CN100406123C - Modified non-type supporter material, its preparation method and application - Google Patents
Modified non-type supporter material, its preparation method and application Download PDFInfo
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Abstract
The present invention relates to an amorphous carrier material and a preparation method and application thereof. The carrier material of the present invention contains the constituents of the following content of 1 to 40w% of zinc oxide, 5 to 70w% of silicon oxide, 5 to 70w% of alumina and 0 to 50w% of other refractory oxide or additive constituent, and has 250 to 600 m<2>/g of specific surface area, 0.6 to 1.5 ml/g of pore volume and 0.2 to 0.8 mmol/g of infrared acidity after being activated under suitable conditions. In the preparation process of the carrier material of the present invention firstly forms alumina bodies and subsequently compounds other substances of the zinc oxide and the silicon oxide. Compared with the prior art, the carrier material of the present invention has the characteristics of large specific surface area and pore volume, strong acidity, etc., and can be used for catalysts of hydrocarbon hydrotreatment, hydrocracking, etc.
Description
Technical field
The invention belongs to the synthetic field of catalyst carrier material, particularly compound unformed refractory oxide catalyst carrier material synthesizes the field.
Background technology
The catalyst of heterogeneous catalysis process generally adopts solid catalyst, and carrier is the important component part of solid catalyst.Carrier generally can be divided into inert carrier and active carrier.Pure-oxide all is inert carrier as silica, aluminium oxide.Some acid base catalyzed reaction need use active carrier, and particularly common acidic catalyst reaction needed is used the active carrier with acid centre.The oxide of different valence state and ligancy forms complex carrier can produce acid centre, and for example common amorphous silicon aluminium is exactly a kind of important catalyst active carrier.On the other hand, some oxides also are compounded in the carrier as the support modification auxiliary agent, for example surface-property-modifying agent, carrier duct modifier, acid modification agent, electronic property modifier etc.Adding by these modifier, they can the modulation carrier acidity, surperficial relaxation function etc., the change of these character not only can have influence on the interaction of carrier and supported active metal component in catalyst preparation process subsequently, and may directly have influence on the performance of catalyst.Common modifier such as titanium oxide, magnesia, zirconia, phosphorous oxide, boron oxide etc., the compound of one or more in them is main carrier component or even active component at some special occasions sometimes.
From the requirement of catalytic reaction, carrier itself must have enough big specific surface and pore volume on the one hand, with the carrying active metal component.For catalytic reaction is carried out effectively, some carrier generally also needs the acidic cleavage function that provides certain, and acid strength and quantity also should be suitable with the collocation of activity of such catalysts metal simultaneously, to improve activity of such catalysts and selectivity.GB2166971 discloses a kind of amorphous silicon aluminium preparation method, and it is earlier after under the high pH (12-12.5) alkali metal aluminate and silicate being mixed, and makes with reacting aluminum sulfate, from the embodiment of this patent SiO of its product sial as can be known again
2Content under situation less than 35w%, specific surface 277m
2/ g, pore volume 0.31ml/g.Though have lytic activity, its shortcoming remains pore volume and specific surface is not high, is not enough to separately as carrier component when carrying the metal component of higher amount.US6174432 discloses a kind of boron-containing alumina carrier preparation method, and the mode of making peptizing agent with boric acid joins and makes the boron alumina support in the aluminium oxide exactly.EP0788270 a kind ofly handles aluminium oxide with waterglass or Ludox, improves the amorphous silicon aluminium product property through hydrothermal treatment consists again, and specific surface also only has 214m
2/ g, and preparation method's condition harshness of this product, the hydrothermal treatment consists energy consumption is big.
CN1108585A discloses a kind of hydrogenation reaction catalyst precursor, comprise catalyst carrier (A) and be loaded in the metal oxide composition (B) that catalyst carrier (A) goes up or mixes with catalyst carrier (A), wherein metal oxide composition (B) comprises cupric oxide, zinc oxide and at least a oxide that is selected from the metal of IIa family in the periodic table, III b family element, lanthanide series and actinides.Chinese patent 96122555 discloses texturing of mixed light-hydrocarbon aromatization catalyst by solid phase reaction in a kind of petrochemical industry, this method for preparing catalyst prepares the ZnHZSM-5 molecular sieve for adopting ion-exchange, then itself and zinc oxide, gama-alumina three kinds of abundant solid phase mixing of material, granulation, roastings are made carrier, with carrier process metal cation platinum, silver, gallium, copper, iron, any three kinds of dippings of nickel, make catalyst again.They are that a kind of mode of mechanical mixture obtains, and can not realize uniformity on molecular level, and modified effect is limited.
Summary of the invention
The object of the present invention is to provide a kind of unformed carrier of multicomponent composite oxide of the II of containing B family metal oxide to be used for the raw material components of catalyst or carrier.The present invention also aims to provide a kind of and stream is neutralized into the multicomponent composite oxide that glue preparation technology obtains a kind of II of containing B family metal oxide content, silica content, aluminium oxide and/or other refractory oxide or additive.
The present invention contains the unformed carrier of multicomponent composite oxide of II B family metal oxide, II B family metal is selected from zinc oxide, zinc oxide content 1-40w%, silica content 5-70w%, alumina content 5-70w%, other refractory oxide or additive component 0-50w%.The weight percentage sum of all components is 100%.
According to the unformed carrier of the multicomponent composite oxide of preparation technology of the present invention and composition thereof, it is formed preferably: the preferred 2-20w% of zinc oxide content, preferably 3-15w%; The preferred 5-50w% of silica content, preferably 15-40w%; The preferred 5-50w% of alumina content, preferably 15-40w%.
According to the unformed carrier of the multicomponent composite oxide of preparation technology of the present invention and composition thereof, has following character under optimum conditions after the activation: specific surface 250-600m
2/ g, pore volume 0.6-1.5ml/g, infrared acidity 0.2-0.8mmol/g.Further, best its specific surface 350-500m
2/ g, pore volume 0.8-1.3ml/g, infrared acidity 0.3-0.6mmol/g.Activation condition generally can be 350～700 ℃ of activation 1～6 hour.
Except zinc oxide, silica and aluminium oxide, can also comprise other refractory oxide and refractory oxide be selected from titanium oxide, magnesia, zirconic one or more, additive is selected from one or more of phosphorous oxide, boron oxide.
The preparation that the present invention contains the multicomponent composite oxide non-type supporter material of II B family metal oxide may further comprise the steps:
(a) under temperature 40-90 ℃, pH value 7.0-10.0 condition, a kind of acid solution and a kind of alkaline precipitating agent and stream joined obtain in the reaction vessel before matrix I;
(b) preceding matrix is stablized 0-60 minute matrix II under the condition of pH value 7-9;
(c) soluble compound of a kind of II of containing B family metal and one or more other compounds are joined obtain the elementary soliquid III of compound among the II;
(d) under optimum conditions the aging 0.5-10h of suspension II I is obtained material IV;
(e) material IV filtration and washing are obtained wet cake V;
(f) the dry and pulverizing back acquisition composite oxide carrier material with wet cake V.
Preparation technology according to the unformed carrier of multicomponent composite oxide of the present invention: described acid solution is to be selected from a kind of in aluminum sulfate, aluminium chloride and the aluminum nitrate; Alkaline precipitating agent is to be selected from a kind of in NaOH, sodium metaaluminate and the ammoniacal liquor; Described and stream the neutralization reaction time at 0.5-2 hour.Aging condition can carry out under 40～90 ℃ at pH value 7-9 and temperature.
The unformed composite oxides of the present invention can be used for hydrotreating catalyst, hydrocracking catalyst etc.When being used for catalyst, can be with above-mentioned unformed composite oxides moulding, one or more in load conventional W, Mo, Ni, the Co isoreactivity metal.
The present invention contains the compound of introducing II B family metal in the unformed preparing carriers process of multicomponent composite oxide of II B family metal oxide, mainly is meant zinc compound.By in carrier, introducing zinc oxide, can improve the interaction of metal and catalyst carrier, if thereby adopt the present invention to contain the unformed carrier of multicomponent composite oxide of II B family metal oxide as the catalyst carrier component, can influence active component and carrier interactions to a certain degree, and directly be reflected on activity of such catalysts and the selectivity.Especially, if use carrier of the present invention at catalyst with acidic cleavage center, it also can change the acid amount and the acid strength of acid centre, and then is that the cracking selectivity of reacting changes, and for example can improve the middle distillates oil selectivity of hydrocracking process by the use of carrier of the present invention.
According to the unformed preparing carriers technology of multicomponent composite oxide of the present invention, best implementation method is to form the preceding matrix of aluminium oxide earlier, and the control neutrality condition obtains the crystalline form of certain feature, make silicon atom replace the aluminium atom site again, this is different from prior art and adopts silicon source impregnated alumina, silicon atom just deposits simply, promptly can not significantly improve acidity, also can make the carrier duct impaired.The characteristics of the unformed compound of the present invention are to make silicon attack aluminium atom and replacing under advantage concentration, thereby have formed a large amount of original acid site frameworks, thereby have higher acidity.Thereby compared with prior art, the unformed compound of the present invention not only has higher acidity, and simultaneously unformedization degree height has very high specific surface and pore volume, thus the unformed carrier of the present invention must hydrothermal treatment consists or alternate manner come reaming.
In order to improve the pore structure character of unformed compound, the unformed preparing carriers technology of multicomponent composite oxide of the present invention is used and stream Stationary pH method, and not only process is easy to control, and product has better character index.The unformed carrier of multicomponent composite oxide of the present invention, specific surface generally can reach 450m
2More than/the g, pore volume can reach more than the 1.2ml/g.
Because the difference of application purpose, acidic cleavage function to the unformed carrier of multicomponent composite oxide of the present invention has different requirements, can adjust the addition of soluble compound of II B family metal and other refractory oxide such as silica, titanium oxide, magnesia by step (c), zirconic addition is adjusted.Procedure of the present invention is simple, control easily, and energy consumption is low, does not need special installation.
Specific implementation method
Further specify Preparation of catalysts method of the present invention, character and effect by the following examples, the scheme among the embodiment is the specific embodiments in scope of the invention claim scope, is not construed as limiting the invention.
Example 1
3.2 liters of red fuming nitric acid (RFNA) aluminum solutions are joined in 7 liters of distilled water, heat simultaneously and stir and obtain rare aluminum nitrate solution (a1), solution A l
2O
3Concentration 6g/100ml.Technical grade 40% dense NaOH is added an amount of distilled water diluting into about 15% weak solution (b1).Industrial zinc ingot metal is added nitric acid dissolve and dilution into about 30% solution (c1).The silicon sol solution of technical grade 25% silica is added an amount of distilled water diluting into about 8% weak solution (d1).
Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 50 ℃, open the container valve that has aluminum nitrate solution (a1) and NaOH (b1) solution respectively simultaneously, 300g amorphous silicon aluminium product is set the flow of (a1) and stream becomes glue and make the neutralization reaction time at 2 hours by preparing, and the flow of adjusting rapidly (b1) makes the pH value of system remain on 7.0, and the temperature of the hierarchy of control is at 50 ℃.After aluminum nitrate has reacted, stop to add NaOH solution, after the alumina sol of generation is stablized 15 minutes, respectively in 10 minutes by finally containing the zinc nitrate solution (c1) that ZnO adds amount of calculation, and by finally containing SiO
2(d1) that amount begins to add metering.After water injection behind the glass solution, begin to wear out at last, keep the pH value 9.0,65 ℃ of temperature.Aging after 10 hours, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, add metering phosphoric acid simultaneously, after stirring 30 fens, filter obtain filter cake and with it at 110 ℃ down after dry 8 hours, pulverize, sieve the present invention's unformed carrier S-1.
Finally consisting of of S-1 product: zinc oxide 2w%, silica 60w%, aluminium oxide 35w%, phosphorus pentoxide 3w%.
Example 2
3.2 liters of red fuming nitric acid (RFNA) aluminum solutions are joined in 7 liters of distilled water, heat simultaneously and stir and obtain rare aluminum nitrate solution (a2), solution A l
2O
3Concentration 6g/100ml.Technical grade 40% dense NaOH is added an amount of distilled water diluting into about 15% weak solution (b2).Industrial zinc ingot metal is added nitric acid dissolve and dilution into about 30% solution (c2).The silica gel solution of technical grade 25% silica is added an amount of distilled water diluting into about 8% weak solution (d2).Amount of calculation chemical pure zirconium sulfate reagent is added an amount of dissolved in distilled water be mixed with solution (e2).Amount of calculation chemical pure titanyl sulfate reagent is added an amount of dissolved in distilled water be mixed with solution (f2).Obtain acid working solution with (a2) with (f2) after the mixing.
Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 45 ℃, open the valve of the container that has above-mentioned acid working solution and sodium hydroxide solution (b2) respectively simultaneously, 300g amorphous silicon aluminium product is set the flow of acid working solution and stream becomes glue and make the neutralization reaction time at 2 hours by preparing, and the flow of adjusting rapidly (b2) makes the pH value of system remain on 7.0, and the temperature of the hierarchy of control is at 50 ℃.After aluminum nitrate has reacted, stop to add NaOH solution, after the alumina sol that generates is stablized 15 minutes, pressed silicon sol solution (d2), chemical pure zirconium sulfate solution (e2) that the final composition requirement of product adds metering zinc nitrate solution (c2), metering respectively at 10 minutes.After adding zirconium sulfate solution, begin to wear out, keep the pH value 9.0,65 ℃ of temperature.Aging after 4 hours, filter colloidal solution and obtain wet cake, after the making beating of filter cake adding distil water again washing repeatedly, filter obtain filter cake and with it at 110 ℃ down after dry 8 hours, pulverize, sieve the present invention's unformed carrier S-2.
Finally consisting of of S-2 product: zinc oxide 5w%, silica 40w%, aluminium oxide 10w%, titanium oxide 20w%, zirconia 25w%.
Example 3
The dense sodium aluminate solution of technical grade is joined in 6 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain sodium aluminate solution (a3), Al
2O
3Concentration 18g/100ml.1.0 liters of concentrated hydrochloric acid solutions are joined in 4 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain dilute hydrochloric acid solution (b3).Industrial zinc ingot metal is added nitric acid dissolve and dilution into about 30% solution (c3).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades and obtain rare water glass solution (d3).Amount of calculation chemical pure zirconium sulfate reagent is added an amount of dissolved in distilled water be mixed with solution (e3).
Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 60 ℃, open the valve of the container that has sodium aluminate solution (a3) and dilute hydrochloric acid solution (b3) respectively simultaneously, 300g amorphous silicon aluminium product is set the flow of (a3) and stream becomes glue and make the neutralization reaction time at 1.5 hours by preparing, and the flow of adjusting rapidly (b3) makes the pH value of system remain on 7.5, and the temperature of the hierarchy of control is at 60 ℃.After metering aluminium chloride and sodium aluminate have reacted, stop neutralization, after the alumina sol that generates is stablized 15 minutes, pressed water glass solution (d3) and chemical pure zirconium sulfate solution (e3) that the final composition requirement of product adds metering zinc nitrate solution (c3), metering respectively at 10 minutes.After adding zirconium sulfate solution at last, begin to wear out, keep the pH value 7.5,65 ℃ of temperature.Aging after 2 hours, filter colloidal solution and obtain wet cake, after the making beating of filter cake adding distil water again washing repeatedly, filter obtain filter cake and with it at 110 ℃ down after dry 8 hours, pulverize, sieve the present invention's unformed carrier S-2.
Finally consisting of of S-1 product: zinc oxide 15w%, silica 40w%, aluminium oxide 40w%, zirconia 5w%.
Example 4
The dense sodium aluminate solution of technical grade is joined in 6 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain sodium aluminate solution (a4), Al
2O
3Concentration 18g/100ml.1.0 liters of concentrated hydrochloric acid solutions are joined in 4 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain dilute hydrochloric acid solution (b4).Industrial zinc ingot metal is added nitric acid dissolve and dilution into about 30% solution (c4).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades and obtain rare water glass solution (d4).Amount of calculation chemical pure titanyl sulfate reagent is added an amount of dissolved in distilled water be mixed with titanyl sulfate solution (e4).
Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 55 ℃, open the valve of the container that has sodium aluminate solution (a4) and dilute hydrochloric acid solution (b4) respectively simultaneously, 300g amorphous silicon aluminium product is set the flow of (a4) and stream becomes glue and make the neutralization reaction time at 1.5 hours by preparing, and the flow of adjusting rapidly (b4) makes the pH value of system remain on 7.5, and the temperature of the hierarchy of control is at 55 ℃.After metering aluminium chloride and sodium aluminate have reacted, stop neutralization, after the alumina sol that generates is stablized 15 minutes, pressed water glass solution (d4) and titanyl sulfate solution (e4) that the final composition requirement of product adds metering zinc nitrate solution (c4), metering respectively at 10 minutes.After adding titanyl sulfate solution at last, begin to wear out, keep the pH value 7.5,65 ℃ of temperature.Aging after 1.5 hours, filter colloidal solution and obtain wet cake, after the making beating of filter cake adding distil water again washing repeatedly, filter obtain filter cake and with it at 110 ℃ down after dry 8 hours, pulverize, sieve the present invention's unformed carrier S-4.
Finally consisting of of S-4 product: zinc oxide 15w%, silica 40w%, aluminium oxide 30w%, titanium oxide 15w%.
Example 5
4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving and obtain aluminum sulfate solution (a5), Al
2O
3The about 7g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b5).Industrial zinc ingot metal is added nitric acid dissolve and dilution into about 30% solution (c5).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades and obtain 8% rare water glass solution (d5).
Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 60 ℃, open the valve of the container that has aluminum sulfate solution (a5) and dilute ammonia solution (b5) respectively simultaneously, 300g amorphous silicon aluminium product is set the flow of (a5) and stream becomes glue and make the neutralization reaction time at 1 hour by preparing, and the flow of adjusting rapidly (b5) makes the pH value of system remain on 8.5, and the temperature of the hierarchy of control is at 60 ℃.After metering aluminium chloride and sodium aluminate have reacted, stop neutralization, after the alumina sol of generation is stablized 15 minutes, pressed the water glass solution (d3) that the final composition requirement of product adds metering zinc nitrate solution (c3), metering respectively at 10 minutes.After water injection behind the glass solution, begin to wear out at last, keep the pH value 7.5,65 ℃ of temperature.Aging after 0.5 hour, filter colloidal solution and obtain wet cake, after the making beating of filter cake adding distil water again washing repeatedly, filter obtain filter cake and with it at 110 ℃ down after dry 8 hours, pulverize, sieve the present invention's unformed carrier S-5.
Finally consisting of of S-5 product: zinc oxide 30w%, silica 10w%, aluminium oxide 60w%.
Example 6
4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving and obtain aluminum sulfate solution (a6), Al
2O
3The about 7g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b6).Industrial zinc ingot metal is added nitric acid dissolve and dilution into about 30% solution (c6).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades and obtain 8% rare water glass solution (d6).Amount of calculation chemical pure zirconium sulfate magnesium nitrate reagent is added an amount of dissolved in distilled water be mixed with solution (e6).
Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 65 ℃, open the valve of the container that has aluminum sulfate solution (a6) and dilute ammonia solution (b6) respectively simultaneously, 300g amorphous silicon aluminium product is set the flow of (a6) and stream becomes glue and make the neutralization reaction time at 1 hour by preparing, and the flow of adjusting rapidly (b6) makes the pH value of system remain on 9.0, and the temperature of the hierarchy of control is at 65 ℃.After metering aluminium chloride and sodium aluminate have reacted, stop neutralization, after the alumina sol that generates is stablized 15 minutes, pressed water glass solution (d6) and magnesium nitrate solution (e6) that the final composition requirement of product adds metering zinc nitrate solution (c6), metering respectively at 10 minutes.After adding magnesium nitrate solution at last, begin to wear out, keep the pH value 7.5,65 ℃ of temperature.Aging after 1.0 hours, filter colloidal solution and obtain wet cake, after the making beating of filter cake adding distil water again washing repeatedly, filter obtain filter cake and with it at 110 ℃ down after dry 8 hours, pulverize, sieve the present invention's unformed carrier S-6.
Finally consisting of of S-6 product: zinc oxide 30w%, silica 15w%, aluminium oxide 50w%, magnesia 5w%.
Example 7
4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving and obtain aluminum sulfate solution (a7), Al
2O
3The about 7g/100ml of concentration.Concentrated ammonia liquor is added an amount of distilled water diluting into about 10% weak aqua ammonia (b7).Industrial zinc ingot metal is added nitric acid dissolve and dilution into about 30% solution (c7).10 liters of distilled water are joined in the concentrated sodium silicate of modulus 3.0 of 4.8 liters of a kind of technical grades and obtain 8% rare water glass solution (d7).Amount of calculation chemical pure acid reagent is added an amount of dissolved in distilled water be mixed with solution (e7).Obtain acid working solution with (a7) with (e7) after the mixing.
Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 75 ℃, open the valve of the container that has aluminum sulfate solution (a7) and dilute ammonia solution (b7) respectively simultaneously, 300g amorphous silicon aluminium product is set the flow of (a7) and stream becomes glue and make the neutralization reaction time at 1 hour by preparing, and the flow of adjusting rapidly (b7) makes the pH value of system remain on 8.0, and the temperature of the hierarchy of control is at 75 ℃.After metering aluminium chloride and sodium aluminate have reacted, stop neutralization, after the alumina sol of generation is stablized 15 minutes, pressed the water glass solution (76) 7 that the final composition requirement of product adds metering zinc nitrate solution (c7), metering respectively at 10 minutes.After adding the sulphur water glass solution at last, begin to wear out, keep the pH value 7.5,65 ℃ of temperature.Aging after 1.0 hours, filter colloidal solution and obtain wet cake, after the making beating of filter cake adding distil water again washing repeatedly, filter obtain filter cake and with it at 110 ℃ down after dry 8 hours, pulverize, sieve the present invention's unformed carrier S-7.
Finally consisting of of S-7 product: zinc oxide 30w%, silica 25w%, aluminium oxide 40w%, magnesia 5w%.
Table 1 amorphous silicon aluminium product property
Example 8
Get the unformed preparing carriers catalyst of the present invention of example 1～7, the preparation method is as follows: get the unformed carrier of the present invention and the aperture alumina adhesive that obtains with the nitric acid peptization according to the proportioning of 60: 40 (dried content meter) mix be rolled into paste after, cross the cylinder bar that φ 1.7mm garden post orifice plate is extruded diameter 1.5mm with banded extruder, 110 ℃ of dryings, again through 500 ℃ of activation 3 hours behind the carrier dipping tungsten nickel hydrogenation metal make tungsten oxide 24w%, nickel oxide 4w%.Numbering is followed successively by C1～C7.
Example 9
Be the reference catalyst of reference preparing carriers, comprise a kind of reference aluminium oxide and reference amorphous silicon aluminium.Wherein the reference aluminium oxide is the industrial products that Fushun No.3 Petroleum Factory produces, the industrial products that the reference amorphous silicon aluminium is produced for the Lanzhou catalyst plant.Method for preparing catalyst and composition are with example 8, and numbering is followed successively by C8, C9.
Example 10
Catalyst C1～C7 is ground respectively and sieves 100 orders are got 0.5g and are seated in and littlely estimate in anti-.Estimate the performance that adopts hydrodesulfurization reaction to assess catalyst.Be reflected on the continuous-flow fixed-bed micro-devices and carry out, loaded catalyst 0.1g mixes with 1.0g quartz sand; The model reaction compound is the n-decane solution that contains the dibenzothiophenes of 5w%; Under 300 ℃ catalyst is carried out presulfurization 4h before the reaction, sulfurized oil is the cyclohexane that contains 10v%CS2; Feed reactant and be adjusted to desired reaction temperature, charging rate 0.2ml/min collects the condensed fluid sample analysis behind the stable reaction 3h; Reaction pressure is 4MPa, hydrogen flow rate 500ml/min; The quantitative analysis of product liquid is carried out having on the gas chromatograph of capillary chromatographic column.
Desulphurizing activated relatively is that benchmark is decided to be 100 with C9, and other catalyst carries out relatively with it.From table 2, the catalyst of the unformed preparing carriers of the present invention all is better than the catalyst of reference preparing carriers on desulfurization performance.
| Numbering | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Desulphurizing activated relatively | 108 | 110 | 112 | 118 | 115 | 117 | 114 | 100 | 90 |
Claims (7)
1. non-type supporter material, it is characterized in that carrier material is the multicomponent composite oxide that contains the IIB family metal oxide, IIB family metal is selected from zinc oxide, zinc oxide content 1-40w%, silica content 5-70w%, alumina content 5-70w%, other refractory oxide or additive component 0-50w%; The specific surface of carrier material is 250-600m
2/ g, pore volume are 0.6-1.5ml/g, and infrared acidity is 0.2-0.8mmol/g; Described refractory oxide be selected from titanium oxide, magnesia, zirconic one or more; Described additive is selected from one or more of phosphorous oxide, boron oxide.
2. according to the described carrier material of claim 1, it is characterized in that described zinc oxide content is 2-20w%, silica content is 5-50w%, and alumina content is 5-50w%.
3. according to the described carrier material of claim 1, it is characterized in that described zinc oxide content is 3-15w%, silica content is 15-40w%, and alumina content is 15-40w%.
4. according to the described carrier material of claim 1, the specific surface that it is characterized in that described carrier material is 350-500m
2/ g, pore volume are 0.8-1.3ml/g, and infrared acidity is 0.3-0.6mmol/g.
5. the preparation method of the described carrier material of the arbitrary claim of claim 1～4 may further comprise the steps:
(a) under temperature 40-90 ℃, pH value 7.0-10.0 condition, a kind of acid solution and a kind of alkaline precipitating agent and stream joined obtain in the reaction vessel before matrix I;
(b) preceding matrix I was stablized under the condition of pH value 7-9 0-60 minute, obtain matrix II;
(c) soluble compound of a kind of II of containing B family metal and one or more other compounds are joined obtain the elementary soliquid III of compound among the II;
(d) under 40～90 ℃, the aging 0.5-10h of suspension II I is obtained material IV at pH value 7-9 and temperature;
(e) material IV filtration and washing are obtained wet cake V;
(f) wet cake V drying, pulverizing and activation back are obtained the composite oxide carrier material;
Wherein the acid solution described in the step (a) is to be selected from a kind of in aluminum sulfate, aluminium chloride and the aluminum nitrate, and alkaline precipitating agent is to be selected from a kind of in NaOH, sodium metaaluminate and the ammoniacal liquor; Other compound described in the step (c) is one or more in titanium, magnesium, zirconium, phosphorus and the boron compound.
6. in accordance with the method for claim 5, it is characterized in that described and stream the neutralization reaction time at 0.5-2 hour.
7. the application of the described carrier material of the arbitrary claim of claim 1～4 in hydrotreating catalyst or hydrocracking catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267874B1 (en) * | 1997-11-18 | 2001-07-31 | Tonengeneral Sekiyu K.K. | Hydrotreating catalyst and processes for hydrotreating hydrocarbon oil with the same |
| CN1382199A (en) * | 1999-12-14 | 2002-11-27 | 菲利浦石油公司 | Desulfurization process and bimetallic sorbent systems for same |
| CN1384770A (en) * | 1999-11-01 | 2002-12-11 | 菲利浦石油公司 | Desulfurization and novel sorbents for same |
| US20050059548A1 (en) * | 1999-08-25 | 2005-03-17 | Khare Gyanesh P. | Desulfurization and novel sorbents for same |
-
2004
- 2004-10-29 CN CNB2004100827059A patent/CN100406123C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267874B1 (en) * | 1997-11-18 | 2001-07-31 | Tonengeneral Sekiyu K.K. | Hydrotreating catalyst and processes for hydrotreating hydrocarbon oil with the same |
| US20050059548A1 (en) * | 1999-08-25 | 2005-03-17 | Khare Gyanesh P. | Desulfurization and novel sorbents for same |
| CN1384770A (en) * | 1999-11-01 | 2002-12-11 | 菲利浦石油公司 | Desulfurization and novel sorbents for same |
| CN1382199A (en) * | 1999-12-14 | 2002-11-27 | 菲利浦石油公司 | Desulfurization process and bimetallic sorbent systems for same |
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