Kaolin Kaolin Kaolin
Clay content, weight % ??50.0 ??50.0 ??50.0 ??50.0 ??50.0 ??50.0
The metal component kind ??Co ??Co ??Co ??Co ??Co ??Co
Metal component content, weight % ??5.0 ??5.0 ??5.0 ??5.0 ??5.0 ??5.0
The metal component average valence ??+1.5 ??0 ??+1.5 ??+1.5 ??+3 ??+3
The ratio of metal component average valence and its maxivalence attitude ??0.5 ??0 ??0.5 ??0.5 ??1 ??1
Metal component distributes Be evenly distributed in the auxiliary agent Be evenly distributed in the auxiliary agent Be evenly distributed in the auxiliary agent Be evenly distributed in the clay Be evenly distributed in the auxiliary agent Be evenly distributed in the auxiliary agent
Embodiment 5
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
Method by example 1 prepares auxiliary agent, different is, with concentration is the zinc nitrate aqueous solution replacement cobalt nitrate aqueous solution of 30.0 weight %, it is 20 weight % that the add-on of deionized water makes the solid content of the slurries that obtain, and the add-on of kaolin, pseudo-boehmite, zinc nitrate aqueous solution makes kaolin butt weight, Al 2O 3With the weight ratio of ZnO be 38.0: 50.0: 12.0.Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the flow of gas mixture is 2000 ml/min, the temperature that described solid contacts with gas mixture is 800 ℃, and be 3 hours duration of contact, obtains cracking additive C5 of the present invention.The ratio of the composition of C5 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.
Embodiment 6
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
Method by example 1 prepares auxiliary agent, different is, with concentration is the copper nitrate aqueous solution replacement cobalt nitrate aqueous solution of 20.0 weight %, in slurries, also added titanium dioxide (chemical pure), it is 20 weight % that the add-on of deionized water makes the solid content of the slurries that obtain, and the add-on of kaolin, titanium dioxide, pseudo-boehmite, copper nitrate aqueous solution makes kaolin butt weight, titanium dioxide, Al 2O 3With the weight ratio of CuO be 42.0: 2.4: 48.0: 7.6.Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the flow of gas mixture is 1000 ml/min, the temperature that described solid contacts with gas mixture is 400 ℃, be 0.5 hour duration of contact, obtains cracking additive C6 of the present invention.The ratio of the composition of C6 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.
Embodiment 7
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
Method by example 1 prepares auxiliary agent, different is, with concentration is the iron nitrate aqueous solution replacement cobalt nitrate aqueous solution of 20.0 weight %, replace pseudo-boehmite with silicon sol and aluminium colloidal sol, do not add aqueous hydrochloric acid, the add-on of kaolin, silicon sol, aluminium colloidal sol and iron nitrate aqueous solution makes kaolin butt weight, silicon oxide, aluminum oxide and Fe 2O 3Weight ratio be 45.0: 20.0: 31.8: 3.2.Reductive atmosphere is hydrogen content 50 volume % and the hydrogen of carbon monoxide content 50 volume % and the gas mixture of carbon monoxide, the flow of gas mixture is 1200 ml/min, the temperature that described solid contacts with gas mixture is 600 ℃, be 0.5 hour duration of contact, obtains cracking additive C7 of the present invention.The ratio of the composition of auxiliary agent C7 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.
Embodiment 8
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
(1) with 3.48 kilograms of concentration is the ammonium molybdate ((NH of 25 weight % 4) 6Mo 7O 24.4H 2O) (solid content is 85.0 weight % for the aqueous solution 3.0 kilograms of (dry basis) kaolin of dipping and 0.5 kilogram of (dry basis) diatomite, Shengzhou, Zhejiang Province city China power diatomite factory product) mixture, 120 ℃ of oven dry, and then with the silver nitrate aqueous solution of 2.77 kilogram of 1.5 weight % dipping, 120 ℃ of oven dry, 600 ℃ of roastings 2 hours obtain containing MoO 316.7 weight % and Ag 2The kaolin of O 0.67 weight % and diatomaceous mixture.
(2) will contain MoO 3And Ag 2The kaolin of O and diatomaceous mixture, pseudo-boehmite and deionized water mix, slowly adding concentration under stirring fast is the hydrochloric acid of 36.5 volume %, regulates the pH value to 1.5 of slurries, and (the industrial trade mark is MOY to add the HY zeolite of phosphorous and rare earth again, lattice constant is 24.59 dusts, Na 2O content is 1.0 weight %, in element phosphor, phosphorus content is 1.2 weight %, and rare earth oxide content is 8.5 weight %, wherein, lanthanum trioxide content is 4.5 weight %, cerium oxide content is 1.1 weight %, and other rare earth oxide content is 2.9 weight %, and the Shandong catalyst plant is produced), it is 25 weight % that the add-on of deionized water makes the solid content of the slurries that obtain, and contains MoO 3And Ag 2The add-on of the kaolin of O and diatomaceous mixture, pseudo-boehmite, MOY zeolite makes kaolin and diatomaceous butt weight, aluminum oxide, the butt weight of MOY zeolite, Ag 2O and MoO 3Weight ratio be 37.0: 20.2: 35: 0.3: 7.5.Reductive atmosphere is the nitrogen of hydrogen content 50 volume % and the gas mixture of hydrogen, and the flow of gas mixture is 2500 ml/min, and the temperature that described solid contacts with gas mixture is 650 ℃, and be 1 hour duration of contact, obtains cracking additive C8 of the present invention.The ratio of the composition of auxiliary agent C8 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 2.
Comparative Examples 3
The explanation of this Comparative Examples contains reference auxiliary agent of highest oxidation state metal component and preparation method thereof.
Method by example 8 prepares auxiliary agent, and different is, not in fixed-bed reactor with solid and the process that the gas mixture of hydrogen and carbon monoxide contacts, obtain reference auxiliary agent CB3.The composition of CB3 is listed in the table 2.
Table 2
Example number ??5 ????6 ????7 ??8 Comparative Examples 3
The auxiliary agent numbering ??C5 ????C6 ????C7 ??C8 ??CB3
The molecular sieve kind ??- ????- ????- ??MOY ??MOY
Molecular sieve content, weight % ??- ????- ????- ??35.0 ??35.0
The heat-resistant inorganic oxide kind ??Al 2O 3 ????Al 2O 3/TiO 2 ????Al 2O 3/SiO 2 ??Al 2O 3 ??Al 2O 3
Heat-resistant inorganic oxide content, weight % ??50.0 ????50.4 ????51.8 ??20.2 ??20.2
Clay types Kaolin Kaolin Kaolin Kaolin/diatomite Kaolin/diatomite
Clay content, weight % ??38.0 ????42.0 ????45.0 ??37.0 ??37.0
The metal component kind ??Zn ????Cu ????Fe ??Ag/Mo ??Ag/Mo
Metal component content, weight % ??12.0 ????7.6 ????3.2 ??0.3/7.5 ??0.3/7.5
The metal component average valence ??+1.4 ????+0.56 ????+1.8 ??0/+3.3 ??+1/+6
The ratio of metal component average valence and its maxivalence attitude ??0.70 ????0.28 ????0.60 ??0/0.55 ??1/1
Metal component distributes Be evenly distributed in the auxiliary agent Be evenly distributed in the auxiliary agent Be evenly distributed in the auxiliary agent Be evenly distributed in the clay Be evenly distributed in the clay
Embodiment 9
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
(1) with 3.09 kilograms of concentration be 3.0 kilograms of (dry basis) kaolin of manganese nitrate aqueous solution dipping of 20.0 weight %, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain containing MnO 29.09 the kaolin of weight %.
(2) with 500 gram NaY (Na 2The heavy % of O content 11, silica alumina ratio is 5.6, the Chang Ling catalyst plant is produced) with the aqueous ammonium chloride solution of 10 liter of 0.15 mol 60 ℃ of exchanges 1 hour down, the filter cake after the filtration was 550 ℃ of roastings 2 hours.Again by above-mentioned steps exchange and roasting twice, obtaining sodium oxide content is the HY zeolite of 0.3 weight % with it.
(3) method by (2) in the example 8 prepares auxiliary agent, and different is, contains MnO with what this example (1) obtained 2Kaolin replace the example 8 described MoO that contain 3And Ag 2The kaolin of O and diatomaceous mixture, the HY type zeolite that obtains with this example (2) replaces the MOY zeolite; Contain MnO 2Kaolin, pseudo-boehmite, the consumption of HY zeolite make kaolin butt weight, Al 2O 3, HY zeolite butt weight and MnO 2The ratio of weight be 50.0: 40.0: 5.0: 5.0.Reductive atmosphere is hydrogen content 80 volume % and the hydrogen of propane content 20 volume % and the gas mixture of propane, the flow of gas mixture is 1500 ml/min, the temperature that described solid contacts with gas mixture is 500 ℃, and be 1 hour duration of contact, obtains cracking additive C9 of the present invention.The ratio of the composition of auxiliary agent C9 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.
Embodiment 10
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
Under agitation, with 3.86 kilograms of concentration be the ammonium meta-vanadate (NH of 5.0 weight % 4VO 3) 3.0 kilograms of (dry basis) kaolin of aqueous solution dipping and 0.225 kilogram of magnesian mixture, 120 ℃ of slurries that oven dry obtains, 550 ℃ of roastings 2 hours obtain containing MgO 6.67 weight %, V 2O 54.44 the kaolin of weight %.
Method by (2) in the example 8 prepares auxiliary agent, and different is with above-mentioned MgO of containing and V 2O 5Kaolin replace the example 8 described MoO that contain 3And Ag 2The kaolin of O and diatomaceous mixture, (the industrial trade mark is DASY, and lattice constant is 24.45 dusts, Na with overstable gamma zeolite 2O content is 1.0 weight %, and the Shandong catalyst plant is produced) replacement MOY zeolite; Contain MgO and V 2O 5Kaolin, pseudo-boehmite, the consumption of DASY zeolite make kaolinic butt weight, magnesium oxide, Al 2O 3, DASY zeolite butt weight and V 2O 5The ratio of weight be 40.0: 3.0: 45.0: 10.0: 2.0; The temperature that described solid contacts with hydrogen is 550 ℃, and the flow of hydrogen is 1000 ml/min, and be 1 hour duration of contact, obtains cracking additive C10 of the present invention.The ratio of the composition of auxiliary agent C10 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.
Embodiment 11
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
With 3.42 kilograms of concentration is 3.0 kilograms of (dry basis) kaolin of gallium chloride aqueous solution dipping of 25 weight % and the mixture of 0.86 kilogram of (dry basis) pseudo-boehmite, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain containing Ga 2O 310.53 the kaolin of weight % and the mixture of aluminum oxide.
To contain Ga 2O 3Kaolin and mixture, silicon sol, aluminium colloidal sol and the deionized water of pseudo-boehmite mix, (the industrial trade mark is ZRP-1 with the zeolite with MFI structure of DASY zeolite and phosphorous and rare earth, in element phosphor, phosphorus content is 2.0 weight %, and rare earth oxide content is 1.0 weight %, wherein, lanthanum trioxide content is 0.53 weight %, cerium oxide content is 0.13 weight %, and other rare earth oxide content is 0.34 weight %, Na 2O content is less than 0.1 weight %, SiO 2With Al 2O 3Mol ratio be 60, the Shandong catalyst plant is produced), mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains Ga 2O 3Kaolin and the consumption of mixture, silicon sol, aluminium colloidal sol, overstable gamma zeolite and the ZSM-5 zeolite of pseudo-boehmite make kaolin butt weight, aluminum oxide, silicon oxide, super stable molecular sieve butt weight, ZRP-1 zeolite butt weight and Ga 2O 3The ratio of weight be 35.0: 30.0: 9.7: 15.0: 5.0: 5.3.With the slurries spraying drying under 150 ℃ temperature that obtains,,, wore out 6 hours with 100% water vapour then at 800 ℃ 550 ℃ of following roastings 2 hours.The solid 200 that obtains is restrained in the fixed bed reduction reactor of packing into, and under 600 ℃ of temperature, feeding flow is the hydrogen of 3000 ml/min, make hydrogen contact 2 hours with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain cracking additive C11 of the present invention.The ratio of the composition of auxiliary agent C11 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.
Embodiment 12
Present embodiment illustrates cracking additive of the present invention and preparation method thereof.
With 5.39 kilograms of concentration is the tin protochloride SnCl of 4.0 weight % 2The aqueous solution, 1.46 kilograms of (dry basis) silicon sol and 3.0 kilograms of (dry basis) kaolin mix, 120 ℃ of oven dry, and 550 ℃ of roastings 3 hours obtain containing SnO 23.7 the kaolin of weight % and the mixture of silicon oxide.
To contain SnO 2Kaolin and mixture, aluminium colloidal sol and the deionized water of silicon oxide mix, add DASY and ZRP-1 zeolite again, mix, it is 25 weight % that the consumption of deionized water makes the solid content of the slurries that obtain, and contains SnO 2Kaolin and the consumption of mixture, aluminium colloidal sol, DASY zeolite and the ZRP-1 zeolite of silicon oxide make kaolin butt weight, aluminum oxide, silicon oxide, DASY zeolite butt weight, ZRP-1 zeolite butt weight and SnO 2The ratio of weight be 35.0: 30.0: 17.0: 11.0: 5.0: 2.0.With the slurries spraying drying under 150 ℃ temperature that obtains,,, wore out 8 hours with 100% water vapour then at 800 ℃ 550 ℃ of following roastings 2 hours.The solid 200 that obtains is restrained in the fixed bed reduction reactor of packing into, and under 650 ℃ of temperature, feeding flow is the hydrogen of 1000 ml/min, make hydrogen contact 1 hour with described solid, make the temperature of reactor reduce to room temperature, unload the solid after the reduction, obtain cracking additive C12 of the present invention.The ratio of the composition of auxiliary agent C12 and the kind of metal component, distribution, average valence and average valence and its maxivalence attitude is listed in the table 3.
Table 3
Example number ??9 ??10 ????11 ????12
The auxiliary agent numbering ??C9 ??C10 ????C11 ????C12
The molecular sieve kind ??HY Super steady Y Super steady Y/ZRP-1 Super steady Y/ZRP-1
Molecular sieve content, weight % ??5.0 ??10.0 ????20.0 ????16.0
The heat-resistant inorganic oxide kind ??Al 2O 3 ??Al 2O 3/MgO ????Al 2O 3/SiO 2 ????Al 2O 3/SiO 2
Heat-resistant inorganic oxide content, weight % ??40.0 ??48.0 ????39.7 ????47.0
Clay types Kaolin Kaolin Kaolin Kaolin
Clay content, weight % ??50.0 ??40.0 ????35.0 ????35.0
The metal component kind ??Mn ??V ????Ga ????Sn
Metal component content, weight % ??5.0 ??2.0 ????5.3 ????2.0
The metal component average valence ??+1.5 ??+2.3 ????+1.6 ????+2.0
The ratio of metal component average valence and its maxivalence attitude ??0.38 ??0.46 ????0.53 ????0.50
Metal component distributes Be evenly distributed in the clay Be distributed in clay and the magnesium oxide Be distributed in clay and the aluminum oxide Be distributed in clay and the silicon oxide
Example 13-24
Following example illustrates method provided by the invention.
Respectively with cracking additive C1-C12 and through 800 ℃, 8 hours HGY-2000R Industrial Catalysis cracking catalyst of 100% water vapour burin-in process (contains super steady Y, rare earth exchanged Y zeolite, aluminum oxide and kaolinic catalytic cracking catalyst, the Shandong catalyst plant is produced) mix, obtain catalyst mixture.On the small stationary bed reaction device, adopt the above-mentioned catalyst mixture that obtains respectively, his-and-hers watches 4 listed boiling ranges are that 329-550 ℃ sulfur-bearing decompressed wax oil carries out catalytic cracking, catalyzer loading amount 4.0 grams.The kind of cracking additive and content in the catalyst mixture, reaction conditions and reaction result are listed among the table 5-7.Sulphur content adopts gas-chromatography-atomic emission spectrometry in the crackate, measures on HP 6890GC-G2350A AED gas-chromatography-Atomic Emission SpectrometerAES.
Wherein, agent-oil ratio refers to the weight ratio of catalyst mixture and described stock oil.
Comparative Examples 4-6
The method of reference auxiliary agent is used in following Comparative Examples explanation.
Method by example 13 is carried out catalytic cracking to identical stock oil, different the is catalyst system therefor mixture is respectively CB1, CB2, CB3 and through 800 ℃, the catalyst mixture of 8 hours HGY-2000R of 100% water vapour burin-in process, the kind of reference auxiliary agent and content in the catalyst mixture, reaction conditions and reaction result are listed in the table 5.
Table 4
The stock oil title Long residuum Decompressed wax oil
Density (20 ℃), gram per centimeter 3 ????0.8906 ????0.9154
Viscosity, millimeter 2/ second
????50℃ ????- ????34.14
????100℃ ????24.84 ????6.96
Bituminous matter, weight % ????0.8 ????0.0
Conradson carbon residue, weight % ????4.3 ????0.18
S, weight % ????0.13 ????2.0
Boiling range, ℃
????IBP ????282 ????329
????10％ ????370 ????378
????50％ ????553 ????436
????90％ ????- ????501
????95％ ????- ????518
????FBP ????- ????550
Table 5
Example number ????13 ????14 ????15 ????16 Comparative Examples 4 Comparative Examples 5
The auxiliary agent kind ????C1 ????C2 ????C3 ????C4 ????CB1 ????CB2
The content of auxiliary agent in catalyst mixture, weight % ????5 ????5 ????5 ????5 ????5 ????5
Temperature of reaction, ℃ ????480 ????480 ????480 ????480 ????480 ????480
Weight hourly space velocity, hour -1 ????16 ????16 ????16 ????16 ????16 ????16
Agent-oil ratio ????6 ????6 ????6 ????6 ????6 ????6
Transformation efficiency, weight % ????71.8 ????70.9 ????71.6 ????71.3 ????66.9 ????67.3
Product yield, weight %
Dry gas ????1.6 ????1.7 ????1.8 ????1.9 ????1.6 ????1.9
Liquefied gas ????12.3 ????12.8 ????12.6 ????13.1 ????11.2 ????11.5
Gasoline ????49.3 ????47.1 ????48.8 ????47.7 ????45.6 ????45.5
Diesel oil ????16.6 ????18.2 ????17.1 ????17.1 ????18.4 ????17.9
Heavy oil ????11.6 ????10.9 ????11.3 ????11.6 ????14.7 ????14.8
Coke ????8.6 ????9.3 ????8.4 ????8.6 ????8.5 ????8.4
Gasoline sulfure content, mg/litre ????613 ????615 ????603.2 ????610.3 ????753.8 ????765.2
The presentation of results of table 5, all contain auxiliary agent 5.0 weight % in the catalyst mixture, compare when containing the catalyst mixture of reference auxiliary agent, adopt when containing the catalyst mixture of cracking additive of the present invention with employing, the hydrocarbon oil conversion rate significantly improves, and the sulphur content in the gasoline product significantly descends.This explanation, when adopting the cracking additive of preferred embodiment of the present invention, method provided by the invention not only has stronger sweetening power, and, also have higher heavy oil conversion performance.
Table 6
Example number ????17 ????18 ????19 ????20 Comparative Examples 6
The auxiliary agent kind ????C5 ????C6 ????C7 ????C8 ????CB3
The content of auxiliary agent in catalyst mixture, weight % ????3 ????5 ????15 ????10 ????10
Temperature of reaction, ℃ ????520 ????520 ????520 ????520 ????520
Weight hourly space velocity, hour -1 ????16 ????16 ????16 ????16 ????16
Agent-oil ratio ????3.5 ????3.5 ????3.5 ????3.5 ????3.5
Transformation efficiency, weight % ????72.3 ????72.1 ????75.6 ????76.3 ????72.3
Product yield, weight %
Dry gas ????1.9 ????2 ????2.5 ????2.5 ????1.9
Liquefied gas ????14.2 ????14 ????15.5 ????16.8 ????14.2
Gasoline ????47.7 ????46.5 ????48.3 ????47.9 ????47.7
Diesel oil ????17.2 ????17.7 ????15.1 ????15.6 ????17.2
Heavy oil ????10.5 ????10.2 ????9.3 ????8.1 ????10.5
Coke ????8.5 ????9.6 ????9.3 ????9.1 ????8.5
Gasoline sulfure content, mg/litre ????700.3 ????710.6 ????625.1 ????589.3 ????810.3
From the result of comparison example 20 and Comparative Examples 6, equally as can be seen, when adopting the cracking additive of preferred embodiment of the present invention, method provided by the invention not only has stronger sweetening power, and, also have higher heavy oil conversion performance.
Table 7
Example number ????21 ????22 ????23 ????24
The auxiliary agent kind ????C9 ????C10 ????C11 ????C12
The content of auxiliary agent in catalyst mixture, weight % ????3 ????5 ????15 ????10
Temperature of reaction, ℃ ????520 ????520 ????520 ????520
Weight hourly space velocity, hour -1 ????16 ????16 ????16 ????16
Agent-oil ratio ????3.5 ????3.5 ????3.5 ????3.5
Transformation efficiency, weight % ????72.3 ????72.1 ????75.6 ????74.3
Product yield, weight %
Dry gas ????1.9 ????2 ????2.5 ????2.3
Liquefied gas ????14.2 ????14 ????15.5 ????16.8
Gasoline ????47.7 ????46.5 ????48.3 ????46.6
Diesel oil ????17.2 ????17.7 ????15.1 ????16.6
Heavy oil ????10.5 ????10.2 ????9.3 ????9.1
Coke ????8.5 ????9.6 ????9.3 ????8.6
Gasoline sulfure content, mg/litre ????698.3 ????710.6 ????625.1 ????610.3
Example 25-27
Following example illustrates method provided by the invention.
Respectively with cracking additive C8, C10, C11 and through 800 ℃, 8 hours CR022 Industrial Catalysis cracking catalyst of 100% water vapour burin-in process (zeolite, aluminum oxide and the kaolinic catalytic cracking catalyst that contain y-type zeolite, have the MFI structure, the Shandong catalyst plant is produced) mix, obtain catalyst mixture.Long residuum content shown in the his-and-hers watches 4 is that 20 weight % and decompressed wax oil content are that the mixing oil of 80 weight % carries out catalytic cracking on the small stationary bed reaction device, and the catalyst mixture loading amount is 90 grams, and reaction conditions and reaction result are listed in the table 8.
Comparative Examples 7
The situation of 8 hours commercial catalysts CR022 of 100% water vapour burin-in process is only used through 800 ℃ in following example explanation.
Press the identical stock oil of method catalytic cracking of example 25, different is, catalyst system therefor is CR022, and reaction result is listed in the table 8.
Table 8
Example number ???25 ???26 ???27 Comparative Examples 7
Catalyzer ???20％C8+80％ ???CR022 ???3％C10+97％ ???CR022 ???10％C11+90％ ???CR022 ???CR022
Temperature of reaction, ℃ ???500 ???500 ???500 ???500
Weight hourly space velocity, hour -1 ???10 ???10 ???10 ???10
Agent-oil ratio ???5 ???5 ???5 ???5
Transformation efficiency, weight % ???74 ???72.5 ???73.4 ???71.6
Product yield, weight %
Dry gas ???1.7 ???1.7 ???1.8 ???1.5
Liquefied gas ???15.2 ???14.6 ???18.4 ???15.2
Gasoline ???49.9 ???48.9 ???45.8 ???47.8
Diesel oil ???17.5 ???18.6 ???17.9 ???19.3
Heavy oil ???8.5 ???8.9 ???8.7 ???9.1
Coke ???7.2 ???7.3 ???7.4 ???7.1
Gasoline sulfure content, mg/litre ???598.3 ???750.6 ???626.5 ???846.3
The result of table 8 shows, method provided by the invention is compared during with independent use catalytic cracking catalyst, uses the described cracking additive of the preferred embodiment of the invention, and the hydrocarbon oil conversion rate is significantly improved, and the sulphur content in the gasoline product significantly descends.This illustrates that again when adopting the cracking additive of preferred embodiment of the present invention, method provided by the invention not only has stronger sweetening power, and, also have higher heavy oil conversion performance.
Example 28
This example illustrates method provided by the invention.
Preparation method according to WO02/18517A1 example 1 adsorbent B, prepare described sorbent material, different is, pseudo-boehmite with identical butt weight replaces DISPAL180 aluminum oxide (DISPAL180 alumina), kaolin replacement bentonite (bentonite) wherein with identical butt weight, with the nickeliferous 23 weight % that obtain, the solid of kaolin 10 weight % and aluminum oxide and zinc oxide carrier is according to the example 1 described condition (reductive condition before Cycle 1 beginning) reduction, obtain adsorbent B (sorbentB), as the described auxiliary agent of method provided by the invention, note is C13 with adsorbent B.
Method according to example 13 of the present invention.Same stock oil is carried out catalytic cracking, and different is to use C13 replaced C 1.Reaction result is listed in the table 9.
Example 29
This example illustrates method provided by the invention.
Method according to CN1384770A example 1 prepares reduced nickel metal solid sorbent material, different is, pseudo-boehmite with identical butt weight replaces the Dispersal aluminum oxide, diatomite is example 8 described diatomite of the present invention, with the composition that contains zinc oxide, silicon oxide, aluminum oxide, calcium sulfate and nickel compound that obtains, according to CN1384770A example 2 described " reductive condition " reduction down, obtain reduced nickel metal solid sorbent material, as the described auxiliary agent of method provided by the invention, note is C14 with this reduced nickel metal solid sorbent material.
Method according to example 13 of the present invention.Same stock oil is carried out catalytic cracking, and different is to use C14 replaced C 1.Reaction result is listed in the table 9.
Table 9
Example number ????28 ????29
The auxiliary agent kind ????C13 ????C14
The content of auxiliary agent in catalyst mixture, weight % ????5 ????5
Temperature of reaction, ℃ ????480 ????480
Weight hourly space velocity, hour -1 ????16 ????16
Agent-oil ratio ????6 ????6
Transformation efficiency, weight % ????70.3 ????71.0
Product yield, weight %
Dry gas ????2.3 ????2.6
Liquefied gas ????11.3 ????10.2
Gasoline ????47.2 ????48.3
Diesel oil ????16.9 ????16.4
Heavy oil ????12.8 ????12.6
Coke ????9.5 ????9.9
Gasoline sulfure content, mg/litre ????650.0 ????645.3
The result of table 9 shows, adopts method provided by the invention, uses clay content to be lower than the cracking additive of 30 weight %, also has stronger sweetening power and heavy oil conversion performance.

Claims (31)

1. cracking method for hydrocarbon oil, this method is included under the cracking conditions, the catalyst mixture of a kind of hydrocarbon ils with a kind of cracking additive and catalytic cracking catalyst contacted, reclaim the catalytic cracking production that sulphur content reduces, described cracking additive contains a kind of carrier and a kind of metal component, it is characterized in that, with the auxiliary agent total amount is benchmark, the content of carrier is 0.1-99.9 weight %, metal oxide in the maxivalence attitude, the content of metal component is 0.1-99.9 weight %, at least a portion of described metal component exists with the reduction valence state, it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more, described carrier is selected from heat-resistant inorganic oxide, clay, molecular sieve and be suitable as in the mineral compound of carrier one or more.
2. method according to claim 1 is characterized in that, is benchmark with the auxiliary agent total amount, and the content of described carrier is 20-99.5 weight %, and in the metal oxide of maxivalence attitude, the content of metal component is 0.5-80 weight %.
3. method according to claim 1, it is characterized in that described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, alkaline earth metal oxide, IB family metal oxide, the IIB family metal oxide.
4. method according to claim 3 is characterized in that described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, magnesium oxide, calcium oxide, the zinc oxide.
5. method according to claim 1, it is characterized in that described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, wilkinite, sodium type wilkinite, the wilkinite through pickling, potter's clay, illite, halloysite, the hectorite.
6. method according to claim 1 is characterized in that, described molecular screening one or more in macropore zeolite and mesopore zeolite.
7. method according to claim 6, it is characterized in that, described molecular screening is from the super steady Y stone of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, one or more in the zeolite with MFI structure of Beta zeolite, the zeolite with MFI structure, phosphorous and/or rare earth.
8. method according to claim 1, it is characterized in that the mineral compound that is suitable as carrier is selected from one or more in the titanate, high-alumina cement, Roman cement, portland cement, clay, mica of silicate, the zinc of phosphoric acid salt, the zinc of aluminate, the zinc of vitriol, the zinc of titanate, the zinc of silicate, the alkaline-earth metal of phosphoric acid salt, the alkaline-earth metal of aluminate, the alkaline-earth metal of the vitriol of alkaline-earth metal, alkaline-earth metal.
9. method according to claim 8, it is characterized in that the mineral compound that is suitable as carrier is selected from one or more in calcium sulfate, calcium aluminate, calcium phosphate, Calucium Silicate powder, Magnesium Silicate q-agent, magnesium aluminate, magnesium titanate, Zinc aluminate, zinc titanate, zinc silicate, high-alumina cement, Roman cement, portland cement, clay, the mica.
10. method according to claim 1, it is characterized in that, described cracking additive contains a kind of heat-resistant inorganic oxide, clay and a kind of metal component, contain or do not contain molecular sieve, with the cracking additive total amount is benchmark, the content of heat-resistant inorganic oxide is 2-68 weight %, the content of clay is greater than 30 to 80 weight %, the content of molecular sieve is 0-40 weight %, metal oxide in described maxivalence attitude, the content of metal component is 0.1-30 weight %, described metal component exists with the reduction valence state, and it is selected from the non-aluminum metal of periodic table of elements IIIA family, IVA family metal, VA family metal, IB family metal, IIB family metal, VB family metal, the group vib metal, VIIB family metal, in the VIII family base metal one or more.
11. method according to claim 10, it is characterized in that, with the auxiliary agent total amount is benchmark, the content of described heat-resistant inorganic oxide is 10-60 weight %, the content of clay is 35-60 weight %, the content of molecular sieve is 0-30 weight %, and in the metal oxide of described maxivalence attitude, the content of metal component is 0.5-20 weight %.
12., it is characterized in that according to claim 10 or 11 described methods, be benchmark with the total amount of described auxiliary agent, the total content of described clay and zeolite is 35-80 weight %.
13. method according to claim 12 is characterized in that, is benchmark with the total amount of described auxiliary agent, the total content of described clay and zeolite is 40-75 weight %.
14., it is characterized in that the ratio of the average valence of described metal component and its maxivalence attitude is 0-0.95 according to claim 10 or 11 described methods.
15. method according to claim 14 is characterized in that, the ratio of the average valence of described metal component and its maxivalence attitude is 0.1-0.7.
16., it is characterized in that described metal component is selected from one or more in gallium, germanium, tin, antimony, bismuth, lead, copper, silver, zinc, cadmium, vanadium, molybdenum, tungsten, manganese, iron, cobalt, the nickel according to claim 10 or 11 described methods.
17. method according to claim 16 is characterized in that, described metal component is selected from one or more in gallium, tin, copper, silver, zinc, vanadium, molybdenum, manganese, iron, the cobalt.
18., it is characterized in that described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide according to claim 10 or 11 described methods.
19. according to claim 10 or 11 described methods, it is characterized in that described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.
20., it is characterized in that described molecular screening one or more in macropore zeolite and mesopore zeolite according to claim 10 or 11 described methods.
21. method according to claim 20, it is characterized in that, described molecular screening is from the overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, one or more in the zeolite with MFI structure of Beta zeolite, the zeolite with MFI structure, phosphorous and/or rare earth.
22., it is characterized in that this auxiliary agent also contains the rare earth metal component according to claim 10 or 11 described methods, be benchmark with the auxiliary agent total amount, in oxide compound, described rare earth metal components contents is 0-50 weight %.
23. method according to claim 22 is characterized in that, described rare earth metal components contents is 0-15 weight %.
24. method according to claim 23 is characterized in that, described rare earth metal is lanthanum, cerium, lanthanum rich norium or cerium-rich mischmetal metal.
25., it is characterized in that this auxiliary agent also contains phosphorus component according to claim 10 or 11 described methods, be benchmark with the auxiliary agent total amount, in element phosphor, the content of described phosphorus component is 0-15 weight %.
26. method according to claim 25 is characterized in that, the content of described phosphorus component is 0-8 weight %.
27. method according to claim 1 is characterized in that, is benchmark with the described total amount that contains the catalyst mixture of cracking additive and catalytic cracking catalyst, described cracking additive accounts for the 0.1-50 weight % of catalyst mixture.
28. method according to claim 27 is characterized in that, is benchmark with the described total amount that contains the catalyst mixture of cracking additive and catalytic cracking catalyst, described cracking additive accounts for the 1-40 weight % of catalyst mixture.
29. method according to claim 1 is characterized in that, described cracking hydrocarbon oil condition comprises that temperature of reaction is 400-700 ℃, and weight hourly space velocity is 10-120 hour -1, the agent weight of oil is than being 1-20.
30. method according to claim 1 is characterized in that, described hydrocarbon ils is selected from oil and boiling range greater than 330 ℃ petroleum fractions.
31. method according to claim 30, it is characterized in that, described hydrocarbon ils is selected from sulfur-bearing or not long residuum, vacuum residuum, the decompressed wax oil of sulfur-bearing, the normal pressure wax oil, straight-run gas oil, propane is light/heavily de-oiling and wax tailings and through long residuum, vacuum residuum, the decompressed wax oil of hydrotreatment, one or more in the normal pressure wax oil.
CN 03147986 2003-06-30 2003-06-30 Cracking process of hydrocarbon oil Expired - Lifetime CN1261527C (en)

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CN103252230A (en) * 2013-04-22 2013-08-21 姚光纯 Method for preparing novel denitration catalyst
CN105289682A (en) * 2014-08-01 2016-02-03 中国石油化工股份有限公司 Hydrocarbon oil desulfurization catalyst and preparation method thereof, and hydrocarbon oil desulfurization method
CN105983426A (en) * 2014-11-27 2016-10-05 Sk新技术株式会社 Amorphous calcium phosphate catalyst for use in production of 1,3-butadiene and methyl ethyl ketone from 2,3-butanediol, and method of preparing the same
CN106268278A (en) * 2016-08-30 2017-01-04 中国石油大学(华东) A kind of catalytic cracking fuel gas sulfur transfer additive of new structure and preparation method thereof
CN107970952A (en) * 2017-11-24 2018-05-01 福州大学 A kind of inferior heavy oil hydrocracking catalyst for suspension bed and preparation method

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103252230A (en) * 2013-04-22 2013-08-21 姚光纯 Method for preparing novel denitration catalyst
CN105289682A (en) * 2014-08-01 2016-02-03 中国石油化工股份有限公司 Hydrocarbon oil desulfurization catalyst and preparation method thereof, and hydrocarbon oil desulfurization method
CN105289682B (en) * 2014-08-01 2017-12-22 中国石油化工股份有限公司 A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105983426A (en) * 2014-11-27 2016-10-05 Sk新技术株式会社 Amorphous calcium phosphate catalyst for use in production of 1,3-butadiene and methyl ethyl ketone from 2,3-butanediol, and method of preparing the same
CN105983426B (en) * 2014-11-27 2020-11-17 Sk新技术株式会社 Amorphous calcium phosphate catalyst for production of 1, 3-butadiene and methyl ethyl ketone from 2, 3-butanediol, and method for preparation thereof
CN106268278A (en) * 2016-08-30 2017-01-04 中国石油大学(华东) A kind of catalytic cracking fuel gas sulfur transfer additive of new structure and preparation method thereof
CN107970952A (en) * 2017-11-24 2018-05-01 福州大学 A kind of inferior heavy oil hydrocracking catalyst for suspension bed and preparation method
CN107970952B (en) * 2017-11-24 2019-09-13 福州大学 A kind of inferior heavy oil hydrocracking catalyst for suspension bed and preparation method

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