CN1123386C - Macroreticular acidic composite carrier and its preparing process - Google Patents
Macroreticular acidic composite carrier and its preparing process Download PDFInfo
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- CN1123386C CN1123386C CN 01114165 CN01114165A CN1123386C CN 1123386 C CN1123386 C CN 1123386C CN 01114165 CN01114165 CN 01114165 CN 01114165 A CN01114165 A CN 01114165A CN 1123386 C CN1123386 C CN 1123386C
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Abstract
The present invention provides a macroporous acidic composite carrier which comprises 10 to 90 wt% of amorphous silica-aluminum, 1 to 50 wt% of beta-zeolite, 1 to 50 wt% of modified Y-zeolite and 0 to 30 wt% of microporous aluminum oxide or other microporous refractory oxides. The carrier is especially suitable for carrying hydrogenized metal in the process of hydrocracking, and has the advantages of high output of intermediate fractional oil and maximal output of diesel oil with a low solidifying point.
Description
Technical field
The present invention relates to a kind of acid carrier and preparation method thereof,, particularly be applicable to support of the catalyst of hydrocracking reaction process and preparation method thereof in particular for support of the catalyst of catalyzed reaction and preparation method thereof.
Background technology
For general catalyzed reaction, carry out effectively in order to make reaction, carrier generally need provide certain acid sites, the related solid catalyst of heterogeneous catalysis process usually more uses amorphous aluminum silicides as one of carrier component, particularly related catalytic reaction process in the petroleum refining process.And amorphous aluminum silicide requires itself must have enough big specific surface and pore volume as carrier component, so that reaction compartment or carrying active metal component to be provided.
But it is this difunctional that present disclosed patent all can not embody basically fully, and GB2166971 discloses a kind of amorphous aluminum silicide preparation method, and this patent working example shows the SiO of its sial
2Content is under the situation less than 35w%, and specific surface area is 277m
2/ g, pore volume is 0.31ml/g, illustrates that its pore volume and specific surface are not high, institute's bearing metal component content is not enough to separately as carrier component when higher.US4738767 discloses a kind of hydrocracking catalyst, because the duct that acid sial can not provide support of the catalyst to need simultaneously need be dispersed on a kind of macroporous aluminium oxide matrix, as γ-Al
2O
3On, this brings restriction for undoubtedly the prescription allotment of carrier, and the homogeneity of also distributing for acid sites in the duct is brought disadvantageous effect simultaneously, and finally has influence on catalyst catalytic performance.
On the other hand, catalyzer and catalytic process thereof all have requirement to the selectivity of reactive behavior and purpose product, and this is that the complicacy of catalyzed reaction and the economy of catalytic process application determine.Like this, to catalyzer and related catalytic material thereof new requirement certainly will be proposed constantly.Zeolite is important catalytic material, and the carrier that therefore contains zeolite component uses very extensive in catalytic process.But because zeolite component is developed the qualification aspect the coordinated that purpose specificity and various ingredients exist, the less use composite zeolite of present carrier and catalyzer thereof component at first in carrier.
US5536687 discloses a kind of catalyzer, has related to a kind of complex carrier, it is characterized in that the compound a kind of unit cell parameters of a kind of β zeolite is not more than the Y zeolite of 2.445nm.This carrier complexes carrying catalyzer that hydrogenation metal obtained mainly uses on light oil type hydrogen cracking catalyst, and the β zeolite examples demonstrates the catalyst activity raising and 50-185 the interior light naphthar yield of cut scope increases.Though this complex systems carrying catalyzer that hydrogenation metal obtained also can be used for the oil type hydrocracking process, but because the characteristic of the β zeolite that uses, the content of β zeolite generally is limited in the narrower scope in middle oil type catalyzer, generally be not more than 10w%, and must be used a kind of γ of being dispersed in-Al
2O
3And so on the sial on the macroporous aluminium oxide matrix.Because component allotment is range limited, this complex systems is used for oil type hydrocracking catalyst, have to activity forced down cause temperature of reaction than higher, so well equilibrium activity and middle distillates oil selectivity this to contradiction.
Summary of the invention
Therefore, purpose of the present invention just is to provide a kind of macroreticular acidic composite carrier and preparation method thereof, makes the gained carrier both have suitable specific surface, pore volume, has the required acid function of the chemical reaction of assurance again.
The characteristics of complex carrier of the present invention are to contain a kind of difunctional macroreticular acidic amorphous silicon al composition, and composite with the composite zeolite component, and said composite zeolite component comprises at least a β zeolite and at least a modified Y zeolite.Weight percent with carrier is a benchmark, and typical complex carrier comprises: (a) amorphous aluminum silicide 10%～90%; (b) β zeolite 1%-50%; (c) Y zeolite 1%-50%; (d) little porous aluminum oxide or other aperture refractory oxide 0～30%.
Further, be benchmark with the weight percent of carrier, preferably include in the complex carrier of the present invention: (a) amorphous aluminum silicide 40%-80%; (b) β zeolite 5%-30%; (c) Y zeolite 5%-30%; (d) little porous aluminum oxide or other aperture refractory oxide 0-20%.
Complex carrier specific surface of the present invention generally is 300-600m
2/ g better is 300-450m
2/ g, preferably 350-450m
2/ g; Pore volume generally is 0.50-0.80ml/g, preferably 0.55-0.75ml/g; The general 0.20-0.60mmol/g of infrared acidity better is 0.25-0.55mmol/g, preferably 0.30-0.50mmol/g; Contain SiO
2Better be 20w%-60w%, preferably 30w%-50w%.
Further, the pore volume that carrier hole diameter of the present invention is 4-15nm accounts for the 50%-90% of total pore volume, and the pore volume of＞20nm is no more than 10% of total pore volume.
The infrared acidity of β zeolite of the related use of support of the catalyst of the present invention generally is 0.05-0.5mmol/g, is preferably 0.1-0.4mmol/g, SiO
2/ Al
2O
3Than (chemical method) generally is 20-150,30-90 preferably, Na
2The O weight content is general＜and 0.2%, best＜0.1%.
The related use Y zeolite of support of the catalyst of the present invention SiO
2/ Al
2O
3Mol ratio is 5-25, is preferably 6-17, and unit cell parameters is 2.420-2.450nm, is preferably 2.425-2.445nm,, infrared acidity generally is 0.20-1.0mmol/g, is preferably 0.30-0.8mmol/g, Na
2The O weight content is general＜and 0.2%, the general 550-850m of specific surface
2/ g.
The macroreticular acidic amorphous aluminum silicide specific surface 300-600m of the related use of complex carrier of the present invention
2/ g is preferably 400-550m
2/ g, pore volume 0.9-1.6ml/g is preferably 1.0-1.5ml/g, and infrared acidity 0.25-0.55mmol/g is preferably 0.30-0.50mmol/g.Described unformed silicon also can phosphorous 1w%-5w%.
Little porous aluminum oxide of the present invention generally is that specific surface is not more than 300m
2/ g, pore volume are not more than the aluminum oxide of 0.52ml/g, and other aperture refractory oxide is meant the oxide compound of other similarity such as silicon-dioxide etc.
The amorphous aluminum silicide of the related use of complex carrier of the present invention can adopt and flow the preparation of Stationary pH method, this method not only process is easy to control, and product has better character index, and the preparation method of the above-mentioned amorphous aluminum silicide of this amorphous aluminum silicide specific surface can be referring to Chinese patent application 97116404.5.
The β zeolite of the related use of complex carrier of the present invention, the preparation method can carry out as follows: the β zeolite slurry after (1) crystallization is complete directly carries out the ammonium salt exchange; (2) the β zeolite after the ammonium salt exchange filter, wash, drying and roasting; (3) the β zeolite that takes off behind the ammonium of roasting carries out acid treatment, filters; (4) the intact β zeolite of acid treatment carries out the pressurized thermal water processing.
Complex carrier of the present invention also uses a kind of modified Y zeolite as the acidic cleavage component simultaneously, compare with the super-hydrophobic Y zeolite of prior art for preparing, the modified Y zeolite of use involved in the present invention has higher degree of crystallinity, specific surface, unit cell parameters, silica alumina ratio and secondary pore, its detailed preparation method can be referring to Chinese patent 96120049.9.It is to utilize the strong open loop activity of Y zeolite to improve in the catalytic reaction process cracking performance to cyclic hydrocarbon and polycyclic aromatic hydrocarbons that complex carrier of the present invention uses the purpose of modified Y zeolite.
The moulding of complex carrier of the present invention can be adopted known various routine techniques, as balling-up or extrusion, but the various forming methods of carrier all are not construed as limiting the invention, complex carrier of the present invention generally adopts the extruded moulding method, extruded moulding generally all needs to add binder ingredients, be beneficial to moulding and guarantee the intensity of moulding bar, tackiness agent generally is that employed aperture aluminum oxide specific surface generally is not more than 300m with the aperture aluminum oxide preparation that is easy to peptization
2/ g, pore volume generally is not more than 0.52ml/g, its character index is not enough to also can not be as the pore volume that carrier had and the contributor of specific surface, the purpose of using it be for its with dilute acid soln peptization with the preparation tackiness agent, in the carrier moulding process, play adhesive effect.Complex carrier of the present invention also can not use little porous aluminum oxide or other aperture refractory oxide, but after each component involved in the present invention mixed, directly adds a certain amount of acid, mix pinch and roll the journey paste after, extruded moulding again.
The carrier strip of moulding is generally garden post bar, and diameter 1.3-1.8mm also can adopt special-shaped bar such as trifolium or Herba Galii Bungei type, gets carrier behind drying, the calcination activation.Carrier strip behind the carrier strip of moulding or the carrying reactive metal needs drying, general drying temperature is at 90-160 ℃, be preferably in 110-140 ℃, time is 6-12 hour, preferably 8-10 hour, the main oven drying that adopts also can adopt other drying mode, and the exsiccant purpose is in order to drive away the material planar water in the support of the catalyst.Behind dry the end, can enter the calcination for activation process, activation temperature is at 450-650 ℃, and preferably 500-600 ℃, the time is 1-10 hour, preferably 3-6 hour.
This complex carrier generally can be used in the various acidic catalyst reactions separately as catalyst component.Simultaneously, above-mentioned scope does not constitute the application limitations to carrier of the present invention, and in other words, complex carrier of the present invention can be applicable to any carrier specific surface and pore volume be had relatively high expectations, the field that needs to bring into play the different zeolites catalytic selectivity again simultaneously.
As required, support of the catalyst of the present invention can further be carried active metal component or other binder component, to adapt to the needs of differential responses.As for hydrocracking catalyst, generally need support the hydrogenation metal component, promptly adopt the saturated or excess solution dipping active metal component in hole, promptly had the hydrocracking catalyst that lytic activity has hydrogenation activity again after the carrier strip drying behind the carrying metal, the activation.
Complex carrier carrying hydrogenation metal of the present invention can be used for hydrocracking process.Especially, utilize this composite macroreticular acidic carrier that contains composite zeolite, the catalyzer that carrying hydrogenation metal component is obtained is particularly suitable for the hydrocracking process of voluminous intermediate oil.Wherein the Y zeolite of use involved in the present invention cooperates with the β zeolite facies of use involved in the present invention, its high-ratio surface and more secondary pore have not only promoted the performance of hydrogenation activity, also help to improve the open loop activity of reaction process to polycyclic aromatic hydrocarbons, not only improve catalyst activity, and can reduce carbon deposit.Compare with reference catalyst, handle a kind of vacuum gas oil equally, show active preferably and higher middle distillates oil selectivity, the low freezing point diesel fuel condensation point that is obtained simultaneously is low, thereby is particularly suitable for using the hydrocracking process that obtains low freezing point diesel fuel in maximum.
Embodiment
Example 1
Preparation for the related amorphous aluminum silicide S1 of catalyzer of the present invention.4000g solid sulphuric acid aluminium is joined in 7.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain alum liquor (a1).Strong aqua is added an amount of distilled water diluting into about 10% weak ammonia (b).10 liters of distilled water are joined in the concentrated sodium silicate of modulus about 3.0 of 4.8 liters of a kind of technical grades, obtain rare water glass solution (c).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has Tai-Ace S 150 and ammoniacal liquor respectively simultaneously, set (a1) flow so that the neutralization reaction time at one hour, and the flow of adjusting rapidly (b) remains on about 7.5 the pH value of system, and the temperature of the hierarchy of control is about 65 ℃.After reacting aluminum sulfate is intact, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add metering (c) 3.3 liters, and after adding in 10 minutes, the weathering process of beginning system keeps the pH value about 8.0, temperature 60-65 ℃.Aging after 50 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again after washing,, refilter and obtain filter cake (d) up to impurity removal is arrived below the index that needs.With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide component S 1.
This silica alumina ratio surface can reach 530m
2/ g, pore volume 1.44ml/g, infrared acidity 0.48mmol/g.
Example 2
Preparation for the related amorphous aluminum silicide S2 of catalyzer of the present invention.3.5 liters of a kind of technical grade Tai-Ace S 150 strong solutions are joined in 4.0 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain alum liquor (a2), Al
2O
3Concentration 8g/l00ml.Strong aqua is added an amount of distilled water diluting into about 10% weak ammonia (b).5 liters of distilled water are joined in modulus 3.0 concentrated sodium silicates of 2.4 liters of technical grades, obtain rare water glass solution (c).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has Tai-Ace S 150 and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a2) flow so that the neutralization reaction time at 1.5 hours, and the flow of adjusting rapidly (b) makes the pH value of system remain on 8.5, and the temperature of the hierarchy of control is at 55 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 15 minutes, by finally containing SiO
2Amount begins to add (c) 6.2 liters in the example 1 of metering, and after adding in 5 minutes, the weathering process of beginning system keeps the pH value 8.5, temperature 60-65 ℃.Aging after 15 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).After (d) pulled an oar once more, add 31.5ml phosphoric acid, continue to stir 30 minutes after-filtration and get filter cake (e), will (e) will (d) in drying under 110 ℃ after 8 hours, pulverize, sieve amorphous aluminum silicide component S 2.
This sial specific surface alive can reach 452m
2/ g, pore volume 1.15ml/g, infrared acidity 0.43mmol/g.
Example 3
Preparation for the related amorphous aluminum silicide S3 of catalyzer of the present invention.3.0 liters of dense liquor alumini chloridis are joined in 4 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a3), Al
2O
3Concentration 4g/100ml.Strong aqua is added an amount of distilled water diluting into about 10% weak ammonia (b).Get one 10 liters steel retort, after adding 2 liters of distilled water in jar and being heated with stirring to 70 ℃, open the valve of the container that has Tai-Ace S 150 and ammoniacal liquor respectively simultaneously, by preparation 600g amorphous aluminum silicide product set (a3) flow so that the neutralization reaction time at 40 minutes, and the flow of adjusting rapidly (b) makes the pH value of system remain on 9.0, and the temperature of the hierarchy of control is at 50-55 ℃.After reacting aluminum sulfate is finished, stop to add ammoniacal liquor, after the alumina sol of generation is stablized 30 minutes, by finally containing SiO
2Amount begins to add (c) 2.0 liters in the metering example 1, and after adding in 10 minutes, the weathering process of beginning system keeps the pH value 9.0, temperature 55-60 ℃.Aging after 30 minutes, filter colloidal solution and obtain wet cake, with the making beating of filter cake adding distil water again washing, refilter and obtain filter cake (d).With (d) at 110 ℃ down after dry 8 hours, pulverize, sieve amorphous aluminum silicide component S 3.
This silica alumina ratio surface can reach 483m
2/ g, pore volume 1.22ml/g, infrared acidity 0.36mmol/g.
Comparative example 1
A kind of sial product of prior art.The industrial preparation step is as follows: add 200 liter distilled water in 2 cubic metres enamel reaction still, be warmed up to 40 ℃ and begin to stir, begin to add water glass solution 300 liters that concentration is 5g/100ml, after in 30 minutes, adding, be warmed up to 45 ℃, adding concentration in 30 minutes is liquor alumini chloridi 300 liters of 5g/100ml.Continue to stir and add ammoniacal liquor, adjust system pH to 8.0, aging 60 minutes.Aging good dope filtration is obtained wet cake, obtain a kind of sial product, be numbered S here through washing, filtration, drying step.
This reference silica alumina ratio surface 283m
2/ g, pore volume 0.78ml/g, infrared acidity 0.49mmol/g.
Example 4
Be β zeolite B1 of the present invention.Get industrial synthetic SiO
2/ Al
2O
325.67, Na
2The Na β zeolite slurry 2000ml of O3.75m%, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, be mixed with the 2.0M ammonium nitrate solution, stir, be warming up to 90～95 ℃, constant temperature stirred 2 hours, was cooled to 50～60 ℃ of filtrations then, wet cake carries out the exchange second time again, and condition is with for the first time.Through the β zeolite of twice ammonium salt exchange, wash to pH and reach 5～6, put into loft drier then, 110～120 ℃ of dryings 6 hours.Dried β zeolite is put into muffle furnace and is rapidly heated to 250 ℃, and constant temperature 2 hours continues to be rapidly heated to 400 ℃ then, and constant temperature is 4 hours again, is warmed up to 540 ℃ at last, constant temperature 10 hours.High-temperature roasting is taken off the β zeolite of ammonium through pulverizing weighing 400g, adds 0.4M HCl4000ml, stirs and is warming up to 90 ℃, and constant temperature stirred 2 hours, the cold filtration washing.Through acid-treated β zeolite filtration washing, then in 110～120 ℃ of dryings 6 hours (butt＞80%).With evenly spraying quantitative water purification on the above-mentioned exsiccant sample, put into airtight hydrothermal treatment consists stove, be warming up to 650 ℃, control pressure 450KPa, room temperature is reduced in constant temperature and pressure roasting 2.5 hours then naturally, promptly obtains the efficiently synthetic β zeolite B1 of the present invention.
This β zeolite SiO
2/ Al
2O
3Than (chemical method) 58, infrared acidity 0.17mmol/g, specific surface can reach 550m
2/ g, Na
2O content 0.04m%.
Example 5
Be β zeolite B2 of the present invention.Get industrial synthetic SiO
2/ Al
2O
325.67, Na
2The Na β zeolite slurry 2000ml of O3.75m%, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, be mixed with the 1.0M ammonium nitrate solution, stir, be warming up to 90～95 ℃, constant temperature stirred 2 hours, was cooled to 50～60 ℃ of filtrations then, wet cake carries out the exchange second time again, and exchange solution is 0.5MNH
4NO
3Through the β zeolite of twice ammonium salt exchange, wash to pH and reach 5～6, put into loft drier then, 110～120 ℃ of dryings 6 hours.Dried β zeolite is put into muffle furnace and is rapidly heated to 250 ℃, and constant temperature 2 hours continues to be rapidly heated to 400 ℃ then, and constant temperature is 4 hours again, is warmed up to 540 ℃ at last, constant temperature 10 hours.High-temperature roasting is taken off the β zeolite of ammonium through pulverizing weighing 400g, adds the HNO of 0.6M
3, stirring and be warming up to 90 ℃, constant temperature stirred 2 hours, the cold filtration washing.Through acid-treated β zeolite filtration washing, then in 110～120 ℃ of dryings 6 hours (butt＞80%).With evenly spraying quantitative water purification on the above-mentioned exsiccant sample, put into airtight hydrothermal treatment consists stove, be warming up to 550 ℃, control pressure 100Kpa, room temperature is reduced in constant temperature and pressure roasting 4 hours then naturally, promptly obtains the efficiently synthetic β zeolite B2 of the present invention.
This β zeolite SiO
2/ Al
2O
3Than (chemical method) 80, infrared acidity 0.28mmol/g, specific surface can reach 650m
2/ g, Na
2O content 0.03m%.
Comparative example 2
Get the industrial synthetic SiO of example 4 equally
2/ Al
2O
325.67, Na
2The Na β zeolite slurry 2000ml of O3.75m%, the β zeolite slurry is quantitatively transferred in the exchange cylinder, the solid-to-liquid ratio of slurries is 1: 5, with water purification solid-to-liquid ratio is diluted to 1: 10 then, stirring is warming up to 50～60 ℃ of press filtrations, mother liquor has separated, and wet cake is put into the exchange cylinder, is mixed with 2.0M NH then
4NO
3Solution 2000l stirs, is warming up to 90～95 ℃ to electricity, and constant temperature stirred 2 hours, was cooled to 50～60 ℃ of filtrations then, and wet cake carries out the ammonium salt exchange second time again, and condition is with for the first time.Other step is with example 4.Be numbered β zeolite B.
Table 1 β zeolite of the present invention and 1 β zeolite solid-liquid separation time of comparative example, product yield
| Example | 1 | 2 | Comparative example 1 |
| The zeolite numbering | B1 | B2 | B |
| Product yield, % | 90 | 95 | 65 |
Example 6
Be modified zeolite of Y-type Z of the present invention.(1) 1M
3Add 130kg industry NH in the liner enamelled swap tank
4NO
3(chemical plant, Dalian product, purity＞99.5%) adds 800 liters of industrial water purification, is made into 2MNH
4NO
3Solution is heated to 70 ℃, adds 120KgNaY zeolite (Wenzhou catalyst plant product, butt 50m%), stirs exchange 3 hours down at 70 ℃, repeats this exchange step 12 times, filters, and is washed to neutrality, obtains Na
2O content is 0.18% Y zeolite, oven dry.(2) zeolite of above-mentioned washing oven dry is put into the high-pressure rotary stove, be rapidly heated to 600 ℃, at 0.1MPa, roasting is 4 hours under 100% water vapour pressure, obtains super-hydrophobic Y zeolite Z of the present invention.
This Y zeolite SiO
2/ Al
2O
3Than 11, infrared acidity 0.34mmol/g, specific surface 700m
2/ g, Na
2O content 0.02m%.
Example 7
Be support C 1 of the present invention.Get the prepared β zeolite B1 22.2g of example 4, example 6 prepared Y zeolite Z 470.6g, example 1 prepared amorphous aluminum silicide S1 542.9g and little porous aluminum oxide (the specific surface area 240m of 285.7g
2/ g, pore volume are 0.42ml/g, trade names SB) mix, the dilute nitric acid solution that adds the concentration 3.1% of 800ml continues to mix and pinches up to becoming paste, extruded moulding, the moulding bar that obtains 110 ℃ dry 8 hours down, 500 ℃ of activation made support C 1 of the present invention in 4 hours.Final group of carrier and character see Table 2.
Example 8
Be support C 2 of the present invention.Get example 5 prepared β zeolite B2 55.6g, a kind of industrial Y zeolite USY (commodity that the Fushun Petrochemical Company catalyst plant is produced) 58.8g and example 2 prepared amorphous aluminum silicide S2 1000g and mix, add molten little porous aluminum oxide (the specific surface area 240m of 285.7g of dilute nitric acid solution glue by the concentration 3.1% of 800ml
2/ g, pore volume are 0.42ml/g, trade names SB) tackiness agent that obtains, continue to mix and pinches up to becoming paste, extruded moulding, institute's moulding bar that obtains is 110 ℃ of dryings 8 hours down, and 500 ℃ activate 4 hours and make support C 2 of the present invention.Final group of carrier and character see Table 2.
Example 9
Be support C 3 of the present invention.Get example 4 prepared β zeolite B1 111.1g, example 6 prepared Y zeolite Z 235.3g and example 2 prepared amorphous aluminum silicide S2 571.4g and mix, add molten little porous aluminum oxide (the specific surface area 240m of 428.6g of dilute nitric acid solution glue by the concentration 3.4% of 1100ml
2/ g, pore volume are 0.42ml/g, trade names SB) tackiness agent that obtains, continue to mix and pinches up to becoming paste, extruded moulding, institute's moulding bar that obtains is 110 ℃ of dryings 8 hours down, and 500 ℃ activate 4 hours and make support C 3 of the present invention.Final group of carrier and character see Table 2.
Example 10
Be support C 4 of the present invention.Get example 4 prepared β zeolite B1 333.3g, example 6 prepared Y zeolite Z 117.6g and example 1 prepared amorphous aluminum silicide S1 428.6g and mix, add molten little porous aluminum oxide (the specific surface area 240m of 428.6g of dilute nitric acid solution glue by the concentration 3.4% of 1100ml
2/ g, pore volume are 0.42ml/g, trade names SB) tackiness agent that obtains, continue to mix and pinches up to becoming paste, extruded moulding, institute's moulding bar that obtains is 110 ℃ of dryings 8 hours down, and 500 ℃ activate 4 hours and make support C 4 of the present invention.Final group of carrier and character see Table 2.
Example 11
Be support C 5 of the present invention.Getting example 5 prepared β zeolite B2 55.6g, a kind of industrial Y zeolite USY (commodity that the Fushun Petrochemical Company catalyst plant is produced) 58.8g and example 3 prepared amorphous aluminum silicide S3 75.7g mixes; do not stopping the mixed dilute nitric acid solution that slowly adds under the situation by the concentration 3.4% of 1100ml of pinching; continue to mix and pinch up to becoming paste; extruded moulding; the moulding bar that obtains 110 ℃ dry 8 hours down, 500 ℃ of activation made support C 5 of the present invention in 4 hours.Final group of carrier and character see Table 2.
Comparative example 3
Be the reference support C.Except the sial component that will use is changed to the reference zeolite that is obtained than example 1, all the other comprise that preparation method and carrier composition are with example 8.
Final group of carrier and character see Table 2.Though kept certain acidity as can be seen, if the refractory oxide of not blending such as macroporous aluminium oxide, its porous index is not high.If carry relatively large active metal component, then be unfavorable for the dispersion of metal.
The carrier of table 2 example 7～11 is formed and physico-chemical property
| Example | 789 10 11 comparative examples 3 |
| Carrier | C1 C2 C3 C4 C5 C |
| Amorphous aluminum silicide | 38 70 40 30 53 70 |
| The β zeolite | 2 5 10 30 45 5 |
| Y zeolite | 40 5 20 10 2 5 |
| The aperture refractory oxide | 20 20 30 30 0 20 |
| Specific surface, m 2/ g pore volume, the infrared acidity of ml/g, mmol/g 4-15nm pore distribution, %＞20nm pore distribution, % | 403 428 384 356 395 290 0.71 0.75 0.67 0.56 0.68 0.50 0.51 0.30 0.41 0.47 0.33 0.48 68 76 84 56 65 60 5 7 4 3 5 11 |
Below carry the embodiment and the reference comparative example thereof of the hydrocracking catalyst that hydrogenation metal obtained for complex carrier of the present invention.Table 3 is the catalyst catalytic performance evaluation result.The related appreciation condition of embodiment is: reaction pressure is 15MPa, and hydrogen to oil volume ratio is 1500, and air speed is 1.5hr
-1Adopt one-stage serial once by technology, handle a kind of heavy Iran VGO of boiling range scope 340 ℃～530, stock oil enters the cracking zone cracking through giving after refining.Middle distillates oil selectivity calculates by (boat coal+diesel oil)/＜370 ℃ of transformation efficiencys, weighs its activity level by reaching the needed temperature of reaction of same conversion 60w%.The evaluating catalyst data of table 3 show, the middle distillates oil selectivity that uses complex carrier of the present invention and catalyzer thereof is than higher, and the diesel oil zero pour of the identical cut scope in its hydrocracking product is all lower, therefore can maximum produce the wide fraction low freezing point diesel fuel.
Example 12
Be the hydrocracking catalyst CAT1 that is obtained after the example 9 carrier carrying hydrogenation metal of the present invention.Method is with 37.5g ammonium metawolframate and the dissolving of 55g nickelous nitrate and demarcates to 85ml, obtains the W-Ni co-impregnated solution.Get the carrier 100g of the present invention that example 9 obtains, with the above-mentioned steeping fluid dipping for preparing, again 110 ℃ of dryings 8 hours, and 500 ℃ activate 3 hours after, obtain catalyzer CAT1A.Nickel oxide 7w% in the catalyzer, Tungsten oxide 99.999 22w%.
Comparative example 4
Be reference catalyst CAT.This hydrocracking catalyst is a kind of industrialized commercial catalyst, is mainly used in the hydrocracking process of producing intermediate oil.The characteristics of catalyzer are that its zeolite component is single Y zeolite component, and catalyst metal content is nickel oxide 7w%, Tungsten oxide 99.999 22w%.
Table 3 evaluating catalyst result
| The catalyzer numbering | The catalyst A catalyst B |
| Temperature of reaction, ℃ middle distillates oil selectivity, % | 376 378 83.5 78.1 |
| Jet fuel yield, m% diesel yield, m% | 31.7 32.0 18.4 14.8 |
| Condensation point of diesel oil, ℃ | Benchmark-4 benchmark |
Claims (12)
1, a kind of macroreticular acidic composite carrier is a benchmark with the weight percent of carrier, comprising: (a) amorphous aluminum silicide 10%-90%; (b) β zeolite 1%-50%; (c) Y zeolite 1%-50%; (d) little porous aluminum oxide or other aperture refractory oxide 0～30%; The specific surface area of complex carrier is 300-600m
2/ g, pore volume are 0.5-0.8ml/g, and infrared acidity is 0.2-0.6mmol/g; Complex carrier comprises SiO
220w%-60w%.
2,, it is characterized in that the infrared acidity of described β zeolite is 0.05-0.5mmol/g, SiO according to the described macroreticular acidic composite carrier of claim 1
2/ Al
2O
3Than being 20-150, Na
2O weight content＜0.2%.
3,, it is characterized in that described Y zeolite SiO according to the described macroreticular acidic composite carrier of claim 1
2/ Al
2O
3Mol ratio is 5.0-25, and unit cell parameters is 2.420-2.450nm, and specific surface is 550-850m
2/ g, infrared acidity 0.20-1.0mmol/g, Na
2O weight content＜0.2%.
4,, it is characterized in that described amorphous aluminum silicide specific surface is 300-600m according to the described macroreticular acidic composite carrier of claim 1
2/ g, pore volume are 0.9-1.6ml/g, and infrared acidity is 0.25-0.55mmol/g.
5, according to the described macroreticular acidic composite carrier of claim 1, it is characterized in that described complex carrier comprises: with vehicle weight per-cent is benchmark, (a) amorphous aluminum silicide 40%-80%; (b) β zeolite 5%-30%; (c) Y zeolite 5%-30%; (d) little porous aluminum oxide or other aperture refractory oxide 0%-20%.
6, according to the described macroreticular acidic composite carrier of claim 1, it is characterized in that described β zeolite silica alumina ratio is 30-90, infrared acidity is 0.1-0.4mmol/g, Na
2O weight content＜0.1%.
7,, it is characterized in that described Y zeolite SiO according to the described macroreticular acidic composite carrier of claim 1
2/ Al
2O
3Be 6.0-17, unit cell parameters is 2.425-2.445nm, and infrared acidity is 0.30-0.8mmol/g.
8,, it is characterized in that described amorphous aluminum silicide specific surface is 400-550m according to the described macroreticular acidic composite carrier of claim 1
2/ g, pore volume are 1.0-1.5ml/g, and infrared acidity is 0.30-0.50mmol/g.
9,, it is characterized in that the phosphorous 1w%-5w% of being of described amorphous aluminum silicide according to the described macroreticular acidic composite carrier of claim 1.
10,, it is characterized in that described carrier specific surface is 300-450m according to the described macroreticular acidic composite carrier of claim 1
2/ g, infrared acidity is 0.25-0.55mmol/g.
11,, it is characterized in that described carrier specific surface is 350-450m according to the described macroreticular acidic composite carrier of claim 1
2/ g, pore volume are 0.55-0.75ml/g, and infrared acidity is 0.30-0.50mmol/g, comprises SiO
230w%-50w%.
12, according to the described macroreticular acidic composite carrier of claim 1, it is characterized in that the pore volume that described carrier hole diameter is 4-15nm accounts for total pore volume 50%-90%, the pore volume of＞20nm is no more than 10% of total pore volume.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 01114165 CN1123386C (en) | 2001-07-02 | 2001-07-02 | Macroreticular acidic composite carrier and its preparing process |
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|---|---|---|---|
| CN 01114165 CN1123386C (en) | 2001-07-02 | 2001-07-02 | Macroreticular acidic composite carrier and its preparing process |
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| CN1123386C true CN1123386C (en) | 2003-10-08 |
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| CN1313206C (en) * | 2004-06-21 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrogenation catalyst of diesel production at most amount and production thereof |
| CN104667996B9 (en) * | 2013-11-26 | 2017-06-16 | 中国石油化工股份有限公司 | Hydrocracking catalyst carrier and preparation method thereof |
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