CN1073617C - Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil - Google Patents
Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil Download PDFInfo
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- CN1073617C CN1073617C CN98114489A CN98114489A CN1073617C CN 1073617 C CN1073617 C CN 1073617C CN 98114489 A CN98114489 A CN 98114489A CN 98114489 A CN98114489 A CN 98114489A CN 1073617 C CN1073617 C CN 1073617C
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Abstract
The present invention relates to a hydrocraking catalyst of nitrogen resistant type productive middle oil. The catalyst is composed of amorphous silicon aluminium which takes 10 to 60W% of the weight of the catalyst, modified Y zeolite which takes 10 to 40W% of the weight of the catalyst, VIB-group metal oxides which take 10 to 40 W%, VIII-group metal oxides which take 1 to 10 W% and IVB-group metal oxides which take 1 to 10W%. The catalyst is used for producing large amounts of middle distillate oil with heavy distillate oil through single-section series connected hydrocracking. The feeding nitrogen content at a cracking section can reach 100 mu g/g. The value of temperature increase brought by the raise of the nitrogen content of each 10 mu g/g at the cracking section is <=1 DEG C.
Description
The present invention relates to hydrocracking catalyst and the preparation and the application of oil in a kind of nitrogen-resistant type fecund.
At present, it is more and more heavier that each refinery, the world all is faced with crude oil, the raw materials quality of refining of petroleum problem worse and worse.Because the requirement of environmental protection aspect, to the requirement of oil fuel quality also increasingly stringent, so hydrocracking become and handled inferior, heavy raw oil, thereby produces one of important means of high-grade fuel oil.The hydrocracking process of being used always at present generally all adopts two sections or one-stage serial flow process, needs the nitride in the stock oil is transformed into ammonia, and then contacts with hydrocracking catalyst.The hydrocracking catalyst that generally contains zeolite is＜10 μ g/g to the requirement of the organic nitrogen compound content in the cracking section feeding, and when cracking zone feed nitrogen content during in the 50 μ g/g left and right sides, the temperature of reaction of general cracking catalyst is higher, poor product quality; At present full scale plant generally is controlled at cracking zone feed nitrogen content below the 10 μ g/g, is beneficial to that hydrocracking catalyst is active to be given full play to; When containing precious metal in the cracking zone catalyzer, then require cracking zone feed nitrogen content＜5 μ g/g, if＜1 μ g/g is then better.Therefore the raw material of higher nitrogen content is carried out one-stage serial or two-stage hydrogenation when handling, contact with the hydrocracking catalyst that contains zeolite at raw material and will pass through unifining process as last nitrogen content is dropped to the scope that the hydrocracking catalyst activity is not fully exerted and is allowed.
The dual-function catalyst that hydrocracking catalyst is made up of hydrogenation component and acidic components, its lytic activity derives from the acidity of carrier.The acid sites of cracking catalyst has very strong adsorption to the nitride in the charging, and promptly nitrogen compound has in various degree toxic action to the acid sites of catalyzer.Therefore the nitrogen content to the hydrocracking catalyst charging should be limited, and could guarantee that activity of such catalysts is fully played.
In general, the acidic components of hydrocracking catalyst, especially to containing the catalyzer of zeolite, the charging that nitrogen compound content is high can make it to poison very soon.So catalyzer patent merchant recommends, nitrogen content should be between 1～20 μ g/g, is very difficult when the nitrogen content among the VGO will make the nitrogen content in the effluent during at 200～2000 μ g/g below 5 μ g/g.Therefore process the operational condition that this raw material must be selected high hydrogen dividing potential drop or low-speed.And for an existing hydroeracking unit, can only realize by adjusting temperature of reaction.The height of nitrogen content has determined the operational condition of one stage hydrofining, to satisfy in second section feeding strict demand to nitrogen content.With the technology viewpoint, the problem that exists is how to handle a large amount of nitride contained in the heavy feed stock, obviously must regulate operational condition, compensate the active deficiency of catalyst for refining by improving temperature or reducing air speed, but start-of-run temperature must remain in the reasonable range (for example 400 ℃).To prevent that thermodynamical restriction because of the polycyclic aromatic hydrocarbons hydrogenation reaction from causing the rapid deactivation of catalyzer.
Though amorphous catalyst has the selectivity height, liquid is received characteristics such as height, and active low, flexibility of operation is poor.For the lytic activity that improves catalyzer damages its middle distillates oil selectivity again with exceeding, then should in the amorphous silicon alumina supporter, add a certain amount of zeolite, and should use the zeolite of nitrogen-resistant type; In addition, the hydrogenation activity of raising catalyzer also helps the raising of catalyzer nitrogen resistance.Giving full play to of hydrogenation activity can be poisoned little inorganic nitrogen compound-ammonia to acid sites with the more hydrogenation quickly of the big organic nitrogen compound of acidity of catalyst center toxic action are generated, and played the provide protection to the acidity of catalyst center.
Current, the crystal formation zeolite that hydrocracking catalyst is commonly used has large pore zeolite such as X type or Y type, especially y-type zeolite, the higher hydrocabon of stock oil can enter in the zeolite cavity and transform, for paraffinic crude, when cuts that will＞343 ℃ are cracked into 165 ℃～343 ℃ cut, the condensation point of diesel oil height that is obtained, and then have influence on the yield of intermediate oil.Another kind ofly be to use pore zeolite or select the shape zeolite such as ZSM-5 is the catalyzer of cracking component, has only chain type, the alkane of short-side chain can enter zeolite structured in, promptly have only straight chain hydrocarbon to be transformed, can dewax and diesel oil in the product and tail oil condensation point are reduced, but because the duct is less, reactant can not in time shift out, cause excessive fragmentation, and middle distillates oil selectivity is descended; The macromole hydrocarbon is difficult for entering on the other hand, and especially when treatment of heavy hydrocarbon material, activity is lower.
US4, the employed zeolite of heavy hydrocarbon conversion catalyst of the common glue method preparation that provides in 313,817 is a ZSM series, and it is represented as H type ZSM-5, and the aperture of this zeolite is less and preparation is complicated, need to use template, and crystallization time is long.This catalyzer contains silicon-aluminium-components such as titanium, when adopting one-stage serial technology, require in the cracking zone charging organonitrogen content best＜10 μ g/g, catalyzer consists of: Ni7W%, W17W%, SiO
222W%, Al
2O
325W%, H-ZSM-517W%, specific surface area＞200m
2/ g.Because it is very sensitive to the nitride in the raw material to contain the catalyzer of ZSM-5, therefore, if the nitrogen compound content in the raw material is higher, influenced the activity of zeolite containing catalyst, if do not adjust temperature of reaction, then quality product descends, change 11 units as pour point, when handling 315 ℃～590 ℃ heavier feeds, cracking zone feed nitrogen content＜1 μ g/g, temperature of reaction reaches 410 ℃.
US3, the hydrocracking catalyst of introducing in 954,671 adopt glue method preparation altogether, are acidic components with the y-type zeolite.Consisting of of this catalyzer: NiO8.8W%, MoO
331.5W%, SiO
212.6W%, Al
2O
331.5W%, Y zeolite 16.0W%, specific surface area 200m
2/ g.When the distillate that uses this catalyst treatment boiling point at 300～490 ℃, air speed is 1.25hr
-1, pressure is 12MPa, and cracking zone feed nitrogen content is 1 μ g/g, and temperature of reaction is higher to be 410 ℃.
US4, the hydrocracking catalyst of a kind of immersion process for preparing of introducing in 097,365 consists of: NiO4.1W%, WO
325.7W%, SiO in the carrier
2/ Al
2O
3=3: 1.When adopting one-stage serial art breading Kuwait vacuum distillate, cracking zone feed nitrogen content is 0.6～10 μ g/g, sulphur content＜10 μ g/g, and the transformation efficiency of＜370 ℃ of cuts is 70%, though middle distillates oil selectivity is higher than 80%, temperature of reaction is up to 420 ℃.
US4 has introduced a kind of usefulness Hydrocarban coversion catalysts of glue method preparation altogether in 495,061, and it consists of: Ni7W%, W17W%, SiO
222W%, Al
2O
325W%, TiO
27%, H-ZSM-5 17W%, specific surface area＞200m
2/ g, this cracking catalyst activity is higher, but contain titanium component in the catalyzer, account for 1～10W% that catalyzer is formed in metal oxide, add with the titanium tetrachloride form, though titanium can suppress the generation of nickel aluminate, and improved the hydrogenation activity of catalyzer to a certain extent, but titanium tetrachloride has very strong volatility, run into airborne moisture and can produce the intensive hydrolysis, generate hydrogen chloride gas and send unpleasant irritating smell, operational difficulty, being difficult to control its add-on accurately, is a shortcoming in this Preparation of Catalyst flow process.
The catalyzer of general common glue method preparation or carrier all adopt filter cake making beating washing to remove impurity, but adopt the method for this filter cake making beating washing, and the filter cake yield is low, complicated operation, and flow process is longer.And,, can cause the cohesiveness of filter cake to descend so if the foreign ion in the filter cake (as nitrate ion and chlorion) is washed off fully at the catalyzer that this method prepares, and the extrusion difficulty, active ingredient runs off in a large number, problems such as catalyst strength difference.
For can be in steady running under the high-nitrogen stock, prior art uses the zeolite molecular sieve of high silica alumina ratio as main acidity source emphatically, and as ZSM-5 series, but ZSM-5 belongs to mesopore zeolite, and the aperture is little.Activity and middle distillates oil selectivity incur loss when the raw material nitrogen content increases, most of patent emphasis interpolation auxiliary agent such as titanium component are also arranged to improve the hydrogenation performance of catalyzer, but the source great majority of titanium component are facile hydrolysiss preferably, volatile material, corrodibility is strong, store and the transportation difficulty, the operation accuracy rate is low, has influenced the assurance of Preparation of catalysts quality.Therefore, the adding mode of titanium component and material choice have bigger influence for the performance of catalyzer.In addition, filter cake making beating washing method complicated operation commonly used, catalyzer cost height, difficult forming.Will invent a kind of yield height, flow process is simple for this reason, not only had higher hydrocracking activity but also can be under cracking zone feed nitrogen content condition with higher the high hydrocracking catalyst of selectivity of steady running and middle oil production be very important.
Purpose of the present invention just is to provide hydrocracking catalyst of oil in a kind of nitrogen-resistant type fecund and preparation method thereof, and this catalyzer has active high and middle distillates oil selectivity height, and characteristics such as flexible operation can be produced a large amount of rocket engine fuels and diesel oil.The present invention also aims to provide a kind of one-stage serial technology, be used to handle the heavy hydrocarbon feedstocks of high nitrogen, the long period steady running is to produce intermediate oil, the raw material of preparing ethylene by steam cracking and lubricant base raw material.
The specific surface area of catalyzer of the present invention: 200～300m
2/ g, pore volume: 0.29～0.40ml/g, the aperture is 3～10 * 10
-10The hole of m accounts for 80～95% of total hole.
Catalyzer of the present invention contains amorphous silicon aluminium 10～60W%, VI B family metal oxide 10～40W%, VIII family metal oxide 1～10W%, IV B family metal oxide 1～10W%, modified Y zeolite 1～40W%.
This kind catalyzer is main carrier with the amorphous aluminum silicide, and part acidity is provided, and makes catalyzer have higher middle distillates oil selectivity.The SiO of amorphous aluminum silicide
2/ Al
2O
3Can be than scope: 1 from 0.1～10.Add the CN96119840.0 modified Y zeolite that partly has better nitrogen resistance simultaneously and increase lytic activity and anti-nitrogen ability.The method of modifying of Y zeolite is existing report in CN96119840.0, and this zeolite is raw material with the y-type zeolite, and making existing high-crystallinity by method such as steam treatment and mineral acid extracting repeatedly has low unit cell parameters again; Existing abundant secondary pore has bigger serface again.This zeolite accounts for 1～40W% in catalyzer, be better when accounting for 5～30W%.
The character of its modified Y zeolite is: SiO
2/ Al
2O
3Than being 9～15; Unit cell parameters is 24.23～24.45 * 10
-10Between the m; Degree of crystallinity is 95～100%; Specific surface area is 750～950m
2/ g; Aperture＞1.7 * 10
-10The hole of m accounts for 40～70% of total hole.Be characterized in that the acid sites number is many, anti-nitrogen ability is strong, with the acid sites of amorphous aluminum silicide coupling composition catalyzer.
VI B family metal is selected from molybdenum and/or tungsten in the catalyzer of the present invention, and its oxide compound accounts for 1～40W% of catalyst weight, and VIII family metal is selected from nickel and/or cobalt, and its oxide compound accounts for 1～10W% of catalyst weight.Adopt a kind of auxiliary agent to make the hydrogenation metal component on carrier, obtain good individual layer simultaneously and disperse, improve activity of such catalysts and stability.This auxiliary agent can be the mixture of the compound of any one or multiple element in the IV family, as titanium, and zirconium, etc., the content of its metal oxide accounts for 1～10W% of catalyst weight.In the present invention we to adopt stable solid sulphuric acid titanium and zirconium oxychloride be raw material rather than titanium tetrachloride, thereby solved the titanium tetrachloride instability, shortcoming such as volatile.
Catalyzer of the present invention adopts glue method preparation altogether, disperses more uniformly in the hope of obtaining metal component, improves hydrogenation activity.And the flow process that adopts first extruded moulding to wash again, the prepared gel dehydration of glue is to carry out under suitable temperature and humidity altogether simultaneously, temperature range is at 40～110 ℃.
The moulding of catalyzer of the present invention can be adopted known various routine techniques, as balling-up or extrusion.Metal supports and can adopt a step or substep glue method altogether, kneading method, pickling process etc.What here introduce is common glue method.With amorphous aluminum silicide involved in the present invention, the salts solution of auxiliary agent and reactive metal and the suspension liquid of modified Y zeolite join in the glue jar with one step of concentration or substep according to a certain percentage, add precipitation agent and make gelatinous mixture.Obtain containing the filter cake of certain moisture after the mixture of gained filters, this filter cake dewaters at a certain temperature, and temperature range is at 40～110 ℃.Extruded moulding then, work in-process bar are at 20～60 ℃, and impurity is removed in washing under pH value 7～12 conditions.30～110 ℃ of dryings, make finished catalyst 480～520 ℃ of following activation.Extruded moulding is generally cylinder shape, also can be special-shaped bar such as trifolium, shapes such as Herba Galii Bungei.Length is generally 3～8mm, and diameter is 1.3～1.8mm.
The technical process that Preparation of catalysts of the present invention adopts first extruded moulding to wash again makes washing carry out under suitable temperature and pH condition simultaneously.Wash temperature is 20～60 ℃, and the pH value is 7～12.Thereby reduce the loss of material in the filter cake making beating washing process and the loss of active metal component.
Catalyzer of the present invention is used for hydrocracking process, be particularly suitable for handling high nitrogen heavy hydrocarbon material, the boiling range scope is 250～600 ℃, generally at 300～550 ℃, nitrogen content is at 50～2500 μ g/g, generally, has the stock oil such as the gas oil of These characteristics, vacuum distillate at 500～2000 μ g/g, deasphalted oil, catalytic cracking turning oil, shale oil, coal tar wet goods.Generally under the condition that hydrogen exists, reaction pressure is 5～20MPa to reaction conditions, and hydrogen to oil volume ratio is 400～2500, and air speed is 0.5～3.0h
-1, temperature of reaction is 300～450 ℃.Hydrocracking process generally comprises the hydrofining of leading portion, is used for the most of S with raw material, the N impurity removal, and make polycyclic aromatic hydrocarbons saturated.Catalyzer of the present invention has higher anti-nitrogen ability, therefore comparatively flexible on technology, can suitably reduce the severity of refining section reaction, promptly reduce temperature of reaction or improve air speed, but also can use this catalyzer separately, promptly adopt single hop list agent art breading heavy hydrocarbon feedstocks, on anti-nitrogen ability, hydrogenation cracking activity and middle distillates oil selectivity, all show use properties preferably.This catalyzer pore distribution concentration, the aperture is 3～10 * 10
-10The pore volume of m accounts for 80～95% of total pore volume.And have high cracking and isomerization activity and high middle distillates oil selectivity.Cooperate employing one-stage serial technology with catalyst for refining, the processing high boiling point, during the higher heavier hydrocarbon feeds production middle runnings oil production of impurity, if cracking zone feed nitrogen content lower (8～10 μ g/g) catalyst reaction temperatures then of the present invention is than present domestic literature--the temperature of reaction of the middle oil type hydrocracking catalyst 3824 that generally uses on the full scale plant of refining of petroleum and chemical industry in January, 1998 report is hanged down 9 ℃, product distributes identical, and quality product is better than the latter.In general, hydrocracking catalyst when cracking zone feed nitrogen content when 10 μ g/g bring up to 50 μ g/g, other processing condition are constant, temperature of reaction must improve 25 ℃ and compensate active loss to make it to reach nitrogen content be 10 μ g/g levels.And catalyzer of the present invention is connected when using cracking zone feed nitrogen content when 10 μ g/g bring up to 100 μ g/g with catalyst for refining, temperature of reaction need only improve 9 ℃ just can to reach nitrogen content be 10 μ g/g levels under the constant situation of other processing condition, through running steady in a long-term deactivation rate＜0.02 ℃/day.Temperature increased value≤1 that the every raising 10 μ g/g of this technology cracking zone feed nitrogen content are brought ℃.
It is simple and reliable that this catalyzer has higher activity and middle distillates oil selectivity and preparation flow, the product yield of catalyzer reaches 95W%, owing to adopted the preparation method of first extruded moulding after scouring, therefore the hydrogenation metal turnover rate is low, avoid the loss of hydrogenation metal, reduced the catalyzer manufacturing cost.
Following example can help you further to understand catalyzer of the present invention and technology, but the present invention is not restricted to content and method in the example.
Example 1
Being total to a kind of of glue method preparation with the present invention, is that the hydrocracking catalyst of raw material is reference catalyst A with the titanium tetrachloride
1, the preparation of working solution
(1) preparation 500ml concentration is 7% sodium tungstate solution.
(2) contain in the 1000ml water purifying container at one and add solid nickelous chloride 45 grams, liquor alumini chloridi 1000ml, stable titanium tetrachloride-acetum 500ml is made solution, and concentration is respectively in nickel oxide 14%, titanium oxide meter 7%, aluminum oxide meter 9%.
(3) preparation 300ml concentration is in rare water glass solution of silicon-dioxide 7%.
(3) solution that (4) will prepare joins in the solution of (2) under stirring state, makes stable working solution.
2, to contain ammonia 12% Dilute Ammonia Solution joins in the working solution among the 1-(4), this constantly stirs therebetween, until the pH value is 5, add the sodium tungstate solution among the 1-(1) this moment, and then adding Dilute Ammonia Solution, make the pH value reach 8.0, become 50 ℃ of glue temperature, the mixture of making wore out 6 hours under stirring state, the y-type zeolite that provides among the CN96119840.0 of adding 7% before aging, the gel of making removed a certain amount of moisture through after filtering in 5 hours at 70 ℃ of oven dryings of temperature, dried material carries out extruded moulding, orifice plate is φ 3mm, and the catalyzer bar is a flush away impurity in 9 the washings at pH, repeated washing 8 times, the catalyzer bar of washes clean descended dry 8 hours at 110 ℃, carried out the finished product that calcination activation is made catalyst A for a short time at 500 ℃ then.Consisting of of catalyst A: WO
3, 23%; NiO, 9%; SiO
2, 30%; TiO
2, 7%; Pore volume, 0.35ml/g; Specific surface area, 280m
2/ g.
Example 2
Catalyst B with the inventive method preparation
Preparation flow is identical with example 1, just changes titanium tetrachloride into zirconium oxychloride.Consisting of of catalyst B: WO
3, 23%; NiO, 9%; SiO
2, 30%; ZrO
2, 7%; Pore volume, 0.37ml/g; Specific surface area, 290m
2/ g.
Example 3
The middle oil type hydrocracking catalyst of reporting in a kind of domestic publication-refining of petroleum and the chemical industry 3824 is reference catalyst.
The classical group of 3824 catalyzer becomes: MoO
3, 20%; NiO, 6%; P, 1.5%; Pore volume, 0.36 ml/g; Specific surface area, 260m
2/ g.
Example 4
Catalyzer C with the inventive method preparation
Preparation flow is identical with example 2, just the add-on of the Y zeolite of CN96119840.0 is brought up to 17% by 7%.Catalyzer C consists of: WO
3, 23%; NiO, 9%; SiO
2, 30%; ZrO
2, 7%; Pore volume, 0.39ml/g; Specific surface area, 295m
2/ g.
Example 5
Catalyzer D with the inventive method preparation
Preparation flow is identical with example 2, just the add-on of the Y zeolite of CN96119840.0 is brought up to 27% by 7%.Catalyzer D consists of: WO
3, 23%; NiO, 9%; SiO
2, 41%; ZrO
2, 7%; Pore volume, 0.41ml/g; Specific surface area, 287m
2/ g.
Example 6
Metal dispersion results for reference catalyst and catalyzer of the present invention
Table 1, ESCA are measured the catalyst surface metallographic phase to atomic percent
Annotate: I
w, I
Al, I
Ni, I
AlBe tungsten, aluminium in the catalyzer, the atomic percent of nickel, aluminium
| Catalyzer | A | B | C | D |
| I w/I Al | 0.10 | 0.12 | 0.13 | 0.11 |
| I Ni/I Al | 0.37 | 0.41 | 0.42 | 0.39 |
Table 2, transmissioning electric mirror determining catalyst surface WS
2Density
Data show, catalyst B of the present invention, and C, D are than the tungsten of reference catalyst A, and it is good that the nickel reactive metal distributes, and the dispersity height is uniformly dispersed.A, B are raw material with isolated island VGO on middle-scale device, have carried out single hop once by the hydrocracking test, and reaction pressure is 14.0MPa, and air speed is 1.12h
-1, hydrogen to oil volume ratio is 1200: 1, stock oil character sees Table 3.
| Catalyzer | A | B | C | D |
| WS 2Density, grain/100nm | 35 | 37 | 38 | 37 |
Table 3, the stock oil character and the evaluation result of evaluation usefulness
| Stock oil character: density (20 ℃), g/cm 3Boiling range, ℃ ASTM-D1160 10%/50% 90%/EBP S, m% N, m% | 0.9183 361/422 479/539 0.98 0.171 | |
| Evaluation result: catalyzer temperature of reaction, ℃ petroleum naphtha, the m% rocket engine fuel, m% diesel oil, the m% hydrogenation tail oil, m% C 5 +Liquid is received, m% hydrogen consumption, % | A 405 9.3 21.8 19.3 48.5 98.9 1.9 | B 402 8.6 23.8 19.9 46.7 98.9 1.7 |
From evaluation result as seen, the activity of catalyst B of the present invention, selectivity all are better than reference catalyst A, and quality product also is better than catalyst A.
Example 7
Catalyzer C of the present invention and 3824 catalyst pores distribute to contrast and list in the table 4.
Table 4, the pore distribution of catalyzer C and 3824 catalyzer
Distribution by the mesopore of the visible catalyzer C of the present invention of table 4 is compared to such an extent that 3824 catalyzer are more concentrated, helps slowing down the diffusion control in the hydrocracking reaction process, improves the middle distillates oil selectivity of catalyzer.
| The catalyzer pore distribution, %＜3nm 3～10nm＞10nm | C 7.1 91 1.9 | 3824 11 85 4 |
Example 8
Catalyzer C of the present invention, 3824 cooperate with catalyst for refining 3936 respectively and carry out one-stage serial hydrocracking test, and used stock oil is the triumph second line of distillation, and reaction pressure is 15.7MPa, volume space velocity R
1/ R
2Be 1.1/1.38, hydrogen to oil volume ratio is R
1/ R
2It is 950: 1/1200: 1.Table 5 has been listed evaluation result and the product property under stock oil character and the different treated oil nitrogen contents.
Table 5, the stock oil character of evaluation usefulness
| Stock oil character: density (20 ℃), g/cm 3Boiling range, ℃ ASTM-D1160 10% 50% 90% EBP S, m% N, m% BMCI value | 0.9100 392 431 476 526 0.56 0.16 44.1 | ||
| Evaluation result: R 2The catalyzer temperature of reaction, R 1/R 2R 1Outlet treated oil nitrogen, μ g/g product distributes and quality, the latent rocket engine fuel freezing point of m% light naphthar heavy naphtha virtue, ℃ smoke point, the mm condensation point of diesel oil, ℃ cetane value hydrogenation tail oil BMCI value C 5 +Liquid is received middle distillates oil selectivity, % | C 385/372 8～10 4.0 9.0 63.8 31.0 ＜-60 27 11.3 -4 60 43.0 15.7 98.3 76.5 | C 375/381 92～110 4.5 9.5 64.2 30.5 ＜-60 27 10.8 -4 60 43.0 16.2 98.3 74.6 | 3824 387/381 4～6 4.2 9.3 62.5 29.7 ＜-60 24 10.0 -3 58.7 45.0 18.9 98.2 74.5 |
From data as seen, under identical processing condition, when cracking zone feed nitrogen content during less than 10 μ g/g, the temperature of reaction of catalyzer C of the present invention is than low 9 ℃ of 3824 catalyzer, the hydrocracking product distributes identical with 3824 catalyzer, and quality product is better than 3824 catalyzer.When cracking zone feed nitrogen content during at 100 μ g/g, it is identical with 3824 catalyzer that the activity of catalyzer C of the present invention and product distribute, and quality product is better than 3824 catalyzer.
Data show, catalyzer C of the present invention is applicable to that vacuum distillate one-stage serial hydrocracking process is to produce intermediate oil, hold concurrently and produce part petroleum naphtha and cracking of ethylene raw material, perhaps tail oil can be produced the lubricant base of high viscosity index (HVI) after solvent dewaxing.At cracking zone feed nitrogen content during at 100 μ g/g, this activity of such catalysts, middle distillates oil selectivity is identical with middle oil type hydrocracking catalyst 3824 operation result under 4～6 μ g/g with stability, and the hydrocracking product property is better than 3824 catalyzer, replace 3824 catalyzer with catalyzer of the present invention, can be under the situation that does not increase reactor the capacity expansion revamping purpose that improves of implement device working ability.
Claims (10)
1, the hydrocracking catalyst of oil in a kind of nitrogen-resistant type fecund, composition is counted amorphous aluminum silicide with catalyst weight: 10～60W%, VI B family metal oxide: 10～40W%, VIII family metal oxide: 1～10W%, IV B family metal oxide: 1～10W%, it is characterized in that catalyzer also contains modified Y zeolite 1～40W%, this modified Y zeolite has SiO
2/ Al
2O
3Than being 9～15, degree of crystallinity is 95～100%, and specific surface area is 750～950m
2/ g, unit cell parameters is 24.23～24.45 * 10
-10Between the m, aperture＞1.7 * 10
-10The hole of m accounts for 40～70% of total hole.
2,, it is characterized in that the specific surface area of catalyzer: 200～300m according to the described hydrocracking catalyst of claim 1
2/ g, pore volume: 0.29～0.40ml/g, the aperture is 3～10 * 10
-10The hole of m accounts for 80～95% of total hole.
3, according to the described hydrocracking catalyst of claim 1, the content that it is characterized in that modified Y zeolite in the catalyzer is 5～30W%.
4, according to the described hydrocracking catalyst of claim 1, it is characterized in that said VI B family metal is selected from Mo and/or W, VIII family metal is selected from Co and/or Ni, and IV B family metal is selected from Ti and/or Zr.
5,, it is characterized in that the content of VI B family metal oxide accounts for 1～40W% of catalyst weight according to the described hydrocracking catalyst of claim 1.
6,, it is characterized in that VIII family metal oxide content accounts for 1～10W% of catalyst weight according to the described hydrocracking catalyst of claim 1.
7,, it is characterized in that the content of IV B family metal oxide accounts for 1～10W% of catalyst weight according to the described hydrocracking catalyst of claim 1.
8, the described Preparation of catalysts method of a kind of claim 1, adopt glue method preparation altogether, with amorphous aluminum silicide involved in the present invention, the salts solution of auxiliary agent and reactive metal and the suspension liquid of modified Y zeolite join in the glue jar in the desired ratio of catalyzer, add precipitation agent and make gelatinous mixture, after filtering, the mixture of gained obtains containing the filter cake of certain moisture, this filter cake dewaters at a certain temperature, cake dewatering/temperature range be 40～110 ℃, the first extruded moulding after scouring in dehydration back is removed impurity, wash temperature is 20～60 ℃, and the pH value is 7～12, and is dry then, activation makes finished catalyst.
9,, it is characterized in that said auxiliary agent is Ti and/or Zr, and add with solid sulphuric acid titanium and/or zirconium oxychloride form according to the described preparation method of claim 8.
10, according to the application of the described catalyzer of claim 1 in hydrocracking process, it is characterized in that adopting the one-stage serial reaction process, reaction conditions is that reaction pressure is 5～20MPa under the condition that hydrogen exists, hydrogen to oil volume ratio is 400～2500, and air speed is 0.5～3.0h
-1, temperature of reaction is 300～450 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114489A CN1073617C (en) | 1998-11-18 | 1998-11-18 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114489A CN1073617C (en) | 1998-11-18 | 1998-11-18 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
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| Publication Number | Publication Date |
|---|---|
| CN1253988A CN1253988A (en) | 2000-05-24 |
| CN1073617C true CN1073617C (en) | 2001-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98114489A Expired - Lifetime CN1073617C (en) | 1998-11-18 | 1998-11-18 | Hydrocraking catalyst of nitrogen-resistant type multiferous middle oil |
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| Country | Link |
|---|---|
| CN (1) | CN1073617C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107303493A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of preparation method of Catalyst For Single-stage Hydrocracking |
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|---|---|---|---|---|
| CN100340640C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | High activity medium oil type hydrocracking catalyst and its preparation method |
| CN100431697C (en) * | 2005-10-19 | 2008-11-12 | 中国石油化工股份有限公司 | Method for preparing catalyst composition |
| CN105505591A (en) * | 2014-09-23 | 2016-04-20 | 中国石油化工股份有限公司 | Method for hydrotreating of biomass pyrolysis oil |
| CN105618117B (en) * | 2014-11-03 | 2018-02-02 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN105621444B (en) | 2014-11-03 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of modified Y molecular sieve and preparation method thereof |
| CN105618115B (en) * | 2014-11-03 | 2018-01-16 | 中国石油化工股份有限公司 | modified Y molecular sieve and preparation method thereof |
| CN105618116B (en) * | 2014-11-03 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN105618121B (en) * | 2014-11-03 | 2018-07-06 | 中国石油化工股份有限公司 | A kind of preparation method of anti-nitrogen hydrocracking catalyst |
| CN106669770B (en) * | 2015-11-09 | 2019-09-10 | 中国石油化工股份有限公司 | A kind of silica-alumina supports and preparation method thereof containing molecular sieve |
| CN106669778B (en) * | 2015-11-09 | 2020-01-10 | 中国石油化工股份有限公司 | Light oil type hydrocracking catalyst and preparation method thereof |
| CN106669783B (en) * | 2015-11-11 | 2019-06-11 | 中国石油化工股份有限公司 | The preparation method of hydrocracking catalyst |
| CN107303494B (en) * | 2016-04-22 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| TWI831784B (en) | 2018-05-28 | 2024-02-11 | 大陸商中國石油化工科技開發有限公司 | NaY molecular sieve with aluminum-rich surface and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954671A (en) * | 1970-04-09 | 1976-05-04 | Chevron Research Company | Hydrotreating catalyst |
| US4097365A (en) * | 1976-03-18 | 1978-06-27 | Union Oil Company Of California | Hydrocracking process and catalyst for production of middle distillate oils |
| US4313817A (en) * | 1979-03-19 | 1982-02-02 | Chevron Research Company | Hydrocarbon conversion catalyst and process using said catalyst |
| US4495061A (en) * | 1980-06-16 | 1985-01-22 | Chevron Research Company | Hydrocarbon conversion catalyst and process using said catalyst |
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- 1998-11-18 CN CN98114489A patent/CN1073617C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954671A (en) * | 1970-04-09 | 1976-05-04 | Chevron Research Company | Hydrotreating catalyst |
| US4097365A (en) * | 1976-03-18 | 1978-06-27 | Union Oil Company Of California | Hydrocracking process and catalyst for production of middle distillate oils |
| US4313817A (en) * | 1979-03-19 | 1982-02-02 | Chevron Research Company | Hydrocarbon conversion catalyst and process using said catalyst |
| US4495061A (en) * | 1980-06-16 | 1985-01-22 | Chevron Research Company | Hydrocarbon conversion catalyst and process using said catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107303493A (en) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | A kind of preparation method of Catalyst For Single-stage Hydrocracking |
| CN107303493B (en) * | 2016-04-22 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of Catalyst For Single-stage Hydrocracking |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1253988A (en) | 2000-05-24 |
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