CN1224457C - Hydrocracking catalyst - Google Patents
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- CN1224457C CN1224457C CN 01130982 CN01130982A CN1224457C CN 1224457 C CN1224457 C CN 1224457C CN 01130982 CN01130982 CN 01130982 CN 01130982 A CN01130982 A CN 01130982A CN 1224457 C CN1224457 C CN 1224457C
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Abstract
The present invention relates to a hydrocracking catalyst which comprises alumina, carriers composed of Y type zeolite and metal oxides in a VIB family and in a VIII family. The Y type zeolite is prepared by adopting the following method: a raw material of Y type zeolite is used to contact an atmosphere comprising vapor. The atmosphere comprising vapor is a gas mixture which is composed of vapor, ammoniac components existing in the form of a mixture of ammonia, chlorine hydride, and/or hydrogen fluoride, ammonium chloride and/or ammonium fluoride, chloric components and/or flluoric components. When the gas mixture is used as a reference, the ammoniac content is from 50 ppm to 30 wt%, and the content of chlorine and/or fluorine is from 50 ppm to 15 wt%. The contact temperature is from 450 to 700 DEG C, and the contact time is from 1 to 10 hours.
Description
Technical field
The invention relates to a kind of hydrocracking catalyst, more particularly, is the hydrocracking catalyst about a kind of nickeliferous, tungsten and zeolite.
Background technology
In recent years, crude oil heavy and poor qualityization tendency are obvious day by day in the world wide.Meanwhile, demand to middle distillate and reformation, steam crack material but constantly increases, this impels the hydrocracking technology that turns to purpose with the high-quality of heavy distillate and lightweight to be developed rapidly, and hydrocracking catalyst is wherein important and one of The key factor.
Hydrocracking catalyst is a kind of bifunctional catalyst, and it has lytic activity and hydrogenation activity simultaneously, promptly contains acidic components and hydrogenation activity component simultaneously, and its acid major part is provided by heat-resistant inorganic oxide that constitutes carrier and/or various zeolite.The hydrogenation activity component generally is selected from the metal oxide of group vib and VIII family in the periodic table of elements.For reaching, need carry out adaptive modulation to acidic components in the catalyst and hydrogenation activity component to adding the different requirements of pyrolysis product.In general, catalyst for distillate hydro-cracking should have good desulfurization, denitrogenation and aromatic saturated hydrogenation performance.The catalyst that is used to produce intermediate oil also should have higher selectivity and anti-nitrogen stability to middle distillate, and the catalyst that is used to produce steam crack material then should have higher cracking activity.The catalyst that is used for processing heavy wax oil under middle pressure also should have higher activity and activity stability.
In hydrocracking catalyst, zeolite commonly used is a y-type zeolite, and the lattice constant y-type zeolite acid site of big (greater than 24.60 dusts) is more, and active higher, being suitable as to produce steam crack material is the active component of purpose hydrocracking catalyst.Yet the outstanding shortcoming of this y-type zeolite is that heat endurance is not high, and after the roasting, its degree of crystallinity is lower, and activity and activity stability also reduce greatly.For improving the heat endurance of y-type zeolite, usually, be prepared into overstable gamma zeolite with the y-type zeolite super stabilizing.The method that the y-type zeolite super stabilizing is the most frequently used is a hydro-thermal method, is about to y-type zeolite and at high temperature contacts with the atmosphere of moisture vapor.
US4,036,739 discloses the method that a kind of catalytically crack hydrocarbons raw material is produced low boiling point hydrocarbon, discloses a kind of preparation method of y-type zeolite in this method, comprises a kind of NH that contains the heavy % of sodium 0.6-5 of (1) roasting
4NaY zeolite, described roasting under the temperature of 600-1650 (315.6-898.9 ℃), and with the water vapour of 0.5Psi contacts at least condition under carry out, the time of contact is to the 24.40-24.64 dust with the structure cell that reduces described zeolite; (2) zeolite after the roasting is carried out ammonium exchange, the condition of exchange makes at least 25% of remaining sodium ion be replaced by ammonium ion, obtains the product of sodium content less than 1 heavy %; (3) product that obtains in (2) step of roasting temperature of 600-1500 (315.6-898.9 ℃), the time of roasting enough effectively removes the ammonium in the zeolite basically, and the lattice constant of zeolite is contracted to below 24.40 dusts.
Though the y-type zeolite stability that adopts said method to obtain is improved,, along with silica alumina ratio reduces (contraction of lattice constant), reduce in the acid site of zeolite, and degree of crystallinity descends, and generates a large amount of non-framework aluminums in zeolite.The existence of non-framework aluminum also directly influences the catalytic performance of zeolite in the zeolite, thereby the activity of the hydrocracking catalyst that contains this y-type zeolite is reduced, make the hydrocracking catalyst that contains this y-type zeolite only be suitable for producing intermediate oil, be not suitable for producing steam crack material.
US4,894,142 disclose a kind of hydrocracking process that is used to produce intermediate oil, contain group vib and VIII family metal component in this technology in the employed catalyst, also contain heat-resistant inorganic oxide and a kind of y-type zeolite in addition, the unit cell dimension of this y-type zeolite is the 24.2-24.40 dust, and ion exchange capacity is used NH greater than 0.07
3The acidity value that-TPD method is measured is less than 2.00.
CN1,169,458A discloses a kind of catalyst for distillate hydro-cracking, this catalyst has following composition: the heavy % of heavy %, tungsten oxide 10-38 of fluorine 0.5-5.0 heavy %, nickel oxide 2.5-6.0, all the other are carrier, this carrier is made up of the aluminium oxide of the heavy % of 20-90 and the zeolite of the heavy % of 10-80, its mesolite is the mesopore or the large pore zeolite of acidity value 1.0-2.0 mM/gram, aluminium oxide is the aluminium oxide of acidity value 0.5-0.8 mM/gram, this activity of such catalysts is not high, only is applicable to the production intermediate oil yet.
CN1,056,514A discloses a kind of hydrotreating catalyst, and this catalyst contains the heavy % nickel oxide of fluorine, 2.5-6.0 of the heavy % of 0.5-5.0, the tungsten oxide of the heavy % of 10-32, and silica alumina ratio is the modenite of 9.5-10.5 or y-type zeolite and the aluminium oxide that silica alumina ratio is 4.5-5.5.This aluminium oxide is made with the aluminum alkoxide Hydrolyze method, and purity forms after roasting greater than water Lu aluminium stone of 65 heavy %.Though this catalyst has higher hydrogenation cracking activity, its hydrogenation cracking activity still remains to be improved, and because the thermal instability of used y-type zeolite, its activity stability is lower.
Summary of the invention
The objective of the invention is to overcome prior art hydrocracking catalyst hydrogenation cracking activity and the not high shortcoming of activity stability, a kind of the have higher hydrogenation cracking activity and the hydrocracking catalyst of activity stability are provided.
Catalyst provided by the invention contains a kind of aluminium oxide and the carrier of y-type zeolite composition and the oxide of group vib and group VIII metal, wherein, described y-type zeolite is the y-type zeolite for preparing as follows: a kind of raw material y-type zeolite is contacted with a kind of atmosphere of moisture vapor, resulting product is carried out the ammonium exchange, washing is also dry, wherein, described raw material y-type zeolite is that a kind of sodium oxide content is not higher than 5 heavy %, lattice constant is the y-type zeolite of 24.6-24.75 dust, the atmosphere of described moisture vapor contains a kind of admixture of gas, this admixture of gas is by water vapour, ammonia components and chlorine and/or fluorine component are formed, described ammonia components and chlorine and/or fluorine component are with ammonia, the form of hydrogen chloride and/or hydrogen fluoride and ammonium chloride and/or ammonium fluoride mixture exists, with described admixture of gas is benchmark, in ammonia, the content of described ammonia components is the heavy % of 50ppm to 30, in chlorine and/or fluorine, the content of described chlorine and/or fluorine component is the heavy % of 50ppm to 15, the temperature of described contact is 450-700 ℃, and be 1-10 hour time of contact.
Compared with prior art, catalyst provided by the invention has higher activity.For example, with the n-decane is the cracking activity of raw material evaluate catalysts on the small fixed hydrocracking unit, in reaction temperature is 370 ℃, pressure 4 MPas, hydrogen to oil volume ratio is 25, and liquid hourly space velocity (LHSV) is under 60 hours-1 the reaction condition, with catalyst provided by the invention with containing the same amount zeolite, the existing catalyst of hydrogenation metal component and auxiliary agent fluorine is compared, and the conversion ratio of n-decane has improved 9.5-13.8%.
Moreover, catalyst provided by the invention also has higher activity stability.For example, catalyst is accelerated inactivation after 100 hours with the heptane that contains pyridine 1 heavy % under the reaction condition that lotus is carved, when using catalyst provided by the invention, the conversion ratio of n-decane is much higher than the conversion ratio of n-decane when using existing catalyst.
The specific embodiment
According to catalyst provided by the invention, in the preparation process of described y-type zeolite, with described admixture of gas is benchmark, in ammonia, the content of described ammonia components is the heavy % of 50ppm to 30, the heavy % of preferred 1-30, in chlorine and or fluorine, described fluorine and/or chlorine components contents are the heavy % of 50ppm-15, are preferably the heavy % of 1-15.The preferred chlorine component of described chlorine and/or fluorine component.
The admixture of gas that the atmosphere of described moisture vapor can just be made up of water vapour, ammonia components and chlorine and/or fluorine component also can be the gaseous mixture of this admixture of gas and inert gas.In the described gaseous mixture, the content of the described admixture of gas of being made up of water vapour, ammonia components and chlorine and/or fluorine component is not less than 10 body %, preferably is not less than 40 body %.Described inert gas refers to not destroy one or more in the zeolite structured arbitrary gas, as in the zero group gas in air, oxygen, nitrogen, the periodic table of elements one or more, because air and nitrogen cheaply are easy to get, therefore, preferred air of described inert gas or nitrogen.
Ammonia components in the described moisture vapor atmosphere and chlorine and/or fluorine component adopt following method to mix with water vapour: by each component ratio in the gas phase, with ammoniacal liquor and ammonium chloride and/or ammonium fluoride and water mixing, all evaporate the mixed solutions that obtain then.At described contact conditions, promptly under 450-700 ℃ the temperature, described ammonia components and chlorine and/or fluorine component exist with ammonia, hydrogen chloride and/or hydrogen fluoride and ammonium chloride and/or ammonium fluoride form of mixtures, and are in chemical balance.
Described moisture vapor atmosphere contacts with described raw material y-type zeolite, can carry out Static Contact in closed container, and the bed that also atmosphere of described moisture vapor can be continued to flow through a described raw material y-type zeolite dynamically contacts.
When described moisture vapor atmosphere and described raw material zeolite carried out Static Contact in closed container, the consumption of described moisture vapor atmosphere should make the water vapour in the moisture vapor atmosphere and the weight ratio of described raw material y-type zeolite be not less than 0.1, is preferably 0.1-4.When described moisture vapor atmosphere dynamically contacted with described raw material y-type zeolite, the flow of described moisture vapor atmosphere should make the amount of the water vapour that every gram catalyst per minute passes through be at least 0.1 gram, is preferably the 0.1-4 gram.
The temperature of described contact is 450-700 ℃, is preferably 500-650 ℃, and the time of contact is 1-10 hour, is preferably 1-3 hour.
Described ammonium exchange can be adopted conventional ammonium ion exchange method, be about to contact with a kind of aqueous solution that contains ammonium ion with zeolite after moisture vapor atmosphere contacts, the condition of contact is: the contact temperature is 60-120 ℃, is preferably 80-100 ℃, and be 1-10 hour time of contact, be preferably 1-3 hour, solvent and solute weight ratio is 3-50, is preferably 5-20, contains in the aqueous solution of ammonium ion, the concentration of ammonium ion is the 0.5-4 mole, is preferably the 0.8-3 mol.The number of times of contact is reduced to below the 1 heavy % sodium oxide content in the zeolite.
According to embodiment preferred of the present invention, the aqueous solution that contains ammonium ion that adopt described ammonium clearing house is the aqueous solution that contains ammonium ion of pH value for 3-6, adopts such aqueous solution that contains ammonium ion can remove the non-framework aluminum of the minute quantity that generates in the zeolite.Adjusting contains the acid of the pH value of aqueous solution of ammonium ion can be with in inorganic acid and the organic acid one or more, example hydrochloric acid, nitric acid, formic acid, acetate, tartaric acid, EDTA etc.
Described raw material y-type zeolite is that a kind of sodium oxide content is not higher than 5 heavy %, and lattice constant is the y-type zeolite of 24.60-24.75 dust, and this zeolite can be purchased and get, and also can prepare with the NaY zeolite with the ammonium ion exchange method.The ammonium ion exchange method is conventionally known to one of skill in the art, and the present invention also is described in front.
According to catalyst provided by the invention, the content of described catalyst carrier mesolite and aluminium oxide is content conventional in the carrier of hydrocracking catalyst, with the catalyst carrier total amount is benchmark, the content of described y-type zeolite is the heavy % of 5-80, the content of aluminium oxide is the heavy % of 20-95, under the preferable case, the content of described y-type zeolite is the heavy % of 10-70, and the content of aluminium oxide is the heavy % of 30-90.
The content of described group vib and group VIII metal oxide is content conventional in the hydrocracking catalyst, with the catalyst total amount is benchmark, the content of described group vib metal oxide is the heavy % of 10-35, be preferably the heavy % of 12-32, the content of group VIII metal oxide is the heavy % of 1-10, is preferably the heavy % of 2-8.Preferred molybdenum of described group vib metal and/or tungsten, more preferably tungsten.Described group VIII element is preferably nickel and/or cobalt, more preferably nickel.
Can also and preferably contain the auxiliary agent fluorine in the catalyst provided by the invention, the content of auxiliary agent fluorine is auxiliary agent fluorine content conventional in the hydrocracking catalyst, is benchmark with the catalyst total amount, and the content of described auxiliary agent is the heavy % of 0.5-9, is preferably the heavy % of 1-7.。
Catalyst provided by the invention is except that described y-type zeolite is the y-type zeolite of method for preparing, and other preparation process is conventional preparation process.
For example, catalyst provided by the invention can adopt following method preparation:
(1) preparation of catalyst carrier.
Precursor with aluminium oxide, be that hydrated alumina mixes with the y-type zeolite of method for preparing, moulding, drying, in 500-650 ℃ of roasting 1-10 hour, the consumption of hydrated alumina and described y-type zeolite makes aluminium oxide and the described y-type zeolite that contains customary amount in the catalyst carrier, as the heavy % of 5-80, and the y-type zeolite of the heavy % of preferred 10-70, the heavy % of 20-95, the aluminium oxide of the heavy % of preferred 30-90.
The dipping of (2) group vibs and group VIII metal.
With (1) catalyst carrier that obtains of step with the aqueous solution dipping that contains group vib and group VIII metallic compound, 100-130 ℃ of oven dry, 300-550 ℃ roasting 1-10 hour.The consumption that contains group vib and group VIII solution of metal compound makes and contains the conventional group vib and the content of group VIII metal oxide in the catalyst, as the heavy % of 10-35, the group vib metal oxide of the preferred heavy % of 12-32, the heavy % of 1-10, the group VIII metal oxide of the heavy % of preferred 2-8.
If contain the auxiliary agent fluorine, before dipping group vib and group VIII metal, go on foot the catalyst carrier that obtains with fluorinated water solution impregnation (1) earlier, and 110-130 ℃ of oven dry, 300-500 ℃ roasting 1-10 hour.The consumption of fluorinated water solution makes and contains conventional fluorine content in the catalyst, as the heavy % of 0.5-9, and the fluorine of the heavy % of preferred 1-7.
Described hydrated alumina is the hydrated alumina that is commonly used to prepare hydrogenation catalyst, as boehmite, gibbsite (generating gama-alumina, η-aluminium oxide after the roasting respectively) etc.These hydrated aluminas are commercially available and get, and also can adopt existing prepared in various methods, as adopting sodium metaaluminate-carbon dioxide process, alkyl aluminum or aluminum alkoxide Hydrolyze method, sodium metaaluminate-methods such as aluminum sulfate method preparation.
Described forming method comprises methods such as compressing tablet, balling-up or extrusion, preferably adopts the method for extruded moulding.
Described fluorinated water solution refers to fluorine-containing inorganic compound aqueous solution, as the ammonium fluoride and/or the hydrofluoric aqueous solution.
Described group vib metallic compound is selected from water-soluble group vib metallic compound, as in ammonium metatungstate, ammonium tungstate, ethyl ammonium metatungstate, metatungstic acid nickel, the ammonium molybdate one or more.Described group VIII metallic compound is selected from water-soluble group VIII metallic compound, as in nickel nitrate, nickel acetate, cobalt nitrate, the cobalt acetate one or more.
Catalyst provided by the invention is applicable to hydrocarbon raw material, as straight run gas oil (straight rungas oils), decompression gas (vacuum gas oils), metal removal oil (demetallizedoils), reduced crude (atmospheric residue), depitching decompression residuum (deasphaltedvacuum residue), coker distillate (coker distillates), catalytic cracking distillate oil (cat cracker distillates), shale oil (shale oil), asphalt sand oil (tar sandoil), liquefied coal coil (coal liquid) etc. carries out hydrocracking, has hydrocarbon fraction than low boiling and lower molecular weight with production.Catalyst provided by the invention is particularly suitable for producing steam crack material.Because catalyst provided by the invention has higher activity, therefore, catalyst provided by the invention can also to heavier oil product, carry out hydrotreatment as the heavy wax oil under middle pressure (6-10 MPa), produces intermediate oil.
The following examples will the present invention will be further described.
Example 1
Following example illustrates the preparation of the used y-type zeolite of catalyst provided by the invention.
(1) (lattice constant is 24.72 dusts, silica alumina ratio SiO with the NaY zeolite
2/ Al
2O
3Be 5.2, sodium oxide content is 12 heavy %, Chang Ling oil plant catalyst plant is produced) be that the aqueous ammonium chloride solution of 2.3 mol mixes with concentration, solvent and solute weight ratio is 10, is warming up to 95 ℃, under agitation carries out ion-exchange 1 hour, filter, spend the ion-cleaning solid product and be not detected to there being chlorion, 120 ℃ of oven dry, obtaining sodium oxide content is the y-type zeolite of 4.8 heavy %.
(2) take by weighing y-type zeolite 60 grams that the sodium oxide content that obtains is 4.8 heavy %, with 40 gram deionized waters, 5 gram ammonium chlorides and 10 gram concentration are that the ammonia spirit of 25 heavy % mixes, and mixture is placed a closed container, and with the suction filtration machine air is wherein extracted out, be warming up to 600 ℃ then, under 600 ℃ temperature, liquid phase part all evaporates, and the ammonia 11.9 that consists of of gas phase weighs %, chlorine 5.8 heavy %, all the other are water vapour.Contact and stop heating after 3 hours.
(3) will be that 4.0 concentration is that the aqueous ammonium chloride solution of 2.3 mol mixes (the pH value of aqueous ammonium chloride solution is regulated with acetate) with zeolite after moisture vapor atmosphere contacts and pH value, solvent and solute weight ratio is 10, under 95 ℃ temperature, carry out ion-exchange 1 hour, filter, spend deionised water to not having acid ion, 120 ℃ of oven dry.With the zeolite after the oven dry and pH value is that 3.0 concentration is that the aqueous ammonium chloride solution of 2.3 mol mixes (the pH value of aqueous ammonium chloride solution is regulated with acetate), solvent and solute weight ratio is 10, under 95 ℃ of temperature, carried out ion-exchange 1 hour, filter, the washing solid product is to there not being acid ion, 120 ℃ of oven dry obtain the used y-type zeolite Z of catalyst provided by the invention
1Table 1 has provided Z
1Physico-chemical property.
Wherein, lattice constant, degree of crystallinity adopt X-ray diffraction method to measure.Specific surface adopts cryogenic nitrogen absorption BET method to measure.Sodium oxide content adopts the X-fluorescence spectrum method for measuring.Non-framework aluminum characterizes with infra-red sepectrometry, and wave number is 3740cm in the infrared spectrum
-1Characteristic peak be the characteristic peak of non-framework aluminum in the zeolite, if there is non-framework aluminum in the zeolite, in the infrared spectrum this characteristic peak can appear, otherwise, this characteristic peak does not then appear.Wherein, described degree of crystallinity is relative crystallinity, and the degree of crystallinity of NaY zeolite described in (1) is decided to be 100%, and the degree of crystallinity of the zeolite of method provided by the invention (or control methods) preparation promptly is the degree of crystallinity with respect to described NaY zeolite.
Comparative Examples 1
The preparation method of this Comparative Examples explanation reference y-type zeolite.
Method by example 1 prepares y-type zeolite, and the step that different is does not contact with y-type zeolite in closed container with moisture vapor atmosphere obtains reference zeolite B
1B
1Physico-chemical property list in the table 1.
Comparative Examples 2
The preparation method of this Comparative Examples explanation reference y-type zeolite.
Method by example 1 prepares y-type zeolite, and different is not add ammonium chloride and ammoniacal liquor, obtains reference y-type zeolite B
2B
2Physico-chemical property list in the table 1.
Example 2
This example illustrates the preparation of the used y-type zeolite of catalyst provided by the invention.
Method by example 1 prepares y-type zeolite, different is the air of not extracting out in the described closed container, under described contact conditions, regulate the content of air, the content that makes the admixture of gas of being made up of water vapour, ammonia components and chlorine component in the gas phase is 50 body %, air content is 50 body %, obtains the invention provides the used y-type zeolite Z of catalyst
2Z
2Physico-chemical property list in the table 1.
Comparative Examples 3
The preparation method of this Comparative Examples explanation reference y-type zeolite.
Method by example 2 prepares y-type zeolite, and different is not add ammoniacal liquor and ammonium chloride, obtains reference y-type zeolite B
3B
3Physico-chemical property list in the table 1.
Example 3-4
Following example illustrates the preparation of the used y-type zeolite of catalyst provided by the invention.
Method by example 1 prepares y-type zeolite, the consumption that contact temperature that different is is respectively 650 ℃ and 500 ℃ water is respectively 21 grams and 200 and restrains, the consumption of ammoniacal liquor is respectively 15 grams and 1 gram, the consumption of ammonium chloride is respectively 10 grams and 4 grams, gas phase is formed the ammonia be respectively 20.1 heavy %, the chlorine of 13.6 heavy %, all the other be ammonia, the 1.3 weight % of water and 2.1 heavy % chlorine, all the other are water, be respectively time of contact 1 hour and 2 hours, and obtained the used y-type zeolite Z of catalyst provided by the invention
3And Z
4Z
3And Z
4Physico-chemical property list in the table 1.
Example 5
This example illustrates the preparation of the used y-type zeolite of catalyst provided by the invention.
(ammonia content is 20 heavy % to the admixture of gas of being made up of water, ammonia components and chlorine component that nitrogen is carried, chlorinity is 10 heavy %, all the other are water), the y-type zeolite bed (y-type zeolite by example 1 (1) preparation) of flow with per 100 gram molecules sieve, the 200 gram water of per minute by placing tube furnace, the consumption of y-type zeolite is 100 grams, nitrogen content is 50 body % in the gas phase, the content of the admixture of gas of being made up of water vapour, ammonia components and chlorine component is 50 body %, the temperature that gas contacts with y-type zeolite is 550 ℃, ventilates to stop ventilation and cooling after 3 hours.
To carry out ammonium exchange and oven dry with the y-type zeolite after moisture vapor gas contacts by the method for (3) in the example 1, obtain the used y-type zeolite Z5 of catalyst provided by the invention.The physico-chemical property of Z5 is listed in the table 1.
Table 1
| Example number | The y-type zeolite numbering | Lattice constant (A) | Specific surface (rice 2/ gram) | Na 2O (heavy %) | Degree of crystallinity (%) | Degree of crystallinity * (％) | The non-framework aluminum characteristic peak |
| 1 | Z 1 | 24.65 | 682 | 0.78 | 70.4 | 64.3 | Do not have |
| Comparative Examples 1 | B 1 | 24.66 | 671 | 0.74 | 66.8 | 56.2 | Do not have |
| Comparative Examples 2 | B 2 | 24.56 | 667 | 0.75 | 65.4 | 58.2 | Have |
| 2 | Z 2 | 24.65 | 656 | 0.85 | 63.5 | 60.5 | Do not have |
| Comparative Examples 3 | B 3 | 24.55 | 676 | 0.83 | 57.0 | 54.5 | Have |
| 3 | Z 3 | 24.68 | 667 | 0.88 | 68.7 | 61.3 | Do not have |
| 4 | Z 4 | 24.65 | 662 | 0.98 | 66.3 | 62.4 | Do not have |
| 5 | Z 5 | 24.65 | 689 | 0.70 | 61.8 | 63.4 | Do not have |
* degree of crystallinity is the degree of crystallinity of 550 ℃ of roastings after 2 hours
The result of table 1 shows: (1) is compared with the y-type zeolite without steam treatment, the used y-type zeolite of catalyst provided by the invention is greatly improved through the degree of crystallinity of 550 ℃ of roastings after 2 hours, and the degree that lattice constant dwindles is very little, improved 14.4% as degree of crystallinity, and lattice constant there is not difference substantially.This explanation is compared with the y-type zeolite that does not carry out steam treatment, when the used y-type zeolite of catalyst provided by the invention does not have obviously to reduce lattice constant, has higher heat endurance.(2) with through steam treatment, do not compare with the y-type zeolite that the chlorine component obtains but do not contain ammonia components in the gas phase, the used y-type zeolite of catalyst provided by the invention has higher degree of crystallinity, and also is like this after 2 hours through 550 ℃ of roastings.Simultaneously, the used y-type zeolite of catalyst provided by the invention does not contain non-framework aluminum, and through steam treatment but do not contain the y-type zeolite that ammonia components and chlorine component obtain in the gas phase tangible non-framework aluminum infrared signature peak is arranged.Everything explanation, the used y-type zeolite of catalyst provided by the invention have the existing higher heat endurance of zeolite, do not have significantly to reduce the lattice constant of zeolite again, have higher crystallization reservation degree, have less non-framework aluminum simultaneously again.
Example 6-10
Following example illustrates catalyst provided by the invention, its preparation and catalytic performance.
(solid content is 75 weight % with boehmite to take by weighing the y-type zeolite Z1-Z5 of example 1-5 preparation respectively, trade name is the SB powder, Germany CONDEA company produces) mix, adding entry again mixes and to pinch, be extruded into circumscribed circle diameter and be 1.8 millimeters trilobal bar, 120 ℃ of oven dry at different roasting temperatures, obtain carrier of hydrocracking catalyst S
1-S
5Table 2 has provided y-type zeolite Z in the preparation process
1-Z
6Consumption, sintering temperature and the roasting time of (dry basis), boehmite (dry basis), water.Table 3 has provided catalyst carrier S
1-S
5Composition, this composition is got by calculating.
Take by weighing catalyst carrier S respectively
2-S
6100 grams (dry basis) flooded 1 hour with the ammonium fluoride aqueous solution of 100 milliliters of variable concentrations, and be filtered to no obvious water droplet with Buchner funnel and drip, 120 ℃ of oven dry, under different temperature, the time that roasting is different.Take by weighing S respectively
1S with the last fluorine of dipping
2-S
6100 grams (dry basis), ammonium metatungstate and nickel nitrate mixed solution with 250 milliliters of variable concentrations flooded 1 hour respectively, was filtered to no obvious drop with Buchner funnel and dripped, 120 ℃ of oven dry, the different time of roasting under different temperatures, obtain hydrocracking catalyst C provided by the invention
1-C
5Table 4 has provided in the preparation process content and the roasting condition of tungsten oxide, nickel oxide in the concentration of used ammonium fluoride solution, ammonium metatungstate and the nickel nitrate mixed solution.Table 5 has provided catalyst C
1-C
5The content and the vector contg of middle tungsten oxide, nickel oxide, fluorine.Wherein, tungsten oxide, nickel oxide content assay method be referring to " petrochemical industry analytical method " (RIPP test method(s)), P360～361, and Science Press (1990), the assay method of fluorine is referring to the P185 that ibidems～187 page.Vector contg=100%-tungsten oxide content-nickel oxide content-fluorine content.
With the decane is raw material, evaluate catalysts C on the small fixed hydrocracking unit
1-C
5Hydrogenation cracking activity, 0.2 milliliter of catalyst loading amount, the catalyst granules diameter is the 0.3-0.45 millimeter, reaction temperature is 370 ℃, reaction pressure is 4.0 MPas, hydrogen to oil volume ratio is 25, liquid hourly space velocity (LHSV) is 60 hours
-1The conversion ratio of n-decane is as shown in table 6.
Comparative Examples 4-5
Following Comparative Examples explanation reference catalyst, its preparation and catalytic performance.
Method by example 6 prepares catalyst carrier and catalyst, and different is to use reference y-type zeolite B respectively
1And B
2Replace Z
1, get reference catalyst carrier S B
1And SB
2And reference catalyst CB
1And CB
2The method of pressing example 6 is to reference catalyst CB
1And CB
2Estimate.Table 2 has provided B in the preparation process
1, B
2, boehmite, water consumption, sintering temperature and roasting time.Table 3 has provided SB
1And SB
2Composition.Table 4 has provided tungsten oxide and the nickel oxide content and the roasting condition of used ammonium metatungstate and nickel nitrate mixed solution in the preparation process.Table 5 has provided CB
1And CB
2Composition.Table 6 has provided evaluation result.
Comparative Examples 6
The explanation of this Comparative Examples reference catalyst, its preparation and catalytic performance.
Method by example 7 prepares catalyst carrier and catalyst, and different is with reference y-type zeolite B
3Replace Z
2, obtain reference catalyst carrier S B
3With reference catalyst CB
3The method of pressing example 7 is to reference catalyst CB
3Carry out activity rating.Table 2 has provided B in the preparation process
3, boehmite, water consumption and sintering temperature and roasting time.Table 3 has provided SB
3Composition.Table 4 has provided tungsten oxide and the nickel oxide content and the roasting condition of used ammonium metatungstate and nickel nitrate mixed solution in the preparation process.Table 5 has provided CB
3The content and the vector contg of middle tungsten oxide and nickel oxide.Table 6 has provided evaluation result.
Table 2
| Example number | Zeolite | Boehmite consumption (gram) | Water (gram) | Sintering temperature (℃) | Roasting time (hour) | |
| Kind | Consumption (gram) | |||||
| 6 | Z 1 | 60 | 40 | 80 | 550 | 4 |
| Comparative Examples 4 | B 1 | 60 | 40 | 80 | 550 | 4 |
| Comparative Examples 5 | B 2 | 60 | 40 | 80 | 550 | 4 |
| 7 | Z 2 | 25 | 75 | 93 | 600 | 4 |
| Comparative Examples 6 | B 3 | 25 | 75 | 93 | 600 | 4 |
| 8 | Z 3 | 10 | 90 | 93 | 650 | 2 |
| 9 | Z 4 | 30 | 70 | 66 | 500 | 8 |
| 10 | Z 5 | 60 | 40 | 66 | 500 | 6 |
Table 3
| Example number | Bearer number | Carrier is formed | ||
| Zeolite type | Zeolite content, heavy % | Alumina content, heavy % | ||
| 6 | S 1 | Z 1 | 60.0 | 40.0 |
| Comparative Examples 4 | SB 1 | B 1 | 60.0 | 40.0 |
| Comparative Examples 5 | SB 2 | B 2 | 60.0 | 40.0 |
| 7 | S 2 | Z 2 | 25.0 | 75.0 |
| Comparative Examples 6 | SB 3 | B 3 | 25.0 | 75.0 |
| 8 | S 3 | Z 3 | 10.0 | 90.0 |
| 9 | S 4 | Z 4 | 30.0 | 70.0 |
| 10 | S 5 | Z 5 | 60.0 | 40.0 |
Table 4
| Example number | 6 | Comparative Examples 4 | Comparative Examples 5 | 7 | Comparative Examples 6 | 8 | 9 | 10 | |
| Bearer number | S 1 | SB 1 | SB 2 | S 2 | SB 3 | S 3 | S 4 | S 5 | |
| The dipping of fluorine | Ammonium fluoride aqueous solution concentration, heavy % | - | - | - | 2.6 | 2.6 | 6.5 | 2.2 | 3.8 |
| Sintering temperature, ℃ | - | - | - | 450 | 450 | 300 | 500 | 380 | |
| Roasting time, hour | - | - | - | 4 | 4 | 8 | 2 | 3 | |
| The dipping of nickel tungsten | Tungsten oxide content in the solution restrains/100 milliliters | 31.20 | 31.20 | 31.20 | 35.50 | 35.50 | 24.60 | 49.05 | 34.88 |
| Nickel oxide content in the solution restrains/100 milliliters | 7.88 | 7.88 | 7.88 | 7.57 | 7.57 | 3.22 | 11.74 | 9.32 | |
| Sintering temperature, ℃ | 500 | 500 | 500 | 450 | 450 | 550 | 350 | 400 | |
| Roasting time, hour | 2 | 2 | 2 | 4 | 4 | 2 | 8 | 6 | |
Table 5
| Example number | The catalyst numbering | Bearer number | Vector contg (heavy %) | WO 3(heavy %) | NiO (heavy %) | Fluorine content (heavy %) |
| 6 | C 1 | S 1 | 75.7 | 19.4 | 4.9 | - |
| Comparative Examples 4 | CB 1 | SB 1 | 75.8 | 19.3 | 4.9 | - |
| Comparative Examples 5 | CB 2 | SB 2 | 75.7 | 19.3 | 5.0 | - |
| 7 | C 2 | S 2 | 71.7 | 22.1 | 4.7 | 1.5 |
| Comparative Examples 6 | CB 3 | SB 3 | 71.8 | 22.0 | 4.6 | 1.6 |
| 8 | C 3 | S 3 | 76.9 | 15.3 | 2.0 | 5.8 |
| 9 | C 4 | S 4 | 61.0 | 30.5 | 7.3 | 1.2 |
| 10 | C 5 | S 5 | 70.0 | 21.7 | 5.8 | 2.5 |
Table 6
| Example number | The catalyst numbering | The n-decane conversion ratio, heavy % |
| 6 | C 1 | 72.6 |
| Comparative Examples 4 | CB 1 | 63.8 |
| Comparative Examples 5 | CB 2 | 64.1 |
| 7 | C 2 | 68.2 |
| Comparative Examples 6 | CB 3 | 62.3 |
| 8 | C 3 | 40.5 |
| 9 | C 4 | 75.2 |
| 10 | C 5 | 67.8 |
The result of table 6 shows, under the close situation of zeolite, tungsten oxide and nickel oxide content, compares with reference catalyst, the invention provides catalyst and has higher hydrogenation cracking activity.The conversion ratio of n-decane has improved 9.5-13.8% than reference catalyst.
Example 11-12
Following example illustrates activity of such catalysts stability provided by the invention.
The surperficial carbon deposit of the inactivation of catalyst and catalyst is closely related, and organic basic nitrogen-containing compound (as pyridine) easily and the generation of the cracking activity center of catalyst is strong adsorbs, thereby the condensation side reaction easily takes place, and finally causes catalyst carbon deposit.In addition, the speed of catalyst surface carbon deposit is also closely related with reaction condition, and when low and/or air speed when higher, catalyst surface carbon deposit speed can be accelerated as hydrogen-oil ratio.Following example just is based on above-mentioned principle, adopts the heptane that contains pyridine as raw material, in higher temperature, under lower hydrogen-oil ratio and the higher air speed, catalyst is accelerated inactivation, investigates activity of such catalysts stability.Being reaction raw materials with the n-decane carries out activity rating to the catalyst of accelerating behind the inactivation, and it is high more to accelerate behind the inactivation conversion ratio of n-decane, illustrates that this activity of such catalysts stability is high more.
The catalyst C that to be respectively charged into 2 milliliters of particle diameters in the reactor of small stationary bed apparatus be the 0.3-0.45 millimeter
1And C
2, be 25 in 4.0 MPas, 370 ℃, hydrogen to oil volume ratio, liquid hourly space velocity (LHSV) is 60 hours
-1Condition under decane is carried out hydrocracking, react after 10 hours, with accelerating the inactivation reaction raw material, the normal heptane that promptly contains the heavy % of pyridine 1 is replaced n-decane, simultaneously, temperature is increased to 400 ℃, hydrogen to oil volume ratio is reduced to 5, liquid hourly space velocity (LHSV) was increased to 300 hours
-1, react and accelerate the inactivation end after 100 hours.Again replace the normal heptane that contains pyridine 1 heavy % with n-decane, reaction temperature is reduced to 370 ℃ simultaneously, hydrogen to oil volume ratio is increased to 25, and liquid hourly space velocity (LHSV) was reduced to 60 hours
-1, the composition that continues 4 hours post analysis products of reaction calculates the conversion ratio of n-decane, and the results are shown in Table 7.
Comparative Examples 7-9
The catalytic performance of following Comparative Examples explanation reference catalyst.
Press the method evaluate catalysts of example 11-12, the different reference catalyst CB that just use respectively
1, CB
2And CB
3Replace catalyst C
4And C
2, the results are shown in Table 7.
Table 7
| Example number | Catalyst | The n-decane conversion ratio, heavy % |
| 11 | C 1 | 35.5 |
| Comparative Examples 7 | CB 1 | 23.8 |
| Comparative Examples 8 | CB 2 | 24.5 |
| 12 | C 2 | 31.5 |
| Comparative Examples 9 | CB 3 | 21.6 |
The result of table 7 shows, after accelerating inactivation, the invention provides hydrocracking catalyst and has the high activity that manys than existing hydrocracking catalyst.This explanation, hydrocracking catalyst provided by the invention has higher activity stability.
Claims (18)
1. hydrocracking catalyst, this catalyst contains a kind of aluminium oxide and the carrier of y-type zeolite composition and the oxide of group vib and group VIII metal, it is characterized in that, described y-type zeolite is the y-type zeolite for preparing as follows: a kind of raw material y-type zeolite is contacted with a kind of atmosphere of moisture vapor, resulting product is carried out the ammonium exchange, washing is also dry, wherein, described raw material y-type zeolite is that a kind of sodium oxide content is not higher than 5 heavy %, lattice constant is the y-type zeolite of 24.6-24.75 dust, the atmosphere of described moisture vapor contains a kind of admixture of gas, this admixture of gas is by water vapour, ammonia components and chlorine and/or fluorine component are formed, described ammonia components and chlorine and/or fluorine component are with ammonia, the form of hydrogen chloride and/or hydrogen fluoride and ammonium chloride and/or ammonium fluoride mixture exists, with described admixture of gas is benchmark, in ammonia, the content of described ammonia components is the heavy % of 50ppm to 30, in chlorine and/or fluorine, the content of described chlorine and/or fluorine component is the heavy % of 50ppm to 15, the temperature of described contact is 450-700 ℃, and be 1-10 hour time of contact.
2. catalyst according to claim 1 is characterized in that, the content of described ammonia components is the heavy % of 1-30, and the content of chlorine and/or fluorine component is the heavy % of 1-15.
3. catalyst according to claim 1 and 2 is characterized in that described chlorine and/or fluorine component refer to the chlorine component.
4. catalyst according to claim 1, it is characterized in that, the admixture of gas that the atmosphere of described moisture vapor is made up of water vapour, ammonia components and chlorine and/or fluorine component, or the gaseous mixture of this admixture of gas and inert gas, in the described gaseous mixture, the content of the described admixture of gas of being made up of water vapour, ammonia components and chlorine and/or fluorine component is not less than 10 body %.
5. catalyst according to claim 4 is characterized in that, the content of the described admixture of gas of being made up of water vapour, ammonia components and chlorine and/or fluorine component is not less than 40 body %.
6. catalyst according to claim 4 is characterized in that described inert gas refers to air or nitrogen.
7. catalyst according to claim 1 is characterized in that, described contact temperature is 500-650 ℃, and be 2-4 hour time of contact.
8. catalyst according to claim 1, it is characterized in that, the atmosphere of described moisture vapor is carried out with contacting in closed container of described raw material y-type zeolite, and it is 0.1-4 that the consumption of the atmosphere of described moisture vapor makes the water vapour in the moisture vapor atmosphere and the weight ratio of described raw material y-type zeolite.
9. catalyst according to claim 1, it is characterized in that, the way of contact of the atmosphere of described moisture vapor and described raw material y-type zeolite is: the atmosphere of moisture vapor flows through the bed of a described raw material y-type zeolite constantly, and it is the 0.1-4 gram that the flow of the atmosphere of described moisture vapor makes the amount of the water vapour that every gram zeolite per minute passes through.
10. catalyst according to claim 1, it is characterized in that, the exchange of described ammonium comprises and will contact with a kind of aqueous solution that contains ammonium ion with zeolite after described moisture vapor atmosphere contacts, the condition of contact is: the contact temperature is 60-120 ℃, be 1-10 hour time of contact, solvent and solute weight ratio is 3-50, contain in the aqueous solution of ammonium ion, the concentration of ammonium ion is the 0.5-4 mol, the number of times of contact is reduced to below the 1 heavy % sodium oxide content in the zeolite, and the described pH that contains the aqueous solution of ammonium ion is 3-6.
11. catalyst according to claim 1 is characterized in that, is benchmark with the total amount of catalyst carrier, the content of described y-type zeolite is the heavy % of 5-80, and the content of aluminium oxide is the heavy % of 20-95.
12. catalyst according to claim 11 is characterized in that, the content of described y-type zeolite is the heavy % of 10-70, and the content of aluminium oxide is the heavy % of 30-90.
13. catalyst according to claim 1 is characterized in that, is benchmark with the catalyst total amount, the content of described group vib metal oxide is the heavy % of 10-35, and the content of group VIII metal oxide is the heavy % of 1-10.
14. catalyst according to claim 13 is characterized in that, the content of described group vib metal oxide is the heavy % of 12-32, and the content of group VIII metal oxide is the heavy % of 2-8.
15., it is characterized in that described group vib metal finger molybdenum and/or tungsten, group VIII metal finger nickel and/or cobalt according to any described catalyst in the claim 1,13 and 14.
16. catalyst according to claim 1 is characterized in that, this catalyst also contains the auxiliary agent fluorine.
17. catalyst according to claim 16 is characterized in that, is benchmark with the total catalyst weight, the content of described auxiliary agent fluorine is the heavy % of 0.5-9.
18. catalyst according to claim 17 is characterized in that, the content of described auxiliary agent fluorine is the heavy % of 1-7.
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| CN 01130982 CN1224457C (en) | 2001-08-29 | 2001-08-29 | Hydrocracking catalyst |
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|---|---|---|---|
| CN 01130982 CN1224457C (en) | 2001-08-29 | 2001-08-29 | Hydrocracking catalyst |
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