CN103041804B - Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method - Google Patents
Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method Download PDFInfo
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Abstract
The invention discloses an aromatic hydrogenation catalyst. The aromatic hydrogenation 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 0.085-0.1. The invention further provides a preparation method of the aromatic hydrogenation catalyst and the aromatic hydrogenation catalyst obtained by the method. In addition, the invention further provides an aromatic hydrogenation catalytic method utilizing the aromatic hydrogenation catalyst. The aromatic hydrogenation 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 catalyst disclosed by the invention can be increased by up to 20%.
Description
Technical field
The present invention relates to a kind of aromatic hydrocarbon hydrogenation catalyst and preparation method thereof, and a kind of aromatic hydrogenation catalysis process.
Background technology
Adopting metal catalyst under lower reaction temperature, carry out aromatic hydrogenation saturated, is a kind of effective means realizing such as clean fuel oil, white oil and top-grade lubricating oil base oil even depth Porous deproteinized bone.
Because metal mold hydrocatalyst for saturating arylhydrocarbon is to sulfur sensitive, therefore prior art adopts the hydrogenation catalyst of sulphided state to carry out except refining desulfurization to raw material except needing, more pay attention to day by day is to the exploitation of the metal catalyst of resistant to sulfur, and is mainly studied from hydrogenation active component and bearer type two aspects.
At Ind.Eng.Chem.Res.1995,34,4284-4289 and Ind.Eng.Chem.Res.1995, all reports in 34,4277-4283 and adds in the second metal (as palladium) to catalyst to improve the method for catalyst resistant to sulfur ability.
CN 1228718A discloses a kind of platinum, palladium bimetallic resistant to sulfur hydrocarbon conversion catalyst, this catalyst comprises platinum-palldium alloy and matrix of oxide, wherein the mol ratio of platinum in the alloy and palladium is 2.5: 1-1: 2.5, preferably 2: 1-1: 1, most preferably 1: 1.5, matrix of oxide contains at least 30 % by weight, preferably the silica of 40 % by weight, catalyst total pore volume > 0.45cm
3/ g, wherein the total pore volume of at least 1%, preferably at least 3% is that aperture is greater than
macropore.
Catalyst aromatic saturation performance and catalyst sulfur resistance can be improved by changing bearer type and optimizing carrier hole structure.Document " petroleum journal (PETROLEUM PROCESSING) 1999,15 (3), 41-45 " reports the noble metal catalyst adopting the silica-alumina supports containing B acid to prepare and has better sulfur resistance.Optimize carrier (catalyst) pore structure, active metal is distributed in effective interval and on the surface, adjusts carrier surface character simultaneously, to improve active metal utilization rate further, make active metal change into effective activated centre all as far as possible.Therefore carrier hole structure and the impact of surface nature on catalyst performance most important.
Carrier many employings aluminium oxide of aromatic hydrocarbon hydrogenation catalyst or amorphous silicon aluminum.The preparation method of amorphous silicon aluminum has multiple, adopts silica-alumina supports prepared by suitable preparation technology, carrier can be made to 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 object of this invention is to provide a kind of aromatic hydrocarbon hydrogenation catalyst of high aromatic saturation performance, this aromatic hydrocarbon hydrogenation catalyst with a kind of acid silica-alumina material of high B acid ratio for carrier; In addition, the present invention also provides the preparation method of this aromatic hydrocarbon hydrogenation catalyst and a kind of aromatic hydrogenation catalysis process.
The invention provides a kind of aromatic hydrocarbon hydrogenation catalyst, this aromatic hydrocarbon hydrogenation catalyst comprises silica-alumina supports and the hydrogenation active metals component of load in this silica-alumina supports, it is characterized in that, described silica-alumina supports is 0.085-0.1 in the ratio of 200 DEG C of infrared B acid of the pyridine recorded and L acid.
The present invention also provides a kind of preparation method of aromatic hydrocarbon hydrogenation catalyst, it is characterized in that, the method comprises the following steps, and (1), by aluminium source and aqueous slkali and plastic, obtains containing aluminium paste liquid; (2) with oxide basis, be the ratio of 1: 2-3 according to aluminum weight ratio, add silicon source to described containing in aluminium paste liquid, ageing obtains solid sediment, and filtration obtains filter cake; (3) described filter cake making beating is obtained sial slurries, with the dry weight of described filter cake for benchmark, the fluosilicic acid of 1-12 % by weight is mixed with described sial slurries and contacts, obtain contacting products therefrom; (4) described contact products therefrom carried out successively filter, wash, first dry, shaping, the second dry and roasting, obtain shaping of catalyst carrier; (5) described shaping of catalyst carrier is contacted with the soluble salt solutions of hydrogenation active metals, then carry out drying and roasting.And the aromatic hydrocarbon hydrogenation catalyst prepared by the method is provided.
In addition, the present invention also provides a kind of aromatic hydrogenation catalysis process, it is characterized in that, the method comprises, under aromatic hydrogenation catalytic condition, under aromatic hydrocarbon hydrogenation catalyst exists, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, described aromatic hydrocarbon hydrogenation catalyst is above-mentioned aromatic hydrocarbon hydrogenation catalyst.
The middle pore property of aromatic hydrocarbon hydrogenation catalyst provided by the invention is obvious, pore distribution concentration, simultaneously containing B acid and L acid site, and the ratio of B acid and L acid comparatively prior art significantly improve.As can be seen from the data of embodiment, compared with prior art and comparative example 1, the hydrogenation activity of aromatic hydrocarbon hydrogenation catalyst of the present invention can increase up to 20%.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the silica-alumina supports of prepared in accordance with the method for the present invention and the X-ray diffraction spectrogram of prior art silica-alumina supports.
Detailed description of the invention
The invention provides a kind of aromatic hydrocarbon hydrogenation catalyst, this aromatic hydrocarbon hydrogenation catalyst comprises silica-alumina supports and the hydrogenation active metals component of load in this silica-alumina supports, it is characterized in that, described silica-alumina supports is 0.085-0.1 in the ratio of 200 DEG C of infrared B acid of the pyridine recorded and L acid.
The infrared B acid of described pyridine is adopt pyridine temperature programming infra-red sepectrometry to obtain with L acid.By sample self-supporting compressing tablet, the original position pond being placed in infrared spectrometer seals, and is warming up to 350 DEG C and is evacuated to 10
-3pa, constant temperature removes the gas molecule of sample adsorption after 1 hour; Import pyridine steam after being cooled to room temperature and keep adsorption equilibrium 30 minutes, be then warming up to 200 DEG C, be again 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, the Pyridine adsorption IR spectra figure of sample through 200 DEG C of desorptions can be obtained.According to 1540cm in Pyridine adsorption IR spectra figure
-1and 1450cm
-1the absorbance of characteristic absorption peak, calculates the relative quantity in B acid site and L acid site.
According to the present invention, preferably, with the weight of silica-alumina supports for benchmark, described silica-alumina supports contain 28-33 % by weight with the silicon of oxide basis, 65-70 % by weight with the aluminium of oxide basis, 0-0.2 % by weight with the alkali metal of oxide basis, be preferably 0.05-0.15 % by weight in the alkali metal of oxide basis and 0.5-4 % by weight with the fluorine of element, be preferably 1-3 % by weight in the fluorine of element.
According to the present invention, preferably, described silica-alumina supports has boehmite crystal phase structure; The specific area of described silica-alumina supports is 300-500m
2/ g, more preferably 400-450m
2/ g; Pore volume is 0.5-1.5ml/g, more preferably 0.8-1.2ml/g, most preferably is 0.9-1ml/g; Average pore diameter is 8-15nm, more preferably 9-12nm, most preferably is 9-10nm.
The difference of aromatic hydrocarbon hydrogenation catalyst of the present invention and prior art is the improvement of carrier, and therefore, the hydrogenation active metals in described hydrogenation active metals component can be the hydrogenation active metals of the various routine of aromatic hydrogenation catalytic field.Preferably, hydrogenation active metals in described hydrogenation active metals component is at least one in periodic table of elements group VIII metal, include but not limited at least one in cobalt, nickel, ruthenium, rhodium, palladium and platinum, further preferably, the hydrogenation active metals in described hydrogenation active metals component is platinum and palladium.
Similarly, in described aromatic hydrocarbon hydrogenation catalyst, the ratio of carrier and hydrogenation active metals also can be conventional various proportions, preferably, with the weight of aromatic hydrocarbon hydrogenation catalyst for benchmark and with oxide basis, in described aromatic hydrocarbon hydrogenation catalyst, the content of hydrogenation active metals component is 0.1-5 % by weight, more preferably 0.2-2 % by weight.When described hydrogenation active metals be platinum and palladium time, with the weight of described hydrogenation active metals for benchmark, the content of described palladium is preferably 30-99 % by weight, more preferably 50-80 % by weight.
The present invention also provides a kind of preparation method of aromatic hydrocarbon hydrogenation catalyst, it is characterized in that, the method comprises the following steps,
(1) by aluminium source and aqueous slkali and plastic, obtain containing aluminium paste liquid;
(2) with oxide basis, be the ratio of 1: 2-3 according to aluminum weight ratio, add silicon source to described containing in aluminium paste liquid, ageing obtains solid sediment, and filtration obtains filter cake;
(3) described filter cake making beating is obtained sial slurries, with the dry weight of described filter cake for benchmark, the fluosilicic acid of 1-12 % by weight is mixed with described sial slurries and contacts, obtain contacting products therefrom, preferably the fluosilicic acid of 2-11 % by weight is mixed with described sial slurries and contact, obtain contacting products therefrom;
(4) described contact products therefrom carried out successively filter, wash, first dry, shaping, the second dry and roasting, obtain shaping of catalyst carrier;
(5) described shaping of catalyst carrier is contacted with the soluble salt solutions of hydrogenation active metals, then carry out drying and roasting.
According to the present invention, in step (1), described aluminium source and aqueous slkali and in them and the condition of plastic can be all the various selections of this area routine.Preferably, described aluminium source is selected from least one in aluminum nitrate, aluminum sulfate and aluminium chloride; Described aqueous slkali is selected from least one in ammoniacal liquor, potassium hydroxide solution, sodium hydroxide solution and sodium aluminate solution.
Can comprise with the step of plastic in described, under agitation, drip described aqueous slkali in the solution of aluminium source, stop after reaching the terminal of plastic, the endpoint pH of described plastic is preferably 7-11, is more preferably 8-10.In described and the temperature of plastic can be 20-90 DEG C, preferably 40-70 DEG C.
According to the present invention, in step (2), described silicon source also can be the various silicon sources of this area routine, and preferably, described silicon source is selected from least one in waterglass, sodium metasilicate, silicon tetraethyl and silica.
In step (2), described ageing can be the aging step of this area routine, and such as, the temperature of ageing is 20-100 DEG C, is preferably 60-90 DEG C; Time is 1-10 hour, is preferably 2-5 hour.
According to the present invention, when containing when there is alkali metal ion in aluminium paste liquid, step also preferably includes in (2), before filtration described solid sediment is carried out ammonium exchange or acid exchanges, it is less than 0.2 % by weight with the alkali-metal content of oxide basis that the condition that ammonium exchanges or acid exchanges makes in the solid sediment after exchanging.
Particularly, the step that described ammonium exchanges can be, by the dry weight of the solid sediment obtained through ripening according to solid sediment: ammonium salt: water is the weight ratio of 1: 0.1-1: 10-30, exchanges 1-3 time at 20-100 DEG C, and each exchange 0.5-1 hour.Described ammonium salt is preferably at least one in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and carbonic hydroammonium.
The step that described acid exchanges can be, by the dry weight of the solid sediment obtained through ripening according to solid sediment: acid: water is the weight ratio of 1: 0.03-0.30: 5-30, at least exchanges 0.2 hour at 20-100 DEG C.Described acid is preferably inorganic acid, and such as, described acid can be selected from least one in sulfuric acid, hydrochloric acid and nitric acid.
In the present invention, the step of described making beating is known to the skilled person, and preferably, the method for making beating for add water in described filter cake, and makes filter cake and water fully be mixed into pulpous state.The addition of the present invention to described water is not particularly limited, preferably, described water add weight be the 5-20 of described filter cake dry weight doubly.
According to the present invention, in step (3), the mode of described mixing contact can for join in described sial slurries by fluosilicic acid, also can for join in described fluosilicic acid by sial slurries, preferably, the mode of described mixing contact is for join fluosilicic acid in described sial slurries.
According to the present invention, in step (3), the condition of described mixing contact preferably includes, and temperature is 20-80 DEG C, and the time is more than 0.5 hour, and further preferably, temperature is 40-70 DEG C, and the time is 0.5-3 hour.
According to the present invention, in step (4), the condition of described filtration and washing can be the condition of this area routine, as washed with a large amount of water.
In step (4), described first drying can adopt baking oven, mesh-belt kiln, converter and fluid bed to carry out drying, when adopting heating means to carry out drying as baking oven, the condition of described first drying preferably includes, and temperature is 100-200 DEG C, and the time is 4-20 hour, further preferably, temperature is 100-150 DEG C, and the time is 5-15 hour, to remove free water.
In step (4), described shaping, condition that the second condition that is dry and roasting also can be this area routine.Such as, optionally can will make the article shaped of arbitrary convenient operation through the first dried described contact products therefrom, as spherical, sheet shape and bar shaped, describedly shapingly can to carry out according to a conventional method, as methods such as compressing tablet, spin or extrusions.In a preferred embodiment, the forming method of described carrier comprises through first dried contact products therefrom extrusion molding on double screw banded extruder.
Wherein, for ensureing the carrying out smoothly of extruded moulding, preferably to adding appropriate water, peptizing agent (as at least one be selected from nitric acid, acetic acid and citric acid), extrusion aid (as being sesbania powder and/or cellulose) mixing in the first dried contact products therefrom.
When extrusion molding, kind and the consumption of the consumption of described water and described extrusion aid, peptizing agent are conventionally known to one of skill in the art, do not repeat them here.
Described second drying also can be conventional method, drying is carried out as adopted baking oven, mesh-belt kiln, converter and fluid bed, when adopting heating means to carry out drying as baking oven, preferred baking temperature is 50-200 DEG C, drying time is 0.3-12 hour, further preferably, baking temperature is 60-150 DEG C, and drying time is 0.5-8 hour.
The method of described roasting and condition can be the conventional method and condition that adopt in catalyst support preparation process, roasting is carried out as adopted mesh-belt kiln, vertical heater, horizontal chamber furnace (oven) and converter, the condition of described roasting is preferably, at 400-900 DEG C of roasting 1-12 hour, further preferably, at 500-750 DEG C of roasting 2-8 hour.
According to the present invention, the conditions such as the kind of the contact conditions in step (5), the soluble salt solutions of hydrogenation active metals and content all can be the normal condition of preparation catalyst.
Particularly, in step (5), the method for described contact can for soaking or spray.The soluble salt solutions of the hydrogenation active metals relative to often liter, the addition of described shaping of catalyst carrier is preferably 800-1200 gram.In element, in the soluble salt solutions of hydrogenation active metals, the concentration of hydrogenation active metals is preferably 1-20g/L.The soluble salt solutions of described hydrogenation active metals can be at least one in the nitrate solution of hydrogenation active metals, Acetate Solution, carbonate solution, chloride solution and soluble complexes solution.The time of dipping can be 2-10 hour.
The kind of described hydrogenation active metals and relative usage, to described corresponding above, do not repeat them here.
After shaping of catalyst carrier contacts with the soluble solution of hydrogenation active metals, also drying and roasting will be carried out.The condition of described drying and roasting can be the condition of this area routine, and the temperature as drying is 100-200 DEG C, and the time is 2-12 hour; The temperature of roasting is 300-600 DEG C, and the time is 2-10 hour.
Described catalyst also preferably includes reduction step before using, and described reduction is preferably carried out in a hydrogen atmosphere, and reduction temperature is preferably 300-550 DEG C, and the recovery time is preferably 2-10 hour.
The present invention also provides the aromatic hydrocarbon hydrogenation catalyst obtained by said method.
The invention provides a kind of aromatic hydrogenation catalysis process, it is characterized in that, the method comprises, under aromatic hydrogenation catalytic condition, under aromatic hydrocarbon hydrogenation catalyst exists, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, described aromatic hydrocarbon hydrogenation catalyst is above-mentioned aromatic hydrocarbon hydrogenation catalyst.
Wherein, described aromatic hydrogenation catalytic condition can be the various conditions of this area routine, and such as, temperature is 100-200 DEG C, and pressure is 0.5-2MPa, and hydrogen to oil volume ratio is 1000-3000, and during liquid, volume space velocity is 1-15h
-1.
Catalyst of the present invention can be used for the aromatic hydrogenation saturated reaction, particularly clean fuel oil of the various raw material containing aromatic hydrocarbons, white oil, lubricating oil and the basic wet goods deepness hydrogenation dearomatization process containing aroamtic hydrocarbon raw material.
Below will be described the present invention by embodiment.In embodiments, the Na of vector product
2o, Al
2o
3, SiO
2, F content with x-ray fluorescence method measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).Thing phase and crystallinity data adopt X-ray diffraction method to measure.The physicochemical data such as specific surface, pore structure adopts nitrogen absorption under low temperature-desorption method to measure.The infrared pyridine adsorption in site measurement method of acid data acquisition measures.Tenor in catalyst is analyzed with x-ray fluorescence method.
Embodiment 1
The present embodiment is for illustration of the preparation of aromatic hydrocarbon hydrogenation catalyst C-1 of the present invention:
(1) getting concentration is 90g Al
2o
3the Al of the 2.0L of/L
2(SO
4)
3solution, in beaker, under agitation, drips ammonia spirit, until system pH=8, in and the temperature of plastic be 55 DEG C, collect containing aluminium paste liquid, adding concentration is under agitation 60g SiO
2the waterglass of the 1.4L of/L, is warming up to 80 DEG C of ageings 2 hours, filters and obtains sial sediment; Use NH
4cl solution presses the sedimentary dry weight of sial: ammonium salt: H
2the weight ratio of O=1: 0.8: 10, at 60 DEG C, ion-exchange is carried out to sial sediment, to remove sodium ion, repeat twice exchange, carry out 0.5 hour at every turn, then filter obtain filter cake, add water by gained filter cake making beating obtain sial slurries, and fluosilicic acid being added to mixing contact in sial slurries, the addition of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2the weight ratio of O is 0.02: 1: 10, and the condition of described mixing contact is react 1 hour at 60 DEG C, and namely filtration is dry at 120 DEG C after washing obtains silica-alumina supports in 15 hours, is designated as BSA-1.
The X-ray diffraction spectral line of BSA-1 is shown in Figure 1; Degree of crystallinity and elementary analytical chemistry composition are listed in table 1; Hole parameter and infrared acid data rows are in table 2.
(2) BSA-1 is extruded into the butterfly bar of ф 1.3 millimeters on double screw banded extruder, butterfly bar after 4 hours, in 600 DEG C of roastings 3 hours, obtains carrier strip SA-1 through 120 DEG C of dryings.
(3) by 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] dissolve in deionized water, be mixed with the maceration extract of 100mL, 100 grams of carrier S A-1 are immersed in maceration extract completely, flood 6 hours, through 120 DEG C of oven dry, 500 DEG C of roastings 4 hours, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as C-1, and its composition is in table 3.
Comparative example 1
This comparative example is for illustration of the preparation of comparative catalyst DBC:
(1) carry out according to the step (1) of embodiment 1, unlike, filter after obtaining filter cake, do not pull an oar, also do not add fluosilicic acid, but directly by filter cake at 120 DEG C dry 15 hours, obtain contrast silica-alumina supports, be designated as DB-1.
The X-ray diffraction spectral line of DB-1 is shown in Figure 1; Degree of crystallinity and elementary analytical chemistry composition are listed in 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 and obtains carrier strip DBSA-1.
(3) according to the step (3) of embodiment 1, carry out load, obtain catalyst DBC to DBSA-1, its composition is in table 3.
Embodiment 2
The present embodiment is for illustration of the preparation of aromatic hydrocarbon hydrogenation catalyst C-2 of the present invention:
Preparation process with embodiment 1, unlike, the addition of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2the weight ratio of O is 0.11: 1: 10, obtains silica-alumina supports, is designated as BSA-2.
The X-ray diffraction spectral line of BSA-2 is shown in Figure 1; Degree of crystallinity and elementary analytical chemistry composition are listed in table 1; Hole parameter and infrared acid data rows are in table 2.
(2) above-mentioned BSA-2 is extruded into the butterfly bar of ф 1.3 millimeters on double screw banded extruder, butterfly bar after 4 hours, in 600 DEG C of roastings 3 hours, obtains carrier strip SA-2 through 120 DEG C of dryings.
(3) by 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] dissolve in deionized water, be mixed with the maceration extract of 110mL, 100 grams of carrier S A-2 are immersed in maceration extract completely, flood 10 hours, through 120 DEG C of oven dry, 550 DEG C of roastings 4 hours, 450 DEG C of hydrogen reducings 3 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as C-2, and its composition is in table 3.
Embodiment 3
The present embodiment is for illustration of the preparation of aromatic hydrocarbon hydrogenation catalyst C-3 of the present invention:
Be 90g Al by concentration
2o
3the Al of the 1.0L of/L
2(SO
4)
3solution and concentration are 102g Al
2o
3/ L, Crater corrosion are the NaAlO of the 0.8L of 1.7
2solution stream adds in continuous gel formation still, keep plastic pH=9.5, the temperature of middle rubber polymer is 70 DEG C, and collect containing aluminium paste liquid, adding concentration is under agitation 60g SiO
2the waterglass of the 1.3L of/L, is warming up to 70 DEG C of ageings 4 hours, filters and obtains sial sediment; Use NH
4cl solution presses the sedimentary dry weight of sial: ammonium salt: H
2the weight ratio of O=1: 1: 15, at 60 DEG C, ion-exchange is carried out to sial sediment, to remove sodium ion, repeat 3 times to exchange, carry out 0.5 hour at every turn, then filter obtain filter cake, add water by gained filter cake making beating obtain sial slurries, and fluosilicic acid being added to mixing contact in sial slurries, the addition of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2the weight ratio of O is 0.04: 1: 12, and the condition of described mixing contact is react 2 hours at 40 DEG C, and namely filtration is dry at 120 DEG C after washing obtains silica-alumina supports in 15 hours, is designated as BSA-3.
The X-ray diffraction spectral line of BSA-3 is shown in Figure 1; Degree of crystallinity and elementary analytical chemistry composition are listed in table 1; Hole parameter and infrared acid data rows are in table 2.
(2) BSA-3 is extruded into the butterfly bar of ф 1.3 millimeters on double screw banded extruder, butterfly bar after 4 hours, in 600 DEG C of roastings 3 hours, obtains carrier strip SA-3 through 120 DEG C of dryings.
(3) by 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] dissolve in deionized water, be mixed with the maceration extract of 105mL, 100 grams of carrier S A-3 are immersed in maceration extract completely, flood 3 hours, through 120 DEG C of oven dry, 450 DEG C of roastings 4 hours, 450 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as C-3, and its composition is in table 3.
Embodiment 4
The present embodiment is for illustration of the preparation of aromatic hydrocarbon hydrogenation catalyst C-4 of the present invention:
Be 90g Al by concentration
2o
3the Al of the 1.4L of/L
2(SO
4)
3solution and concentration are 102g Al
2o
3/ L, Crater corrosion are the NaAlO of the 0.8L of 1.7
2solution stream adds in continuous gel formation still, keep plastic pH=9.5, the temperature of middle rubber polymer is 70 DEG C, and collect containing aluminium paste liquid, adding concentration is under agitation 60g SiO
2the waterglass of the 1.25L of/L, is warming up to 70 DEG C of ageings 4 hours, filters and obtains sial sediment; The sedimentary dry weight of sial is pressed: hydrogen chloride: H with hydrochloric acid solution
2the weight ratio of O=1: 0.1: 15, at 70 DEG C, ion-exchange is carried out to sial sediment, to remove sodium ion, exchange carries out 2 hours, then filter obtain filter cake, add water by gained filter cake making beating obtain sial slurries, under intense agitation, described sial slurries are added to mixing contact in fluosilicic acid weak solution (concentration is 0.87 % by weight), the consumption of described fluosilicic acid is fluosilicic acid: the dry weight of filter cake: H
2the weight ratio of O is 0.07: 1: 8, and the condition of described mixing contact is react 1.5 hours at 50 DEG C, and namely filtration is dry at 120 DEG C after washing obtains silica-alumina supports in 15 hours, is designated as BSA-4.
The degree of crystallinity of BSA-4 and elementary analytical chemistry composition are listed in table 1; Hole parameter and infrared acid data rows are in table 2.
(2) BSA-4 is extruded into the butterfly bar of ф 1.3 millimeters on double screw banded extruder, butterfly bar after 4 hours, in 600 DEG C of roastings 3 hours, obtains carrier strip SA-4 through 120 DEG C of dryings.
(3) by 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] dissolve in deionized water, be formulated as 105mL maceration extract, 100 grams of carrier S A-4 are immersed in maceration extract completely, flood 3 hours, through 120 DEG C of oven dry, 450 DEG C of roastings 4 hours, 450 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as C-4, and its composition is in table 3.
Table 1
| Sample ID | Degree of crystallinity (%) | Na 2O(％) | Al 2O 3(％) | SiO 2(％) | F(％) |
| BSA-1 | 44.0 | 0.12 | 66.7 | 30.6 | 1.90 |
| BSA-2 | 49.1 | 0.10 | 66.9 | 30.6 | 2.24 |
| BSA-3 | 43.5 | 0.13 | 65.8 | 31.7 | 1.87 |
| BSA-4 | 46.3 | 0.12 | 67.6 | 29.6 | 2.05 |
| DB-1 | 40.3 | 0.14 | 67.5 | 31.9 | 0 |
Table 2
Table 3
| Sample ID | 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 |
From table 1 and table 2, the silica-alumina supports in catalyst provided by the invention is compared with the silica-alumina supports in comparative example 1, and degree of crystallinity is higher, and B acid significantly improves (exceeding more than one times than comparative example) with the ratio of L acid.
Comparative example 2
This comparative example is for illustration of the aromatic hydrogenation activity of comparative catalyst DBC.
The micro-inverse spectral apparatus of continuous-flow carries out activity rating to catalyst, feedstock oil is the hexane solution containing 10 % by weight toluene, catalyst loading amount is 1 gram, reaction condition is: pressure is 1.0 MPas, feedstock oil input is 0.2 ml/min, hydrogen to oil volume ratio is 2000, and temperature is 150 DEG C, reacts sampling after 3 hours and carries out online gas chromatographic analysis.Toluene Hydrogenation active A is undertaken calculating that (in formula, x is Toluene Hydrogenation conversion ratio, x=100 × (10%-P by formula I
toluene level in product)/10%):
Embodiment 5-8
The aromatic hydrogenation activity of aromatic hydrocarbon hydrogenation catalyst of the present invention is described.
Evaluating catalyst method (i.e. the assay method of Toluene Hydrogenation activity) is with comparative example 2.With the Toluene Hydrogenation activity of comparative catalyst DBC for 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 in formula II
cfor the Toluene Hydrogenation of each catalyst of the present invention is active, A
dBCfor the Toluene Hydrogenation of comparative catalyst DBC is active.Activity evaluation (namely relative Toluene Hydrogenation is active) is listed in table 4.
Table 4
| Sample ID | Relative Toluene Hydrogenation is active |
| C-1 | 118 |
| C-2 | 126 |
| C-3 | 122 |
| C-4 | 125 |
| DBC | 100 |
Activity evaluation shows, the active Toluene Hydrogenation activity comparing comparative catalyst DBC of Toluene Hydrogenation of catalyst of the present invention can increase up to 20%.
In addition, also can be combined between various different 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. an aromatic hydrocarbon hydrogenation catalyst, this aromatic hydrocarbon hydrogenation catalyst comprises silica-alumina supports and the hydrogenation active metals component of load in this silica-alumina supports, it is characterized in that, described silica-alumina supports is 0.085-0.1 in the ratio of 200 DEG C of infrared B acid of the pyridine recorded and L acid.
2. aromatic hydrocarbon hydrogenation catalyst according to claim 1, wherein, with the weight of silica-alumina supports for benchmark, described silica-alumina supports contain 28-33 % by weight with the silicon of oxide basis, 65-70 % by weight with the aluminium of oxide basis, 0-0.2 % by weight with the alkali metal of oxide basis, and 0.5-4 % by weight in the fluorine of element.
3. aromatic hydrocarbon hydrogenation catalyst according to claim 1, wherein, described silica-alumina supports has boehmite crystal phase structure; The specific area of described silica-alumina supports is 300-500m
2/ g, pore volume is 0.5-1.5ml/g, and average pore diameter is 8-15nm.
4. aromatic hydrocarbon hydrogenation catalyst according to claim 1, wherein, the hydrogenation active metals in described hydrogenation active metals component is at least one in periodic table of elements group VIII metal.
5. aromatic hydrocarbon hydrogenation catalyst according to claim 4, wherein, the hydrogenation active metals in described hydrogenation active metals component is platinum and palladium.
6., according to the aromatic hydrocarbon hydrogenation catalyst in claim 1-5 described in any one, wherein, with the weight of aromatic hydrocarbon hydrogenation catalyst for benchmark and with oxide basis, in described aromatic hydrocarbon hydrogenation catalyst, the content of hydrogenation active metals component is 0.1-5 % by weight.
7. a preparation method for aromatic hydrocarbon hydrogenation catalyst, is characterized in that, the method comprises the following steps,
(1) by aluminium source and aqueous slkali and plastic, obtain containing aluminium paste liquid;
(2) with oxide basis, be the ratio of 1: 2-3 according to aluminum weight ratio, add silicon source to described containing in aluminium paste liquid, ageing obtains solid sediment, and filtration obtains filter cake;
(3) described filter cake making beating is obtained sial slurries, with the dry weight of described filter cake for benchmark, the fluosilicic acid of 1-12 % by weight is mixed with described sial slurries and contacts, obtain contacting products therefrom;
(4) described contact products therefrom carried out successively filter, wash, first dry, shaping, the second dry and roasting, obtain shaping of catalyst carrier;
(5) described shaping of catalyst carrier is contacted with the soluble salt solutions of hydrogenation active metals, then carry out drying and roasting.
8. method according to claim 7, wherein, in step (1), described aluminium source is selected from least one in aluminum nitrate, aluminum sulfate and aluminium chloride; Described aqueous slkali is selected from least one in ammoniacal liquor, potassium hydroxide solution, sodium hydroxide solution and sodium aluminate solution.
9. method according to claim 7, wherein, in step (1), the endpoint pH of described plastic is 7-11.
10. method according to claim 7, wherein, in step (2), described silicon source is selected from least one in waterglass, sodium metasilicate, silicon tetraethyl and silica.
11. methods according to claim 7, wherein, step also comprises in (2), before filtration described solid sediment is carried out ammonium exchange or acid exchanges, it is less than 0.2 % by weight with the alkali-metal content of oxide basis that the condition that ammonium exchanges or acid exchanges makes in the solid sediment after exchanging.
12. methods according to claim 7, wherein, in step (3), the mode of described mixing contact is for join fluosilicic acid in described sial slurries.
13. methods according to claim 7, wherein, in step (3), the condition of described mixing contact comprises, and temperature is 20-80 DEG C, and the time is more than 0.5 hour.
14. according to the method in claim 7-13 described in any one, and wherein, in step (5), the soluble salt solutions of the hydrogenation active metals relative to often liter, the addition of described shaping of catalyst carrier is 800-1200 gram.
15. according to the method in claim 7-13 described in any one, and wherein, in step (5), in element, in the soluble salt solutions of hydrogenation active metals, the concentration of hydrogenation active metals is 1-20g/L.
16. according to the method in claim 7-13 described in any one, wherein, in step (5), the soluble salt solutions of described hydrogenation active metals is at least one in the nitrate solution of hydrogenation active metals, Acetate Solution, carbonate solution, chloride solution and soluble complexes solution.
17. according to the method in claim 7-13 described in any one, and wherein, described hydrogenation active metals is at least one in periodic table of elements group VIII metal.
18. methods according to claim 17, wherein, described hydrogenation active metals is platinum and palladium.
19. aromatic hydrocarbon hydrogenation catalysts obtained by the method in claim 7-18 described in any one.
20. 1 kinds of aromatic hydrogenation catalysis process, it is characterized in that, the method comprises, under aromatic hydrogenation catalytic condition, under aromatic hydrocarbon hydrogenation catalyst exists, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, described aromatic hydrocarbon hydrogenation catalyst is the aromatic hydrocarbon hydrogenation catalyst in claim 1-6 and 19 described in any one.
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| JP7158953B2 (en) * | 2017-08-18 | 2022-10-24 | 中国石油化工股▲ふん▼有限公司 | Catalyst for producing light aromatic hydrocarbons from heavy aromatic hydrocarbons, production method and application thereof |
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| CN1210755A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Amorphous silica-alumina and its preparing method |
| 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 |
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| CN1210755A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Amorphous silica-alumina and its preparing method |
| 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 |
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