CN1081223C - Process for preparing bimetallic catalyst containing pt and pd - Google Patents
Process for preparing bimetallic catalyst containing pt and pd Download PDFInfo
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- CN1081223C CN1081223C CN98117511A CN98117511A CN1081223C CN 1081223 C CN1081223 C CN 1081223C CN 98117511 A CN98117511 A CN 98117511A CN 98117511 A CN98117511 A CN 98117511A CN 1081223 C CN1081223 C CN 1081223C
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Abstract
The present invention relates to a preparation method of a bimetallic catalyst containing platinum and palladium, which comprises: a solution with a dissolved platinum compound or a dissolved palladium compound, which is contained in a first solvent, contacts a carrier; a solution with another dissolved palladium compound or another dissolved platinum compound, which is contained in a second solvent, contacts the carrier; the carrier is dried and calcined. The method is characterized in that the carrier is only dried after primary contact, the platinum compound or the palladium compound reacts with the palladium compound or the platinum compound, and a reaction product is difficultly dissolved in the second solvent or is indissolvable in the second solvent. The catalyst prepared with the method, which can be used in the hydrogenation process of high-sulfur raw oil, has the advantages of high hydrogenation activity and sulphur resisting performance.
Description
The invention relates to the preparation method who contains noble metal catalyst, more specifically say so about the preparation method of platiniferous and palladium catalyst.
On the substrate material in the load periodic table of elements catalyzer of group VIII noble metals have very high hydrogenation activity, can be used for multiple hydrocarbon conversion reactions.But this catalyzer is relatively responsive to sulphur, and the sulphur of trace can make its activity obviously descend and influences its activity stability in the raw material.On the other hand, serious day by day with the tendency of crude oil poor qualityization in the world wide, in crude oil and the various distillate thereof, the content of sulphur improves constantly, and therefore, for this class catalyzer, improves its sulfur resistance and has very big Practical significance.
Result of study shows that the acidity of the character of noble metal catalyst sulfur resistance and carrier, particularly carrier is relevant.Support acidity is strong more, and the noble metal catalyst sulfur resistance is good more.
Reforming catalyst is being studied the back discovery, Pt-Sn, Pt-Re are poorer than the anti-sulphur of single Pt catalyzer, and Pt-Ge is stronger than the anti-sulphur of single Pt catalyzer.This explanation, the sulfur resistance of noble metal catalyst is except outside the Pass having with carrier character, add another metal after, alloying effect also can resist the sulphur generation significantly to be influenced.
The USP3 of Ashland house journal in 1976,943, the method of hydrotreating that 053 to disclose a kind of boiling point be the 200-700 Fahrenheit degree, contain the hydrocarbon fraction of aromatic hydrocarbons and olefin component, this method is included in a kind of catalyzer and exists down, be enough to cause under the condition of at least a portion aromatic hydrocarbons contained in the described hydrocarbon fraction and hydrogenation of olefins that described hydrocarbon fraction is contacted with hydrogen, and described catalyzer contains platinum and the palladium of the heavy % of 0.2-1 respectively, wherein, the mol ratio of platinum and palladium is 1: 2 to 1: 6.This Preparation of catalysts method comprises:
(1). a kind of inert support is contacted with a kind of aqueous solution that contains Platinic chloride and a kind of Palladous chloride simultaneously;
(2). the mixture that drying obtains;
(3). in the 842-1022 Fahrenheit degree, the dried mixture of roasting in inert atmosphere; And,
(4). reduce described dried mixture.
Described inert support can be any oxide carrier, preferably has the aluminum oxide of high surface area, and as beta-aluminum oxide, eta aluminum oxide, gama aluminum oxide, bayerite, a diaspore, acid carrier are as amorphous aluminum silicide.This method finds that first load platinum and the bimetallic catalyzer of palladium on the carrier present than single Pt, anti-sulphur that single Pd is much better than.Hydrogenation, the benzene hydrogenation that this catalyzer can be used for aromatic hydrocarbons, alkene prepares hexanaphthene, benzene hydrogenation prepares reactions such as methylcyclopentane.Sulphur content can be up to 1000ppm in the hydrocarbon fraction.
CN1,053,636A discloses a kind of catalyst used for hydrogenation of distilled oil fraction, and this catalyzer is made of platinum and the palladium active ingredient of amorphous silicon oxide-alumina supporter that contains the heavy % aluminum oxide of 1-13 and the heavy % of 0.2-2.0, and wherein, the weight ratio of platinum and palladium is 1-5.Its preparation method is:
(1). will contain the amorphous silicon oxide-aluminum oxide of certain amount of alumina, under 15-150 ℃, after mineral acid soaks 1-15 hour part dealuminzation, with deionized water wash to there not being chlorion, amorphous silicon oxide-alumina supporter that a kind of 1-13 of containing weighs the % aluminum oxide is made in 100-120 ℃ of oven dry;
(2). with above-mentioned carrier through containing the steeping fluid of platinum and palladium, at room temperature with the saturated pickling process in hole dipping 3-5 hour, 100-130 ℃ of oven dry, under the 350-500 ℃ of air roasting 3-5 hour.Steeping fluid is by Palladous chloride, Platinic chloride and mineral acid, and preferably hydrochloric acid and water are formulated.This catalyzer has good sulfur resistance and aromatic saturated hydrogenation activity, can be used for the hydrogenation process of sulphur content up to 6000ppm (in thiophene phenol, in sulphur 2285ppm) distillate.
USP 5,308,814 disclose a kind of catalyzer that is applicable to the hydrocarbon raw material hydrogenation, this catalyzer contains and a kind ofly contains the carrier of y-type zeolite and in total catalyst weight, platinum and the palladium of the heavy % of each 0.1-2.0, described palladium and platinum are with 5: 1-1: 2 weight ratio loads on the described carrier that contains y-type zeolite, contains the heavy % sodium of 1.5-6.0 in the described y-type zeolite.This Preparation of catalysts method adopts soaks method altogether, and steeping fluid is Pt (NH
3)
4Cl
2, Pd (NH
3)
4Cl
2Mixing solutions.This catalyzer has higher hydrogenation activity.
USP5,346,612 to disclose a kind of be the method for hydrotreating of the hydrocarbon raw material formed of the hydrocarbon of 150-700 Fahrenheit degree basically by boiling point, this method is included under the hydroconversion condition, in the presence of a kind of catalyzer with described raw material and H-H reaction, described catalyzer contains the carrier of hydrogenation metal and a kind of Beta of containing zeolite, and described hydrogenation metal comprises that content is palladium and the platinum of the heavy % of 0.1-2.0 separately, and the sodium content of described Beta zeolite is the heavy % of 1ppm-3.Speak of in this patent specification, the method that hydrogenation component is incorporated on the carrier can adopt method well known to those skilled in the art, as pickling process, ion exchange method, and preferred pickling process.Can being impregnated on the carrier respectively or jointly of platinum and palladium.Suitable steeping fluid comprises, but is not limited to Platinic chloride, Palladous chloride, chlorination four ammino palladiums and chlorination four ammino platinum.With contain other zeolites, compare as the catalyzer of y-type zeolite, mordenite, this catalyzer that contains the Beta zeolite has higher hydrogenating desulfurization and denitrification activity.
Platinum-palladium bimetallic catalyst sulfur resistance is well extensively admitted than monometallic, and wherein the alloying effect of platinum and palladium is one of main method that improves the anti-sulphur of noble metal catalyst, and therefore a lot of documents have carried out big quantity research to alloying effect.It is generally acknowledged that alloying effect has the cause of following three aspects: (1), geometrical effect (2), electronic effect (ligand effect) (3), bimetallic synergistic effect.In order to guarantee that platinum-palladium bimetallic catalyst can have stronger anti-sulphur and stronger activity, the bimetallic synergy of bringing into play platinum and two kinds of components of palladium to greatest extent is an effective means, and its key is to guarantee that more platinum and palladium form alloy.
Yet method is soaked in the general employing of preparation method of platinum, palladium bimetallic catalyst altogether in the prior art.Though, USP5,346,612 have spoken of can being impregnated into respectively on the carrier of platinum and palladium, but, on the one hand, its used steeping fluid is Platinic chloride, Palladous chloride, chlorination four ammino palladiums and chlorination four ammino platinum solution, and on the other hand, those skilled in the art all know, the so-called technology of soaking of dividing, generally comprise a kind of metal compound solution is impregnated on the carrier, dry and through high-temperature roasting, metallic compound is decomposed, flood the compound of another kind of metal again, so that this metallic compound is unlikely under the dissolving when another components of metal compounds of dipping.Because precious metal content in catalyzer is lower usually, adopt and existingly soak method altogether or the branch method of soaking is introduced platinum and palladium in catalyzer, the dispersity of precious metal is than higher in the catalyzer, therefore, the alloying level of platinum and palladium is just lower in the catalyzer of preparing, most of platinum and palladium exist with the form of pt atom bunch or palladium cluster, can not give full play to the bimetallic synergy of platinum, two kinds of components of palladium.So the platinum palladium bimetallic catalyst activity and the anti-sulphur of prior art for preparing all must further improve.
The objective of the invention is to overcome the not high shortcoming of prior art catalyzer sulfur resistance, a kind of preparation method with platiniferous and palladium bimetal component catalyst of higher sulfur resistance and hydrogenation activity is provided.
The preparation method of platiniferous provided by the invention and palladium bimetal component catalyst comprises that the solution that will be dissolved with a kind of platinum or palladium compound in first kind of solvent contacts with a kind of carrier, again the solution that is dissolved with another kind of palladium or platinic compound in second kind of solvent is contacted with this carrier, dry also roasting, wherein, the contact back is only through super-dry for the first time, described platinum or palladium compound and palladium or platinic compound easily react, reaction product indissoluble or be insoluble to described second kind of solvent.
Described first kind of solvent can be identical with second kind of solvent, also can be different, be selected from water and maybe can dissolve described platinum or palladium compound or palladium or platinic compound, and indissoluble is separated or do not dissolve described platinum or the various organic solvents of palladium compound and palladium or platinic compound reaction product.Described platinum or palladium compound and palladium or platinic compound can be various platinum or the palladium compounds that meet above-mentioned condition.
The situation that is water with described first kind of solvent and second kind of solvent is that example is described the present invention in detail below.
In this case, Preparation of catalysts method provided by the invention comprises that the solution that will be dissolved with a kind of platinum or palladium compound in first kind of solvent contacts with a kind of carrier, again the solution that is dissolved with another kind of palladium or platinic compound in second kind of solvent is contacted dry and roasting with this carrier.Wherein, the contact back is only through super-dry for the first time, described platinum or palladium compound and palladium or platinic compound easily react, reaction product indissoluble or be insoluble to described second kind of solvent, described first kind of solvent and second kind of solvent are water, and the solution of described platinum or palladium compound refers to have the aqueous solution of the noble metal complexes of following anhydrous chemical expression:
PdX
4Y
2(or PtX
4Y
2)
Wherein, Y is selected from chlorion or nitrate ion; X is ammonia or amine or the polyamines that contains 1-15 carbon atom, preferred ammonia or contain the amine or the diamines of 1-10 carbon atom, more preferred ammonia, pyridine or quadrol.The solution that described another kind contains palladium or platinic compound refers to chlorine palladium acid (H
2PdCl
4) or inferior Platinic chloride (H
2PtCl
4) the aqueous solution.
Described carrier can be selected from one or more in the hydrogenation catalyst various carriers commonly used, as being selected from molecular sieve, various heat-resistant inorganic oxides, one or more in gac, carbon fiber, the various clay.Described molecular sieve can be selected from the aluminosilicate zeolite of natural or synthetic, in the non-zeolite molecular sieve one or more.Described aluminosilicate zeolite is selected from various aluminosilicate zeolites, as in A type zeolite, L zeolite, X type zeolite, y-type zeolite, Beta zeolite, mordenite, ZSM series zeolite, the omega zeolite one or more.Described non-zeolite molecular sieve can be selected from the molecular sieve that part silicon in the zeolite molecular sieve or aluminium are replaced by heteroatoms, as in phosphate aluminium molecular sieve, HTS, the boron aluminum molecular screen one or more.Described heat-resistant inorganic oxide can be selected from the heat-resistant inorganic oxide that is commonly used for support of the catalyst, as in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide, aluminum oxide-magnesium oxide, zirconium white, titanium oxide, the chromic oxide one or more.Described clay can be the various clays that are commonly used for support of the catalyst, as in kaolin, halloysite, polynite, wilkinite, the sepiolite one or more.Carrier commonly used is the carrier of silicon oxide, aluminum oxide, silica-alumina and silicon aluminate zeolite and silicon oxide, aluminum oxide or silica-alumina.Wherein, carrier the most commonly used is aluminum oxide, silica-alumina and contains y-type zeolite or the carrier of Beta zeolite and silicon oxide, aluminum oxide or silica-alumina.Wherein more preferably contain the heavy % of y-type zeolite 10-100, the carrier of heavy % of preferred 40-100 and surplus aluminum oxide.
The solution that is dissolved with a kind of platinum or palladium compound in described first kind of solvent and a kind of carrier contact and second kind of solvent in be dissolved with another kind of palladium or platinic compound solution can adopt existing variety of way with contacting of this carrier, as the method that can adopt dipping, the method for immersion, when carrier is in the time of can carrying out the material of ion-exchange, can also adopt the method for ion-exchange.
Described is PdX with anhydrous chemical expression
4Y
2(or PtX
4Y
2) the aqueous solution of noble metal complexes contact with carrier and with chlorine palladium acid (H
2PdCl
4) or inferior Platinic chloride (H
2PtCl
4) the process that contacts with carrier of the aqueous solution do not have sequencing.In other words, can be PdX with anhydrous chemical expression earlier
4Y
2(or PtX
4Y
2) the aqueous solution of noble metal complexes contact with carrier, again with chlorine palladium acid (H
2PdCl
4) or inferior Platinic chloride (H
2PtCl
4) the aqueous solution contact with this carrier.Also can be earlier with chlorine palladium acid (H
2PdCl
4) or inferior Platinic chloride (H
2PtCl
4) the aqueous solution contact with carrier, be PdX with anhydrous chemical expression again
4Y
2(or PtX
4Y
2) the aqueous solution of noble metal complexes contact with this carrier.When described carrier when containing Zeolite support, is PdX with anhydrous chemical expression earlier preferably
4Y
2(or PtX
4Y
2) the aqueous solution of noble metal complexes contact with carrier, again with chlorine palladium acid (H
2PdCl
4) or inferior Platinic chloride (H
2PtCl
4) the aqueous solution contact with this carrier, help the dispersion of precious metal in zeolite like this.
According to Preparation of catalysts method provided by the invention, platinum and the palladium content in catalyzer is convention amount, is benchmark with the catalyst weight, and the total content of platinum and palladium can be the heavy % of 0.05-15, the heavy % of preferred 0.1-10, the heavy % of more preferred 0.1-5.The weight ratio of platinum and palladium can in very large range change, but the weight ratio of platinum and palladium is generally 0.1-10, preferred 0.1-5.
Described preparation method and time Platinic chloride (H that contains the noble metal complexes aqueous solution
2PtCl
4) preparation method of the aqueous solution can find (1) J.W.Mellor, A Comprehensive Treatiseon Inorganic and Theoretical Chemistry, Longmans from following document, Green and Co., Volume15, P592-684, Volume 16, P1-416,1937.(2)C.A.Jacobson，Encyclopendia of Chemical Reactions，Reinhold Publishing CorporationsVolume 5，P301-321，P433-481，1953。Chlorine palladium acid (H
2PdCl
4) can adopt the ordinary method preparation.
Described drying and roasting can be carried out in the temperature and time scope of routine, can be from room temperature to platinum or the decomposition temperature of palladium compound as the exsiccant temperature, be generally room temperature to 300 ℃, preferred 100-150 ℃, can be 0.5 hour-several days time of drying, preferred 1-10 hour.Maturing temperature can be 350-650 ℃, and preferred 500-600 ℃, roasting time can be 0.5-10 hour, preferred 1-5 hour.
One of method characteristics provided by the invention are to use the method for contact respectively when introducing two kinds of precious metals, between twice contact only through super-dry, and without roasting.Two of characteristics be used respectively two kinds different, easily react and form sedimentary platinum or the compound of palladium and the compound of palladium and platinum.The situation that with the solvent is water is an example, when with PdX
4Y
2(or PtX
4Y
2) aqueous solution contacts with carrier and dry back, again with chlorine palladium acid (H
2PdCl
4) or inferior Platinic chloride (H
2PtCl
4) when the aqueous solution contacts with carrier, the reaction below taking place:
Can also contain a kind of auxiliary agent in the catalyzer of method preparation provided by the invention, described auxiliary agent is selected from the simple substance of VIIA family in the periodic table of elements, IB family, IIIB family, IVB group, group vib and VIIB family element or in the compound one or more, as the simple substance of fluorine and/or Cu, Ag, Sc, Y, La system, Ac system, Ti, Zr, Hf, Cr, Mo, W, Mn, Re or in the oxide compound one or more.The simple substance of the preferred fluorine of described auxiliary agent and/or Cu, Ag, La, Ti, Zr, Cr, Mo, W, Mn or in the oxide compound one or more.Gross weight with catalyzer is a benchmark, and the content of described auxiliary agent is the heavy % of 0.05-20, the heavy % of preferred 0.1-15, the heavy % of more preferred 0.1-10.Described auxiliary agent can adopt the whole bag of tricks before or after introducing platinum and palladium, introduce as pickling process, ion exchange method.
The catalyzer of method preparation provided by the invention can be used for boiling point 125-625 ℃ distillate, and as the hydrotreatment process of straight run gas oil, vacuum gas oil, catalytic cracking distilled oil, coker distillate, sulphur content can be up to 3000ppm in the stock oil.The catalyzer of method provided by the invention preparation also is suitable for boiling point 125-625 ℃ distillate hydrogenation and takes off aromatic hydrocarbons, to produce the distillate of low arene content.The catalyzer of method preparation provided by the invention also is suitable for use as diesel oil hydrogenation deeply de-aromatizing catalyst for reaction.Its processing condition of using are the hydrogenation technique condition of routine, when being used for distillate hydrogenation and taking off the reaction of aromatic hydrocarbons as catalyzer when method provided by the invention preparation, the hydrogenation technique condition can change in following ranges: temperature of reaction 200-350 ℃, preferred 250-320 ℃, reaction pressure greater than 2 MPas, be preferably greater than 3 MPas, liquid hourly space velocity 0.5-10 hour
-1, preferred 1-5 hour
-1, hydrogen to oil volume ratio is greater than 200, preferably be not less than 350.
The catalyzer of method preparation provided by the invention can directly use when being used for above-mentioned hydrotreatment, hydrogenation dearomatization hydrocarbon reaction, also can convert it into sulphided state and use.Vulcanization process can adopt existing various method for pre-sulphuration, as the method for prevulcanized in the device, the method for the outer prevulcanized of device.Employed vulcanizing agent is conventional vulcanizing agent.
The catalyzer of method preparation provided by the invention preferably reduces precious metal wherein when being used for above-mentioned hydrotreatment, hydrogenation dearomatization hydrocarbon reaction, uses to go back ortho states.Method of reducing can adopt existing various method of reducing, and as using hydrogen at reduction temperature 250-500 ℃, preferred 300-500 ℃, the recovery time reduced under preferred 1-10 hour the condition greater than 0.5 hour.
The following examples will the present invention will be further described.
Example 1
The preparation of this example explanation palladium complex aqueous solution.
Take by weighing 37 gram pyridines, be dissolved in 200 ml deionized water, add Palladous chloride (PdCl
2) 20.5 grams, under agitation be heated to 70 ℃, obtain shallow yellow transparent solution, add deionized water and be diluted to 500 milliliters, dichloro four pyridines that obtain concentration and be 24.6 milligrams of palladium/milliliters close palladium solution.
Example 2
The preparation of this example explanation platinum complex aqueous solution.
Take by weighing 20.0 gram commercially available product Platinic chloride (H
2PtCl
66H
2O), be dissolved in 200 ml deionized water, under agitation be heated to more than 70 ℃, each in batches a small amount of hydrazine hydrochloride (N that adds
2H
42HCl) totally 2.06 restrain, obtain the scarlet time platinum acid chloride solution of platiniferous 37 mg/ml.
The scarlet time platinum acid chloride solution of the above-mentioned platiniferous that obtains 37 mg/ml is divided into equal two parts, in a copy of it, adds quadrol 5.00 grams, be heated to 85 ℃, obtain shallow yellow transparent solution.Add deionized water and be diluted to 250 milliliters, the dichloro diethylamine that obtains concentration and be 14.8 milligrams of platinum/milliliters closes platinum solution.
Example 3
Prepare catalyzer by method provided by the invention.
Quantitatively take by weighing NaY zeolite (sodium oxide content 10.3 heavy %, SiO
2/ Al
2O
3=5.0, Chang Ling refinery catalyst plant is produced) add 10 heavy % ammonium chloride solutions, under liquid- solid ratio 10 and 90 ℃ of stirrings, carried out ion-exchange 3 hours, filter, with deionized water wash to there not being chlorion, 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 2 hours.The solid product that obtains carries out ion-exchange 2 times again under similarity condition, but not roasting gets the NH that sodium oxide content 1.2 weighs %
4Y zeolite.Wherein, sodium oxide content adopts aas determination.
With the NH that obtains
4 Y zeolite 100 grams (dry basis) and 40 gram pseudo-boehmite (dry basises, Chang Ling refinery catalyst plant is produced) mix, add deionized water and mix the trilobal bar of pinching, be extruded into 1.6 millimeters of circumscribed circle diameters, 120 ℃ of dryings 2 hours, 550 ℃ of roastings 2 hours, get support of the catalyst, be designated as A.
Take by weighing carrier A 100 grams (butt) that obtain, add 300 ml deionized water, dichloro four pyridines that drip 1 preparation of 24.4 milliliters of examples under the stirring at room close palladium solution and are warming up to 80 ℃ and carried out ion-exchange 2 hours, filter, spend ion-cleaning to there not being chlorion, dried 2 hours for 120 ℃, must contain the NH of palladium complex
4Y zeolite.
Quantitatively measure 6.0 milliliters of the scarlet time platinum acid chloride solutions of platiniferous 37 mg/ml of example 2 preparation, thin up to 300 milliliter is with the above-mentioned NH that contains palladium complex that obtains
4Y zeolite mixes, and is warming up to 80 ℃ of contacts 2 hours, filters, and, dries 2 hours for 120 ℃ to no acid ion with deionized water wash, and 550 ℃ of roastings 2 hours make catalyzer DA-1.
Table 1 has provided the composition of catalyzer DA-1, and in the table 1, zeolite content is got by calculating, and palladium and platinum content adopt x-ray fluorescence spectrometry.
Comparative Examples 1
The preparation of reference catalyst.
Press USP 5,308, the method of 814 examples 1 prepares reference catalyst B-1, and different is that used carrier is example 3 described carrier A, and palladium content is that 0.63 gram, platinum content are 0.21 gram in chlorination four ammino palladiums and the chlorination four ammino platinum mixing solutionss, the mixing solutions consumption is 80 milliliters, bake out temperature is 120 ℃, and drying time is 2 hours, and maturing temperature is 550 ℃, roasting time is 2 hours, gets reference catalyst B-1.Table 1 has provided the composition of B-1.
Example 4
Prepare catalyzer by method provided by the invention.
The preparation method is with example 3, and just to close the consumption of palladium solution be 12.2 milliliters to dichloro four pyridines, 3.0 milliliters of platiniferous scarlet time platinum acid chloride solution consumptions.Get the catalyzer DA-2 of method preparation provided by the invention.Table 1 has provided the composition of catalyzer DA-2.
Example 5
Prepare catalyzer by method provided by the invention.
The preparation method is with example 3, and just to close the consumption of palladium solution be 75.0 milliliters to dichloro four pyridines, 18.0 milliliters of platiniferous scarlet time platinum acid chloride solution consumptions.Make the catalyzer DA-3 of method preparation provided by the invention.Table 1 has provided the composition of catalyzer DA-3.
Example 6
Prepare catalyzer by method provided by the invention.
The preparation method is that the step of NaY zeolite ion-exchange is omitted with example 3, directly is 23 Hydrogen Beta zeolite (sodium oxide content is 0.2 heavy %, and Chemical Plant of Nankai Univ. produces) 100 gram (butt) replacements 100 gram NH with silica alumina ratio
4Y zeolite gets the catalyzer DA-4 of method preparation provided by the invention.Table 1 has provided the composition of catalyzer DA-4.
Comparative Examples 2
The preparation of reference catalyst.
Press USP5,346, the preparation of 612 examples, 4 disclosed methods contains the reference catalyst B-2 of Beta zeolite, different is that used zeolite is example 6 used Beta zeolites of the present invention, the carrier that contains Beta zeolite 71.4 heavy %, aluminum oxide 28.6 heavy % with chlorination four ammino palladiums and chlorination four ammino platinum mixing solutions direct impregnation 100 grams, palladium content is that 0.63 gram, platinum content are 0.21 gram in chlorination four ammino palladiums and the chlorination four ammino platinum mixing solutionss, the mixing solutions consumption is 80 milliliters, bake out temperature is 120 ℃, and drying time is 2 hours; Maturing temperature is 550 ℃, and roasting time is 2 hours, gets reference catalyst B-2.Table 1 has provided the composition of B-2.
Example 7
Prepare catalyzer by method provided by the invention.
Method for preparing catalyst just omits the step of ion-exchange of NaY zeolite and adding additives moulding with example 4, replaces carrier A with 100 grams (butt) of the sial bead after the dealumination treatment, gets the catalyzer DA-5 of method preparation provided by the invention.Table 1 has provided the composition of catalyzer DA-5.
Wherein, the sial bead after the described dealumination treatment is according to CN1, and 053, (produce, amorphous Si O by Lanzhou Oil Refinery to the sial bead for the method that 636A example 1-4 provides
2-Al
2O
3, Al
2O
3Content 12 heavy %) carry out the hydrochloric acid dealumination treatment.Sial bead consumption 500 grams, concentration is that the hydrochloric acid soln consumption of 20 heavy % is 1500 milliliters.Sial bead Al behind the dealuminzation
2O
3Content 3.8 heavy %.
Comparative Examples 3
The preparation of reference catalyst.
Press CN1,053,636A example 5 disclosed methods prepare catalyst B-3, take by weighing 0.28 gram commercially available product Platinic chloride (H
2PtCl
66H
2O) and 0.53 the gram PdCl
2(analytical pure) adds concentrated hydrochloric acid (analytical pure, 36%) 0.8 milliliter, and thin up to 65 milliliter obtains steeping fluid.With obtaining steeping fluid dipping 100 grams example 7 described Al of the present invention
2O
3The heavy % dealuminzation of content 3.8 sial beads, 120 ℃ of dryings 2 hours, 550 ℃ of roastings 2 hours, reference catalyst B-3.Table 1 has provided the composition of catalyst B-3.
Example 8
Prepare catalyzer by method provided by the invention.
Take by weighing 1.05 gram PdCl
2(analytical pure) adds concentrated hydrochloric acid (analytical pure, 36%) 1.5 milliliters, and thin up to 200 milliliter obtains chlorine palladium acid solution, floods in type 100 and restrains γ-Al with obtaining chlorine palladium acid solution
2O
3Cloverleaf pattern bar (the Chang Ling refinery is produced for 1.6 millimeters of diameters, dry basis) 2 hours was dried 2 hours for 120 ℃.The platinum complex dichloro diethylamine of measuring 13.9 milliliters of examples 2 preparation closes platinum solution, and thin up to 200 milliliter floods the above-mentioned palladium carrier that contains, kept 2 hours, 120 ℃ of dryings 2 hours, 550 ℃ of roastings 2 hours, the catalyzer DA-6 of method preparation provided by the invention.Table 1 has provided the composition of catalyzer DA-6.
Comparative Examples 4
The preparation of reference catalyst.
Press USP3,943,053 methods that provide prepare reference catalyst B-4.Acidic solution dipping 100 grams example 8 described γ-Al of the present invention with Platinic chloride that contains palladium 0.63 gram, platinum 0.21 gram and Palladous chloride
2O
3Cloverleaf pattern bar 2 hours, 120 ℃ of dryings 2 hours, 550 ℃ of roastings 2 hours, reference catalyst B-4.Table 1 has provided the composition of catalyst B-4.
Example 9
Prepare catalyzer by method provided by the invention.
The preparation method is with example 3, and just to close the consumption of palladium solution be 24.4 milliliters to dichloro four pyridines, 54 milliliters of platiniferous scarlet time platinum acid chloride solution consumptions.Get the catalyzer DA-9 of method preparation provided by the invention.Table 1 has provided the composition of catalyzer DA-9.
Table 1
| Example number | The catalyzer numbering | Kind of carrier | Al in the carrier 2O 3Content, heavy % | Pt content, heavy % | Pd content, heavy % |
| 3 | DA-1 | Y/Al 2O 3 | 28.6 | 0.2 | 0.6 |
| Comparative Examples 1 | B-1 | Y/Al 2O 3 | 28.6 | 0.2 | 0.6 |
| 4 | DA-2 | Y/Al 2O 3 | 28.6 | 0.1 | 0.3 |
| 5 | DA-3 | Y/Al 2O 3 | 28.6 | 0.6 | 1.8 |
| 6 | DA-4 | β/Al 2O 3 | 28.6 | 0.2 | 0.6 |
| Comparative Examples 2 | B-2 | β/Al 2O 3 | 28.6 | 0.2 | 0.6 |
| 7 | DA-5 | SiO 2-Al 2O 3 | 3.8 | 0.1 | 0.3 |
| Comparative Examples 3 | B-3 | SiO 2-Al 2O 3 | 3.8 | 0.1 | 0.3 |
| 8 | DA-6 | γ-Al 2O 3 | 100 | 0.2 | 0.6 |
| Comparative Examples 4 | B-4 | γ-Al 2O 3 | 100 | 0.2 | 0.6 |
| 9 | DA-7 | Y/Al 2O 3 | 28.6 | 1.8 | 0.6 |
Example 10-16
Following example illustrates the hydrogenation activity and the sulfur resistance of the catalyzer of method preparation provided by the invention.
Characterize the hydrogenation activity of catalyzer with the toluene hydrogenation activity.Hexane solution with the toluene that contains the heavy % of toluene 60 that contains 3000ppm sulphur is a reactant, the hydrogenation activity of evaluate catalysts DA-1, DA-2, DA-3, DA-4, DA-5, DA-6, DA-7 on 10 milliliters of small stationary bed bioreactors.1.5 milliliters of catalyzer loading amounts (catalyst particle size is the 40-60 order), reaction pressure 4.0 MPas, liquid hourly space velocity 4.0 hours
-1, hydrogen to oil volume ratio 4000, the gas chromatographic analysis reaction product is used in sampling in 2 hours after the stable reaction.Before the reaction beginning, earlier at 300 ℃, 4.0 MPas, be the hydrogen reducing catalyzer 2 hours of 400 ml/min with flow velocity.The transformation efficiency of toluene is as shown in table 2 under the differential responses temperature.
Comparative Examples 5-8
The hydrogenation activity of following Comparative Examples explanation reference catalyst.
Press the condition evaluating activity of such catalysts of example 10-16, just catalyst system therefor is catalyst B-1, B-2, B-3, the B-4 of Comparative Examples 1-4 preparation.The transformation efficiency of toluene is listed in the table 2 under the differential responses temperature.
Table 2
| Example number | The catalyzer numbering | Toluene conversion, heavy % | ||
| 240℃ | 260℃ | 280 | ||
| 10 | DA-1 | 35.5 | 47.3 | 65.7 |
| Comparative Examples 5 | B-1 | 23.1 | 28.9 | 44.1 |
| 11 | DA-2 | 19.5 | 25.0 | 35.4 |
| 12 | DA-3 | 66.3 | 73.1 | 99.4 |
| 13 | DA-4 | 24.1 | 31.2 | 46.3 |
| Comparative Examples 6 | B-2 | 16.4 | 20.2 | 35.4 |
| 14 | DA-5 | 33.2 | 42.2 | 63.3 |
| Comparative Examples 7 | B-3 | 25.2 | 35.7 | 50.3 |
| 15 | DA-6 | 1.2 | 2.8 | 7.1 |
| Comparative Examples 8 | B-4 | 0.1 | 0.5 | 2.7 |
| 16 | DA-7 | 58.4 | 67.3 | 93.5 |
The result of table 2 shows, when sulphur content is identical in raw material, compares with the identical catalyzer of existing composition, and the catalyzer of method preparation provided by the invention has higher hydrogenation activity.
Example 17
This example further specifies the sulfur resistance and the activity stability thereof of catalyzer provided by the invention.
This example is a reaction raw materials with the hexane solution of the toluene of sulfur-bearing 3000ppm, toluene level 60 heavy %, and the catalyzer DA-1 that example 3 is prepared carries out stability experiment.Be reflected in the described small stationary bed bioreactor of example 10-16 and carry out.Catalyzer loading amount, reductive condition are with example 10-16, and reaction conditions is except that temperature is 280 ℃, and other is with example 10-16.Toluene conversion over time as shown in Figure 1.
The result of Fig. 1 shows, the hydrogenation reaction that catalyzer provided by the invention is used for toluene, when sulphur content in the raw material during up to 3000ppm, prolongation with the reaction times, toluene conversion fluctuates within the specific limits, do not see obvious downward trend, illustrate that catalyzer provided by the invention not only has higher activity, and have very high activity stability and good sulfur resistance.
Example 18-19
Below aromatic hydrogenation activity and the sulfur resistance of example when catalyst treatment oil product provided by the invention is described.
With the straight-run diesel oil after the hydrotreatment is reaction raw materials, on 100 milliliters of hydrogenation units, the catalyzer DA-1 of example 3 preparations, the catalyzer DA-5 of example 7 preparations is carried out activity rating.20 milliliters of catalyzer loading amounts also add 20 milliliters of quartz sand dilutions (catalyzer and thinner granularity are all the 20-40 order).Before the reaction beginning, prior to 400 ℃, with pressure 4 MPas, the hydrogen reducing catalyzer of flow velocity 400 ml/min 4 hours, then, and at 300 ℃, pressure 4 MPas, volume space velocity is 1 hour during liquid
-1, under the condition of hydrogen to oil volume ratio 500 catalyzer DA-1, DA-5 are carried out activity rating.Stable reaction was taken a sample after 24 hours, used the efficient liquid phase chromatographic analysis aromaticity content, and evaluation result sees Table 3.
Comparative Examples 9-10
Arene saturating activity when this Comparative Examples explanation reference catalyst is handled oil product.
Press the activity of the method evaluate catalysts of example 18-19, just catalyst system therefor is reference catalyst B-1, the B-3 of Comparative Examples 1 and Comparative Examples 3 preparations.Evaluation result is listed in the table 3.Table 3
| Catalyzer | Sulphur content ppm | Nitrogen content ppm | Total aromaticity content (heavy %) | Mononuclear aromatics content (heavy %) | Double ring arene content (heavy %) | Polycyclic aromatic hydrocarbon content (heavy %) |
| Stock oil | 346 | 16 | 24.4 | 20.1 | 3.5 | 0.8 |
| DA-1 | 113 | 2 | 4.8 | 3.5 | 1.1 | 0.2 |
| B-1 | 145 | 3 | 7.7 | 5.6 | 1.8 | 0.3 |
| DA-5 | 169 | 5 | 18.8 | 15.3 | 3.1 | 0.4 |
| B-3 | 235 | 4 | 22.1 | 18.1 | 3.4 | 0.6 |
The result of table 3 shows, compares with the identical catalyzer of existing composition, and the catalyst treatment sulfur-bearing fraction that adopts method provided by the invention to prepare has higher hydrogenation activity when oily.
Claims (14)
1. the preparation method of platiniferous and palladium bimetal component catalyst, comprise that the solution that will be dissolved with a kind of platinum or palladium compound in first kind of solvent contacts with a kind of carrier, again the solution that is dissolved with another kind of palladium or platinic compound in second kind of solvent is contacted with this carrier, dry also roasting, it is characterized in that, for the first time the contact back is only through super-dry, and described platinum or palladium compound and palladium or platinic compound easily react, reaction product indissoluble or be insoluble to described second kind of solvent.
2. according to the described method of claim 1, it is characterized in that described first kind of solvent and second kind of solvent are water, the solution of described platinum or palladium compound refers to have the aqueous solution of the noble metal complexes of following anhydrous chemical expression:
PdX
4Y
2(or PtX
4Y
2)
Wherein, Y is selected from chlorion or nitrate ion; X is ammonia or amine or the polyamines that contains 1-15 carbon atom; The solution that described another kind contains palladium or platinic compound refers to the aqueous solution of acid of chlorine palladium or inferior Platinic chloride.
3. according to the described method of claim 2, it is characterized in that the X in the described anhydrous chemical expression is ammonia or amine or the diamines that contains 1-10 carbon atom.
4. according to the described method of claim 3, it is characterized in that described X is ammonia, pyridine or quadrol.
5. according to claim 1 or 2 described methods,, it is characterized in that described carrier is selected from molecular sieve, heat-resistant inorganic oxide, one or more in gac, carbon fiber, the clay.
6. according to the described method of claim 5, it is characterized in that described molecular screening is from the aluminosilicate zeolite of natural or synthetic, in the non-zeolite molecular sieve one or more; Described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, silica-alumina, aluminum oxide-magnesium oxide, chromic oxide, titanium oxide, the chromic oxide; Described clay is selected from one or more in kaolin, halloysite, polynite, wilkinite, the sepiolite.
7. according to the described method of claim 6, it is characterized in that described aluminosilicate zeolite is selected from one or more in A type zeolite, L zeolite, X type zeolite, y-type zeolite, Beta zeolite, mordenite, ZSM series zeolite, the omega zeolite; Described non-zeolite molecular sieve is selected from one or more in the molecular sieve that part silicon in the zeolite molecular sieve or aluminium replaced by heteroatoms.
8. according to the described method of claim 5, it is characterized in that described carrier is the carrier of silicon oxide, aluminum oxide, silica-alumina or silicon aluminate zeolite and silicon oxide, aluminum oxide or silica-alumina.
9. described according to Claim 8 method is characterized in that described carrier is aluminum oxide, silica-alumina or contains y-type zeolite or the carrier of Beta zeolite and silicon oxide, aluminum oxide or silica-alumina.
10. according to the described method of claim 9, it is characterized in that described carrier is the carrier that contains heavy % of y-type zeolite 40-100 and surplus aluminum oxide.
11., it is characterized in that platinum and the palladium content in catalyzer is the heavy % of 0.1-10 according to the described method of claim 1.
12., it is characterized in that platinum and the palladium content in catalyzer is the heavy % of 0.1-5 according to the described method of claim 11.
13., it is characterized in that the weight ratio of platinum and palladium is 0.1-10 in the catalyzer according to the described method of claim 1.
14., it is characterized in that the weight ratio of platinum and palladium is 0.1-5 in the catalyzer according to the described method of claim 13.
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| CN98117511A CN1081223C (en) | 1998-08-18 | 1998-08-18 | Process for preparing bimetallic catalyst containing pt and pd |
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|---|---|---|---|
| CN98117511A CN1081223C (en) | 1998-08-18 | 1998-08-18 | Process for preparing bimetallic catalyst containing pt and pd |
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| CN1081223C true CN1081223C (en) | 2002-03-20 |
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| CN101745383B (en) * | 2008-12-08 | 2012-08-08 | 中国石油天然气股份有限公司 | Deeply hydrodearomatized catalyst and preparation method |
| FR2968578B1 (en) * | 2010-12-14 | 2013-06-28 | IFP Energies Nouvelles | NOVEL PROCESS FOR THE PREPARATION OF PALLADIUM CATALYSTS AND THE USE OF THESE CATALYSTS IN SELECTIVE HYDROGENATION |
| CN105521778B (en) * | 2014-09-28 | 2017-11-28 | 中国石油化工股份有限公司 | A kind of bimetallic catalyst of platiniferous and palladium and preparation method and application and aromatic saturation process |
| CN104383968B (en) * | 2014-12-07 | 2016-03-02 | 富阳鸿祥技术服务有限公司 | A kind of preparation method of titanium oxide-sepiolite-activated carbon composite carrier |
| CN111085186A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Regular carrier catalyst with desulfurization effect and preparation and application thereof |
| CN111085197A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Regular carrier catalyst with desulfurization effect and preparation and application thereof |
| CN111659378A (en) * | 2020-05-22 | 2020-09-15 | 安徽师范大学 | Montmorillonite-supported palladium-based catalyst, preparation method and application thereof |
| CN112844466B (en) * | 2021-02-02 | 2022-03-25 | 华南农业大学 | Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3943053A (en) * | 1974-10-04 | 1976-03-09 | Ashland Oil, Inc. | Selective hydrogenation of aromatics and olefins in hydrocarbon fractions |
| CN1053636A (en) * | 1990-01-19 | 1991-08-07 | 中国石油化工总公司石油化工科学研究院 | A kind of catalyst used for hydrogenation of distilled oil fraction |
| US5308814A (en) * | 1991-10-01 | 1994-05-03 | Amoco Corporation | Distillate hydrogenation catalyst |
| US5346612A (en) * | 1993-02-19 | 1994-09-13 | Amoco Corporation | Distillate hydrogenation utilizing a catalyst comprising platinum, palladium, and a beta zeolite support |
-
1998
- 1998-08-18 CN CN98117511A patent/CN1081223C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3943053A (en) * | 1974-10-04 | 1976-03-09 | Ashland Oil, Inc. | Selective hydrogenation of aromatics and olefins in hydrocarbon fractions |
| CN1053636A (en) * | 1990-01-19 | 1991-08-07 | 中国石油化工总公司石油化工科学研究院 | A kind of catalyst used for hydrogenation of distilled oil fraction |
| US5308814A (en) * | 1991-10-01 | 1994-05-03 | Amoco Corporation | Distillate hydrogenation catalyst |
| US5346612A (en) * | 1993-02-19 | 1994-09-13 | Amoco Corporation | Distillate hydrogenation utilizing a catalyst comprising platinum, palladium, and a beta zeolite support |
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