CN102247864A - Preparation method of catalyst for hydrogenation desulfurization and denitrification of light-weight oil - Google Patents
Preparation method of catalyst for hydrogenation desulfurization and denitrification of light-weight oil Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst for hydrogenation desulfurization and denitrification of light-weight oil and is characterized in that the composition of the catalyst comprises a carrier, an auxiliary agent and active metals, wherein the carrier contains aluminum oxide, titanium oxide and silicon oxide; the auxiliary agent is phosphorus; the active metals are oxides of nickel, molybdenum and tungsten; and on the basis of the catalyst, the contents of all components in percentage by weight are as follows: 1 to 4 percent of cobalt oxide, 3 to 10 percent of nickel oxide, 2 to 12 percent of molybdenum oxide, 18 to 30 percent of tungsten oxide, 2 to 5 percent of phosphorus pentoxide, 2 to 15 percent of titanium oxide, 2 to 20 percent of silicon oxide, and the balance of aluminum oxide. The catalyst is obtained by the steps of carrier preparation, co-immersion, calcination and the like.
Description
Technical field
The invention belongs to oil refining and catalysis technical field, be specifically related to a kind of light oil hydrogenation desulfurization and denitrogenation Preparation of catalysts method.
Background technology
Along with the heaviness of crude oil and the increasingly stringent of poor qualityization and environmental regulation, sulphur, nitrogen content in the diesel oil hydrogenation raw material constantly rise, and the sulfur content restriction is more and more lower in the product, and traditional hydrogen addition technology is faced with new challenges.The core of hydrofinishing technology is a Hydrobon catalyst.Up-to-date domestic and international scientific research and practical result mainly show following aspect: by further passing through the modulation active component, use the NEW TYPE OF COMPOSITE carrier, introduce the proper assistant modification, and add metal chelating agent etc. in the dipping preparation process, improve the hydrogenation activity of catalyst and increase the service life, satisfy the demand that catalyst updating is regenerated.
CN00122929.2 discloses a kind of hydrodenitrogenation catalyst and preparation method thereof, and catalyst is a carrier with aluminium oxide or siliceous aluminium oxide, is active component with Mo-Ni, adds boron additive.By making stable alkaline Mo-Ni-B solution, and adopt and soak technology altogether, make the hydrodenitrogenationactivity activity of catalyst be improved.This catalyst adopts step impregnation, and technological process is long, introduces ammoniacal liquor simultaneously, and environment is unfriendly.
CN94103999.4 discloses a kind of heavy oil hydrogenating treatment catalyst, is carrier with siliceous and aluminium oxide phosphorus, particularly by a kind of siliceous and the macroporous aluminium oxide of phosphorus and the carrier that little porous aluminum oxide is mixed with, supports molybdenum, nickel, P elements.Silicon in the carrier and phosphorus are scattered in glue and add.
CN99112940.7 discloses a kind of preparation method of hydrorefining catalyst for hydrocarbon, to be loaded with the γ-Al of titanium and phosphorus
2O
3Be carrier, active component is one of one of VIII family or its combination, group vib or its combination.γ-the Al of titaniferous and phosphorus
2O
3Carrier prepares with kneading method, and the activity component impregnation method adds.The preparation method of carrier is: the mixed solution of a water alumina dry glue and titanium chloride and phosphorus-containing compound is fully mixed pinch, moulding, carry out drying, washing, calcination steps then and obtain Ti-P-γ-Al
2O
3Carrier.
Adopt a kind of highly active hydrogenation catalyst that has in the petroleum hydrocarbon hydrotreating method that USP4880524 proposes.This catalyst is Ni-Mo/Al
2O
3Type, specific area is greater than 300m
2/ g, less than the aperture of 7nm greater than 70%.This catalyst has hydrofinishing activity preferably for light ends oil, but the reactive metal of its load is two kinds of components of Ni, Mo, just present domestic price, and molybdenum oxide therefore for domestic oil refining enterprises, adopts Ni-Mo/Al than tungsten oxide price height
2O
3The type catalyst can increase production cost.
Though the research and development and the commercial Application of present domestic low-sulfur and ultra-low-sulphur diesel Hydrobon catalyst have obtained remarkable progress, but compare with advanced foreign technology, also there is a certain distance, should strengthen the understanding of the catalysis essence of clean diesel Hydrobon catalyst, strengthen the exploitation of novel catalyst carrier and reactive metal location impregnating key technology.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of preparation method who more is applicable to the Hydrobon catalyst of light oil hydrodesulfurization is provided.
At petroleum refining field, γ-Al
2O
3Being the first-selected carrier of Hydrobon catalyst, also is present most widely used catalyst carrier.But because single alumina support easily forms stronger interaction with active component, the cenotype of generation catalytically inactive, and only contain L acid, but when the high nitrogen petrol and diesel oil of hydrotreatment, γ-Al
2O
3L acid site and basic nitrogen strong absorption easily takes place, suppress the catalyst depth hydrodesulfurization performance.These drawbacks limit the application of single aluminium oxide in the heavy distillate catalyst carrier for hydrgenating.
Usually, for the not high gasoline and diesel hydrogenation catalyst for refining of nitrogen content, select conventional γ-Al for use
2O
3As carrier, select Ni, Co, Mo, W isoreactivity metal component for use.Co-Mo type catalyst is suitable for hydrodesulfurization; Ni-Mo type catalyst is suitable for hydrodenitrogeneration and desulfurization; Ni-W type catalyst is suitable for hydrodenitrogeneration, aromatic hydrocarbons is saturated, and has certain hydrodesulfurization activity.Though Ni-Mo/Al
2O
3The type catalyst is (as HC-K, KF-848 etc.) for light ends oil hydrodenitrogeneration preferably and desulphurizing activated is arranged, be widely adopted abroad, but its reactive metal is two kinds of components of Ni, Mo, just present domestic price, molybdenum oxide therefore for domestic oil refining enterprises, adopts Ni-Mo/Al than tungsten oxide price height
2O
3The type catalyst can increase production cost.
For this reason, the present invention has developed and has been applicable to light oil hydrogenation desulfurization and denitrogenation catalyst, and this catalyst is with Al
2O
3-ZrO
2-SiO
2-TiO
2Multivariant oxide is complex carrier, is active metal component, is auxiliary agent with P with W-Mo-Ni-Co quaternary metal.In complex carrier, introduce ZrO
2, SiO
2Modulation carrier surface acidity, the ratio of strong acid in suitably improving helps the open loop fracture of azacyclo-, improves denitrification activity; Introduce ZrO simultaneously
2, SiO
2Can improve the specific area and the pore volume of carrier, improve the decentralization of reactive metal; Introduce TiO
2Improve active component and carrier and interact, so that improve the catalytic desulfurization activity.
The present invention simultaneously adopts room temperature complexing method, be active metal component, be auxiliary agent with W-Mo-Ni-Co quaternary metal, prepared the stable common maceration extract of solubility property, and adopt the saturated dipping technique of substep with P, supported active metal component and auxiliary agent, the decentralization and the utilization rate of raising metal.Characteristics such as described catalyst has the specific surface height, pore volume is big, intensity is high, surface acidity is moderate, hydrodesulfurization, denitrogenation and alkene saturated activity height, preparation cost are low.
The present invention is a kind of light oil hydrogenation desulfurization and denitrogenation Preparation of catalysts method, it is characterized in that:
The composition of catalyst comprises carrier, auxiliary agent, reactive metal; Active component comprises the oxide of nickel, molybdenum and tungsten; Auxiliary agent is a phosphorus; Carrier comprises aluminium oxide and titanium oxide, silica; Each component is that the weight percent content of benchmark is with the catalyst: cobalt oxide accounts for 1～6wt%, is preferably 1～4wt%; Nickel oxide accounts for 1～15wt%, is preferably 3～10wt%; Molybdenum oxide is 2～12wt%; Tungsten oxide accounts for 12～35wt%, is preferably 18～30wt%; Phosphorus pentoxide accounts for 2～5wt%; Titanium oxide accounts for 2～15wt%; Silica accounts for 2～20wt%, and all the other are aluminium oxide;
Aluminium oxide precursor in the described carrier is the macropore boehmite; Add additive in the preparation process of carrier, comprise peptizing agent, expanding agent and extrusion aid; Described peptizing agent is a salpeter solution; Extrusion aid is selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol; Expanding agent is selected from organic acid such as citric acid, oxalic acid, maleic acid, malic acid or macromolecule polyalcohol such as polyethylene glycol (different polymerization degree has different reaming effects);
Titanium dioxide in the described carrier is joined in the macroporous aluminium oxide powder by metatitanic acid or Nano titanium dioxide and introduces through pinching to mix, or is introduced by metatitanic acid four n-propyl solution; Silica is introduced by Ludox; Zirconium dioxide is introduced by the aqueous solution of zirconyl nitrate; Three kinds of auxiliary agents shared proportion in carrier is respectively titanium dioxide 2～15wt%, silica 5～20wt%, zirconia 5～15wt%; All the other components are aluminium oxide, and it is the Al of skeleton that the three constitutes with the aluminium oxide
2O
3-ZrO
2-SiO
2-TiO
2The multicomponent composite oxide carrier;
Introduced auxiliary agent phosphorus in the described catalyst, its existence form in catalyst is a phosphorus pentoxide, and its introducing mode is introduced in the preparing carriers process for adding peptizing agent with phosphoric acid, or introduces in the process of dipping reactive metal for phosphoric acid adds co-impregnated solution; There is bibliographical information to allocate in the co-impregnated solution and introduces the activity that auxiliary agent phosphorus more helps improving metal with the mode of the common impregnated carrier of reactive metal with phosphoric acid; Described auxiliary agent is 2～5wt% with the content of form in catalyst of phosphorus pentoxide;
Described catalyst has added a small amount of complexing agent in the process of preparation co-impregnated solution, the adding of complexing agent can improve the stability of co-impregnated solution, and can improve metal dispersity and using rate of metal, and then improves metal active.Described complexing agent is one or more in ethylene glycol, ethylenediamine, monoethanolamine, diethanol amine, triethanolamine, aminotriacetic acid and the ethylenediamine tetra-acetic acid.
Described Preparation of catalysts method may further comprise the steps:
(1) preparation of carrier: earlier macropore boehmite, zirconia, metatitanic acid and Ludox are mixed, add peptizing agent, extrusion aid and expanding agent again, in kneader, mix and pinch into magma shape plastic, add extruded moulding in the banded extruder then, profile is cloverleaf pattern, bunge bedstraw herb shape or butterfly; Wet bar obtains Al through health, drying and high-temperature roasting
2O
3-ZrO
2-TiO
2-SiO
2The multivariant oxide complex carrier; The drying condition of carrier is 80～200 ℃ of down dry 2～15h, and roasting condition is at 550～650 ℃ of following roasting 1～8h;
(2) preparation of co-impregnated solution: at room temperature, active metal salt, complexing agent and auxiliary agent are added in the solvent, solvent is deionized water or ammonia spirit, evenly stirs dissolving down, obtains stable maceration extract, places standby behind the constant volume;
(3) Preparation of catalysts: because active component is more in the co-impregnated solution, concentration is higher, so its dilution is divided into isopyknic two parts after one times, dipping is so that the evenly dispersion on carrier of each active component in two steps; The carrier strip that makes in the step (1) is placed dipping tank, add a copy of it co-impregnated solution, dry in baking oven behind the dipping, roasting in the Muffle furnace; Treat that little after the roasting is cooled to room temperature, add another part co-impregnated solution, again through super-dry, roasting, obtain required catalyst behind the dipping; Wherein, the dip time of catalyst, each step all can be 2～7h; Behind first step dipping, baking temperature is 80～150 ℃, and be 2～12h drying time, and sintering temperature is 350～480 ℃, and roasting time is 1～8h; Catalyst behind the second step dipping, its baking temperature is 80～150 ℃, and be 2～12h drying time, and sintering temperature is 420～550 ℃, and roasting time is 1～8h.
The technique effect that the present invention reaches:
A kind of light oil hydrogenation desulfurization and denitrogenation Preparation of catalysts method provided by the invention, has higher specific area, pore volume is big, pore-size distribution is concentrated, surface acidity is moderate, active component decentralization height, characteristics such as mechanical strength is big, be more suitable for the light oil hydrogenation desulfurization and denitrogenation Catalysts and its preparation method of Yu Haiyang oil, compared with prior art, it is moderate to have big molecular sulfur, azacyclo-and a catalyst suction-operated, little to the catalyst activity inhibitory action, simultaneously C-S key, C-N key open loop fracture efficient height, catalyst hydrogenation desulfurization, denitrification effect are good; Reactive metal utilization rate height, hydrogenation is effective, the low advantage that waits of preparation cost.Described feedstock oil is straight-run diesel oil, coker gasoline, coker gas oil and catalytic diesel oil etc. inferior, and wherein nitrogen content is 2000-3000 μ g/g, and sulfur content is 2000-3000 μ g/g.The operating condition of described hydrogenation reaction is: the operating pressure of reaction is 5～15MPa, 300～450 ℃ of reactor middle part temperature, volume space velocity 0.5～3.0h during liquid
-1, hydrogen to oil volume ratio 500～1000.
The specific embodiment
Below will further set forth feature of the present invention, but be not limited to example by concrete example.The percentage that below relates to all is weight percentage.
Embodiment 1,
By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sneaks into sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and oxalic acid 10g, add deionized water, in kneader, mediate mixing, after the banded extruder extruded moulding, obtain little of the clover of diameter 1.5mm.Dry 12h in 120 ℃ of baking ovens, roasting 4h in 500 ℃ of Muffle furnaces gets carrier Z-A, and its character sees Table 1.
Under the room temperature, in the 120mL deionized water, add 42g six water ammonium metatungstates, 25g four water ammonium heptamolybdates, 37g six water nickel nitrates and 4g ethylene glycol, stir, treat that it dissolves fully after, be settled to 200mL and obtain first step co-impregnated solution, place standby.Get little of the carrier that the step makes before the 120g and add above-mentioned co-impregnated solution in dipping tank, dipping 3h, the bar that will wet subsequently be at 120 ℃ of baking oven inner drying 7h, 400 ℃ of roasting 4h in the Muffle furnace.
Under the room temperature, in the 120mL deionized water, add 2g ethylene glycol, stir, after treating to dissolve fully, be settled to 200mL and obtain the second step co-impregnated solution, place standby.Be cooled to room temperature with little behind the preceding one-step baking, co-impregnated solution mixes therewith, and dipping 3h, the bar that will wet subsequently be at 120 ℃ of baking oven inner drying 7h, 450 ℃ of roasting 4h in the Muffle furnace, catalyst A, its character sees Table 2.
Embodiment 2,
By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sneaks into metatitanic acid 23g, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and oxalic acid 10g, add deionized water, in kneader, mediate mixing, after the banded extruder extruded moulding, obtain little of the bunge bedstraw herb of diameter 1.5mm.At 120 ℃ of baking oven inner drying 12h, 550 ℃ of roasting 4h in Muffle furnace get carrier Z-B, and its character sees Table 1.
Under the room temperature, add the 7g monoethanolamine in the 120mL deionized water, the dissolving back adds 46g six water ammonium metatungstates, 25.5g four water ammonium heptamolybdates, 35g six water nickel nitrates and 5g phosphoric acid, treats that it dissolves fully, is settled to 200mL and obtains stablizing co-impregnated solution.Co-impregnated solution is divided into isopyknic two parts, places standby.
Get little of the carrier that the step makes before the 120g and add in a copy of it co-impregnated solution in dipping tank, flood 3h under the room temperature, the bar that will wet subsequently is at 120 ℃ of baking oven inner drying 7h, 430 ℃ of roasting 4h in the Muffle furnace, and it is standby to lower the temperature.Treat little be cooled to room temperature after, add in another part co-impregnated solution, at room temperature flood 3h, the bar that will wet subsequently is at 120 ℃ of baking oven inner drying 7h, 500 ℃ of roasting 4h promptly get catalyst B in the Muffle furnace, its character sees Table 2.
Embodiment 3,
By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sneak into metatitanic acid 24g, 25% Ludox 63g, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and polyethylene glycol (degree of polymerization 2000) 10g, add deionized water, in kneader, mediate mixing, after the banded extruder extruded moulding, obtain little of the clover of diameter 1.5mm.120 ℃ of dry 12h in baking oven, 550 ℃ of roasting 4h in Muffle furnace, the character of gained carrier Z-C sees Table 1.
Under the room temperature, in the 30mL concentrated ammonia liquor, add the 8g aminotriacetic acid, adding deionized water to liquor capacity after the dissolving is 120mL, drip nitric acid to pH 3～4, add 44g six water ammonium metatungstates, 26g four water ammonium heptamolybdates, 36g six water nickel nitrates, 6g phosphoric acid successively after stable, treat that it dissolves fully, be settled to 200mL and obtain stable co-impregnated solution.Co-impregnated solution is divided into isopyknic two parts, places standby.
Get little of the carrier that the step makes before the 120g and add a copy of it co-impregnated solution in dipping tank, flood 3h under the room temperature, the bar that will wet subsequently is at 120 ℃ of baking oven inner drying 7h, 420 ℃ of roasting 4h in the Muffle furnace, and it is standby to lower the temperature.Treat little be cooled to room temperature after, add in another part co-impregnated solution, at room temperature flooded 3 hours, the bar that will wet subsequently is at 120 ℃ of baking oven inner drying 7h, 480 ℃ of roasting 4h promptly get catalyst C in the Muffle furnace, its character sees Table 2.
Embodiment 4,
By a kind of macropore aluminum hydroxide solid elastomer powder 240g, its alumina content is 70%, sneak into zirconyl nitrate 54g, metatitanic acid 24g, 25% Ludox 63g, sesbania powder 6g, 66% red fuming nitric acid (RFNA) 9g and polyethylene glycol (degree of polymerization 2000) 10g, add deionized water, in kneader, mediate mixing, after the banded extruder extruded moulding, obtain little of the clover of diameter 1.5mm.120 ℃ of dry 12h in baking oven, 550 ℃ of roasting 4h in Muffle furnace, the character of gained carrier Z-D sees Table 1.
Under the room temperature, in the 30mL concentrated ammonia liquor, add the 8g aminotriacetic acid, adding deionized water to liquor capacity after the dissolving is 120mL, drip nitric acid to pH 3～4, add 44g six water ammonium metatungstates, 26g four water ammonium heptamolybdates, 36g six water nickel nitrates, 13g cobalt nitrate hexahydrate 6g phosphoric acid successively after stable, treat that it dissolves fully, be settled to 200mL and obtain stable co-impregnated solution.Co-impregnated solution is divided into isopyknic two parts, places standby.
Get little of the carrier that the step makes before the 120g and add a copy of it co-impregnated solution in dipping tank, flood 3h under the room temperature, the bar that will wet subsequently is at 120 ℃ of baking oven inner drying 7h, 420 ℃ of roasting 4h in the Muffle furnace, and it is standby to lower the temperature.Treat little be cooled to room temperature after, add in another part co-impregnated solution, at room temperature flooded 3 hours, the bar that will wet subsequently is at 120 ℃ of baking oven inner drying 7h, 480 ℃ of roasting 4h promptly get catalyst C in the Muffle furnace, its character sees Table 2
Table 1
Table 2
* reference agent: industrial Ni-Mo/Al
2O
3The class catalyst.
Embodiment 4-6,
This example illustrates the hydrogenation reaction performance of catalyst provided by the invention for high nitrogen inferior distillate oil.
The evaluation feedstock oil that adopts is the high nitrogen inferior distillate oil of the high-sulfur miscella that is provided by the CNOOC refinery.This feedstock oil belongs to the naphthene base crude oil of the high nitrogen of high-sulfur, is mixed by straight-run diesel oil, catalytic diesel oil, coker gasoline and coker gas oil.
Adopt the fixed bed hydrogenation device of 200mL respectively catalyst A, B, C, D to be carried out hydrogenation reaction performance evaluation.
Presulfiding of catalyst condition: use to contain 3wt%CS
2The boat coal, with air speed 1.0h
-1, hydrogen to oil volume ratio 500: 1 under the operating pressure of 8.0MPa, carries out presulfurization to catalyst.
Pre-vulcanization process is as follows:
Under 120 ℃, advance presulfurization oil, behind the oil-feed 2h, constant temperature sulfuration 2h; Begin to heat up, be warming up to 150 ℃, constant temperature sulfuration 4h with 15 ℃/h; Be warming up to 230 ℃ with 6 ℃/h, constant temperature sulfuration 10h; Be warming up to 290 ℃ with 6 ℃/h, constant temperature sulfuration 6h; Be warming up to 340 ℃ with 10 ℃/h, constant temperature sulfuration 6h; At last be cooled to 200 ℃ naturally, presulfurization finishes.
The evaluation response condition is: operating pressure 8.0MPa, and 340 ℃ of reaction temperatures, hydrogen to oil volume ratio 600: 1, volume space velocity are 1.5h
-1Evaluation result sees Table 3.
Comparative Examples 1,
The explanation of this Comparative Examples is from controlling catalyst and industrial reference agent (Ni-Mo/Al
2O
3Class) performance comparison.
Adopt with example 4 same procedure and estimate the reference agent, its evaluating data sees Table 3.
Table 3
* industrial reference agent: Ni-Mo/Al
2O
3The class catalyst.
Evaluation result in the table 3 can illustrate, catalyst provided by the invention when being used for the hydrodesulfurization reaction of high nitrogen inferior distillate oil, at pressure 8.0MPa, 340 ℃ of temperature, hydrogen-oil ratio is 600: 1, volume space velocity is 1.5h
-1Process conditions under, reached higher desulfurization performance, also have simultaneously higher denitrogenation and olefin saturation performance energy.
Adopt catalyst A, B, the C of preparation method of the present invention preparation, the catalytic activity of D progressively to rise, wherein with Al
2O
3-ZrO
2-SiO
2-TiO
2For the activity of the catalyst D of complex carrier is the highest, desulfurization degree 98.7%, denitrification percent 97.8%, degree of olefin saturation 98.2% has all surpassed industrial reference agent.
Claims (2)
1. light oil hydrogenation desulfurization and denitrogenation Preparation of catalysts method is characterized in that:
(1) composition of catalyst comprises carrier, auxiliary agent, reactive metal; Carrier comprises aluminium oxide and titanium oxide, silica; Auxiliary agent is a phosphorus; Reactive metal comprises the oxide of nickel, molybdenum and tungsten; Each component is that the weight percent content of benchmark is with the catalyst: cobalt oxide accounts for 1～6wt%; Nickel oxide accounts for 1～15wt%; Molybdenum oxide is 2～12wt%; Tungsten oxide accounts for 12～35wt%; Phosphorus pentoxide accounts for 2～5wt%; Titanium oxide accounts for 2～15wt%; Silica accounts for 2～20wt%, and all the other are aluminium oxide;
Aluminium oxide precursor in the described carrier is the macropore boehmite; Add additive in the preparation process of carrier, comprise peptizing agent, expanding agent and extrusion aid; Described peptizing agent is a salpeter solution; Extrusion aid is selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol; Expanding agent is selected from organic acid such as citric acid, oxalic acid, maleic acid, malic acid or macromolecule polyalcohol such as polyethylene glycol;
Titanium dioxide in the described carrier is joined in the macroporous aluminium oxide powder by metatitanic acid or Nano titanium dioxide and introduces through pinching to mix, or is introduced by metatitanic acid four n-propyl solution; Silica is introduced by Ludox; Zirconium dioxide is introduced by the aqueous solution of zirconyl nitrate; Three kinds of auxiliary agents shared proportion in carrier is respectively titanium dioxide 2～15wt%, silica 5～20wt%, zirconia 5～15wt%; All the other components are aluminium oxide, and it is the Al of skeleton that the three constitutes with the aluminium oxide
2O
3-ZrO
2-SiO
2-TiO
2The multicomponent composite oxide carrier;
Introduced auxiliary agent phosphorus in the described catalyst, its existence form in catalyst is a phosphorus pentoxide, and its introducing mode is introduced in the preparing carriers process for adding peptizing agent with phosphoric acid, or introduces in the process of dipping reactive metal for phosphoric acid adds co-impregnated solution; Described auxiliary agent is 2～5wt% with the content of form in catalyst of phosphorus pentoxide;
Described catalyst has added a small amount of complexing agent in the process of preparation co-impregnated solution, described complexing agent is selected from and is in ethylene glycol, ethylenediamine, monoethanolamine, diethanol amine, triethanolamine, aminotriacetic acid and the ethylenediamine tetra-acetic acid one or more;
(2) described Preparation of catalysts method may further comprise the steps:
(1) preparation of carrier: earlier macropore boehmite, zirconia, metatitanic acid and Ludox are mixed, add peptizing agent, extrusion aid and expanding agent again, in kneader, mix and pinch into magma shape plastic, add extruded moulding in the banded extruder then, profile is cloverleaf pattern, bunge bedstraw herb shape or butterfly; Wet bar obtains Al through health, drying and high-temperature roasting
2O
3-ZrO
2-TiO
2-SiO
2The multivariant oxide complex carrier; The drying condition of carrier is 80～200 ℃ of down dry 2～15h, and roasting condition is at 550～650 ℃ of following roasting 1～8h;
(2) preparation of co-impregnated solution: at room temperature, active metal salt, complexing agent and auxiliary agent are added in the solvent, solvent is deionized water or ammonia spirit, evenly stirs dissolving down, obtains stable maceration extract, places standby behind the constant volume;
(3) Preparation of catalysts: because active component is more in the co-impregnated solution, concentration is higher, so its dilution is divided into isopyknic two parts after one times, dipping is so that the evenly dispersion on carrier of each active component in two steps; The carrier strip that makes in the step (1) is placed dipping tank, add a copy of it co-impregnated solution, dry in baking oven behind the dipping, roasting in the Muffle furnace; Treat that little after the roasting is cooled to room temperature, add another part co-impregnated solution, again through super-dry, roasting, obtain required catalyst behind the dipping; Wherein, the dip time of catalyst, each step all can be 2～7h; Behind first step dipping, baking temperature is 80～150 ℃, and be 2～12h drying time, and sintering temperature is 350～480 ℃, and roasting time is 1～8h; Catalyst behind the second step dipping, its baking temperature is 80～150 ℃, and be 2～12h drying time, and sintering temperature is 420～550 ℃, and roasting time is 1～8h.
2. according to the described preparation method of claim 1, it is characterized in that:
(1) composition of catalyst comprises carrier, auxiliary agent, reactive metal; Carrier comprises aluminium oxide and titanium oxide, silica; Auxiliary agent is a phosphorus; Reactive metal comprises the oxide of nickel, molybdenum and tungsten; Each component is that the weight percent content of benchmark is with the catalyst: cobalt oxide accounts for 1～4wt%; Nickel oxide accounts for 3～10wt%; Molybdenum oxide is 2～12wt%; Tungsten oxide accounts for 18～30wt%; Phosphorus pentoxide accounts for 2～5wt%; Titanium oxide accounts for 2～15wt%; Silica accounts for 2～20wt%, and all the other are aluminium oxide.
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