CN103041832A - Aromatic hydrogenation saturation catalyst, preparation method thereof and aromatic hydrogenation catalytic method - Google Patents
Aromatic hydrogenation saturation catalyst, preparation method thereof and aromatic hydrogenation catalytic method Download PDFInfo
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Abstract
The invention discloses an aromatic hydrogenation saturation catalyst. The aromatic hydrogenation saturation catalyst comprises a silicon-aluminum carrier and a hydrogenation active metal component loaded on the silicon-aluminum carrier, and is characterized in that the proportion of pyridine infrared B acid to L acid of the silicon-aluminum carrier, which is measured at the temperature of 200 DEG C, is 0.13-0.15. The invention further provides a preparation method of the aromatic hydrogenation saturation catalyst and the aromatic hydrogenation saturation catalyst obtained by the method. In addition, the invention further provides an aromatic hydrogenation catalytic method utilizing the aromatic hydrogenation saturation catalyst. The aromatic hydrogenation saturation catalyst provided by the invention has the advantages of obvious mesoporous property and centralized pore distribution, simultaneously contains centers of B acid and L acid, and obviously increases the proportion of the B acid to the L acid in comparison with the prior art. Data of an embodiment shows that compared with the prior art, namely a contrast example 1, the hydrogenation activity of the aromatic hydrogenation saturation catalyst disclosed by the invention can be increased by above 20%.
Description
Technical field
The present invention relates to a kind of hydrocatalyst for saturating arylhydrocarbon and preparation method thereof, and a kind of aromatic hydrogenation catalysis process.
Background technology
It is saturated to adopt metal catalyst to carry out aromatic hydrogenation under lower reaction temperature, is to realize a kind of effective means of taking off aromatic hydrocarbons such as clean fuel oil, white oil and top-grade lubricating oil base oil even depth.
Because the metal mold hydrocatalyst for saturating arylhydrocarbon is to sulfur sensitive, therefore prior art is carried out the refining desulfurization raw material except needs adopt the hydrogenation catalyst of sulphided state, more pay attention to day by day is to the exploitation of the metal catalyst of anti-sulphur, and mainly studied from hydrogenation activity component and two aspects of bearer type.
At Ind.Eng.Chem.Res.1995,34,4284-4289 and Ind.Eng.Chem.Res.1995, all reported among 34, the 4277-4283 add the second metal (such as palladium) in the catalyst to improve the method for the anti-sulphur ability of catalyst.
CN 1228718A discloses a kind of platinum, the palladium bimetallic hydrocarbon conversion catalyst of anti-sulphur, this catalyst comprises platinum-palldium alloy and matrix of oxide, wherein the mol ratio of the platinum in alloy and palladium is 2.5: 1-1: 2.5, preferred 2: 1-1: 1, most preferably 1: 1.5, matrix of oxide contains at least 30 % by weight, the silica of preferred 40 % by weight, catalyst total pore volume＞0.45cm
3/ g, wherein at least 1%, preferred at least 3% total pore volume be the aperture greater than
Macropore.
By changing bearer type and optimizing the carrier hole structure and can improve catalyst aromatic saturation performance and catalyst sulfur resistance.Document " petroleum journal (PETROLEUM PROCESSING) 1999,15 (3), 41-45 " has been reported and has been adopted the noble metal catalyst of the silica-alumina supports preparation that contains B acid to have better sulfur resistance.Optimize carrier (catalyst) pore structure, reactive metal is distributed on effective interval and the surface, adjust simultaneously carrier surface character, with further raising reactive metal utilization rate, make reactive metal all change into as far as possible effective activated centre.Therefore carrier hole structure and surface nature are most important on the impact of catalyst performance.
The carrier of hydrocatalyst for saturating arylhydrocarbon adopts aluminium oxide or amorphous silicon aluminum more.Amorphous aluminum silicide material preparation method has multiple, adopts the silica-alumina supports of suitable preparation technology's preparation, can make carrier have optimum pore structure and surface acidity, and then affect hydrogenation activity and the sulfur resistance of noble metal catalyst.
Summary of the invention
The hydrocatalyst for saturating arylhydrocarbon that the purpose of this invention is to provide a kind of high aromatic saturation performance, this hydrocatalyst for saturating arylhydrocarbon is take a kind of acid silica-alumina material of high B acid ratio as carrier; In addition, the present invention also provides preparation method and a kind of aromatic hydrogenation catalysis process of this hydrocatalyst for saturating arylhydrocarbon.
The invention provides a kind of hydrocatalyst for saturating arylhydrocarbon, this hydrocatalyst for saturating arylhydrocarbon comprises silica-alumina supports and the hydrogenation active metals component that loads on this silica-alumina supports, it is characterized in that described silica-alumina supports is 0.13-0.15 in the ratio of 200 ℃ of infrared B acid of the pyridine that records and L acid.
The present invention also provides a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon, it is characterized in that, the method may further comprise the steps, and (1) is neutralized into glue with aluminium source and aqueous slkali, obtains containing aluminium paste liquid; (2) in oxide, be 1 according to the sial weight ratio: the ratio of 1-1.5, add the silicon source in the aluminium paste liquid to described containing, ageing obtains solid sediment, and filtration obtains filter cake; (3) making beating of described filter cake is obtained the sial slurries, take the dry weight of described filter cake as benchmark, the fluosilicic acid of 1-12 % by weight is contacted with described sial slurries mixing, obtain contacting products therefrom; (4) described contact products therefrom filtered successively, wash, the first drying, moulding, the second drying and roasting, obtain the shaping of catalyst carrier; (5) described shaping of catalyst carrier is contacted with the soluble-salt solution of hydrogenation active metals, then carry out drying and roasting.And provide the hydrocatalyst for saturating arylhydrocarbon that is prepared by the method.
In addition, the present invention also provides a kind of aromatic hydrogenation catalysis process, it is characterized in that, the method comprises, under the aromatic hydrogenation catalytic condition, in the presence of hydrocatalyst for saturating arylhydrocarbon, will contain raw material and the hydrogen haptoreaction of aromatic hydrocarbons, wherein, described hydrocatalyst for saturating arylhydrocarbon is above-mentioned hydrocatalyst for saturating arylhydrocarbon.
The middle pore property of hydrocatalyst for saturating arylhydrocarbon provided by the invention is obvious, and pore distribution concentration contains B acid and L acid site simultaneously, and the ratio of B acid and L acid obviously improves than prior art.Can find out from the data of embodiment, be that Comparative Examples 1 is compared with prior art, and the hydrogenation activity of hydrocatalyst for saturating arylhydrocarbon of the present invention is high more than 20%.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, and consists of the part of specification, is used from explanation the present invention with the following specific embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the X-ray diffraction spectrogram of silica-alumina supports and the prior art silica-alumina supports of prepared in accordance with the method for the present invention.
The specific embodiment
The invention provides a kind of hydrocatalyst for saturating arylhydrocarbon, this hydrocatalyst for saturating arylhydrocarbon comprises silica-alumina supports and the hydrogenation active metals component that loads on this silica-alumina supports, it is characterized in that described silica-alumina supports is 0.13-0.15 in the ratio of 200 ℃ of infrared B acid of the pyridine that records and L acid.
The infrared B acid of described pyridine is to adopt pyridine temperature programming infra-red sepectrometry to obtain with L acid.With sample self-supporting compressing tablet, place the original position pond of infrared spectrometer to seal, be warming up to 350 ℃ and be evacuated to 10
-3Pa, constant temperature remove the gas molecule of sample absorption after 1 hour; Import pyridine steam maintenance adsorption equilibrium 30 minutes after being cooled to room temperature, then be warming up to 200 ℃, again be evacuated to 10
-3Pa and under this vacuum desorption 30 minutes, be down to room temperature and take the photograph spectrum, sweep limits is 1400-1700cm
-1, can obtain sample through the pyridine adsorption infrared spectrogram of 200 ℃ of desorptions.According to 1540cm in the pyridine adsorption infrared spectrogram
-1And 1450cm
-1The absorbance of characteristic absorption peak is calculated the relative quantity in B acid site and L acid site.
According to the present invention, preferably, take the weight of silica-alumina supports as benchmark, described silica-alumina supports contains the silicon in oxide of 42-46 % by weight, the aluminium in oxide of 52-56 % by weight, the alkali metal in oxide of 0-0.2 % by weight, be preferably the 0.05-0.15 % by weight in the alkali metal of oxide and the fluorine in element of 0.5-4 % by weight, be preferably the fluorine in element of 1-3 % by weight.
According to the present invention, preferably, described silica-alumina supports has the boehmite crystal phase structure; The specific area of described silica-alumina supports is 200-400m
2/ g, more preferably 300-350m
2/ g; Pore volume is 0.5-1.0ml/g, and more preferably 0.7-0.9ml/g most preferably is 0.8-0.9ml/g; Average pore diameter is 8-15nm, and more preferably 10-13nm most preferably is 10-11nm.
The difference of hydrocatalyst for saturating arylhydrocarbon of the present invention and prior art is the improvement of carrier, and therefore, the hydrogenation active metals in the described hydrogenation active metals component can be the hydrogenation active metals of the various routines of aromatic hydrogenation catalytic field.Preferably, hydrogenation active metals in the described hydrogenation active metals component is at least a in the periodic table of elements group VIII metal, include but not limited at least a in cobalt, nickel, ruthenium, rhodium, palladium and the platinum, further preferably, the hydrogenation active metals in the described hydrogenation active metals component is platinum and palladium.
Similarly, the ratio of carrier and hydrogenation active metals also can be the various proportions of routine in the described hydrocatalyst for saturating arylhydrocarbon, preferably, take the weight of hydrocatalyst for saturating arylhydrocarbon as benchmark and with oxide, the content of hydrogenation active metals component is the 0.1-5 % by weight in the described hydrocatalyst for saturating arylhydrocarbon, more preferably the 0.2-2 % by weight.When described hydrogenation active metals was platinum and palladium, take the weight of described hydrogenation active metals as benchmark, the content of described palladium was preferably the 30-99 % by weight, more preferably the 50-80 % by weight.
The present invention also provides a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon, it is characterized in that, the method may further comprise the steps,
(1) aluminium source and aqueous slkali are neutralized into glue, obtain containing aluminium paste liquid;
(2) in oxide, be 1 according to the sial weight ratio: the ratio of 1-1.5, add the silicon source in the aluminium paste liquid to described containing, ageing obtains solid sediment, and filtration obtains filter cake;
(3) described filter cake making beating is obtained the sial slurries, take the dry weight of described filter cake as benchmark, the fluosilicic acid of 1-12 % by weight is contacted with described sial slurries mixing, obtain contacting products therefrom, preferably the fluosilicic acid with the 4-12 % by weight contacts with described sial slurries mixing, obtains contacting products therefrom;
(4) described contact products therefrom filtered successively, wash, the first drying, moulding, the second drying and roasting, obtain the shaping of catalyst carrier;
(5) described shaping of catalyst carrier is contacted with the soluble-salt solution of hydrogenation active metals, then carry out drying and roasting.
According to the present invention, in the step (1), the condition that described aluminium source and aqueous slkali and they are neutralized into glue all can be the various selections of this area routine.Preferably, described aluminium source is selected from least a in aluminum nitrate, aluminum sulfate and the aluminium chloride; Described aqueous slkali is selected from least a in ammoniacal liquor, potassium hydroxide solution, sodium hydroxide solution and the sodium aluminate solution.
The described step that is neutralized into glue can comprise, under stirring condition, described aqueous slkali is dripped in the solution of aluminium source, stops after reaching into the terminal point of glue, and the endpoint pH of described one-tenth glue is preferably 7-11, more preferably 8-10.The described temperature that is neutralized into glue can be 20-90 ℃, is preferably 40-70 ℃.
According to the present invention, in the step (2), described silicon source also can be the various silicon source of this area routine, and preferably, described silicon source is selected from least a in waterglass, sodium metasilicate, silicon tetraethyl and the silica.
In the step (2), described ageing can be the aging step of this area routine, and for example, the temperature of ageing is 20-100 ℃, is preferably 60-90 ℃; Time is 1-10 hour, is preferably 2-5 hour.
According to the present invention, when in containing aluminium paste liquid, having alkali metal ion, step also preferably includes in (2), before filtration, described solid sediment carried out ammonium exchange or acid exchange, the condition of ammonium exchange or acid exchange so that in the solid sediment after the exchange take the alkali-metal content of oxide below 0.2 % by weight.
Particularly, the step of described ammonium exchange can for, the solid sediment that will obtain through ripening according to the dry weight of solid sediment: ammonium salt: water is 1: the weight ratio of 0.1-1: 10-30 20-100 ℃ of lower the exchange 1-3 time, exchanges 0.5-1 hour at every turn.Described ammonium salt is preferably at least a in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and the carbonic hydroammonium.
The step of described acid exchange can for, the solid sediment that will obtain through ripening according to the dry weight of solid sediment: acid: water is 1: the weight ratio of 0.03-0.30: 5-30 exchanges 0.2 hour at least under 20-100 ℃.Described acid is preferably inorganic acid, and for example, described acid can be selected from least a in sulfuric acid, hydrochloric acid and the nitric acid.
Among the present invention, the step of described making beating is as well known to those skilled in the art, and preferably, the method for making beating is for to add entry in described filter cake, and makes filter cake and water fully be mixed into pulpous state.The present invention is to the not special restriction of the addition of described water, and preferably, the adding weight of described water is 5-20 times of described filter cake dry weight.
According to the present invention, in the step (3), the mode of described mixing contact can be for joining fluosilicic acid in the described sial slurries, also can be for the sial slurries are joined in the described fluosilicic acid, preferably, the mode of described mixing contact is for to join fluosilicic acid in the described sial slurries.
According to the present invention, in the step (3), the condition of described mixing contact preferably includes, and temperature is 20-80 ℃, and the time is more than 0.5 hour, and further preferably, temperature is 40-70 ℃, and the time is 0.5-3 hour.
According to the present invention, in the step (4), the condition of described filtration and washing can be the condition of this area routine, as washing with a large amount of water.
In the step (4), described the first drying can adopt baking oven, mesh-belt kiln, converter and fluid bed to carry out drying, when adopting heating means such as baking oven to carry out drying, the condition of described the first drying preferably includes, and temperature is 100-200 ℃, and the time is 4-20 hour, further preferably, temperature is 100-150 ℃, and the time is 5-15 hour, to remove free water.
In the step (4), the condition of described moulding, the second drying and roasting also can be the condition of this area routine.For example, can optionally will make the arbitrarily article shaped of convenient operation through the first dried described contact products therefrom, such as sphere, sheet shape and bar shaped, described moulding can be carried out according to a conventional method, such as methods such as compressing tablet, spin or extrusions.In a kind of preferred embodiment, the forming method of described carrier comprises through first dried contact products therefrom extrusion molding on double screw banded extruder.
Wherein, be to guarantee carrying out smoothly of extruded moulding, preferably to through adding an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid at least a), extrusion aid (as being sesbania powder and/or cellulose) in the first dried contact products therefrom and mixing.
When extrusion molding, the kind of the consumption of described water and described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not repeat them here.
Described the second drying also can be conventional method, as adopt baking oven, mesh-belt kiln, converter and fluid bed to carry out drying, when adopting heating means such as baking oven to carry out drying, preferred baking temperature is 50-200 ℃, be 0.3-12 hour drying time, further preferably, baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.
The method of described roasting and condition can be conventional method and the condition that adopts in the catalyst carrier preparation process, as adopt mesh-belt kiln, vertical heater, horizontal chamber furnace (oven) and converter to carry out roasting, the condition of described roasting is preferably, at 400-900 ℃ of roasting 1-12 hour, further preferably, at 500-750 ℃ of roasting 2-8 hour.
According to the present invention, the conditions such as the kind of the contact conditions in the step (5), the soluble-salt solution of hydrogenation active metals and content all can be the normal condition of preparation catalyst.
Particularly, in the step (5), the method for described contact can be for soaking or spray.The soluble-salt solution of the hydrogenation active metals with respect to every liter, the addition of described shaping of catalyst carrier are preferably the 800-1200 gram.In element, the concentration of hydrogenation active metals is preferably 1-20g/L in the soluble-salt solution of hydrogenation active metals.The soluble-salt solution of described hydrogenation active metals can be in nitrate solution, acetate solution, carbonate solution, chloride solution and the soluble complexes solution of hydrogenation active metals at least a.The time of dipping can be 2-10 hour.
The kind of described hydrogenation active metals is described corresponding with relative consumption and preamble, does not repeat them here.
The shaping of catalyst carrier also will carry out drying and roasting with after the soluble solution of hydrogenation active metals contacts.The condition of described drying and roasting can be the condition of this area routine, is 100-200 ℃ such as the temperature of drying, and the time is 2-12 hour; The temperature of roasting is 300-600 ℃, and the time is 2-10 hour.
Described catalyst also preferably includes reduction step before using, and described reduction is preferably carried out under hydrogen atmosphere, and reduction temperature is preferably 300-550 ℃, and the recovery time is preferably 2-10 hour.
The present invention also provides the hydrocatalyst for saturating arylhydrocarbon that is made by said method.
The invention provides a kind of aromatic hydrogenation catalysis process, it is characterized in that, the method comprises, under the aromatic hydrogenation catalytic condition, in the presence of hydrocatalyst for saturating arylhydrocarbon, raw material and the hydrogen haptoreaction that will contain aromatic hydrocarbons, wherein, described hydrocatalyst for saturating arylhydrocarbon is above-mentioned hydrocatalyst for saturating arylhydrocarbon.
Wherein, described aromatic hydrogenation catalytic condition can be the various conditions of this area routine, and for example, temperature is 100-200 ℃, and pressure is 0.5-2MPa, and hydrogen to oil volume ratio is 1000-3000, and volume space velocity is 1-15h during liquid
-1
Catalyst of the present invention can be used for the deepness hydrogenation dearomatization process that various aromatic hydrogenation saturated reaction, particularly clean fuel oil, white oil, lubricating oil and the basic wet goods that contain the raw material of aromatic hydrocarbons contain aroamtic hydrocarbon raw material.
Below will describe the present invention by embodiment.In each embodiment, the Na of vector product
2O, Al
2O
3, SiO
2, F content measures (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publishes) with x-ray fluorescence method.Phase and crystallinity data adopt X-ray diffraction method to measure.The materialization such as specific surface, pore structure the data nitrogen absorption under low temperature-desorption method is measured.The infrared pyridine adsorption in site measurement of acid the data method is measured.Tenor in the catalyst is analyzed with x-ray fluorescence method.
Present embodiment is used for illustrating the preparation of hydrocatalyst for saturating arylhydrocarbon C-1 of the present invention:
(1) be 90g Al with concentration
2O
3The Al of the 1.0L of/L
2(SO
4)
3Solution and concentration are 102gAl
2O
3/ L, causticity are than the NaAlO that is 2.5 1.0L
2Solution and stream add in the continuous gel formation still, are held in glue pH=10, and the temperature that is neutralized into glue is 70 ℃, collect to contain aluminium paste liquid, and adding concentration under stirring condition is 60g SiO
2The waterglass of the 2.5L of/L is warming up to 80 ℃ of ageings 2 hours, filters to obtain the sial sediment; Use NH
4Cl solution is pressed the sedimentary dry weight of sial: ammonium salt: H
2O=1: 0.8: 15 weight ratio, under 60 ℃, the sial sediment is carried out ion-exchange, to remove sodium ion, repeat twice exchange, carried out 0.5 hour at every turn, and then filtered and obtain filter cake, add water the making beating of gained filter cake is obtained the sial slurries, and fluosilicic acid is added in the sial slurries mixes contact, the addition of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2The weight ratio of O is 0.04: 1: 8, and the condition of described mixing contact is 60 ℃ of lower reactions 1 hour, namely gets silica-alumina supports in 15 hours in 120 ℃ of lower dryings after the filtration washing, is designated as BSA-1.
The X-ray diffraction spectral line of BSA-1 is shown among Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in the table 1; Hole parameter and infrared acid data rows are in table 2.
(2) BSA-1 is extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, the butterfly bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains carrier strip SA-1 through 120 ℃ of dryings.
(3) with 992 milligrams of nitric acid, four ammonia platinum [Pt (NH
3)
4(NO
3)
2] and 840 milligrams of nitric acid four ammonia palladium [Pd (NH
3)
4(NO
3)
2] in deionized water, dissolve, be mixed with the maceration extract of 100mL, immerse 100 gram carrier S A-1 in the maceration extract fully, flooded 6 hours, through 120 ℃ of oven dry, 500 ℃ of roastings 4 hours, 350 ℃ of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after the reduction is designated as C-1, and its composition sees Table 3.
Comparative Examples 1
This Comparative Examples is used for the preparation of explanation comparative catalyst DBC:
(1) carry out according to the step (1) of embodiment 1, different is, filter obtain filter cake after, do not pull an oar, do not add fluosilicic acid yet, but directly filter cake namely got the contrast silica-alumina supports in lower dry 15 hours at 120 ℃, be designated as DB-1.
The X-ray diffraction spectral line of DB-1 is shown among Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in the table 1; Hole parameter and infrared acid data rows are in table 2.
(2) according to the step (2) of embodiment 1, DB-1 is made carrier strip DBSA-1.
(3) according to the step (3) of embodiment 1, DBSA-1 is carried out load, obtain catalyst DBC, its composition sees Table 3.
Present embodiment is used for illustrating the preparation of hydrocatalyst for saturating arylhydrocarbon C-2 of the present invention:
Preparation process is with embodiment 1, and different is that the addition of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2The weight ratio of O is 0.12: 1: 8, obtains silica-alumina supports, is designated as BSA-2.
The X-ray diffraction spectral line of BSA-2 is shown among Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in the table 1; Hole parameter and infrared acid data rows are in table 2.
(2) BSA-2 is extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, the butterfly bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains carrier strip SA-2 through 120 ℃ of dryings.
(3) with 893 milligrams of nitric acid, four ammonia platinum [Pt (NH
3)
4(NO
3)
2] and 2941 milligrams of nitric acid four ammonia palladium [Pd (NH
3)
4(NO
3)
2] in deionized water, dissolve, be mixed with the maceration extract of 110mL, immerse 100 gram carrier S A-2 in the maceration extract fully, flood after 10 hours and filter, through 120 ℃ of oven dry, 550 ℃ of roastings 4 hours, 450 ℃ of hydrogen reducings 3 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after the reduction is designated as C-2, and its composition sees Table 3.
Present embodiment is used for illustrating the preparation of hydrocatalyst for saturating arylhydrocarbon C-3 of the present invention:
Be 90g Al with concentration
2O
3The Al of the 0.8L of/L
2(SO
4)
3Solution and concentration are 102g Al
2O
3/ L, causticity are than the NaAlO that is 1.7 1.0L
2Solution and stream add in the continuous gel formation still, are held in glue pH=9, and the temperature that is neutralized into glue is 60 ℃, collect to contain aluminium paste liquid, and adding concentration under stirring condition is 60gSiO
2The waterglass of the 2.5L of/L is warming up to 80 ℃ of ageings 2 hours, filters to obtain the sial sediment; Use NH
4Cl solution is pressed the sedimentary dry weight of sial: ammonium salt: H
2O=1: 0.6: 15 weight ratio, at 60 ℃ the sial sediment is carried out ion-exchange and remove sodium ion, repeat 3 exchanges, carried out 0.5 hour at every turn, then filter and obtain filter cake, add water the making beating of gained filter cake is obtained the sial slurries, and fluosilicic acid is added to mixing contact in the sial slurries, the addition of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2The weight ratio of O is 0.10: 1: 10, and the condition of described mixing contact is 40 ℃ of lower reactions 1.5 hours, namely gets silica-alumina supports in 15 hours in 120 ℃ of lower dryings after the filtration washing, is designated as BSA-3.
The X-ray diffraction spectral line of BSA-3 is shown among Fig. 1; Degree of crystallinity and elementary analytical chemistry form lists in the table 1; Hole parameter and infrared acid data rows are in table 2.
(2) BSA-3 is extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, the butterfly bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains carrier strip SA-3 through 120 ℃ of dryings.
(3) with 893 milligrams of nitric acid, four ammonia platinum [Pt (NH
3)
4(NO
3)
2] and 2101 milligrams of nitric acid four ammonia palladium [Pd (NH
3)
4(NO
3)
2] in deionized water, dissolve, be mixed with the maceration extract of 105mL, immerse 100 gram carrier S A-3 in the maceration extract fully, flooded 3 hours, through 120 ℃ of oven dry, 450 ℃ of roastings 4 hours, 450 ℃ of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after the reduction is designated as C-3, and its composition sees Table 3.
Embodiment 4
Present embodiment is used for illustrating the preparation of hydrocatalyst for saturating arylhydrocarbon C-4 of the present invention:
Be 90g Al with concentration
2O
3The Al of the 1.35L of/L
2(SO
4)
3Solution and concentration are 102g Al
2O
3/ L, causticity are than the NaAlO that is 1.7 1.0L
2Solution and stream add in the continuous gel formation still, are held in glue pH=9, and the temperature that is neutralized into glue is 60 ℃, collect to contain aluminium paste liquid, and adding concentration under stirring condition is 60gSiO
2The waterglass of the 2.6L of/L is warming up to 80 ℃ of ageings 2 hours, filters to obtain the sial sediment; Press the sedimentary dry weight of sial with hydrochloric acid solution: hydrogen chloride: H
2O=1: 0.1: 10 weight ratio, under 70 ℃, the sial sediment is carried out ion-exchange and remove sodium ion, exchange was carried out 0.5 hour, then filter and obtain filter cake, add water the making beating of gained filter cake is obtained the sial slurries, under intense agitation, described sial slurries are added to mixing contact in the fluosilicic acid weak solution (concentration is 8.25 % by weight), the consumption of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2The weight ratio of O is 0.09: 1: 12, and the condition of described mixing contact is 50 ℃ of lower reactions 2 hours, namely gets silica-alumina supports in 15 hours in 120 ℃ of lower dryings after the filtration washing, is designated as BSA-4.
The degree of crystallinity of BSA-4 and elementary analytical chemistry form lists in the table 1; Hole parameter and infrared acid data rows are in table 2.
(2) BSA-4 is extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, the butterfly bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains carrier strip SA-4 through 120 ℃ of dryings.
(3) with 893 milligrams of nitric acid, four ammonia platinum [Pt (NH
3)
4(NO
3)
2] and 2101 milligrams of nitric acid four ammonia palladium [Pd (NH
3)
4(NO
3)
2] in deionized water, dissolve, be formulated as the 105mL maceration extract, 100 gram carrier S A-4 are immersed in the maceration extract fully, flooded 3 hours, through 120 ℃ of oven dry, 450 ℃ of roastings 4 hours, 450 ℃ of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after the reduction is designated as C-4, and its composition sees Table 3.
Table 1
| The sample title | Degree of crystallinity (%) | Na 2O(％) | Al 2O 3(％) | SiO 2(％) | F(％) |
| BSA-1 | 28.5 | 0.12 | 54.5 | 43.1 | 2.09 |
| BSA-2 | 33.4 | 0.12 | 53.0 | 44.4 | 2.31 |
| BSA-3 | 30.7 | 0.09 | 52.9 | 44.3 | 2.25 |
| BSA-4 | 32.4 | 0.10 | 53.8 | 43.7 | 2.14 |
| DB-1 | 24.5 | 0.14 | 55.2 | 44.1 | 0 |
Table 2
Table 3
| The sample title | Pt content (% by weight) | Pd content (% by weight) |
| C-1 | 0.50 | 0.30 |
| C-2 | 0.45 | 1.05 |
| C-3 | 0.45 | 0.75 |
| C-4 | 0.45 | 0.75 |
| DBC | 0.50 | 0.30 |
By table 1 and as seen from Table 2, the silica-alumina supports in the catalyst provided by the invention is compared with the silica-alumina supports in the Comparative Examples 1, and degree of crystallinity is higher, and B acid significantly improves (exceeding more than one times than Comparative Examples) with the ratio of L acid.
Comparative Examples 2
This Comparative Examples is used for the aromatic hydrogenation activity of explanation comparative catalyst DBC.
On the little inverse spectral apparatus of continuous-flow, catalyst is carried out activity rating, feedstock oil is the hexane solution that contains 10 % by weight toluene, the catalyst loading amount is 1 gram, reaction condition is: pressure is 1.0 MPas, the feedstock oil input is 0.2 ml/min, hydrogen to oil volume ratio is 2000, and temperature is 150 ℃, and reacting took a sample after 3 hours carries out online gas chromatographic analysis.Toluene hydrogenation activity A by formula I calculates that (x is the toluene hydrogenation conversion in the formula, x=100 * (10%-P
Toluene level in the product)/10%):
Embodiment 5-8
The aromatic hydrogenation activity of hydrocatalyst for saturating arylhydrocarbon of the present invention is described.
Evaluating catalyst method (being the assay method of toluene hydrogenation activity) is with Comparative Examples 2.Take the toluene hydrogenation activity of comparative catalyst DBC as 100, then the relative toluene hydrogenation activity of catalyst of the present invention can calculate according to formula II:
Relative toluene hydrogenation activity=A
C/ A
DBC* 100% formula II
A among the formula II
CBe the toluene hydrogenation activity of each catalyst of the present invention, A
DBCToluene hydrogenation activity for comparative catalyst DBC.Activity rating result (being relative toluene hydrogenation activity) lists in the table 4.
Table 4
| The sample title | Relative toluene hydrogenation activity |
| C-1 | 120 |
| C-2 | 128 |
| C-3 | 122 |
| C-4 | 126 |
| DBC | 100 |
Activity rating is the result show, the toluene hydrogenation activity comparison of catalyst of the present invention is higher more than 20% than the toluene hydrogenation activity of catalyst DBC.
In addition, also can carry out any combination between the various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (20)
1. hydrocatalyst for saturating arylhydrocarbon, this hydrocatalyst for saturating arylhydrocarbon comprises silica-alumina supports and the hydrogenation active metals component that loads on this silica-alumina supports, it is characterized in that described silica-alumina supports is 0.13-0.15 in the ratio of 200 ℃ of infrared B acid of the pyridine that records and L acid.
2. hydrocatalyst for saturating arylhydrocarbon according to claim 1, wherein, take the weight of silica-alumina supports as benchmark, described silica-alumina supports contains the silicon in oxide of 42-46 % by weight, the aluminium in oxide of 52-56 % by weight, the alkali metal in oxide of 0-0.2 % by weight, and the fluorine in element of 0.5-4 % by weight.
3. hydrocatalyst for saturating arylhydrocarbon according to claim 1, wherein, described silica-alumina supports has the boehmite crystal phase structure; The specific area of described silica-alumina supports is 200-400m
2/ g, pore volume are 0.5-1.0ml/g, and average pore diameter is 8-15nm.
4. hydrocatalyst for saturating arylhydrocarbon according to claim 1, wherein, the hydrogenation active metals in the described hydrogenation active metals component is at least a in the periodic table of elements group VIII metal.
5. hydrocatalyst for saturating arylhydrocarbon according to claim 4, wherein, the hydrogenation active metals in the described hydrogenation active metals component is platinum and palladium.
6. the described hydrocatalyst for saturating arylhydrocarbon of any one according to claim 1-5, wherein, take the weight of hydrocatalyst for saturating arylhydrocarbon as benchmark and with oxide, the content of hydrogenation active metals component is the 0.1-5 % by weight in the described hydrocatalyst for saturating arylhydrocarbon.
7. the preparation method of a hydrocatalyst for saturating arylhydrocarbon is characterized in that, the method may further comprise the steps,
(1) aluminium source and aqueous slkali are neutralized into glue, obtain containing aluminium paste liquid;
(2) in oxide, be 1 according to the sial weight ratio: the ratio of 1-1.5, add the silicon source in the aluminium paste liquid to described containing, ageing obtains solid sediment, and filtration obtains filter cake;
(3) making beating of described filter cake is obtained the sial slurries, take the dry weight of described filter cake as benchmark, the fluosilicic acid of 1-12 % by weight is contacted with described sial slurries mixing, obtain contacting products therefrom;
(4) described contact products therefrom filtered successively, wash, the first drying, moulding, the second drying and roasting, obtain the shaping of catalyst carrier;
(5) described shaping of catalyst carrier is contacted with the soluble-salt solution of hydrogenation active metals, then carry out drying and roasting.
8. method according to claim 7, wherein, in the step (1), at least a in white aluminum nitrate, aluminum sulfate and the aluminium chloride selected in described aluminium source; Described aqueous slkali selects at least a in white ammoniacal liquor, potassium hydroxide solution, sodium hydroxide solution and the sodium aluminate solution.
9. method according to claim 7, wherein, in the step (1), the endpoint pH of described one-tenth glue is 7-11.
10. method according to claim 7, wherein, in the step (2), at least a in plain boiled water glass, sodium metasilicate, silicon tetraethyl and the silica selected in described silicon source.
11. method according to claim 7, wherein, step also comprises in (2), before filtration, described solid sediment carried out ammonium exchange or acid exchange, the condition of ammonium exchange or acid exchange so that in the solid sediment after the exchange take the alkali-metal content of oxide below 0.2 % by weight.
12. method according to claim 7, wherein, in the step (3), the mode of described mixing contact is for to join fluosilicic acid in the described sial slurries.
13. method according to claim 7, wherein, in the step (3), the condition of described mixing contact comprises that temperature is 20-80 ℃, and the time is more than 0.5 hour.
14. the described method of any one according to claim 7-13, wherein, in the step (5), the soluble-salt solution of the hydrogenation active metals with respect to every liter, the addition of described shaping of catalyst carrier is the 800-1200 gram.
15. the described method of any one according to claim 7-13, wherein, in the step (5), in element, the concentration of hydrogenation active metals is 1-20g/L in the soluble-salt solution of hydrogenation active metals.
16. the described method of any one according to claim 7-13, wherein, in the step (5), the soluble-salt solution of described hydrogenation active metals is at least a in the nitrate solution of hydrogenation active metals, acetate solution, carbonate solution, chloride solution and the soluble complexes solution.
17. the described method of any one according to claim 7-13, wherein, described hydrogenation active metals is at least a in the periodic table of elements group VIII metal.
18. method according to claim 17, wherein, described hydrogenation active metals is platinum and palladium.
19. the hydrocatalyst for saturating arylhydrocarbon that is made by the described method of any one among the claim 7-18.
20. aromatic hydrogenation catalysis process, it is characterized in that, the method comprises, under the aromatic hydrogenation catalytic condition, in the presence of hydrocatalyst for saturating arylhydrocarbon, raw material and the hydrogen haptoreaction that will contain aromatic hydrocarbons, wherein, described hydrocatalyst for saturating arylhydrocarbon is the described hydrocatalyst for saturating arylhydrocarbon of any one in claim 1-6 and 19.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021023172A1 (en) | 2019-08-05 | 2021-02-11 | 中国石油化工股份有限公司 | Full conversion method and device for producing light aromatic hydrocarbons from catalytic diesel |
| CN113617361A (en) * | 2021-05-19 | 2021-11-09 | 盘锦浩业化工有限公司 | Preparation method of non-noble metal aromatic hydrocarbon hydrofining catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048835A (en) * | 1989-07-15 | 1991-01-30 | 中国石油化工总公司石油化工科学研究院 | The preparation method of rich silicon molecular sieve by crystal skeleton |
| CN1448217A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Alumina supporter containing flurine and its preparing process |
-
2011
- 2011-10-17 CN CN201110314963.5A patent/CN103041832B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1048835A (en) * | 1989-07-15 | 1991-01-30 | 中国石油化工总公司石油化工科学研究院 | The preparation method of rich silicon molecular sieve by crystal skeleton |
| CN1448217A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Alumina supporter containing flurine and its preparing process |
Non-Patent Citations (1)
| Title |
|---|
| 扈林杰等: "负载贵金属芳烃饱和催化剂抗硫性能研究I.载体酸性的影响", 《石油学报（石油加工）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021023172A1 (en) | 2019-08-05 | 2021-02-11 | 中国石油化工股份有限公司 | Full conversion method and device for producing light aromatic hydrocarbons from catalytic diesel |
| CN113617361A (en) * | 2021-05-19 | 2021-11-09 | 盘锦浩业化工有限公司 | Preparation method of non-noble metal aromatic hydrocarbon hydrofining catalyst |
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