CN102205241B - Aromatic hydrogenated saturated catalyst and application thereof - Google Patents
Aromatic hydrogenated saturated catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to an aromatic hydrogenated saturated catalyst and an application thereof. The catalyst contains an aluminum oxide carrier and a hydrogenation metal component, wherein the aluminum oxide carrier is prepared by roasting pseudoboehmite; the pseudoboehmite contains pseudoboehmite P1 meeting the following relational expression: n is more than or equal to 1.1 but is less than or equal to 2.5; n is equal to D(031)/D(120); the D(031) indicates a crystallite dimension of a crystal plane represented by a 031 peak in an XRD (x-ray diffraction) spectrogram of a pseudoboehmite crystalline grain; the D(120) indicates the crystallite dimension of the crystal plane represented by a 120 peak in the XRD spectrogram of the pseudoboehmite crystalline grain; the 031 peak is the peak with a 2theta of 34-43 degrees in the XRD spectrogram; the 120 peak is the peak with the 2theta of 23-33 degrees in the XRD spectrogram; D is equal to K lambda/(B cosine theta); K is a Scherrer constant number; lambda is a diffraction wavelength of a target-type material; B is a half peak width of a diffraction peak; and 2theta is the position of the diffraction peak. Compared with the similar catalyst prepared by using the prior art, the catalyst provided by the invention has better hydrogenation activity and sulfur-resisting property.
Description
Technical field
The present invention relates to a kind of hydrocatalyst for saturating arylhydrocarbon and application thereof.
Background technology
It is saturated to adopt metal catalyst to carry out aromatic hydrogenation under lower reaction temperature, is a kind of effective means that realizes taking off such as clean fuel oil, white oil and top-grade lubricating oil base oil even depth virtue.
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, all reported in 34,4284～4289 and Ind.Eng.Chem.Res.1995,34,4277～4283 add second metal such as palladium in the catalyst to improve the method for catalyst tolerates sulphur ability.
ZL 97197514 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 heavy %, the silica of preferred 40 heavy %, catalyst total pore volume＞0.45cm
3/ g, wherein at least 1%, preferred at least 3% total pore volume is that the aperture is greater than 1000
Macropore.
Improve the another kind of important way of catalyst hydrogenation performance and optimize carrier (catalyst) pore structure exactly, reactive metal is distributed on effective interval and the surface, adjust carrier surface character simultaneously, with further raising reactive metal utilization rate, make reactive metal all change into effective activated centre as far as possible.Therefore carrier hole structure and surface nature are most important to the influence of catalyst performance.The carrier of aromatic hydrocarbon hydrogenation catalyst adopts aluminium oxide more, and the precursor of aluminium oxide is hydrated alumina, as boehmite, its particle size, pattern, degree of crystallinity etc. exert an influence to character such as the pore volume of catalyst, pore size distribution, specific areas, and then influence activity of such catalysts and selective.
Summary of the invention
The objective of the invention is on the basis of existing technology, the better aromatic hydrocarbon hydrogenation catalyst of a kind of performance and application thereof are provided.
The invention provides a kind of metal mold hydrocatalyst for saturating arylhydrocarbon, this catalyst contains alumina support and hydrogenation metal component, wherein alumina support is made through roasting by a kind of boehmite, described boehmite comprises the boehmite P1 of a kind of 1.1≤n≤2.5, n=D (031)/D (120) wherein, the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak refers to that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks refer to that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, and B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
The invention provides a kind of aforementioned catalyst at the application process of aromatic hydrogenation saturation history.
Compare with the catalyst that prior art provides, the invention provides catalyst when being used for the aromatic hydrogenation reaction, hydrogenation performance and sulfur resistance are higher.
For example, adopt the inventive method to prepare boehmite P1-1, its n value is 1.80, the n value of the boehmite P2-1 of Comparative Examples 1 method preparation is 0.89, carrier loaded same metal component by P1-1 and P2-1 preparation is prepared into catalyst C1 and DC1, adopts a kind of white oil raw material to carry out hydrogenation reaction.Catalyst C1 is at 240 ℃ of reaction temperatures, air speed 0.5h
-1The time gained white oil product character can reach the standard of food-level white oil.And adopt catalyst DC1, at 240 ℃ of reaction temperatures, air speed 0.4h
-1The time, the character of gained white oil product just can reach the standard of food-level white oil.Illustrate that catalyst of the present invention has higher hydrogenation activity.
The specific embodiment
According to the invention provides catalyst, wherein, the n of preferred described boehmite P1 satisfies 1.2≤n≤2.2.
The preparation method of the boehmite of described 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted with acid or alkali carry out precipitation reaction, perhaps organic aluminum contained compound is contacted the reaction that is hydrolyzed with water, obtain hydrated alumina; The above-mentioned hydrated alumina that obtains is worn out, wherein, described aluminum contained compound solution and acid or alkali contact or described organic aluminum contained compound and water contact and hydrated alumina aging in any one process in the presence of the grain growth conditioning agent, carry out, described grain growth conditioning agent is for can regulate the material of the speed of growth of crystal grain on different crystal faces.
As long as although make hydrolysis or precipitation reaction and aging in one of arbitrary process in the presence of the grain growth conditioning agent, carry out realizing purpose of the present invention, but under the preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out in the presence of the grain growth conditioning agent, can make the n of gained boehmite like this in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growth conditioning agent, the consumption of grain growth conditioning agent is the 0.5-10 weight % that treats organic aluminum contained compound weight of hydrolysis in the selective hydrolysis reaction, more preferably 1-8.5 weight %, further preferred 5-8.5 weight %; The consumption of grain growth conditioning agent is the inorganic 0.5-10 weight % that contains al reactant weight in the described precipitation reaction, more preferably 1-8.5 weight %, further preferred 5-8.5 weight %; In the described ageing process, the consumption of grain growth conditioning agent can be preferably 1-8.5 weight % for the 0.5-10 weight % of hydrated alumina weight, further preferred 5-8.5 weight %.Unless stated otherwise, among the present invention, the consumption of described grain growth conditioning agent is that benchmark calculates with the weight of aluminium oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina respectively.Also be, in aluminium oxide, in the described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of inorganic aluminum contained compound weight, in the described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of organic aluminum contained compound weight, and in the described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of hydrated alumina weight.
Among the present invention, described grain growth conditioning agent can be the various materials that can regulate the speed of growth of crystal grain on different crystal faces, particularly can regulate crystal grain at the material of the speed of growth of 120 crystal faces and 031 crystal face, be preferably alditol and carboxylate thereof, be specifically as follows in D-sorbite, glucose, gluconic acid, gluconate, ribitol, ribonic acid, the ribose hydrochlorate one or more.Described gluconate and ribose hydrochlorate can be their soluble-salt separately, for example, can be in sylvite, sodium salt and the lithium salts one or more.
In boehmite preparation process of the present invention, adding mode to described grain growth conditioning agent is not particularly limited, the grain growth conditioning agent can be added separately, also can be in advance the grain growth conditioning agent be mixed with wherein one or more raw materials, and then the raw material that will contain the grain growth conditioning agent reacts.
Wherein, described inorganic aluminum contained compound solution can be various aluminum salt solutions and/or aluminate solution, and described aluminum salt solution can be various aluminum salt solutions, for example can be one or more the aqueous solution in aluminum sulfate, aluminium chloride, the aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use two kinds or more of mixing back.Described aluminate solution is aluminate solution arbitrarily, as sodium aluminate solution and/or potassium aluminate.Because its acquisition is easy and price is low, preferred sodium aluminate solution.Aluminate solution also can be used alone or as a mixture.
Concentration to described aluminum salt solution and/or aluminate solution is not particularly limited, and preferably counts the 0.2-1.1 mol with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, the oxalic acid one or more, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid.Described carbonic acid can original position produces by feed carbon dioxide in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, and the concentration of preferred H+ is the 0.2-2 mol.
Described aqueous slkali can for hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, the potassium hydroxide; Preferred salt is selected from one or more in sodium metaaluminate, potassium metaaluminate, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, the potash.Concentration to described aqueous slkali is not particularly limited, and the concentration of preferred OH-is the 0.2-4 mol.When during as alkali, when calculating the consumption of described grain growth conditioning agent, also considering the amount of corresponding aluminium oxide in sodium metaaluminate and/or the potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can with water generation hydrolysis, producing in the aluminum alkoxide of aqua oxidation aluminum precipitation one or more, for example can be in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctanol aluminium one or more.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and the preferred water yield is greater than the required amount of stoichiometry.
In boehmite preparation process of the present invention, the described condition of precipitation reaction that makes is not particularly limited, preferred pH value is 3-11, more preferably 6-10; Temperature can be 30-90 ℃, is preferably 40-80 ℃.
Wherein, it is conventionally known to one of skill in the art making the method for aluminum precipitation by the control of consumption to alkali in the reactant or acid.
Condition to described hydrolysis is not particularly limited, as long as water contacts with aluminum alkoxide hydrolysis generation hydrated alumina takes place, and the condition that hydrolysis specifically takes place is conventionally known to one of skill in the art.
Wherein, can in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, add the compound of crystal grain growth regulating effect, also can add aqueous slkali or acid solution and suitably regulate the pH value to 7-10, under suitable temperature, wear out then.Separate then, washing, drying.
Described acid solution or aqueous slkali can be with above-described identical or different.
Described aging temperature is preferably 35-98 ℃, and ageing time is preferably 0.2-6 hour.
According to method provided by the invention, the described known technology that is separated into this area is as the method for filtration or centrifugation or evaporation.
In boehmite preparation process of the present invention, after aging, also comprise the washing and the dry step that often comprise in the preparation boehmite process, described washing and dry method are preparation boehmite conventional process.For example, can use oven dry, forced air drying or spray-dired method.Generally speaking, baking temperature can be 100-350 ℃, is preferably 120-300 ℃.
According to the preparation method of boehmite of the present invention, an embodiment preferred may further comprise the steps:
(1) will contain the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution and stream or batch (-type) and join and carry out precipitation reaction in the reaction vessel, obtain the hydrated alumina slurries; Perhaps in deionized water, add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide, obtain the hydrated alumina slurries;
(2) filter cake behind the hydrated alumina dope filtration that step (1) is obtained adds in the aluminium oxide slurries that water making beating obtains again again, adds the grain growth conditioning agent, after regulating pH and being 7-10, in 35-98 ℃ of aging 0.2-6 hour; Also the hydrated alumina slurries that above-mentioned steps (1) can be obtained without filter the grain growth conditioning agent exist or not in the presence of be under the 7-10 at pH, in 35-98 ℃ of aging 0.2-6 hour;
(3) product that filter, washing step (2) obtains;
(4) product that obtains of drying steps (3) obtains the boehmite of 1.1≤n provided by the invention≤2.5.
In the preferred cobalt of described hydrogenation active metals component, nickel, ruthenium, rhodium, palladium, the platinum one or more, be benchmark in metal and with the catalyst, the hydrogenation metal components contents is 0.1 weight %-5 weight %, and more preferably the hydrogenation metal components contents is 0.2 weight %-1 weight %.One preferred embodiment in, described hydrogenation activity component is platinum and the combination of palladium bimetallic, when described hydrogenation metal component is platinum and the combination of palladium bimetallic, it is 0.3～1.0 that said Pd/ (Pt+Pd) weight ratio preferably satisfies, and further preferred Pd/ (Pt+Pd) weight ratio is 0.5～0.8.
According to catalyst provided by the invention, described catalyst is looked different the article shaped that require can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.
Catalyst provided by the invention can adopt the conventional method preparation, for example, when the invention provides catalyst and be bar shaped catalyst, its preparation method comprises: (1) will comprise the boehmite P1 of described 1.1≤n≤2.5, the boehmite P1 extruded moulding of preferred 1.2≤n≤2.2, dry and roasting prepares alumina support; Wherein, when extrusion molding, can in described boehmite, add an amount of extrusion aid and/or adhesive, extrusion molding then; The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, and for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, the poly-ethanol; The temperature of described drying can be 100-200 ℃, is preferably 120-150 ℃; The temperature of roasting can be 400-650 ℃, is preferably 450-600 ℃, and roasting time is 1-15 hour, is preferably 3-10 hour; (2) adopt the method for dipping in described alumina support, to introduce the hydrogenation metal component, dry and roasting; Wherein, described drying condition is preferably: 100～200 ℃ of temperature, and the time is 2～12 hours; Described roasting condition is preferably: 300～600 ℃ of temperature, the time is 2～10 hours.Described dipping method is conventional method, and for example, preparation contains the solution of the compound of described hydrogenation active metals component, afterwards by the method dipping that soaks or spray, dry and roasting.The described compound that contains the hydrogenation activity component is selected from one or more in these their soluble compounds, for example, can be in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals one or more.
According to catalyst provided by the invention, wherein, described boehmite optionally can also comprise the boehmite P2 except the boehmite of 1.1≤n≤2.5, described P2 is the boehmite of n＜1.1, preferred P2 is the boehmite of 0.8＜n＜1.1, and further preferred P2 is the boehmite of 0.85≤n≤1.05.When described composition contains P2, be benchmark in oxide and with the boehmite total amount, the content of described P2 is not more than 70 weight %, further preferably is not more than 50 weight %, more preferably is not more than 30 weight %.Described P2 is that the boehmite of 0.8＜n＜1.1 can be to be selected from the boehmite that commercially available commodity also can adopt any one prior art for preparing.
When described boehmite comprises boehmite P2 except the boehmite of 1.1≤n≤2.5, also comprise the step of introducing this boehmite in the described Preparation of catalysts method.For example, in described extrusion step, the method for P1 and P2 mixing, extruded moulding and roasting is introduced.
Described catalyst preferably also comprises a step of reducing 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 hours.
The catalyst that the inventive method provides can be used for the deepness hydrogenation dearomatization process of aromatic hydrogenation saturated reaction, particularly clean fuel oil, white oil and lube base wet goods.
The hydrogenation dearomatization process conditions are: reaction temperature is that 200～380 ℃, hydrogen dividing potential drop are that 0.5～15 MPa, liquid volume air speed are 0.1～5 hour
-1, hydrogen to oil volume ratio is 100～3000.
The following examples will the present invention is further illustrated.
Agents useful for same in the example except specifying, is chemically pure reagent.
The n value of all boehmites adopts XRD method to measure in the example of the present invention.The XRD test is carried out at SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep speed is 2 °/minute.According to the Scherrer formula: (D is crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) be that grain size that the calculation of parameter at 23-33 ° of peak goes out (120) is D (120), is that the grain size that the calculation of parameter at 34-43 ° of peak goes out (031) is D (031) with 2 θ with 2 θ respectively, and by formula n=D (031)/D (120) calculates the n value.
The boehmite P2 of boehmite P1, n＜1.1 of employed 1.1≤n≤2.5 in the embodiment of the invention, preparation method and originate as follows:
P1-1, adopt following method preparation:
In one 2 liters retort and stream add 1000 ml concns be 48 gram aluminium oxide/liter aluminum trichloride solution and 300 milliliters contain 200 gram aluminium oxide/liter, the causticity coefficient is 1.58, D-sorbite content is 1.82 grams per liters sodium aluminate solution carries out precipitation reaction, reaction temperature is during 80 ℃, conditioned reaction logistics capacity make and the pH value is 4.0, reaction time 15 minutes; Adding concentration in the gained slurries is the weak aqua ammonia adjusting slurries pH to 10.0 of 5 weight %, and be warming up to 80 ℃, aging 3 hours, filter with vacuum filter then, behind to be filtered the finishing, replenished adding 20 liters of deionized waters (80 ℃ of temperature) flush cake about 30 minutes at filter cake.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, control spray dryer outlet temperature about 2 minutes of dry materials time, obtains hydrated alumina P1-1 100-110 ℃ of scope after the drying.Adopt XRD to characterize, P1-1 has structure of similar to thin diaspore.The n value that adopts XRD method to calculate P1-1 is listed in the table 1.
P1-2, adopt following method preparation:
To contain 210 gram aluminium oxide/liter, the causticity coefficient is 1.62 high concentration NaAlO
2Solution and deionized water are mixed with Al
2O
3Concentration is 5 liters of the solution of 40 grams per liters, adds the NaAlO that gluconic acid sodium salt 16.3 grams obtain containing gluconic acid sodium salt then
2Solution is transferred in the one-tenth glue reactor of cumulative volume 8L then, and the reactor ratio of height to diameter is 8, bottom band CO
2Gas distributor.The control solution temperature is 25 ± 5 ℃, feeds the CO of concentration 90 volume % from reactor bottom
2Gas becomes the glue reaction, becomes the control of glue temperature at 20-40 ℃, regulates CO
2Gas flow is 15 ± 2 liters/minute, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes into the glue reaction.With aging 4 hours of gained slurries heat temperature raising to 70 ℃, filter with vacuum filter then, to be filtered intact after, replenish at filter cake and to add 20 liters of deionized waters (70 ℃ of temperature) flush cake about 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, obtain hydrated alumina P1-2.XRD characterizes demonstration, and P1-2 has structure of similar to thin diaspore, characterizes the n value that calculates P1-2 through XRD and lists in the table 1.
P2-1, adopt following method preparation:
Method according to P1-1 prepares boehmite, and different is, does not contain D-sorbite in the sodium aluminate solution, and drying obtains hydrated alumina P2-1.XRD characterizes demonstration, and P2-1 has structure of similar to thin diaspore, characterizes the n value that calculates P2-1 through XRD and lists in the table 1.
P2-2 is the commercial boehmite SB powder that German Condea company aluminium alcoholates Hydrolyze method is produced, and the n value that adopts the XRD characterizing method to calculate the P2-2 powder is listed in the table 1.
Repeatedly prepare according to the method described above, to obtain enough for the boehmite raw material that uses in the example.
Table 1
* the degree of crystallinity with the commercial SB powder of Condea company is 100%.
Embodiment 1
Catalysts and its preparation method provided by the invention is described.
200 gram boehmite P1-1 and methylcellulose 5.0 grams are mixed, add the aqueous solution of nitric acid that 3.0 milliliters in nitric acid and deionized water 180 grams mix, fully mix and pinch, extruding diameter at banded extruder then is 1.8 millimeters cloverleaf pattern bar, drying is 4 hours under 120 ℃, 650 ℃ of roastings 2 hours in air then obtain carrier Z1.With nitric acid four ammonia platinum [Pt (NH
3)
4(NO
3)
2] 992 milligrams and nitric acid four ammonia palladium [Pd (NH
3)
4(NO
3)
2] 840 milligrams in deionized water dissolving be formulated as maceration extract, immerse 100 gram carrier Z1 in the maceration extract fully, flood after 6 hours and filter, through 120 ℃ of oven dry, 500 ℃ of roastings 4 hours, 350 ℃ of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, catalyst after the reduction is designated as C1, and its composition sees Table 2.Tenor in the catalyst is with the x-ray fluorescence method analysis.
Embodiment 2
Catalysts and its preparation method provided by the invention is described.
With nitric acid four ammonia platinum [Pt (NH
3)
4(NO
3)
2] 893 milligrams and nitric acid four ammonia palladium [Pd (NH
3)
4(NO
3)
2] 2941 milligrams in deionized water dissolving be formulated as maceration extract, immerse 100 gram carrier Z1 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, catalyst after the reduction is designated as C2, and its composition sees Table 2.Tenor in the catalyst is with the x-ray fluorescence method analysis.
Embodiment 3
Catalysts and its preparation method provided by the invention is described.
150 gram boehmite P1-2,50 gram boehmite P2-2 and methylcellulose 5.0 grams are mixed, add the aqueous solution of nitric acid that 4.0 milliliters in nitric acid and deionized water 170 grams mix, fully mix and pinch, extruding diameter at banded extruder then is 1.4 millimeters cloverleaf pattern bar, drying is 4 hours under 120 ℃, 550 ℃ of roastings 4 hours in air then obtain carrier Z2.With nitric acid four ammonia platinum [Pt (NH
3)
4(NO
3)
2] 893 milligrams and nitric acid four ammonia palladium [Pd (NH
3)
4(NO
3)
2] 2941 milligrams in deionized water dissolving be formulated as maceration extract, immerse 100 gram carrier Z2 in the maceration extract fully, flood after 3 hours and filter, through 120 ℃ of oven dry, 450 ℃ of roastings 4 hours, 450 ℃ of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, catalyst after the reduction is designated as C3, and its composition sees Table 2.Tenor in the catalyst is with the x-ray fluorescence method analysis.
Comparative Examples 1
Comparative catalyst and preparation method thereof is described.
Method for preparing catalyst is identical with embodiment 1, and different is to replace P1-1 with boehmite P2-1.Catalyst after the reduction is designated as DC1, and its composition sees Table 2.
Comparative Examples 2
Comparative catalyst and preparation method thereof is described.
Method for preparing catalyst is identical with embodiment 2, and different is that boehmite P2-1 is replaced P1-1.Catalyst after the reduction is designated as DC2, and its composition sees Table 2.
Table 2
Embodiment 4
This example illustrates Application of Catalyst provided by the invention.
Adopt a kind of high viscosity naphthenic base white oil raw material to carry out evaluating catalyst, its character sees Table 3.Be reflected on 100 milliliters of hydrogenation reaction devices and carry out, catalyst is C1, and its particle diameter is 0.30～0.45 millimeter.Process conditions and reaction result see Table 4.
Embodiment 5
This example illustrates Application of Catalyst provided by the invention.
Adopt a kind of high viscosity naphthenic base white oil raw material to carry out evaluating catalyst, its character sees Table 3.Be reflected on 100 milliliters of hydrogenation reaction devices and carry out, catalyst is C2, and its particle diameter is 0.30～0.45 millimeter.Process conditions and reaction result see Table 4.
Comparative Examples 4
Identical with example 4 conditions, difference is that catalyst is DC1.Reaction result sees Table 4.
Comparative Examples 5
Identical with example 5 conditions, difference is that catalyst is DC2.Reaction result sees Table 4.
Table 3
Table 4
The result of table 4 shows that catalyst of the present invention has active preferably when being applied to the white oil hydrogenation, and under higher air speed, the white oil product can reach the standard of food-level white oil.
Embodiment 6
This example illustrates Application of Catalyst provided by the invention.
At pressure 6.0MPa, 240 ℃ of temperature, air speed 2.0h
-1Reaction condition under the C3 catalyst has been carried out the investigation of sulfur resistance with the direct steaming gasoline (arene content 13%) of sulfur content 150 μ g/g.Test data shows that the initial stage takes off fragrant rate and can reach 80%, and turning round after 7 days is 75%, fall 6%.
Comparative Examples 6
Identical with example 6 conditions, difference is that catalyst is DC2.Taking off fragrant rate at start of run is 40%, turns round to reduce to 20% after 7 days, and fall reaches 50%.
By the result of example 6 and Comparative Examples 6 as can be seen, hydrogenation activity and the sulfur resistance of catalyst provided by the invention obviously improve.
Claims (9)
1. metal mold hydrocatalyst for saturating arylhydrocarbon, this catalyst contains alumina support and hydrogenation active metals component, described hydrogenation active metals component is selected from cobalt, nickel, ruthenium, rhodium, palladium, in the platinum one or more, be benchmark in metal and with the catalyst, the hydrogenation metal components contents is 0.1 weight %-5 weight %, wherein alumina support is made through roasting by a kind of boehmite, described boehmite comprises the boehmite P1 of a kind of 1.1≤n≤2.5, n=D (031)/D (120) wherein, the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak refers to that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks refer to that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
2. catalyst according to claim 1 is characterized in that, the n of described boehmite P1 satisfies 1.2≤n≤2.2.
3. catalyst according to claim 1 is characterized in that, is benchmark in metal and with the catalyst, and the hydrogenation metal components contents is 0.2 weight %-1 weight %.
4. according to claim 1 or 3 said catalyst, hydrogenation activity component wherein is platinum and palladium bimetallic, and the bimetallic Pd/ of said platinum and palladium (Pt+Pd) weight ratio is 0.3～1.
5. according to the said catalyst of claim 4, Pd/ wherein (Pt+Pd) weight ratio is 0.5～0.8.
6. catalyst according to claim 1 is characterized in that, contains the boehmite P2 of 0.8＜n＜1.1 in the described boehmite, is benchmark in oxide and with the boehmite total amount, and the content of described P2 is not more than 70 weight %.
7. catalyst according to claim 6 is characterized in that, described P2 is the boehmite of 0.85≤n≤1.05, is benchmark in oxide and with the boehmite total amount, and the content of described P2 is not more than 50 weight %.
8. catalyst according to claim 7 is characterized in that, is benchmark in oxide and with the boehmite total amount, and the content of described P2 is not more than 30 weight %.
9. the arbitrary described catalyst of claim 1-8 is in the application of aromatic hydrogenation saturation history.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010136690 CN102205241B (en) | 2010-03-31 | 2010-03-31 | Aromatic hydrogenated saturated catalyst and application thereof |
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| CN106466601A (en) * | 2015-08-14 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and the application of the catalyst prepared by the method and this catalyst |
| CN106552646B (en) * | 2015-09-30 | 2020-04-28 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for catalyzing ring opening of naphthenic hydrocarbon by hydrogenolysis |
| CN107629814B (en) * | 2016-07-19 | 2019-07-12 | 中国科学院大连化学物理研究所 | A kind of aromatic hydrocarbons plus hydrogen saturation process |
| CN108085058B (en) * | 2016-11-22 | 2019-07-12 | 中国科学院大连化学物理研究所 | A kind of method of hydrocarbon ils deeply de-aromatizing |
| CN107096533B (en) * | 2017-06-02 | 2019-07-12 | 钦州学院 | A kind of benzene hydrogenating catalyst and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510112A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Metal aromatic hydrosaturation catalyst |
| CN1647857A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Macroporous aluminium oxide carrier and its preparing method |
| CN1803996A (en) * | 2005-01-14 | 2006-07-19 | 中国石油化工股份有限公司 | Diesel oil hydrotreating catalyst and method for preparing the same |
| CN101444732A (en) * | 2007-11-28 | 2009-06-03 | 中国石油化工股份有限公司 | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof |
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| EP1826178A4 (en) * | 2004-11-22 | 2009-05-27 | Idemitsu Kosan Co | Iron-containing crystalline aluminosilicate, hydrocracking catalyst comprising the aluminosilicate, and method of hydrocracking with the catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1510112A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Metal aromatic hydrosaturation catalyst |
| CN1647857A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Macroporous aluminium oxide carrier and its preparing method |
| CN1803996A (en) * | 2005-01-14 | 2006-07-19 | 中国石油化工股份有限公司 | Diesel oil hydrotreating catalyst and method for preparing the same |
| CN101444732A (en) * | 2007-11-28 | 2009-06-03 | 中国石油化工股份有限公司 | C9 aromatic hydrocarbon lightening catalyst and lightening method thereof |
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