CN101570694A - Catalytic cracking sulfur-reducing material and preparation method thereof - Google Patents
Catalytic cracking sulfur-reducing material and preparation method thereof Download PDFInfo
- Publication number
- CN101570694A CN101570694A CNA2008101056511A CN200810105651A CN101570694A CN 101570694 A CN101570694 A CN 101570694A CN A2008101056511 A CNA2008101056511 A CN A2008101056511A CN 200810105651 A CN200810105651 A CN 200810105651A CN 101570694 A CN101570694 A CN 101570694A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- reducing material
- sulfur
- catalytic cracking
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a catalytic cracking sulfur-reducing material and a preparation method thereof. The catalytic cracking sulfur-reducing material comprises the following compositions by weight percent: 0.5 to 20 percent of vanadium as calculated by V2O5, 0.1 to 30 percent of aluminum as calculated by Al2O3, 0.1 to 30 percent of titanium as calculated by TiO2, and the balance of silicon oxide, and the total weight of various compositions is 100 percent. The preparation method comprises the following steps: firstly, dissolving a surfactant into acid water solution, wherein the solution temperature is between 25 and 95 DEG C; secondly, mixing a silicon source and the acid water solution containing the surfactant for hydrolysis after the surfactant is completely dissolved, and obtaining sol; thirdly, curing the sol at a temperature of between 30 and 80 DEG C to obtain wet gel; fourthly, continuously aging the obtained wet gel for 1 to 10 days at a temperature of between 30 and 200 DEG C; fifthly, drying the aged wet gel for 1 to 7 days at a temperature of between 50 and 120 DEG C; and sixthly, roasting the dried gel for 1 to 20 hours at a temperature of between 300 and 800 DEG C to obtain the mesoporous sulfur-reducing material. The catalytic cracking sulfur-reducing material has high petroleum hydrocarbon cracking activity and obvious desulfurization activity.
Description
Technical field
The present invention relates to a kind of sulphur effect of falling that has, be used for the catalytic cracking of hydrocarbon process, reduce catalytic cracking sulfur-reducing material of sulfur content of catalytic cracking gasoline and preparation method thereof.
Background technology
Catalytically cracked gasoline accounts for more than 80% of gasoline product total amount, in the gasoline product more than 90% of sulphur content from catalytic gasoline.Original position removes sulfide synchronously in the catalytic cracking process process, need not increase investment, by add a spot of sulfur prodegradant in catalytic cracking process, does not influence the distribution and the quality of cracked product, can reduce the sulphur content of catalytically cracked gasoline more effectively.
US6,482,315 disclose the non-molecular sieve desulfurizer of the high vanadium amount of a kind of load, and carrier is an aluminum oxide.Be with independent composition and catalytic cracking activity catalyzer (normally faujusite such as Y zeolite) combination, be used for catalytic cracking process handle hydrocarbon raw material, produce low-sulphur oil and other liquid product.
US6,974,787 disclose a kind of sulfur-lowing catalyst removes sulphur in the catalytically cracked gasoline.Catalyzer is a carrier by porous molecular screen, load the oxidation valence state stability that can improve catalyzer greater than zero metal such as Ce, V and active.Molecular sieve is generally super-stable Y molecular sieves, mainly falls the preferred V of sulphur active ingredient, and desulfurization catalyst also can be used as independent additive and uses.
JP2003-027067 discloses a kind of catalyzer that removes sulphur in the catalytically cracked gasoline, this catalyzer comprises a kind of inorganic porous material, and uniform loading at least a in the metals such as V, Zn, Ni, Fe, Co, this catalyzer can be used in the fluidized catalytic cracker of mink cell focus.
CN1754941A discloses a kind of composition with desulfidation, contain in the said composition contain the v element and the second metallic element M in a kind of skeleton structure molecular sieve as the desulfurization constituent element, said second metal M is selected from a kind of in periodic table of elements IIA, IIB, IVB, VIB, VIIB, VIIIB or the lanthanide series rare-earth elements.Said composition can be applied in the catalytic cracking, under the situation that does not influence conventional FCC operational condition, effectively reduces the content of sulfur in gasoline of FCC process, and improves the hydrothermal stability of FCC catalyzer.
CN1472281A discloses a kind of preparation method of catalytic cracking sulfur-reducing auxiliary agent, be that to adopt content of vanadium be 0.3%-1.2% and micro-activity greater than 45 catalytic cracking poiser directly as the catalytic cracking sulfur-reducing auxiliary agent, or behind activated and/or the loaded metal constituent element zinc as the catalytic cracking sulfur-reducing auxiliary agent.CN1552802A discloses a kind of cracking additive with desulfidation, this auxiliary agent contains a kind of heat-resistant inorganic oxide, clay and a kind of metal component, contain or do not contain molecular sieve, with the auxiliary agent 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.
Add the active ingredient vanadium and have and goodishly fall the sulphur effect and fall the sulphur selectivity preferably in the sulfur prodegradant material, still this interpolation component is toxic to catalytic cracking catalyst under the high-temperature water thermal environment.It is generally acknowledged, vanadium on catalyzer with the effect of zeolite framework aluminium, can form vanadic acid aluminium.Vanadic acid aluminium can produce V again 650 ℃ of decomposition
2O
5So vanadium is non-stoichiometric to the murder by poisoning of zeolite, cause the avalanche of catalyzer mesolite crystalline, the matrix of catalyzer is because of the fusing sintering.Sodium in the catalyzer and vanadium form low-melting vanadic acid sodium and improve the transport property of vanadium, increase the destructiveness of vanadium to molecular sieve.Vanadium can make activity of such catalysts descend in actual production, and transformation efficiency reduces, and the productive rate of purpose product descends.Coke yield raises, and is a kind of permanent poisoning of catalyst, and is very big to the influence of catalytic cracking unit economic benefit.
There are some researches show that when different types of catalytic cracking catalyst was distinguished the vanadium of load different content, its product distributed and the gasoline composition all can change.The degree of crystallinity of catalyzer and lattice constant, specific surface area, little index alive etc. all reduce along with the increase of load content of vanadium on the catalyzer.Vanadium distributes to the catalytic cracking product and has bigger influence, increase along with content of vanadium on the catalyzer, reaction conversion ratio reduces, gas yield increases in the product, diesel yield increases, and gasoline yield increases along with the increase of content of vanadium earlier, descends rapidly then, generally speaking, the catalytic cracking product distributes and has worsened.Alkene in the gasoline, naphthene content raise along with the increase of content of vanadium on the catalyzer.
Therefore, in the sulfur prodegradant material, add vanadium, importantly guarantee vanadium can diffusive migration to Primary Catalysts and destroy the structure and the cracking activity of main catalytic cracking catalyst.
CN1974726A openly provides removing and has shown high desulfurization activity and the high desulfurization catalyst that is used for catalytically cracked gasoline of cracking activity aspect the sulphur composition of gasoline fraction, and described catalyzer contains in the small spherical particle of porous inorganic oxide with median size the particle shape vanadium oxide 0.1～10 micrometer range in of V2O5 note in 0.3～3wt% scope.In addition, the small spherical particle of porous inorganic oxide is made of crystallized silicon aluminosilicate zeolitic and porous inorganic oxide matrix, also contains antimony.When the FCC catalyzer that contains crystal silicon-aluminate zeolite is used with the small spherical particle of porous inorganic oxide, because vanadium oxide exists with the particle shape, therefore the diffusion of vanadium oxide in catalyst particle in the use in FCC apparatus is few, and what can not take place that vanadium oxide causes destroys crystallized silicon aluminosilicate zeolitic crystalline.
CN1542088A discloses a kind of cracking product sulfur-lowing catalyst, and this catalyzer contains the vanadium component, and a kind of heat-resistant inorganic oxide carrier and a kind of alkaline earth metal component, the mol ratio of vanadium and alkaline-earth metal are 10: 1-1: 40.By inference, may form the vanadate of alkaline-earth metal between vanadium and the alkaline-earth metal, the vanadate of alkaline-earth metal both can make vanadium give full play to desulfidation, can make vanadium can not form the liquid vanadic acid again, had avoided the loss of vanadium and to the erosion of contained framework of molecular sieve in the catalytic cracking catalyst.
The sulfur prodegradant great majority are to have found that on the basis that sulphur shifts this agent has the effect that reduces the gasoline total sulfur, therefore, usually follow and adopt the body material of catalytic cracking catalyst to prepare auxiliary agent, as: Y type, ZSM-5 equimolecular sieve and common silica-alumina material.But heavy and variation along with the change of raw material, the molecule of poisonous and harmful impurity such as increasing raw material and sulfide thereof has surpassed 3nm (for example residual oil catalytic cracking), traditional micropore catalytic material is because the duct is little, diffusion is subjected to serious restriction, has limited macromolecular catalyzed reaction to a great extent.Mesoporous material shows good macromole cracking performance in catalytic cracking reaction, help improving the crude oil transformation efficiency, reduces the heavy oil yield, is subjected to paying attention to widely.Disclose a kind of preparation method of porous vanadium silica-alumina material as CN1853775A, this method is that aluminium source and alkaline solution are neutralized into glue under room temperature to 85 ℃, and becoming glue terminal point pH is 7～11; Then according to SiO
2: Al
2O
3=1: weight ratio (0.6-9) adds the silicon source, room temperature to 90 ℃ following wearing out 1～10 hour; Add the vanadium source again, room temperature to 90 ℃ following the continuation aging 1～10 hour; The gained solid sediment is carried out ammonium exchange washing to remove foreign ion; 100 ℃～150 ℃ oven dry down, obtained vanadium silica-alumina material in 1～20 hour 300 ℃～700 ℃ following roastings then, the anhydrous compound of this material is formed, and counts (0-0.3) Na with the oxide weight ratio
2O (40-85) Al
2O
3(10-60) SiO
2(0.5-15) V
2O
5The porous vanadium silica-alumina material of this method preparation has macromole cracking function and desulphurizing activated.
Summary of the invention
The purpose of this invention is to provide a kind of with silicon oxide and vanadium and be mixed with aluminium and/or the catalytic cracking sulfur-reducing material of titanium and preparation method thereof, this sulfur-reducing material has high hydrothermal stability, and the cracking activity height especially has high desulphurizing activated and selectivity aspect the macromole sulfide in the gasoline fraction removing crackate.
Sulfur-reducing material provided by the invention is to be the mesoporous material of matrix with the silicon oxide, and main desulphurizing activated component is a vanadium, is 100% with total amount of material, with V
2O
5The incorporation of meter vanadium is 0.5～20 weight %, is preferably 1.5～10 weight %, mixes aluminium and/or titanium, wherein with Al
2O
3The incorporation of meter aluminium is 0.1～30 weight %, is preferably 5～15 weight %; With TiO
2The doping of meter titanium is 0.1～30 weight %, is preferably 0.1～10 weight %.
Material preparation method provided by the invention comprises preparation process such as colloidal sol preparation, gelation, gel wear out, drying, roasting.At first with surfactant dissolves in acidic aqueous solution, solvent temperature is in 25～95 ℃ of scopes; After treating that tensio-active agent dissolves fully, silicon source and the acidic aqueous solution mixed hydrolysis that contains tensio-active agent are obtained colloidal sol; Under 30～80 ℃, make colloidal sol be cured as wet gel then; The wet gel that obtains continued down aging 1～10 day at 30～200 ℃; The aging wet gel of finishing is following dry 1～7 day at 50～120 ℃; The xerogel that drying is finished obtained mesoporous sulfur-reducing material in 1～20 hour 300～800 ℃ of following roastings.Tensio-active agent and acidic aqueous solution are 4: 10～50 by weight.
In the method provided by the invention, used tensio-active agent is: the nonionogenic tenside fatty alcohol-polyoxyethylene ether, and as C
16EO
10, C
16EO
18, C
16EO
15Deng; Also can be segmented copolymer polyvinyl ether-polypropylene ether-glymes (EO
n-PO
m-EO
n), as EO
20-PO
70-EO
20(P123), EO
106-PO
70-EO
106(F127) etc.; Also can be alkyl quaternary ammonium salts type cats product, as cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride etc.The mass ratio of silica content is in 0.2～3 scope in employed tensio-active agent addition and the final butt of material.
In the method provided by the invention, employed acid is nitric acid, sulfuric acid, hydrochloric acid or acetate, and concentration is 1mol/L.Employed silicon source is tetramethoxysilance, tetraethoxysilance or silicon sol or silicon oxide.
Among the sulfur-reducing material preparation method provided by the invention, the doping way of active ingredient vanadium is the in-situ doped method in the sol-gel process.Here saidly in-situ dopedly being meant that the compound with vanadium directly adds in the forerunner's reactant for preparing colloidal sol, is exactly that vanadium compound is joined in the acidic aqueous solution of preparation colloidal sol specifically, makes mixing of vanadium compound and other precursors realization molecular levels.Can guarantee that in the sol gel reaction process vanadium can evenly spread in the material skeleton, and then realize the effectively fixing of vanadium.The material skeleton vanadium employed vanadium source of mixing comprises the mixture of any or they in vanadium oxalate, naphthenic acid vanadium, nitric acid vanadium, Vanadosulfuric acid, vanadium chloride, vanadium oxychloride, ammonium meta-vanadate, adjacent ammonium vanadate, pyrovanadic acid ammonium, vanadic acid, the Vanadium Pentoxide in FLAKES.
Among the sulfur-reducing material preparation method provided by the invention, the doping way of other active ingredient aluminium and titanium also is the in-situ doped method in the sol-gel process.The used aluminium source of the doping of aluminium comprises aluminum nitrate, Tai-Ace S 150, aluminum chloride, aluminum isopropylate or Tributyl aluminate.Wherein adopt inorganic aluminium source doping mode, add in the acidic aqueous solution of preparation colloidal sol in advance in the aluminium source; And adopt organoaluminum source doping mode, add in the silicon source in advance in the aluminium source, and with silicon source thorough mixing.The used titanium source of the doping of titanium comprises any in inorganic ti sources such as titanium tetrachloride, titanous chloride, titanyl sulfate or the organic titanium sources such as metatitanic acid fourth fat, titanium isopropylate.Wherein adopt the inorganic ti sources doping way, add in the acidic aqueous solution of preparation colloidal sol in advance in the titanium source; And adopt organic titanium source doping mode, add in the silicon source in advance in the titanium source, and with silicon source thorough mixing.
Among the sulfur-reducing material preparation method provided by the present invention, it is characterized in that preparing in the mesoporous sulfur-reducing material process in sol-gel method for improving the hydrothermal stability of material, wet gel will be handled through the high temperature ageing of long period.The aged temperature is 30～200 ℃ of scopes, in preferred 60～150 ℃ scope.Digestion time is 1～10 day scope, in preferred 2～5 days scopes.
Sulfur-reducing material provided by the present invention has the meso-hole structure feature, and its pore size distribution is concentrated, and specific surface area is 200～1000m
2/ g, pore volume is 0.3～2ml/g, mean pore size is between 2～20nm.Bigger aperture helps the macromolecular reaction thing, the especially quick transmission diffusion of macromole sulfide, and huge specific surface area provides more reaction active site.
Sulfur-reducing material provided by the invention can be used as sulfur-bearing oil hydrocarbon material catalytic cracking process sulfur prodegradant, mixes with main cracking catalyst and uses to reduce the sulphur content in crackate, the especially pressure gasoline.Sulphur content and processing condition according to stock oil feature, gasoline products requirement, determine sulfur-reducing material provided by the invention and the cracking catalyst ratio in catalyst mixture, generally, the content of catalyzer provided by the invention is 0.1～50 weight %, be preferably 1～30 weight %, more preferably 5～20 weight %.Can also contain other auxiliary agents in the described catalyst mixture, as ignition dope, sulfur transfer additive, octane enhancing additive, fecund third rare auxiliary agent etc.In addition, sulfur-reducing material provided by the invention also can have the active catalytic cracking catalyst of the sulphur of falling with making beating such as molecules of active components sieve, clay, the substrate material spray-dried preparation in back.Described sulfur-bearing oil raw material can be selected from one or more in long residuum, vacuum residuum, decompressed wax oil, normal pressure wax oil, straight-run gas oil, the wax tailings.
Embodiment
In the embodiment and Comparative Examples of the following stated, the specific surface area of sulfur-reducing material, pore volume, mean pore size are measured by cryogenic nitrogen adsorption-desorption method.Sulphur content is by the HP5890 type gas chromatograph for determination of configuration atomic emission spectrum detector in the oil product.
Embodiment 1
Present embodiment illustrates sulfur-reducing material provided by the invention and preparation method thereof.
With 12g tensio-active agent fatty alcohol-polyoxyethylene ether (C
16EO
10) add 90g and contain in the acidic aqueous solution of 1mol/L nitric acid, stir down at 60 ℃ and tensio-active agent was fully dissolved in 2 hours; Quantitative vanadium oxalate is dissolved in the above-mentioned surfactant soln, stirred 20 minutes; The 38g tetramethoxysilance is added in the above-mentioned solution, and vigorous stirring 10 minutes obtains limpid colloidal sol; Colloidal sol is packed in the seal box, and the water-bath that places 50 ℃ is until gel; Wet gel continues to wear out 3 days in 50 ℃ water-bath; Take out wet gel, remove and separate out mother liquor,, promptly made vanadium doping sulfur-reducing material provided by the invention in 5 hours 500 times roastings again, be designated as SV-01 60 ℃ of following oven dryings 6 days.The addition of vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value doping of meter vanadium is 5 weight %.The pore structure characterization data of obtained sulfur-reducing material sees Table 1.
Comparative Examples 1
The preparation method of sulfur-reducing material is introduced in the adding of this Comparative Examples explanation vanadium with impregnation method.
The material preparation process is close with embodiment 1, but the introducing in vanadium source is not in sol-gel process, but with in the water-soluble solution of quantitative vanadium oxalate, mode by incipient impregnation, the mesopore silicon oxide carrier that obtains after the above-mentioned roasting is added in the vanadium oxalate solution of configuration, and the addition of vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value charge capacity of meter vanadium is 5 weight %.Room temperature dipping 12 hours, the material after will flood then promptly made 500 times roastings and contrasts sulfur-reducing material SV-02 100 ℃ of following oven dryings 10 hours in 5 hours.The pore structure characterization data of obtained contrast sulfur-reducing material sees Table 1.
Embodiment 2
Present embodiment illustrates sulfur-reducing material provided by the invention and preparation method thereof.
With 12g tensio-active agent fatty alcohol-polyoxyethylene ether (C
16EO
10) add 70g and contain in the acidic aqueous solution of 1mol/L nitric acid, stir down at 60 ℃ and tensio-active agent was fully dissolved in 2 hours; Quantitative aluminum nitrate and vanadium oxalate are dissolved in the above-mentioned surfactant soln, stirred 20 minutes; The 38g tetramethoxysilance is added in the above-mentioned solution, and vigorous stirring 10 minutes obtains limpid colloidal sol; Colloidal sol is packed in the seal box, and the water-bath that places 50 ℃ is until gel; Wet gel continues to wear out 3 days in 50 ℃ water-bath; Take out wet gel, remove and separate out mother liquor,, promptly made vanadium provided by the invention, aluminium doping sulfur-reducing material in 5 hours 500 times roastings again, be designated as SAV-01 60 ℃ of following oven dryings 6 days.The addition of vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value doping of meter vanadium is 5 weight %, and the addition of aluminum nitrate makes in the sulfur-reducing material butt that finally makes with Al
2O
3The calculated value doping of meter aluminium is 10 weight %.The pore structure characterization data of obtained sulfur-reducing material sees Table 1.
Comparative Examples 2
The preparation method of sulfur-reducing material is introduced in the adding of this Comparative Examples explanation vanadium with impregnation method.
The material preparation process is close with embodiment 2, but the introducing in vanadium source is not in sol-gel process, but with in the water-soluble solution of quantitative vanadium oxalate, mode by incipient impregnation, the mesoporous aluminium doped silicon oxide carrier that obtains after the above-mentioned roasting is added in the vanadium oxalate solution of configuration, and the addition of vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value charge capacity of meter vanadium is 5 weight %.Room temperature dipping 12 hours, the material after will flood then promptly made 500 times roastings and contrasts sulfur-reducing material SAV-02 100 ℃ of following oven dryings 10 hours in 5 hours.The pore structure characterization data of obtained contrast sulfur-reducing material sees Table 1.
Embodiment 3
Present embodiment illustrates sulfur-reducing material provided by the invention and preparation method thereof.
With 12g tensio-active agent fatty alcohol-polyoxyethylene ether (C
16EO
10) add 120g and contain in the acidic aqueous solution of 1mol/L nitric acid, stir down at 70 ℃ and tensio-active agent was fully dissolved in 2 hours; Quantitative vanadium oxalate is dissolved in the above-mentioned surfactant soln, stirred 20 minutes; To stir 20 minutes in the quantitative metatitanic acid fourth fat adding 38g tetramethoxysilance; Mixing solutions with metatitanic acid fourth fat and tetramethoxysilance adds in above-mentioned tensio-active agent and the vanadium oxalate solution then, and vigorous stirring 10 minutes obtains limpid colloidal sol; Colloidal sol is packed in the seal box, and the water-bath that places 40 ℃ is until gel; Wet gel continues to wear out 3 days in 40 ℃ water-bath; Take out wet gel, remove and separate out mother liquor,, promptly made vanadium provided by the invention, titanium doped sulfur-reducing material in 5 hours 500 times roastings again, be designated as STV-01 60 ℃ of following oven dryings 6 days.The addition of vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value doping of meter vanadium is 2.2 weight %; The addition of metatitanic acid fourth fat makes in the sulfur-reducing material butt that finally makes with TiO
2The calculated value doping of meter titanium is 10 weight %.The pore structure characterization data of obtained sulfur-reducing material sees Table 1.
Comparative Examples 3
The preparation method of sulfur-reducing material is introduced in the adding of this Comparative Examples explanation vanadium with impregnation method.
The material preparation process is close with embodiment 3, but the introducing in vanadium source is not in sol-gel process, but with in the water-soluble solution of quantitative vanadium oxalate, mode by incipient impregnation, the mesoporous titanium doped silica support that obtains after the above-mentioned roasting is added in the vanadium oxalate solution of configuration, and the addition of vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value charge capacity of meter vanadium is 5 weight %.Room temperature dipping 12 hours, the material after will flood then promptly made 500 times roastings and contrasts sulfur-reducing material STV-02 100 ℃ of following oven dryings 10 hours in 5 hours.The pore structure characterization data of obtained contrast sulfur-reducing material sees Table 1.
Embodiment 4
Present embodiment illustrates sulfur-reducing material provided by the invention and preparation method thereof.
With 12g tensio-active agent fatty alcohol-polyoxyethylene ether (C
16EO
10) add 120g and contain in the acidic aqueous solution of 1mol/L nitric acid, stir down at 70 ℃ and tensio-active agent was fully dissolved in 2 hours; Quantitative vanadium oxalate and aluminum nitrate are dissolved in the above-mentioned surfactant soln, stirred 20 minutes; To stir 20 minutes in the quantitative metatitanic acid fourth fat adding 38g tetramethoxysilance; Mixing solutions with metatitanic acid fourth fat and tetramethoxysilance adds in above-mentioned tensio-active agent, vanadium oxalate and the aluminum nitrate solution then, and vigorous stirring 10 minutes obtains limpid colloidal sol; Colloidal sol is packed in the seal box, and the water-bath that places 50 ℃ is until gel; Wet gel continues to wear out 3 days in 50 ℃ water-bath; Take out wet gel, remove and separate out mother liquor,, promptly made vanadium provided by the invention, aluminium, titanium doped sulfur-reducing material in 5 hours 500 times roastings again, be designated as SATV-21 60 ℃ of following oven dryings 6 days.The addition of vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value doping of meter vanadium is 2.2 weight %; The addition of aluminum nitrate makes in the sulfur-reducing material butt that finally makes with Al
2O
3The calculated value doping of meter aluminium is 10 weight %; The addition of metatitanic acid fourth fat makes in the sulfur-reducing material butt that finally makes with TiO
2The calculated value doping of meter titanium is 10 weight %.The pore structure characterization data of obtained sulfur-reducing material sees Table 1.
Embodiment 5-6
Present embodiment illustrates sulfur-reducing material provided by the invention and preparation method thereof.
Method according to embodiment 4 prepares sulfur-reducing material, the aging condition of different is wet gel for 50 ℃ after aging 1 day respectively again 100 ℃ down aging 2 days or 150 ℃ aging 2 days down, promptly get vanadium provided by the invention, aluminium, titanium doped mesoporous sulfur-reducing material SATV-22 and SATV-23 after drying, the roasting.The pore structure characterization data of obtained sulfur-reducing material sees Table 1.
Embodiment 7-9
Present embodiment illustrates sulfur-reducing material provided by the invention and preparation method thereof.
Method according to embodiment 4 prepares sulfur-reducing material, and the addition of different is vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value doping of meter vanadium is 4.4 weight %, and the aging condition of wet gel be 50 ℃ after aging 1 day respectively again 50 ℃ aging 2 days down, or under 100 ℃, wore out 2 days, or under 150 ℃, wore out 2 days, promptly get vanadium provided by the invention, aluminium, titanium doped mesoporous sulfur-reducing material SATV-41, SATV-42 and SATV-43 after drying, the roasting.The pore structure characterization data of obtained sulfur-reducing material sees Table 1.
Embodiment 10-12
Present embodiment illustrates sulfur-reducing material provided by the invention and preparation method thereof.
Method according to embodiment 4 prepares sulfur-reducing material, and the addition of different is vanadium oxalate makes in the sulfur-reducing material butt that finally makes with V
2O
5The calculated value doping of meter vanadium is 6.6 weight %, and the aging condition of wet gel be 50 ℃ after aging 1 day respectively again 50 ℃ aging 2 days down, or under 100 ℃, wore out 2 days, or under 150 ℃, wore out 2 days, promptly get vanadium provided by the invention, aluminium, titanium doped mesoporous sulfur-reducing material SATV-61, SATV-62 and SATV-63 after drying, the roasting.The pore structure characterization data of obtained sulfur-reducing material sees Table 1.Table 1
| Sample | Specific surface area (m 2.g -1) | Pore volume (ml.g -1) | Mean pore size (nm) |
| SV-01 | 840 | 0.62 | 5.2 |
| SV-02 | 805 | 0.57 | 4.5 |
| SAV-01 | 732 | 0.46 | 3.6 |
| SAV-02 | 662 | 0.42 | 3.2 |
| STV-01 | 886 | 0.55 | 4.3 |
| STV-02 | 779 | 0.50 | 4.1 |
| SATV-21 | 830 | 0.53 | 2.7 |
| SATV-22 | 649 | 1.06 | 6.1 |
| SATV-23 | 431 | 1.21 | 8.2 |
| SATV-41 | 741 | 0.50 | 3.0 |
| SATV-42 | 590 | 0.82 | 5.1 |
| SATV-43 | 345 | 1.21 | 14.1 |
| SATV-61 | 599 | 0.52 | 3.8 |
| SATV-62 | 516 | 1.31 | 8.1 |
| SATV-63 | 344 | 1.21 | 12.1 |
Embodiment 13
The fall sulfur additives of the mesoporous sulfur-reducing material of the inventive method preparation as catalytic cracking process adopted in the present embodiment explanation, to the influence of stock oil transformation efficiency, heavy oil yield and crackate sulphur content.Is that the Industrial Catalysis cracking catalyst of MLC-500 is mixed with mesoporous sulfur-reducing material with 1: 9 weight ratio and model, and wherein the Main physical chemical property index of MCL-500 type catalyzer is as shown in table 2.Before carrying out reaction evaluating, mixed catalyst will be at 800 ℃, and burin-in process is 4 hours under the 100% water vapor condition.The aging mixed catalyst that finishes sieves out 20-40 purpose particle after compressing tablet, pulverizing standby.The sulfur-reducing material evaluation method adopts the fixed fluidized bed reaction unit of catalytic cracking, and appreciation condition is: catalyst levels 6g, and each oil inlet quantity 1.5g, temperature of reaction is 500 ℃.Estimating with stock oil is grand celebration decompressed wax oil (VGO1), and the physicochemical property of stock oil are as shown in table 3.The catalytic cracking evaluation result is listed in the table 4.
Table 2
| Chemical constitution (m%) | Index |
| RE 2O 3 | 2.7 |
| Al 2O 3 | 55.9 |
| Na 2O | 0.29 |
| Specific surface (m 2·g -1) | 153 |
| Pore volume (cm 3·g -1) | 0.174 |
| Abrasion index (%) | 1.5 |
| Size-grade distribution (%) | |
| 0～40(μm) | 22.4 |
| 0～80(μm ) | 46.1 |
| 0～110(μm) | 77.6 |
| Heavy metal vanadium (μ gg -1) | ＜0.05 |
| Micro-activity (%) | 65 |
| Lattice constant (nm) | 2.4292 |
Table 3
Annotate: VGO is a decompressed wax oil; VCR is a vacuum residuum.
Table 4
As can be seen from Table 4, adopt in the sol-gel process sulfur-reducing material SV-01, SAV-01, the STV-01 of the preparation of original position doping method to have and fall the sulphur effect preferably, contrast 17.00 μ g/g in the blank sample MLC-500 catalytic cracking catalyst reaction after product gasoline, be reduced to 10.7,8.89,9.61 μ g/g respectively, fallen the sulphur rate more than 37%.See quite from dry gas, coke yield, do not have very big change with blank sample MLC-500 catalyzer.And compare with the sample that adopts pickling process to add vanadium, from falling the sulphur effect, it is also better that the sulphur rate falls in the material that pickling process makes, but the sample that adopts pickling process doping vanadium is in fixed fluidized bed evaluation procedure, compare with blank sample MLC-500 catalyzer, dry gas yied rises, and coke yield increases, and light oil transformation efficiency and total conversion rate all descend.Therefore, fall the sulphur effect preferably, the distribution and the quality of catalytic cracking production produced bigger negative impact, analyze simultaneously and may destroy catalyst structure though adopt this method doping vanadium to play.
Embodiment 14
Method by example 13 is carried out the catalytic cracking evaluation to sulfur-reducing material and MLC-500 Industrial Catalysis cracking catalyst mixed catalyst, and different is that raw materials used oil is that grand celebration decompressed wax oil (VGO2) content is that 70 weight % and grand celebration vacuum residuum (VCR) content are the mixture of 30 weight %.The physicochemical property of stock oil are as shown in table 3.The catalytic cracking evaluation result is listed in table 5, table 6, the table 7.
Table 5
Table 6
Table 7
Claims (7)
1. catalytic cracking sulfur-reducing material preparation method, it is characterized in that: based on silicon oxide, main active component is a vanadium, mixes aluminium and/or titanium, with V
2O
5The incorporation of meter vanadium is 0.5～20 weight %, with Al
2O
3The incorporation of meter aluminium is 0.1～30 weight %, with TiO
2The incorporation of meter titanium is 0.1～30 weight %, and surplus is a silicon oxide, and each composition gross weight is 100%;
At first with surfactant dissolves in acidic aqueous solution, solvent temperature is in 25～95 ℃ of scopes; After treating that tensio-active agent dissolves fully, silicon source and the acidic aqueous solution mixed hydrolysis that contains tensio-active agent are obtained colloidal sol; Under 30～80 ℃, make colloidal sol be cured as wet gel then; The wet gel that obtains continued down aging 1～10 day at 30～200 ℃; The aging wet gel of finishing is following dry 1～7 day at 50～120 ℃; The xerogel that drying is finished obtained mesoporous sulfur-reducing material in 1～20 hour 300～800 ℃ of following roastings;
The mass ratio of silica content is 0.2～3 in the final butt of tensio-active agent addition and material;
Tensio-active agent and acidic aqueous solution are 4: 10～50 by weight;
Acidic aqueous solution concentration is 1mol/L.
2. a kind of catalytic cracking sulfur-reducing material preparation method according to claim 1 is characterized in that: tensio-active agent is fatty alcohol-polyoxyethylene ether, segmented copolymer polyvinyl ether-polypropylene ether-glymes, cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
3. a kind of catalytic cracking sulfur-reducing material preparation method according to claim 1 is characterized in that: employed silicon source is tetramethoxysilance, tetraethoxysilance, silicon sol or silicon oxide.
4. a kind of catalytic cracking sulfur-reducing material preparation method according to claim 1 is characterized in that: used aluminium source is aluminum nitrate, Tai-Ace S 150, aluminum chloride, aluminum isopropylate or Tributyl aluminate.
5. a kind of catalytic cracking sulfur-reducing material preparation method according to claim 1 is characterized in that: the vanadium source is the mixture of any or they in vanadium oxalate, naphthenic acid vanadium, nitric acid vanadium, Vanadosulfuric acid, vanadium chloride, vanadium oxychloride, ammonium meta-vanadate, adjacent ammonium vanadate, pyrovanadic acid ammonium, vanadic acid, the Vanadium Pentoxide in FLAKES.
6. a kind of catalytic cracking sulfur-reducing material preparation method according to claim 1 is characterized in that: the titanium source is titanium tetrachloride, titanous chloride, titanyl sulfate, metatitanic acid fourth fat or titanium isopropylate.
7. the catalytic cracking sulfur-reducing material of a kind of catalytic cracking sulfur-reducing material preparation method preparation according to claim 1, it is characterized in that: based on silicon oxide, main active component is a vanadium, mixes aluminium and/or titanium, with V
2O
5The incorporation of meter vanadium is 0.5～20 weight %, with Al
2O
3The incorporation of meter aluminium is 0.1～30 weight %, with TiO
2The incorporation of meter titanium is 0.1～30 weight %, and surplus is a silicon oxide, and each composition gross weight is 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810105651A CN101570694B (en) | 2008-04-30 | 2008-04-30 | Catalytic cracking sulfur-reducing material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810105651A CN101570694B (en) | 2008-04-30 | 2008-04-30 | Catalytic cracking sulfur-reducing material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101570694A true CN101570694A (en) | 2009-11-04 |
| CN101570694B CN101570694B (en) | 2012-10-17 |
Family
ID=41230180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810105651A Active CN101570694B (en) | 2008-04-30 | 2008-04-30 | Catalytic cracking sulfur-reducing material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101570694B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102114421A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院大连化学物理研究所 | Catalytic cracking desulfurization auxiliary and application thereof |
| CN102274721A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Desulfurization additive for product obtained by hydrocarbon oil cracking and preparation and application thereof |
| CN109698012A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | A method of for predicting octane number |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6548440B1 (en) * | 1999-05-26 | 2003-04-15 | Science & Technology Corporation @ Unm | Synthesis of attrition-resistant heterogeneous catalysts using templated mesoporous silica |
| CN1608989A (en) * | 2004-09-16 | 2005-04-27 | 华东师范大学 | Process of preparing mesoporous Si-Al material |
| CN100434161C (en) * | 2005-04-29 | 2008-11-19 | 中国石油化工股份有限公司 | Production of porous vanadium silica-alumina material |
-
2008
- 2008-04-30 CN CN200810105651A patent/CN101570694B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102114421A (en) * | 2009-12-30 | 2011-07-06 | 中国科学院大连化学物理研究所 | Catalytic cracking desulfurization auxiliary and application thereof |
| CN102274721A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Desulfurization additive for product obtained by hydrocarbon oil cracking and preparation and application thereof |
| CN102274721B (en) * | 2010-06-10 | 2013-06-05 | 中国石油化工股份有限公司 | Desulfurization additive for product obtained by hydrocarbon oil cracking and preparation and application thereof |
| CN109698012A (en) * | 2017-10-23 | 2019-04-30 | 中国石油化工股份有限公司 | A method of for predicting octane number |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101570694B (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1034223C (en) | Cracking catalyst for processing low-carbon olefines | |
| CN102523735B (en) | Silica-stabilized ultrafine anatase titania, vanadia catalysts, and methods of production thereof | |
| CA2661635C (en) | Catalyst for removal of nitrogen oxide, and method for removal of nitrogen oxide | |
| CN100497531C (en) | Cracking catalyst | |
| CN102895940B (en) | Hydrocarbon oil desulphurization adsorbent, and preparation method and application thereof | |
| CN102078821B (en) | Cracking catalyst containing mesoporous silica-alumina materials | |
| CN103962176B (en) | A kind of Cracking catalyst that improves catalytically cracked gasoline octane number | |
| CN104549423A (en) | Metal modified Y zeolite and preparation method and application thereof | |
| CN104549391B (en) | Supported type vanadium phosphorus oxide catalyst and preparation method thereof | |
| CN104556120A (en) | Preparation method of metal modified Y type molecular sieve | |
| WO2005042404A1 (en) | Molecular sieve with mfi structure containing phosphorus and metal components, preparation process and use thereof | |
| WO2017020847A1 (en) | Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst | |
| WO2017020848A1 (en) | Molecular sieve modification method and catalytic cracking catalyst containing molecular sieve | |
| CA1290737C (en) | Vanadium passivating agent for use in a conversion catalyst and methodof making same | |
| CN105582973B (en) | A kind of catalyst for cracking heavy oil and preparation method thereof | |
| EP4173704A1 (en) | ZSM-5/ß CORE-SHELL MOLECULAR SIEVE AND SYNTHESIS AND USE THEREOF | |
| CN105618108B (en) | A kind of method of modifying of Y type molecular sieve | |
| CN101570694B (en) | Catalytic cracking sulfur-reducing material and preparation method thereof | |
| US7622413B2 (en) | Multifunctional additive for maximizing properties relevant to the process of fluid catalytic cracking and the process for preparation thereof | |
| CA1216835A (en) | Hydrocarbon conversion catalysts | |
| CN101117591B (en) | Catalytic cracking catalyst and preparation method therefor | |
| CN1042201C (en) | Cracking catalyst of rich producing olefines | |
| CN101590432B (en) | Modified clay and preparation method thereof | |
| CN102114421A (en) | Catalytic cracking desulfurization auxiliary and application thereof | |
| CN106145153A (en) | Modified Y zeolite and preparation thereof and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |