CN1055961C - Hydrocracking catalyst containing amorphous aluminum silicide - Google Patents
Hydrocracking catalyst containing amorphous aluminum silicide Download PDFInfo
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- CN1055961C CN1055961C CN97121663A CN97121663A CN1055961C CN 1055961 C CN1055961 C CN 1055961C CN 97121663 A CN97121663 A CN 97121663A CN 97121663 A CN97121663 A CN 97121663A CN 1055961 C CN1055961 C CN 1055961C
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Abstract
The present invention relates to a hydrocracking catalyst, particularly to a hydrocracking catalyst used for producing middle distillate oil. The present invention comprises a component of amorphous silicon aluminium of which the content is from 30 to 60w%, small-pore alumina adhesive agents, at least one kind of elements in group VIB and at least one kind of elements in group VIII. The specific surface of the catalyst is from 150 to 300m<2>/g, the pore volume is from 0.25 to 0.50 ml/g, the pore distribution of 4 to 15 nms is from 60 to 90%, and the infrared acidity is from 0.30 to 0.50 mmol/g. In the catalyst, a component of acidic silicon aluminium with a high specific surface and a large pore volume is adopted, so the reactivity and the selectivity of the catalyst are well matched.
Description
The present invention relates to a kind of hydrocracking catalyst,, produce the catalyzer of intermediate oil in particular for treatment of heavy hydrocarbon class raw material.
Hydrocracking catalyst is a kind of bifunctional catalyzer, both had hydrogenation activity, also has lytic activity, hydrogenation activity is generally provided by hydrogenation metal, lytic activity is generally provided by the acid carrier component, the tart source comprises zeolite, sial etc. in the carrier, and the carrier of hydrocracking catalyst also needs to provide specific surface and pore volume with carrying hydrogenation metal and reaction compartment simultaneously.In the prior art, be used for bearing metal in the middle oil type hydrocracking catalyst carrier and provide reaction compartment, generally belong to the inert support component, as γ-Al mainly by macropore refractory oxide component
2O
3If acid sial also can provide the specific surface and the space of metal carrying when acid sites is provided, Preparation of catalysts process and quality control are simplified, also can make catalyzer adapt to the differential responses requirement to have bigger allotment handiness, acid sites and duct are present in the homogeneity that same homogeneous component is had simultaneously, can make hydrogenation activity and lytic activity better matching.But it is this difunctional that present disclosed patent all can not embody basically fully.
Especially, in order to increase the flexibility of operation of catalyzer, to adapt to the raw material of handling the variation day by day that is faced on the market, at present, oil type hydrocracking catalyst all needs sial and crystal type zeolite component to be used in general, to satisfy the double requirements of active and middle distillates oil selectivity, this just needs to add a certain amount of zeolite to improve catalyst activity.But for middle oil type hydrocracking process, reactive activity and selectivity are a pair of contradiction, under square one, active raising will be accompanied by optionally sacrifices, can be by adjust the ratio that sial and zeolite component suit in carrier, reach activity required in the reaction process and optimum position optionally, in other words, promptly the acidity of sial and zeolite content and support acidity component thereof realizes the acidic cleavage function of catalyzer and the coupling of hydrogenating function in the catalyzer by adjusting.Particularly for middle oil type hydrocracking catalyst, amount of zeolite and zeolite acidity can not be too high, otherwise can influence the middle distillates oil selectivity of catalyzer, activity be required under the lower situation, can adopt the hydrocracking catalyst of simple sial component at lay special stress on catalyzer middle distillates oil selectivity.
US4738767 discloses a kind of hydrocracking catalyst that is used for, and need be dispersed in than high-ratio surface with than the refractory oxide such as the γ-Al of large pore volume as the amorphous aluminum silicide of acidic components
2O
3Go up with jointly as the carrier of catalyzer, this be since the sial that this patent catalyzer uses be with aluminum precipitation in silicon gel duct, the so-called grafting of acquisition is the glue sial altogether, its specific surface and pore volume are all less, are not enough to carry a large amount metal component.US4517074 also uses similar sial of above-mentioned patent and dispersion system thereof to be used for oil type hydrocracking catalyst, and has been used zeolite component, because more alumina component is arranged, and for making the SiO of dispersion system
2Content reaches 20-65%, makes catalyzer have higher lytic activity, the sial SiO that is comprised
2Content requirement is up to 50-90%, and so high silicon sial is dispersed in macroporous aluminium oxide can produce uneven phenomenon, causes the part duct narrow and small on the one hand, and the forfeiture katalysis is that part duct shortage acid sites reactive behavior is low on the other hand.Also may cause more acid sites to accumulate in some duct, in catalyst runs, embody partial excessive fragmentation and middle distillates oil selectivity is descended, and carbon deposit seriously reaches the duct obstruction and makes catalyzer later stage activity or stability decreases after the running certain period.
US4721696, US4758300 disclose a kind of siliceous aluminum oxide, and the preparation method is a pH value swing method, the main support of the catalyst component of handling sulfur-bearing and metallic impurity hydrocarbon material as hydrofining, have bigger hole, pore volume 1.0-2.0ml/g, specific surface is at 180-320m
2/ g, though specific surface and pore volume are all than the normally used acid sial height of hydrocracking catalyst, but its silicone content generally is no more than 15w%, and a spot of silicon is purpose as structural stabilizing agent rather than so that more acid sites to be provided, so not too be fit to hydrocracking catalyst.Its specific surface neither be too high in addition, is generally less than 400m
2/ g, carrying a large amount metal can have influence on the dispersiveness of metal and be unfavorable for the performance of hydrogenation activity.
Importance based on sial centering oil type hydrocracking catalyst, prior art also relates to the preparation of some novel sial, GB2166971 discloses a kind of amorphous aluminum silicide preparation method especially, promptly earlier after under the high pH (12-12.5) alkali metal aluminate and silicate being mixed, make with reacting aluminum sulfate again, from the embodiment of this patent as can be known, the SiO of its product amorphous aluminum silicide
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.In addition, this patent preparation characteristic is to adopt pump short mix mode to become glue, and to the equipment requirements height, the production difficulty is big, has certain production limitation.
The objective of the invention is to, a kind of both had suitable specific surface, the catalyzer of pore volume are provided, have enough acidic cleavage functions again, be used for the hydrocracked, treated heavy hydrocarbon material, particularly high aromatic hydrocarbons hydrocarbon material inferior, voluminous intermediate oil.The present invention also aims to, a kind of Preparation of catalysts method is provided, the acid site of catalyzer is evenly distributed, pore distribution concentration, promote the dispersion of metal component.Further aim of the present invention is, amorphous silicon component of the employed high-ratio surface of a kind of catalyzer of the present invention, large pore volume, high acidity and preparation method thereof is provided.
Catalyzer of the present invention contains sial component 30-60w% and 0-20w%Y type zeolite component, after it is mixed, adding through the aperture alumina adhesive 15-30w% of sour peptization mix pinch, roll agglomerating after, extruded moulding on banded extruder and obtain carrier, carry hydrogenation metal again, the hydrogenation metal oxide aggregate is 20-35w%.
Catalyst specific surface 150-300m of the present invention
2/ g, pore volume 0.25-0.50ml/g, the 4-15nm pore distribution is at 60-90%, infrared acidity 0.30-0.50mmol/g.Catalyst characteristics of the present invention is to comprise a kind of sial, the sial Si that catalyzer of the present invention is related
2O content is 15-50w%, the general 350-550m of specific surface
2/ g, the general 0.9-1.4ml/g of pore volume, infrared acidity 0.35-0.55mmol/g.
The feature of catalyzer of the present invention is to contain a kind of difunctional sial component involved in the present invention, be used to provide the main carrier component of acidic cleavage function and conduct carrying hydrogenation metal, and can be aided with zeolite component, acidity that it is moderate and strength of acid can provide than the demulcent cracking performance, while high-ratio surface and large pore volume can carry the hydrogenation metal of a large amount and promote the dispersion of metal, pore distribution is moderate, generally at 4-15nm, more effective reaction space can be provided, be suitable as the middle oil type hydrocracking catalyst that needs medium lytic activity and high hydrogenation activity.
The moulding of catalyzer of the present invention can be adopted various known routine techniquess, as balling-up or extrusion, but its various forming methods all are not construed as limiting the invention, general extruded moulding method commonly used, catalyzer of the present invention promptly adopts the extruded moulding mode, therefore need to add the tackiness agent of a certain amount of aperture aluminum oxide, be beneficial to moulding and guarantee the intensity of moulding bar through rare nitric acid peptization.Tackiness agent generally is to prepare with the aperture aluminum oxide that is easy to peptization, and the employed aperture aluminum oxide of catalyzer of the present invention specific surface generally is not more than 280m
2/ g, pore volume generally are not more than 0.45ml/g, and its purpose is not enough to provide the contributor of the pore volume and the specific surface of reaction needed, its objective is through the nitric acid peptization to play adhesive effect with the preparation tackiness agent.Preparation process is after sial 30-60w% involved in the present invention and 0-20w% zeolite component are mixed, adding mixes through the aperture alumina adhesive 15-30w% of sour peptization and pinches, rolls agglomerating back and (prepare catalyzer as the use blending method, also need to add the hydrogenation metal component of calculated amount in the mixture), extruded moulding on banded extruder and obtain carrier carries hydrogenation metal again and obtains catalyzer of the present invention.Wherein, the employed zeolite of catalyzer of the present invention is a y-type zeolite, and acidity is low, generally at 0.35-0.45mmol/g, guarantees the middle distillates oil selectivity of catalyzer of the present invention in the time of with raising catalyst activity of the present invention.The general pickling process that adopts of the metal carrying of catalyzer of the present invention, method comprise saturated dipping and or excess solution dipping.Hydrogenation metal oxide aggregate of the present invention is 20-35w%, carries at least a group vib element and at least a VIII family element, and general hydrogenation metal is W and Ni or Mo and Ni.
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.The carrier strip of moulding or the carrier strip behind the bearing metal need drying, general drying temperature is at 90-160 ℃, preferably 110-140 ℃, time is 6-12 hour, preferably 8-10 hour, the main oven drying that adopts can certainly adopt other drying mode, and the exsiccant purpose all 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.
The related sial of catalyzer of the present invention can be separately as the carrier component of a kind of large pore volume and high-ratio surface, this sial adopts fractional precipitation formula homogeneous phase copolymerization method rather than pickling process or pH value swing method to prepare, do not need other last handling processes such as hydrothermal treatment consists yet, the sial amorphization degree height that obtains, have very high pore volume and specific surface, higher acidity is provided again, not only has been beneficial to the turnover of reactant and resultant but also suitable lytic activity is provided.
In order to improve the pore structure character of amorphous aluminum silicide, the related sial of catalyzer of the present invention uses and stream Stationary pH method, and not only process is easy to control, and sial has better character index.The physico-chemical property characteristics of the amorphous aluminum silicide that catalyzer of the present invention is related are the general 15-50w% of silicon oxide-containing, preferably 20-40w%; Specific surface 350-550m
2/ g, preferably 400-500m
2/ g; Pore volume 0.9-1.4ml/g, preferably 1.0-1.3ml/g; Infrared acidity 0.30-0.55mmol/g, preferably 0.35-0.45mmol/g.
Wherein, the related amorphous aluminum silicide of catalyzer of the present invention prepares by following process:
(a) a kind of acid aluminium salt solution and a kind of alkaline precipitating agent and stream are joined in the reaction vessel of small amount of deionized water, at pH value 7.0-9.0, temperature 50-70 ℃ forms colloidal sol, and the neutralization reaction time is 1-2 hour.
(b) (a) stablized under the condition of pH8-9 0-60 minute.
(c) in 5-10 minute, a kind of silicon compound is joined in (b).
(d) at pH value 7.5-9.5,50-70 ℃ following ℃ aging (c) 10-60 minute.
(e) filter and wash (d).
(f) (e) drying and crushing is obtained sial involved in the present invention.
In the related amorphous aluminum silicide preparation process of catalyzer of the present invention, (a) in acid aluminium salt can be Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3In a kind of, alkaline precipitating agent can be NaOH, NH
4OH, Na
2AlO
3In a kind of.But in industrial application, Al
2(SO
4)
3Used at large; And different alkaline precipitating agents can make (a) middle alumina substrate that obtains difference to some extent, and the aluminum oxide micelle size order that general different precipitation agent obtained is: NaOH＜Na
2AlO
3＜NH
4OH, (c) in related silicon compound can be water glass, silicon sol.Amorphous aluminum silicide preparation process involved in the present invention or method can use different precipitation agents to make amorphous aluminum silicide within physico-chemical property scope of the present invention.
In the sial preparation process involved in the present invention, (a) the pH value in is generally at 7.0-9.0, preferably 7.5-8.5; Temperature 50-70 ℃, preferably 55-65 ℃; (b) the general 0-60 of the stabilizing take in minute, preferably 15-45 minute.Condition enactment in the invention described above condition and range all can obtain the acid amorphous aluminum silicide of the high-ratio surface large pore volume within the physico-chemical property scope of the present invention.
The related amorphous aluminum silicide preparation process of catalyzer of the present invention does not resemble some prior art, the too much meeting that the silicon amount is introduced has influence on the specific surface and the pore volume size of the finished product strongly, amorphous aluminum silicide involved in the present invention still can obtain high-ratio surface large pore volume amorphous aluminum silicide in a very wide silicone content scope.Because the related sial preparation characteristic of catalyzer of the present invention; the time that silicon compound adds step (b) acquisition product should add in the short period of time; to guarantee in this reaction system the advantage concentration of silicon ion in for some time, the aluminum oxide micelle matrix that comes attack to form before this.Certainly, owing to stir the efficient of mass transfer, the time can not be too short, and the joining day is generally at 5-10 minute, best 5 minutes.
After introducing the silicon source, the pH value of reaction system will have the process and the trend of a variation, being presented on the alumina substrate is the forming process that has begun amorphous aluminum silicide, this process is different from the silicon alclad method of prior art, but the primary oxidation silicon particle that the established alumina substrate of silicon ion attack and being accompanied by forms after silicon ion, free aluminum ion, the introducing system and the interaction of elementary amorphous aluminum silicide micelle.After reaction reaches balance, continue the certain condition of control, finish (d) process, this process should be a generalized weathering process, has comprised that promptly reaction forms the process of amorphous aluminum silicide, has also comprised resultant amorphization process subsequently.In this process, pH value, temperature, digestion time all are important controlled variable, general pH value 7.5-9.5, preferably 8.0-8.5; Temperature 50-70 ℃, preferably 55-65 ℃; General 0-60 of time minute, preferably 15-45 minute.
Behind aging the end, process (e) and (d) can be according to the method for routine, with the amorphous aluminum silicide washing that obtains removing impurity such as iron, sodium, sulfate radical, chlorion, and dry, pulverizing and obtain the related amorphous aluminum silicide of catalyzer of the present invention.The purpose that removes impurity is at the related amorphous aluminum silicide of catalyzer of the present invention during as the carrier of catalyzer or acidic components, unlikely activity of such catalysts or the stability of having influence on of its impurity level.The drying of amorphous aluminum silicide involved in the present invention can be used oven drying or spraying drying, generally adopts oven drying, descends dry 6-10 hour at 110 ℃, makes the butt of final amorphous aluminum silicide reach 60-80w%.Dried amorphous aluminum silicide sieves, and the particle diameter more than 90% is below 150 orders, below general 200 orders.
The related amorphous aluminum silicide of catalyzer of the present invention also can contain the phosphorus of 0-5w%, and purpose is to improve the distribution in aperture, also may produce delicate influence to later catalyst catalytic performance.Method is that above-mentioned amorphous aluminum silicide is pulled an oar once more, adds the phosphoric acid of metering, makes the phosphorous 0-5w% of amorphous aluminum silicide, refilter, dry also, pulverize and obtain phosphorous amorphous aluminum silicide involved in the present invention.
Because the related sial preparation characteristic of catalyzer of the present invention has been avoided forming more strong acid center under crystallization tendency, and guarantees that silicon and aluminium atom interact effectively, thereby forms the sial with more acid sites and high-ratio surface large pore volume.The related sial of catalyzer of the present invention has solved under high silicon content, and the deficiency of sial pore structure makes sial amorphization degree height involved in the present invention, shows specific surface and pore volume height, also has higher acidity simultaneously.Because the preparation characteristic of sial involved in the present invention makes it have more acid sites, and strength of acid is moderate, cooperates with the zeolite of sufficient quantity and suitable acidity, can obtain to be used to prepare the support of the catalyst of the present invention and the catalyzer thereof of the high middle distillates oil selectivity of high reactivity.
Catalyzer of the present invention is used to obtain the hydrocracking process of intermediate oil, have good active and middle distillates oil selectivity, its process is in the presence of hydrogen catalyzer of the present invention to be contacted with heavy hydrocarbon material, reaction pressure is generally in 5-20MPa or under the high pressure, temperature of reaction 350-450 ℃, reaction velocity 0.1-5.0, hydrogen-oil ratio 100-10000.Related catalyst S iO of the present invention
2Content 20-40w%, the best 180-250m of specific surface
2/ g, the best 0.30-0.45ml/g of pore volume, the best 0.30-0.50mmol/g of the infrared acidity of catalyzer.
Compared with prior art, catalyzer of the present invention has adopted high-ratio surface, large pore volume and has had the silica-alumina supports component of enough acid sitess, make and to add the nonacid component macroporous aluminium oxide that the duct is provided in the catalyzer, and only need add a spot of binding agent, to guarantee the intensity of catalyzer, thereby the effective ingredient of support of the catalyst is improved greatly, and improved the homogeneity that acid sites distributes simultaneously in the duct, realized the better coupling of reactive behavior and middle distillates oil selectivity.Catalyst preparation process of the present invention is simple, convenient, and easy handling relatively is fit to industrial production.Catalyzer of the present invention is particularly suitable for obtaining the hydrocracking process of intermediate oil, has good active and middle distillates oil selectivity.
Because catalyzer of the present invention has comprised the acid sial of high-ratio surface involved in the present invention, large pore volume, bigger space and specific surface carrying hydrogenation metal is provided, and make hydrogenation metal have higher dispersiveness, make catalyzer of the present invention not only have certain cracking performance, have more high hydrogenation activity.As seen from Table 1, the support of the catalyst that contains sial involved in the present invention has high-ratio surface and large pore volume, like this when carrying a large amount reactive metal, can make the individual layer dispersion amount of metal on carrier higher, help the dispersion of metal, also finally help the performance of hydrogenation activity, be particularly suitable as middle oil type hydrocracking catalyst, satisfied catalyst activity and needs optionally.As seen from Table 5, the petroleum naphtha virtue that catalyzer of the present invention obtains is dived high, the diesel cetane-number height, boat coal aromaticity content is low, prove that catalyzer of the present invention has stronger condensed-nuclei aromatics open loop ability owing to having high hydrogenation activity, thereby impel polycyclic aromatic hydrocarbons to transform to the lower boiling product, from the catalyzer of the present invention＞370 ℃ tail oil analytical data of mass spectrum of table 5 as can be seen, total naphthenic hydrocarbon and the aromaticity content of the tail oil that the high aromatic hydrocarbons heavy hydrocarbon material of catalyst treatment of the present invention obtains is low, and corresponding paraffinicity is much higher, the hydrogenation of net product degree of saturation is big, illustrate that catalyzer of the present invention has high hydrogenation activity and strong open loop ability, the poor heavy raw material of the high aromatic hydrocarbons of the suitable processing of these characteristics.In addition, catalyzer of the present invention cooperates an amount of zeolite component to make catalyst acidity moderate and have a moderate lytic activity, thereby be used for characteristics that oil type hydrocracking catalyst has the high middle distillates oil selectivity of high reactivity (referring to the evaluation result of table 3 the present invention and reference catalyst, the stock oil character of use involved in the present invention sees Table 2), therefore be suitable for especially under hydrocracking condition, treatment of heavy hydrocarbon class raw material is to obtain the middle oil type hydrocracking catalyst of middle distillate oil.
Catalyzer of the present invention is used for hydrocracking process, be used for treatment of heavy hydrocarbon material, the boiling range scope of heavy hydrocarbon material is at 250-600 ℃, generally at 300-550 ℃, have These characteristics stock oil such as gas oil, decompression fraction oil, take off pitch prill oil, catalytic cracking circulation wet goods or other various mixing heavy hydrocarbon materials.Catalyzer of the present invention is used to obtain the hydrocracking process of intermediate oil, has the characteristics of voluminous intermediate oil.Hydrocracking process involved in the present invention be hydrogen exist and certain reaction pressure and temperature of reaction under raw material and carrier of the present invention carried the catalyzer that hydrogenation metal obtained contact, hydrocracking process generally comprises the hydrofining of leading portion, be used for removing the most S of stock oil, N, and polycyclic aromatic hydrocarbons is saturated.Reaction pressure is preferably under the hydrogen pressure of 10-15MPa, and the best 360-430 of temperature of reaction ℃, reaction velocity 0.5-3.0, hydrogen-oil ratio 1000-5000.Especially, the hydrocracking process of production middle distillate oil generally under high pressure, hydrocracking process preferably is limited in 370-410 ℃ as the temperature of reaction of important control parameter, can determine according to use properties, product structure needs and the handled hydrocarbon raw material of catalyzer.
Example 1
Preparation for the related amorphous aluminum silicide 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 (a).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 (a) 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 sial.Specific surface after this sial activation can reach 504m
2/ g, pore volume 1.31ml/g, infrared acidity 0.48mmol/g.
Example 2
Be catalyzer of the present invention related carrier A and catalyzer CA.Take by weighing the sial 102.5g that is obtained in the example 1, Y zeolite component (SiO
2/ Al
2O
3Be 9.5, infrared acidity 0.44mmol/g) 60.6g, behind the mixing, add gelatin tackiness agent that 250g adds the nitric acid peptization by the little porous aluminum oxide of pore volume 0.42ml/g roll agglomerating after, put into the banded extruder extruded moulding, drying, activate carrier A, drying, activation obtained CA again with the 165ml excessive dipping of Mo-Ni co-impregnated solution 60gA one hour again.Catalyst activated hydrogenation metal oxide aggregate is 26w%.
Example 3
Be catalyzer of the present invention related carrier B and catalyzer CB.Take by weighing the sial 116.5g that is obtained in the example 1, the Y zeolite component 30.5g of example 2, behind the mixing, add gelatin tackiness agent that 250g adds the nitric acid peptization by the little porous aluminum oxide of pore volume 0.42ml/g roll agglomerating after, put into the banded extruder extruded moulding, drying, activate carrier B, again with the 160ml saturated dipping of W-Ni co-impregnated solution 60gB, again drying, activate and obtain CB.Catalyst activated hydrogenation metal oxide aggregate is 32w%.
Comparative example 1
Be reference support C and catalyzer CC.Take by weighing a kind of specific surface 280m
2/ g, pore volume 0.76ml/g, SiO
2The sial 104.8g of content 35w%, the Y zeolite component 30.5g of example 2, behind the mixing, add gelatin tackiness agent that 250g adds the nitric acid peptization by the little porous aluminum oxide of pore volume 0.42ml/g roll agglomerating after, put into the banded extruder extruded moulding and get drying, activated carrier C, drying, activation obtain reference catalyst CC again with the 160m saturated dipping of 1W-Ni co-impregnated solution 60gC again.Catalyst activated hydrogenation metal oxide aggregate is 31w%.
Find out that from table 1 carrier and catalyzer physico-chemical property the carrier of comparative example and catalyzer pore volume thereof and specific surface are all lower, can influence the dispersion of metal undoubtedly.With above-mentioned example 3,4, the catalyzer of comparative example 1,2 is estimated.Estimating with stock oil is triumph VGO, and main character sees Table 2.Evaluation result under above-mentioned appreciation condition finds out that catalyzer involved in the present invention has good middle distillates oil selectivity on the basis of greater activity.
Table 1. carrier and catalyzer physico-chemical property
Support/catalyst numbering A CA B CB C CC
Specific surface, m
2/ g 395 256 408 213 303 188
Pore volume, ml/g 0.72 0.35 0.68 0.40 0.55 0.264-15nm pore distribution, the infrared total acid of %-82.5-83.3-79.1, mmol/g-0.41-0.38-0.39 table 2. raw material oil properties density, d
4 200.9066 boiling range, ℃ IBP 346 10% 38850% 43390% 489EP 526 mass spectroscopy, w% paraffinic hydrocarbons 18.3 naphthenic hydrocarbon 43.1 aromatic hydrocarbons 34.8 colloids 3.8 carbon residues, w% 0.01S, w% 0.59N, ppm 1419BMCI value 43.2 table 3. evaluating catalysts are catalyzer numbering CA CB CC relative response temperature as a result, ℃ 375 380 380 middle distillates oil selectivities, w% 80.1 82.2 78.3 tables 4 catalyzer of the present invention and reference catalyst product property comparative catalyst catalyzer reference catalyst of the present invention reformer feed virtue are dived, w% 63.6 60.5 boat coal smoke points, mm 27 27 aromatic hydrocarbons, w% 1.9 4.1 condensation point of diesel oil, ℃-3 0 cetane value (actual measurement) 63.8 61.2 tail oil BMCI values, 10.8 10.4 tables 5 catalyzer tail oil of the present invention analytical data of mass spectrum stable hydrocarbon 98.7 paraffinic hydrocarbonss 51.3 naphthenic hydrocarbon 47.4 aromatic hydrocarbons 1.0
Claims (9)
1. hydrocracking catalyst, contain amorphous silicon al composition and aperture alumina adhesive, the content of amorphous aluminum silicide is 30-60w%, at least a group vib element and at least a VIII family element, hydrogenation metal oxide compound total content is 20-35w%, surplus is the aperture alumina adhesive, it is characterized in that catalyst specific surface 150-300m
2/ g, pore volume 0.25-0.50ml/g, the 4-15nm pore distribution is at 60-90%, infrared acidity 0.30-0.50mmol/g.
2. according to the catalyzer of claim 1, it is characterized in that wherein also containing the Y zeolite component of 0-20w%.
3. according to the catalyzer of claim 1, it is characterized in that sial component S iO2 content 15-50w% wherein.
4. according to the catalyzer of claim 1, it is characterized in that wherein sial ratio of component surface 350-550m
2/ g, pore volume 0.9-1.4ml/g.
5. according to the catalyzer of claim 1, it is characterized in that sial ratio of component surface 400-500m wherein
2/ g, pore volume 1.0-1.3ml/g, infrared acidity is 0.35-0.55mmol/g.
6. according to the catalyzer of claim 2, it is characterized in that containing in the catalyzer SiO
220-40w%.
7. according to the catalyzer of claim 1, it is characterized in that hydrogenation metal is selected from W and Ni or Mo and Ni.
8. according to the catalyzer of claim 1, it is characterized in that the pore volume in 4-15nm aperture accounts for the 60-90% of the total pore volume of catalyzer.
9. according to the catalyzer of claim 1, it is characterized in that catalyst specific surface is 180-250m
2/ g, pore volume 0.30-0.45ml/g, infrared acidity 0.35-0.45mmol/g.
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| CN100448952C (en) * | 2005-04-29 | 2009-01-07 | 中国石油化工股份有限公司 | Hydrogenation cracking catalyst composition containing zeolite |
| US8883669B2 (en) | 2005-04-29 | 2014-11-11 | China Petroleum & Chemical Corporation | Hydrocracking catalyst, a process for producing the same, and the use of the same |
| US9469817B2 (en) | 2014-02-20 | 2016-10-18 | China Petroleum & Chemical Corporation | Hydrocracking catalyst and use of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698148B (en) * | 2009-10-20 | 2012-05-30 | 武汉凯迪工程技术研究总院有限公司 | Noble metal catalyst used in hydrocracking and isomerization of Fischer-Tropsch synthetic wax and preparation method thereof |
| CN102489336B (en) * | 2011-12-29 | 2015-10-14 | 北京三聚环保新材料股份有限公司 | A kind of organic sulfur hydrogenation catalyst carrier and preparation method thereof |
| CN112295570A (en) * | 2020-11-11 | 2021-02-02 | 山西新华防化装备研究院有限公司 | Preparation method of in-situ formed carbon-based catalyst |
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| US4758330A (en) * | 1987-03-11 | 1988-07-19 | Phillips Petroleum Company | Hydrotreating employing silica-modified alumina |
| CN1040611A (en) * | 1988-08-26 | 1990-03-21 | 国际壳牌研究有限公司 | Hydrocracking catalyst and the application in hydrocracking process thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4758330A (en) * | 1987-03-11 | 1988-07-19 | Phillips Petroleum Company | Hydrotreating employing silica-modified alumina |
| CN1040611A (en) * | 1988-08-26 | 1990-03-21 | 国际壳牌研究有限公司 | Hydrocracking catalyst and the application in hydrocracking process thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448952C (en) * | 2005-04-29 | 2009-01-07 | 中国石油化工股份有限公司 | Hydrogenation cracking catalyst composition containing zeolite |
| US8883669B2 (en) | 2005-04-29 | 2014-11-11 | China Petroleum & Chemical Corporation | Hydrocracking catalyst, a process for producing the same, and the use of the same |
| US9469817B2 (en) | 2014-02-20 | 2016-10-18 | China Petroleum & Chemical Corporation | Hydrocracking catalyst and use of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1218091A (en) | 1999-06-02 |
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