CN1231215A - Catalyst containing crystal silicon-aluminate zeolite and noble metal and preparation process thereof - Google Patents
Catalyst containing crystal silicon-aluminate zeolite and noble metal and preparation process thereof Download PDFInfo
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- CN1231215A CN1231215A CN 98101244 CN98101244A CN1231215A CN 1231215 A CN1231215 A CN 1231215A CN 98101244 CN98101244 CN 98101244 CN 98101244 A CN98101244 A CN 98101244A CN 1231215 A CN1231215 A CN 1231215A
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Abstract
The catalyst containing crystal silicoaluminate zeolite and noble metal consists of 0.05-1.5 wt.% of reduced noble metal, 0.05-20 wt.% of adjuvant and the rest of carrier containing acidic zeolite. Said adjuvant can be one or more of elementary substances of oxides of elements selected from IB group, III B group, IVB group, VIB group and VII B group in periodic table of chemical elements. As compared with existent technology, said catalyst possesses higher catalytic activity and higher resistance to sulfur poisoning, so that it is specially applicable to drastic dearomatization of distillate oil containing 3000 ppm of sulfur.
Description
The invention relates to a kind of Catalysts and its preparation method that contains crystal silicon-aluminate zeolite.The Catalysts and its preparation method of more specifically saying so and containing crystal silicon-aluminate zeolite and noble metal about a kind of.
In recent years, the demand of the distillate that boiling point is 125～625 ℃ constantly increases, and generally, the content of alkene and aromatic hydrocarbons is higher in these cuts, need further carry out hydrogenation with the higher product of productive value.For example, in the diesel oil distillate, particularly in the secondary processing diesel oil, arene content can reach more than 70% sometimes, and high arene content has increased the discharging of pollutant, has also reduced the Cetane number of diesel oil simultaneously.Be the environmental requirement of satisfying increasingly stringent and the combustibility that improves diesel oil, it is very necessary that diesel oil is carried out deeply de-aromatizing.Contain the noble metal of VIII family in the periodic table of elements and the catalyst of crystal silicon-aluminate zeolite and can be used for this type of hydrogenation reaction.
EP519573 disclose a kind of on carrier the catalyst of one or more noble metals of load, wherein, described carrier contains a kind of zeolite, this zeolite adopts the preparation of following method: with lattice constant less than 24.65 dusts, silica alumina ratio greater than 5 and alkali metal or the alkaline earth metal content raw material y-type zeolite that is lower than 0.3 heavy % (is benchmark with the tenor) contact with the aqueous solution of one or more alkali metal containings or alkaline-earth metal ions, it is alkali metal or alkaline earth metal content 1.5 times in the raw material y-type zeolite at least that the condition of contact is enough to make final alkali metal or alkaline earth metal content.This catalyst can be used for aromatic saturated hydrogenation reaction in the sour distillate oil.Owing to contain more alkali metal or alkaline-earth metal in the carrier that this catalyst adopted, the acidity of carrier a little less than, its advantage is to have reduced cracking reaction.
Te Kaiping 7-155610 discloses that a kind of the silica alumina ratio of this y-type zeolite is 4-10 at the catalyst that contains at least a VIII of load family noble metal on a kind of carrier of y-type zeolite, lattice constant 24.40-24.60 dust, and alkali metal or alkaline earth metal content are lower than 0.3 heavy %.This catalyst can be used for the hydrogenation reaction of the following feedstock oil of sulfur-bearing 0.2 heavy %.
The shortcoming of the catalyst of above-mentioned noble metal that contains VIII family in the periodic table of elements and crystal silicon-aluminate zeolite is relative responsive to sulphur, increases its catalytic activity with sulfur content and descends seriously, and the existence of sulphur seriously influences activity of such catalysts stability in the oil product.
As everyone knows, in the hydrotreatment process of hydrocarbon ils, aromatic saturated hydrogenation (HDA) is than difficult many of hydrodesulfurization (HDS) and hydrodenitrogeneration (HDN), and the saturated hydrogenation of mononuclear aromatics is more difficult.HDA is the reaction that a strong exothermic reaction and molecular number reduce, and the rising of reaction temperature reduction and reaction pressure is to reacting favourable.Therefore, for the aromatic hydrocarbons in the deep removal diesel oil distillate, generally take two-stage process, first section elder generation is under higher temperature, the Hydrobon catalyst that adopt to be fit to (being generally one or both the catalyst in the oxide of one or both and tungsten and molybdenum in the oxide of nickel-loaded on the alumina support or cobalt) carries out hydrofinishing to remove most sulphur and nitrogen in the oil product, second section under lower temperature, adopt the highly active ortho states noble metal catalyst of going back to make aromatic hydrogenation.
WO96/03208 discloses a kind of catalyst, this catalyst contain a kind of refractory oxides carrier, as reactive metal, content is the chromium that exists with oxide or sulfide of the metal of at least a VIII family of 2～15 heavy % and 5～40 heavy %.This catalyst is to be suitable for above-mentioned first section Hydrobon catalyst, though this catalyst has higher hydrodenitrogeneration, hydrodesulfurization activity, but, its aromatic hydrogenation activity is lower, particularly the mononuclear aromatics hydrogenation activity is very low, and another shortcoming of this catalyst is that bullion content is too high, causes the catalyst cost higher.
One of purpose of the present invention provides a kind ofly to be had high aromatic hydrogenation activity simultaneously and has higher sulfur resistance again, and the noble metal that contains VIII family in the periodic table of elements that bullion content is lower and the catalyst of crystal silicon-aluminate zeolite, two of purpose of the present invention provide this Preparation of catalysts method.
Catalyst provided by the invention by 0.05～1.5 heavy % also noble metal, the auxiliary agent of 0.05～20 heavy % and the carrier that contains acid zeolite of surplus of ortho states form, described auxiliary agent is selected from one or more in I B family, III B family, IV B family, group VIB and VII B family's element simple substance or the oxide in the periodic table of elements.
Preparation of catalysts method provided by the invention is included in the carrier that contains acid zeolite introduces precious metal chemical complex, dry, roasting, and the noble metal of introducing with hydrogen reducing, wherein, also comprise a step of introducing the compound of auxiliary agent on the described carrier that contains acid zeolite before reduction step, the consumption of described precious metal chemical complex and auxiliary compound makes the noble metal that contains 0.05～1.5 heavy % in the final catalyst and the auxiliary agent of 0.05～20 heavy %.
According to catalyst provided by the invention, described auxiliary agent is selected from the simple substance of m family in the periodic table of elements, III B family, IV B group, group VIB and VII B family element or in the oxide one or more, as the simple substance of Cu, Ag, Sc, Y, La system, Ac system, Ti, Zr, Hf, Cr, Mo, W, Mn, Re or in the oxide one or more.The simple substance of the preferred Cu of described auxiliary agent, Ag, La, Ti, Zr, Cr, Mo, W, Mn or in the oxide one or more.The content of described auxiliary agent preferred 0.1～15 heavy %, more preferred 0.1～10 heavy %.
According to catalyst provided by the invention, the described carrier that contains acid zeolite can be the carrier that contains various acid zeolites in the prior art, it can be pure acid zeolite, also can be the composition of acid zeolite and other carrier and/or binding agent, can be the composition of one or more compositions in acid zeolite and aluminium oxide, silica, the aluminium oxide-silicon oxide as it.The described content that contains the carrier mesolite of acid zeolite is 10～100 heavy %, preferred 30～100 heavy %, more preferred 30～80 heavy %.Described zeolite can be selected from the used various zeolites in this field in the prior art, and as various mesopores or large pore zeolite, preferred zeolite is one or more in faujasite, ZSM series zeolite, Beta zeolite, modenite and the omega zeolite.More preferred zeolite is one or more in y-type zeolite, modenite, ZSM series zeolite, the Beta zeolite.
According to catalyst provided by the invention, noble's metal of described VIII family is selected from one or more among Pt, Pd, Ru, Rh, Ir, the Os, more preferred Pt and/or Pd.Gross weight with catalyst is a benchmark, and the content of described VIII family noble metal can be 0.05～1.5 heavy %, preferred 0.1～1.5 heavy %.
In the Preparation of catalysts method provided by the present invention, described acid zeolite is generally a kind of h-type zeolite, described h-type zeolite can prepare with conventional method, as na-pretreated zeolite being carried out ion-exchange with conventional ammonium ion exchange method, dry, form ammonium type zeolite, this ammonium type zeolite can directly be introduced noble metal and/or auxiliary agent, also can be with the precursor mixed-forming of this ammonium type zeolite and described other carrier or binding agent, introduce noble metal or auxiliary agent after drying, the roasting, this ammonium type zeolite can form h-type zeolite through roasting in the Preparation of catalysts process.Described ammonium type zeolite also can directly be prepared into h-type zeolite through roasting, introduces noble metal and/or auxiliary agent again.
The introducing method of described precious metal chemical complex adopts conventional method, as adopting ion-exchange or infusion process.Carrying out ion-exchange or when dipping, the used solution that contains noble metal can be the solution of using always that contains noble metal, and usually, the described solution that contains noble metal is with chloroplatinic acid, palladium bichloride or contain the aqueous solution of noble metal ammino-complex, as chlorination four ammino palladium [Pd (NH
3)
4] Cl
2, nitric acid four ammino palladium [Pd (NH
3)
4] NO
3)
2, chlorination four ammino platinum [Pt (NH
3)
4] Cl
2, nitric acid four ammino platinum [Pt (NH
3)
4] (NO
3)
2Deng the aqueous solution.
The introducing method of described auxiliary compound can adopt ion-exchange or infusion process, more preferred infusion process.Described auxiliary compound is selected from and contains described auxiliary agent soluble compound, as soluble chloride, sulfate, nitrate and/or ammonium salt, as with or without the copper chloride of the crystallization water, copper nitrate, copper sulphate, silver nitrate, lanthanum chloride, lanthanum nitrate, titanium sulfate, zirconyl nitrate, chloride zirconium acyl, chromium chloride, chromic nitrate, ammonium chromate, ammonium molybdate, ammonium tungstate, thing acid ammonium, manganese chloride or manganese nitrate or the like partially.
The introducing of described noble metal and auxiliary compound can be carried out also can successively carrying out simultaneously.As adopt the mode of successively carrying out, preferably carry out drying and roasting behind introducing noble metal or the auxiliary compound.Described drying can be normal temperature to 200 ℃, preferred 100～200 ℃.The temperature of described roasting is 300～700 ℃, and preferred 350～650 ℃, the time of roasting is generally greater than 0.5 hour, preferred 1～6 hour.
Carrier behind introducing noble metal and the auxiliary agent must drying and roasting.Described drying can be normal temperature to 200 ℃, preferred 100～200 ℃.The temperature of described roasting is 300～700 ℃, and preferred 350～650 ℃, the time of roasting is generally worked energetically 0.5 hour, preferred 1～6 hour.
Described condition commonly used when the condition of the carrier of the introducing noble metal after the dry and roasting and auxiliary agent is the reduction noble metal with hydrogen reducing, as 250～500 ℃ of reduction temperatures, preferred 300～500 ℃, the recovery time is generally works energetically 0.5 hour, preferred 1～10 hour.Described reduction is preferably in catalyst and is used for carrying out before the hydrogenation reaction.Sell when therefore, described catalyst is preferably in oxidation state, store or transportation.
As a kind of preferred scheme, the concrete steps of Preparation of catalysts method provided by the invention comprise:
(1), carries out ion-exchange with the aqueous solution and the acid zeolite that contain noble metal, or with the aqueous solution dipping acid zeolite that contains noble metal, dry, the precursor that adds other carrier and/or binding agent then in proportion, mix aftershaping, 100～200 ℃ of dryings, 300～700 ℃ of roastings more than 0.5 hour, preferred 1～6 hour, make the carrier that contains noble metal.
(2), contain the carrier of noble metal, 100～200 ℃ of dryings, and in 300～700 ℃, preferred 350～650 ℃ of roastings are more than 0.5 hour, preferred 1～6 hour, must contain the carrier of precious metal chemical complex and auxiliary compound with the aqueous solution dipping that contains auxiliary agent.
(3), before being used for hydrogenation reaction, under 300～500 ℃ temperature, contain the carrier of precious metal chemical complex and auxiliary compound with hydrogen reducing, promptly get catalyst provided by the invention.
As the preferred scheme of another kind, the concrete steps of Preparation of catalysts method provided by the invention comprise:
(1), earlier acid zeolite is mixed aftershaping, 100～200 ℃ of dryings, 300～700 ℃ of roastings more than 0.5 hour with the precursor of other carrier and/or binding agent in proportion, make the carrier that contains acid zeolite, carry out ion-exchange with the aqueous solution that contains noble metal and acid zeolite, or contain the carrier of acid zeolite with the aqueous solution dipping that contains noble metal, 100～200 ℃ of dryings, 300～700 ℃ of roastings are more than 0.5 hour, preferred 1～6 hour, make the carrier that contains precious metal chemical complex.
(2), contain the carrier of noble metal, 100～200 ℃ of dryings and in 300～700 ℃, preferred 350～650 ℃ of roastings are more than 0.5 hour, preferred 1～6 hour, must contain the carrier of precious metal chemical complex and auxiliary compound with the aqueous solution dipping that contains auxiliary agent.
(3), before being used for hydrogenation reaction, under 300～500 ℃ temperature, contain the carrier of precious metal chemical complex and auxiliary compound with hydrogen reducing, promptly get catalyst provided by the invention.
Catalyst provided by the invention has higher activity than the catalyst with prior art for preparing when same noble metal load capacity, more good anti-sulfur poisonous performance can be used for the hydrotreatment of sulfur-bearing up to the 3000ppm distillate.For example, be reaction raw materials with the hexane solution of the toluene that contains the heavy % of toluene 60 of sulfur-bearing 3000ppm, toluene is carried out hydrogenation reaction, 260～300 ℃ of reaction temperatures, reaction pressure 4 MPas, liquid hourly space velocity (LHSV) 4 hours
-1Under the condition of hydrogen to oil volume ratio 4000, adopt the palladium 0.6 heavy % that contains provided by the invention, when containing the catalyst of chromium or tungsten 0.3～9.6 heavy % and balance carriers (described carrier is made up of 71 heavy %HY zeolites and 29 heavy % aluminium oxide), when 260 ℃ of reaction temperatures, toluene conversion is 22.7～37.7 weight %, during 280 ℃ of reaction temperatures, toluene conversion is 38.3～62.2 heavy %, and during 300 ℃ of reaction temperatures, toluene conversion is 57.6～82.9 heavy %.And adopt specially open the disclosed noble metal of flat 7-155610, zeolite, alumina content is identical but do not contain the catalyst of chromium or tungsten, when 260 ℃ of reaction temperatures, toluene conversion has only 20.1 heavy %, during 280 ℃ of reaction temperatures, toluene conversion has only 35.2 heavy %, during 300 ℃ of reaction temperatures, toluene conversion has only 53.5 heavy %.
Catalyst provided by the invention is compared with the disclosed catalyst of WO96/03208, though have lower bullion content, has higher aromatic hydrocarbons, particularly mononuclear aromatics saturated hydrogenation activity.(be lower than 310 ℃) under lower reaction temperature, catalyst provided by the invention also has the desulfurization removing nitric activity higher than the disclosed catalyst of WO96/03208.For example, adopt the heavy % of palladium 0.58 that contains provided by the invention, chromium 2.4 heavy %, carrier was the catalyst that 5 HY zeolite and 29 heavy % aluminium oxide are formed by 71 heavy % silica alumina ratios, 300 ℃ of reaction temperatures, reaction pressure 4 MPas, liquid hourly space velocity (LHSV) 1 hour
-1Under the condition of hydrogen to oil volume ratio 500, to sulfur content 346ppm, nitrogen content 16ppm, total arene content 24.4 heavy %, mononuclear aromatics content 20.1 heavy %, double ring arene content 3.5 heavy %, the straight-run diesel oil of polycyclic aromatic hydrocarbon content 0.8 heavy % carries out hydrofinishing, in the product behind the hydrogenation, sulfur content drops to 150ppm, and nitrogen content drops to 4ppm, and total arene content and mononuclear aromatics all drop to 4.5 heavy %.And adopt the disclosed palladium 4.31 that contains of WO96/03208 to weigh %, chromium 14.2 heavy % carriers are the catalyst of same vehicle and contain palladium 4.30 heavy %, chromium 14.1 heavy % carriers for by 71 heavy % silica alumina ratios be 11 sealumination modified Y zeolite and 29 heavy % aluminium oxide form catalyst, under the same conditions, to identical feedstock oil hydrofinishing, sulfur content drops to 196ppm and 180ppm respectively in the product, nitrogen content drops to 12ppm and 8ppm respectively, total arene content only drops to 23.6 heavy % and 23.4 heavy % respectively, mononuclear aromatics only drops to 23.2 heavy % and 22.8 heavy % respectively, also contains a certain amount of double ring arene and polycyclic aromatic hydrocarbon in the product.
Catalyst provided by the invention can be used for the fraction oil hydrogenation refining of 125～625 ℃ of boiling points.The distillate hydrogenation that catalyst provided by the invention is particularly suitable for 125～625 ℃ of boiling points takes off aromatic hydrocarbons, to produce the distillate of low arene content.Catalyst provided by the invention is particularly suited for as diesel oil hydrogenation deeply de-aromatizing catalyst for reaction.Its process conditions of using are the hydrogenation technique condition of routine, when taking off the reaction of aromatic hydrocarbons as being used for distillate hydrogenation when catalyst provided by the invention, the hydrogenation technique condition can change in following ranges: 200～350 ℃ of reaction temperatures, preferred 250～320 ℃, reaction pressure is worked energetically 2 MPas, is preferably greater than 3 MPas, liquid hourly space velocity (LHSV) 0.5～10 hour
-1, preferred 1～5 hour
-1, hydrogen to oil volume ratio is preferably greater than 500 greater than 200.
Fig. 1 is a catalyst provided by the invention when being used for the toluene hydrogenation reaction, and toluene conversion is with the variation diagram in reaction time.
The following examples will the present invention will be further described.The raw materials used commercially available prod that is in the example.
Example 1～5
Following example illustrates Catalysts and its preparation method provided by the invention.
(silica alumina ratio is 5 quantitatively to take by weighing the NaY zeolite, sodium oxide content 10.3 heavy %), the ammonium chloride solution that adds quantitative 10 heavy %, 80～90 ℃ of temperature and under stirring, under 10: 1 condition of liquid-solid ratio, carried out ion-exchange 3 hours, filter, spend deionised water to there not being chlorion, 120 ℃ of dryings 2 hours, 550 ℃ of roastings 2 hours are pulverized.Under similarity condition, carry out the exchange of 2 secondary ions again, but not roasting obtains NH
4Y zeolite, its sodium oxide content are 1.2 heavy %.Wherein silica alumina ratio adopts magic angle nuclear magnetic resonance spectrometry to measure, and sodium content adopts aas determination.
(1) load of noble metal active component
Take by weighing NH
4NY zeolite 1000 grams (butt) add 3000 ml deionized water, and dripping 244 ml concns under the stirring at room is the dichloro four ammino palladium solution of 24.6 milligrams of palladium/milliliters, is warming up to 80 ℃, exchange 2 hours, filter, washing is to there not being chlorion, 120 ℃ of dryings 2 hours are pulverized, and obtain PdNH
4The Y zeolite.
(2) shaping of catalyst
With PdNH
4Y zeolite 1000 gram (butt) and boehmite (butt) 400 grams, mixes with small amount of water are even, mix and pinch, and extrusion is made the trilobal cross bar of 1.6 millimeters of circumscribed circle diameters, 120 ℃ of dryings 2 hours, and 650 ℃ of roastings 2 hours obtain containing the carrier of Pd.
(3) preparation of chromium-containing catalyst
Take by weighing the carrier that contains Pd that (2) make, under agitation flooded 4 hours with the ammonium chromate aqueous solution, 120 ℃ of dryings are 2 hours then, and 450 ℃ of roastings 2 hours make the catalyst DA-1 of oxidation state, DA-2.Each raw material addition sees Table 1 in the dipping process of chromium.
Table 1
| Example number | The catalyst numbering | Contain Pd carrier consumption (gram) | Ammonium chromate consumption (gram) | Water consumption (milliliter) |
| ????1 | ????DA-1 | ????100 | ????0.9 | ????75 |
| ????2 | ????DA-2 | ????100 | ????7.4 | ????75 |
(4) preparation of tungsten-containing catalyst
What take by weighing that (2) make contains the Pd carrier, under agitation floods 4 hours with ammonium metatungstate aqueous solution, and 120 ℃ of dryings are 2 hours then, and 550 ℃ of roastings 3 hours make the catalyst DA-3 of oxidation state, DA-4, DA-5.Each raw material consumption sees Table 2 in the dipping process of tungsten.Wherein, the ammonium metatungstate consumption is with (NH
4)
10W
12O
41.11H
2The O meter.
Table 3 has provided the content of metal ingredient in the catalyst that makes.In the table 3, the content of Pd adopts x-ray fluorescence spectrometry, and the content of Cr and W is got by calculating.
Table 2
| Example number | The catalyst numbering | Contain Pd carrier consumption (gram) | Ammonium metatungstate consumption (gram) | Water consumption (milliliter) |
| ????3 | ????DA-3 | ????100 | ????0.9 | ????75 |
| ????4 | ????DA-4 | ????100 | ????3.5 | ????75 |
| ????5 | ????DA-5 | ????100 | ????14.0 | ????75 |
Comparative Examples 1
Open flat 7-155610 example 1 disclosed method according to the spy and prepare catalyst, different is that used zeolite is example 1～5 used NH of the present invention
4The Y zeolite, NH
4Y zeolite and boehmite consumption are with example 1～5, and precious metal chemical complex is dichloro four ammino palladiums, and exchange, drying and roasting condition are also with example 1～5, and the reference catalyst of the oxidation state that obtains is numbered B-1, and its tenor sees Table 3.
Table 3
| Example number | The catalyst numbering | Pd (heavy %) | Cr (heavy %) | W (heavy %) |
| ????1 | ????DA-1 | ????0.60 | ????0.3 | ????/ |
| ????2 | ????DA-2 | ????0.58 | ????2.4 | ????/ |
| ????3 | ????DA-3 | ????0.60 | ????/ | ????0.6 |
| ????4 | ????DA-4 | ????0.58 | ????/ | ????2.4 |
| ????5 | ????DA-5 | ????0.54 | ????/ | ????9.6 |
| Comparative Examples 1 | ????B-1 | ????0.60 | ????/ | ????/ |
Example 6～9
Following example illustrates Catalysts and its preparation method provided by the invention.
(1) carrier moulding
With example 1～5 used NH
4Y zeolite 400 gram (butt) with boehmite 600 grams (butt), mix, add deionized water and mix and pinch, extrusion is made the trilobal cross bar of 1.6 millimeters of circumscribed circle diameters, 120 ℃ of dryings 2 hours, 650 ℃ of roastings 2 hours.
(2) load of active component platinum
With platinum acid chloride solution impregnated carrier 4 hours, 120 ℃ of dryings were 2 hours then according to listed each the raw material consumption of table 4 for carrier after the moulding, and 550 ℃ of roastings 4 hours must contain Pt carrier Z-1 and Z-2.
Table 4
| Carrier consumption (gram) | H 2PtCl 6.6H 2O consumption (gram) | Water consumption (milliliter) | Bearer number |
| ????400 | ????21.4 | ????300 | ????Z-1 |
| ????600 | ????10.7 | ????450 | ????Z-2 |
(3) load of auxiliary agent
What take by weighing quantitatively that (2) make contained Pt carrier Z-1 or Z-2, with the aqueous solution dipping of containing metal auxiliary agent 4 hours.120 ℃ of dryings are 2 hours then, and 600 ℃, roasting 2 hours makes the catalyst DA-6 of oxidation state, DA-7, DA-8, DA-9.Each raw material consumption sees Table 5 in the dipping process of auxiliary agent.
The catalyst DA-6 that makes, DA-7, DA-8, tenor sees Table 6 among the DA-9.In the table 6, the content of Pt adopts x-ray fluorescence spectrometry, and the content of Ti, Mn, Cu and La is got by calculating.
Table 5
| Example number | Used carrier | Carrier heavy (gram) | Maceration extract volume (milliliter) | The maceration extract solute | Solute heavy (gram) |
| ????6 | ????Z-1 | ????100 | ????75 | ?Ti(SO 4) 2 | ?25.1 |
| ????7 | ????Z-2 | ????100 | ????75 | ?Mn(NO 3) 2 | ?16.3 |
| ????8 | ????Z-2 | ????100 | ????75 | ?Cu(NO 3) 2 | ?14.8 |
| ????9 | ????Z-2 | ????100 | ????75 | ?La(NO 3) 3 | ?11.7 |
Comparative Examples 2～3
According to (1) described method and NH in the example 6～9
4The consumption of NaY zeolite, boehmite prepares catalyst carrier, prepares reference catalyst by each raw material consumption shown in (2) described method and the table 4 and condition in the example 6～9, makes the catalyst of oxidation state, and it is numbered B-2 and B-3, and its tenor sees Table 6.
Table 6
| Example number | The catalyst numbering | Pt (heavy %) | The auxiliary agent kind | Auxiliary agent content (heavy %) |
| ????6 | ????DA-6 | ????1.76 | ????Ti | ????5.0 |
| ????7 | ????DA-7 | ????0.59 | ????Mn | ????5.0 |
| ????8 | ????DA-8 | ????0.60 | ????Cu | ????5.0 |
| ????9 | ????DA-9 | ????0.60 | ????La | ????5.0 |
| Comparative Examples 2 | ????B-2 | ????1.81 | ????/ | ????/ |
| Comparative Examples 3 | ????B-3 | ????0.60 | ????/ | ????/ |
Example 10～14
Following example illustrates the catalytic activity and the sulfur resistance of catalyst provided by the invention.
In 10 milliliters of small stationary bed bioreactors, be respectively charged into the catalyst DA-1～DA-5 of the oxidation state of 1.5 milliliters of examples, 3～11 preparations, prior to 300 ℃, with pressure 4 MPas, the hydrogen reducing catalyst of flow velocity 400 ml/min 2 hours.Then, be reaction raw materials with the hexane solution of the toluene that contains the heavy % of toluene 60 that contains 3000ppm sulphur, respectively at 260 ℃, 280 ℃, 300 ℃, pressure 4 MPas, volume space velocity is 4 hours during liquid
-1, under the condition of hydrogen to oil volume ratio 4000 catalyst after the described reduction is carried out activity rating.Stable reaction was taken a sample after 2 hours, used gas chromatographic analysis, and evaluation result sees Table 7.
Comparative Examples 4
This Comparative Examples illustrates that the catalytic activity of catalyst provided by the invention and sulfur resistance obviously are better than prior art.
Press the method reducing catalyst of example 10～14 and the activity of evaluate catalysts, just catalyst system therefor is the reference catalyst B-1 of Comparative Examples 1 preparation, and evaluation result is listed in the table 7.
Table 7
| Catalyst | Toluene conversion, heavy % | ||
| 260 ℃ of reaction temperatures | 280 ℃ of reaction temperatures | 300 ℃ of reaction temperatures | |
| ????DA-1 | ????26.1 | ????39.3 | ????59.5 |
| ????DA-2 | ????52.3 | ????62.2 | ????82.9 |
| ????DA-3 | ????22.7 | ????38.3 | ????57.6 |
| ????DA-4 | ????37.7 | ????46.7 | ????66.1 |
| ????DA-5 | ????35.3 | ????43.2 | ????62.3 |
| ????B-1 | ????20.1 | ????35.2 | ????53.5 |
Example 15～18
This example illustrates the catalytic activity and the sulfur resistance of catalyst provided by the invention.
Press the method reducing catalyst of example 10～14 and the activity of evaluate catalysts, just catalyst system therefor is the oxidized catalyst DA-6 of example 6～9 preparations, DA-7, and DA-8, DA-9, evaluation result sees Table 8.
Comparative Examples 5～6
Following Comparative Examples illustrates that the catalytic activity of catalyst provided by the invention and sulfur resistance obviously are better than prior art.
Press the method reducing catalyst of example 15～18 and the activity of evaluate catalysts, just catalyst system therefor is the reference catalyst B-2 and the B-3 of Comparative Examples 2～3 preparations, and evaluation result is listed in the table 8.
Table 8
| Catalyst | Toluene conversion, heavy % | ||
| 260 ℃ of reaction temperatures | 280 ℃ of reaction temperatures | 300 ℃ of reaction temperatures | |
| ?DA-6 | ????78.9 | ????89.2 | ????95.3 |
| ?DA-7 | ????55.1 | ????65.7 | ????80.6 |
| ?DA-8 | ????60.9 | ????72.3 | ????85.4 |
| ?DA-9 | ????58.1 | ????67.6 | ????82.3 |
| ?B-2 | ????70.3 | ????81.5 | ????90.2 |
| ?B-3 | ????50.6 | ????61.7 | ????77.0 |
The presentation of results of table 7 and table 8, activity of such catalysts provided by the invention and sulfur resistance obviously are better than the existing catalyst of identical bullion content.
Comparative Examples 7
Prepare catalyst according to WO96/03208 example 1 disclosed method, each material consumption and condition.Not being both used zeolite is the NH of example 1～5 preparation
4Y zeolite, the precursor of alumina binder are example 1～5 described boehmite, and catalyst carrier is made up of the Y zeolite of 71 heavy % and the aluminium oxide of 29 heavy %.The catalyst of chromium and palladium carries out presulfurization by the method for WO96/03208 example 1 on carrying, and gets reference catalyst B-4.Tenor among the B-4 is listed in the table 9.
Comparative Examples 8
Prepare catalyst according to WO96/03208 example 1 disclosed method, each material consumption and condition.Not being both used zeolite is sealumination modified Y zeolite (silica alumina ratio is 11, sodium oxide content 0.5 heavy %, Chang Ling oil plant catalyst plant product), and the precursor of alumina binder is example 1～5 a described boehmite.The catalyst of chromium and palladium carries out presulfurization by the method for WO96/03208 example 1 on carrying, and gets reference catalyst B-5.Tenor among the B-5 is listed in the table 9.
Table 9
| Example number | The catalyst numbering | Pd (heavy %) | Cr (heavy %) | W (heavy %) |
| Comparative Examples 4 | ????B-4 | ????4.31 | ????14.2 | ????/ |
| Comparative Examples 5 | ????B-5 | ????4.30 | ????14.1 | ????/ |
Example 19
Hydrogenation activity when this example illustrates catalyst treatment oil product provided by the invention.
The oxidized catalyst DA-2 that the 20 milliliters of examples 2 of packing in 100 milliliters of medium-sized fixed bed reactors prepare, and add 20 milliliters of quartz sands dilutions (catalyst and quartz sand size are all 20～40 orders).In 400 ℃, with pressure 4 MPas, the hydrogen reducing catalyst of flow velocity 400 ml/min 4 hours.With the straight sulfur diesel after the hydrotreatment is reaction raw materials, and the catalyst after the reduction is carried out activity rating, and reaction condition is 300 ℃ of reaction temperatures, reaction pressure 4 MPas, and volume space velocity is 1 hour during liquid
-1, hydrogen to oil volume ratio 500.Stable reaction is sample analysis after 24 hours, and evaluation result sees Table 10.Wherein, the arene content efficient liquid phase chromatographic analysis, sulphur and nitrogen content are analyzed with the microcoulomb method.
Comparative Examples 9～10
Following Comparative Examples explanation reference catalyst B-4, the catalytic activity when B-5 handles oil product.
Press the activity of the method evaluate catalysts of example 19, just catalyst system therefor is respectively reference catalyst B-4, the B-5 of Comparative Examples 7～8 preparations, and catalyst B-4, B-5 are without the process with hydrogen reducing, and evaluation result is listed in the table 10.
Table 10
| Catalyst | Sulfur content ppm | Nitrogen content ppm | Total arene content (heavy %) | Mononuclear aromatics content (heavy %) | Double ring arene content (heavy %) | Polycyclic aromatic hydrocarbon content (heavy %) |
| Feedstock oil | 346 | ????16 | ????24.4 | ????20.1 | ????3.5 | ????0.8 |
| ?DA-2 | ?150 | ????4 | ????4.5 | ????4.5 | ????0 | ????0 |
| ?B-4 | ?196 | ????12 | ????23.6 | ????23.2 | ????0.4 | ????0 |
| ?B-5 | ?180 | ????8 | ????23.4 | ????22.8 | ????0.5 | ????0.1 |
The result of table 10 shows that catalyst provided by the invention is compared with the disclosed catalyst of WO96/03208, though have lower bullion content, has higher aromatic hydrocarbons, particularly mononuclear aromatics saturated hydrogenation activity.(be lower than 310 ℃) under lower reaction temperature, catalyst provided by the invention also has the desulfurization removing nitric activity higher than the disclosed catalyst of WO96/03208.
Example 20
This example further specifies the sulfur resistance and the activity stability thereof of catalyst provided by the invention.
This example is to contain 3000ppmw sulphur, and the hexane solution of the toluene of toluene level 60 heavy % is a reaction raw materials, and the catalyst DA-2 that example 2 is prepared carries out stability experiment.Be reflected in example 10～14 described small stationary bed bioreactors and carry out.Catalyst loading amount, reducing condition are with example 10～14, and reaction condition is except that temperature is 280 ℃, and other is with example 10～14.Toluene conversion over time as shown in Figure 1.
The result of Fig. 1 shows, the hydrogenation reaction that catalyst provided by the invention is used for toluene, when sulfur content in the raw material during up to 3000ppm, prolongation with the reaction time, toluene conversion fluctuates within the specific limits, do not see obvious downward trend, illustrate that catalyst provided by the invention not only has higher activity, and have very high activity stability and good sulfur resistance.
Claims (17)
1. catalyst that contains crystal silicon-aluminate zeolite and noble metal, it is characterized in that this catalyst by 0.05～1.5 heavy % also noble metal, the auxiliary agent of 0.05～20 heavy % and the carrier that contains acid zeolite of surplus of ortho states form, described auxiliary agent is selected from one or more in I B family, III B family, IV B family, group VIB and VII B family's element simple substance or the oxide in the periodic table of elements.
2. according to the described catalyst of claim 1, it is characterized in that described auxiliary agent is selected from the simple substance of Cu, Ag, La, Ti, Zr, Cr, Mo, W, Mn or in the oxide one or more.
3. according to claim 1 or 2 described catalyst, the content that it is characterized in that described auxiliary agent is 0.1～10 heavy %.
4. according to the described catalyst of claim 1, it is characterized in that the content of zeolite is 10～100 heavy % in the described carrier that contains acid zeolite.
5. according to the described catalyst of claim 4, it is characterized in that the content of zeolite is 30～100 heavy % in the described carrier that contains acid zeolite.
6. according to the described catalyst of claim 5, it is characterized in that the content of zeolite is 30～80 heavy % in the described carrier that contains acid zeolite.
7. according to each described catalyst in the claim 1,4,5,6, it is characterized in that described zeolite is selected from one or more in y-type zeolite, modenite, ZSM series zeolite, the Beta zeolite in the described carrier that contains acid zeolite.
8. according to the described catalyst of claim 7, it is characterized in that described zeolite is selected from y-type zeolite.
9. according to the described catalyst of claim 1, it is characterized in that the described carrier that contains acid zeolite refers to the composition that acid zeolite and aluminium oxide are formed.
10. according to the described catalyst of claim 9, it is characterized in that described acid zeolite refers to the HY zeolite.
11., it is characterized in that noble's metal of described VIII family is selected from Pt and/or Pd according to the described catalyst of claim 1.
12., it is characterized in that according to claim 1 or 11 described catalyst, be benchmark with the gross weight of catalyst, the content of noble's metal of described VIII family is 0.1～1.5 heavy %.
13. being included in the carrier that contains acid zeolite, claim 1 Preparation of catalysts method introduces precious metal chemical complex, dry, roasting, and the noble metal of introducing with hydrogen reducing, wherein, also comprise a step of introducing auxiliary compound on the described carrier that contains acid zeolite before reduction step, the consumption of described precious metal chemical complex and auxiliary compound makes the noble metal that contains 0.05～1.5 heavy % in the final catalyst and the auxiliary agent of 0.05～20 heavy %.
14., it is characterized in that the introducing method of described auxiliary compound adopts infusion process according to the described method of claim 13.
15., it is characterized in that described auxiliary compound is selected from soluble chloride, sulfate, nitrate and/or the ammonium salt that contains described auxiliary agent according to the described method of claim 13.
16., it is characterized in that described auxiliary compound is selected from copper chloride, copper nitrate, copper sulphate, silver nitrate, lanthanum chloride, lanthanum nitrate, titanium sulfate, zirconyl nitrate, chloride zirconium acyl, chromium chloride, chromic nitrate, ammonium chromate, ammonium molybdate, ammonium tungstate, ammonium metatungstate, manganese chloride or the manganese nitrate with or without the crystallization water according to the described method of claim 15.
17. according to the described method of claim 13, when it is characterized in that the described noble metal of introducing with hydrogen reducing, reduction temperature is 300～500 ℃, 1～10 hour time of reduction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640122A (en) * | 2012-10-05 | 2018-10-12 | 巴斯夫欧洲公司 | The method for preparing zeolitic material using elemental precursor |
| CN108816278A (en) * | 2018-05-31 | 2018-11-16 | 上海华谊（集团）公司 | A kind of long chain alkane isomerization catalyst and its preparation method and application |
| CN111068747A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing isopropyl benzene by hydrogenolysis and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1020282C (en) * | 1990-05-11 | 1993-04-14 | 中国石油化工总公司石油化工科学研究院 | Catalyst for hydrotreating heavy fraction of oil |
| AU638336B2 (en) * | 1990-07-05 | 1993-06-24 | Mobil Oil Corporation | Production of high viscosity index lubricants |
| EP0519573B1 (en) * | 1991-06-21 | 1995-04-12 | Shell Internationale Researchmaatschappij B.V. | Hydrogenation catalyst and process |
| JP3268961B2 (en) * | 1994-06-06 | 2002-03-25 | 松下電器産業株式会社 | General lighting fluorescent lamps and general lighting fixtures |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640122A (en) * | 2012-10-05 | 2018-10-12 | 巴斯夫欧洲公司 | The method for preparing zeolitic material using elemental precursor |
| CN108816278A (en) * | 2018-05-31 | 2018-11-16 | 上海华谊（集团）公司 | A kind of long chain alkane isomerization catalyst and its preparation method and application |
| CN111068747A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing isopropyl benzene by hydrogenolysis and application thereof |
| CN111068747B (en) * | 2018-10-18 | 2023-08-08 | 中国石油化工股份有限公司 | Catalyst for preparing isopropylbenzene by hydrogenolysis and application thereof |
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