CN102160996B - Composition of boehmite and silicon-containing compound and silicon oxide-alumina prepared from same - Google Patents
Composition of boehmite and silicon-containing compound and silicon oxide-alumina prepared from same Download PDFInfo
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Abstract
The invention discloses a composition of boehmite and a silicon-containing compound and silicon oxide-alumina prepared from the same. The composition of the boehmite and the silicon-containing compound is characterized in that: the boehmite comprises at least one boehmite P1 of which n is less than or equal to 1.1 or more than or equal to 2.5, wherein n is equal to D (031)/D (120); the D (031) expresses a grain size of a crystal face represented by 031 peak in an X-ray diffraction (XRD) spectrum of boehmite grains; the D (120) expresses the grain size of the crystal face represented by 120 peak in the XRD spectrum of the boehmite grains; the 031 peak indicates the peak that 2 theta is 34 to 43 DEG in the XRD spectrum; the 120 peak indicates the peak that the 2 theta is 23 to 33 DEG in the XRD spectrum; D is equal to K lambda/(Bcos theta); the K is Scherrer constant; the lambda is the diffraction wavelength of a target-type material; B is the peak breadth of a diffraction peak; and the 2 theta is the position of the diffraction peak. Compared with the prior art, a hydrogenation catalyst which is prepared from the silicon oxide-alumina provided by the invention has high hydrocarbon hydrotreating performance.
Description
Technical field
The present invention relates to composition and the silica-alumina prepared therefrom of a kind of boehmite and silicon-containing compound.
Background technology
Silica-alumina is because having better pore structure, specific surface, heat-resistant stability and solid acid character, and Chang Zuowei adsorbent or catalyst carrier are used.In prior art, a lot of reports about silica-alumina carrier and preparation method thereof are arranged.For example:
Document (" aluminium oxide-silicon oxide is preparation and the rare-earth-doped modification research of nano-powder ", functional material, 2004,35 the 6th phases of volume, 788 pages) reported that a kind of aluminium oxide-silicon oxide is the preparation of nano-powder, comprise that nano level active Al (OH) x that adopts the aluminium powder hydrolysis and prepare is aluminum feedstock, take waterglass as the silicon raw material, and with Al
2O
3/ SiO
2Be basic recipe at=2: 1, after introducing appropriate dispersant, fully mixes.Control by the pH value, to coat depositing technology, at surface, Al source parcel one deck Si raw material, thereby form the Al-Si complex at a certain temperature, go the work techniques such as sodium, Solid-Liquid Separation, drying and calcining through washing, prepare Al
2O
3-SiO
2Powder.
ZL95103291 discloses a kind of preparation method of silica-alumina carriers, comprise a kind of aluminium compound is mixed to obtain a kind of solution with a kind of silicon compound, wherein aluminium compound is aluminum alcoholate or aluminum carboxylate, and silicon compound is pure SiClx or silicone compounds; Make solution hydrolysis under acid condition and under 50-150 ℃, obtain gelinite after cooling, obtain paste after removing excessive volatile matter, carry out afterwards extrusion molding, and obtain described carrier 300-700 ℃ of roasting.
ZL03157163 discloses a kind of silica-alumina with structure of similar to thin diaspore and preparation method thereof, contains the silica of 5-60 % by weight after its roasting, the aluminium oxide of 40-95 % by weight.It is characterized in that, the N value of described silica-alumina is 0.2-1, described N=P1/P2.P1 is that in the solid 27Al NMR spectrogram of described silica-alumina, chemical shift is the peak area at 60 ± 0.1-0.2ppm place, and P2 is that in the solid 27Al NMR spectrogram of described silica-alumina, chemical shift is the peak area at 5 ± 0.1-0.2ppm place.Described preparation method comprises the mixed liquor of a kind of boehmite of preparation and water, introduces afterwards a kind of solution of silicon-containing compound, and is aging and dry.
ZL200380105512 discloses a kind of preparation method of the cogelled catalyst of amorphous silica-alumina very uniformly, comprise: aqueous silicate solution is acutely mixed with the aqueous solution of acid aluminium salt, the pH that keeps simultaneously solution is lower than 3.0 and guarantee that described aluminium salt and silicate solutions fully mix tempestuously, are formed on the acidifying Ludox in aluminum salt solution; In the situation that the described solution of violent mixing adds alkaline precipitating agent that the pH of described solution is risen to greater than 3.0 gradually, produce cogelled slurries in described acidifying Ludox/aluminum salt solution; In the situation that the described cogelled slurries of violent mixing make whole cogelled slurries keep even pH to continue to add alkaline precipitating agent, make final pH in the scope of 5-9; Wash the common gelling of described precipitation; With the cogelled finished catalyst that is processed into described precipitation.
ZL200410048355 discloses a kind of silica-alumina, the silica that contains the 5-60 % by weight after its dehydration, the aluminium oxide of 40-95 % by weight, the preparation method of this silica-alumina comprises a kind of salic water mixed liquid of preparation, introduce afterwards a kind of solution, aging and dry of silicon-containing compound, the solution of wherein said silicon-containing compound is a kind of mother liquor of synthesis of molecular sieve.
ZL01815324 discloses a kind of hydrotreating catalyst for heavy oil, contain at least a vib metal that is selected from molybdenum, tungsten, chromium and/or at least a VIII family metal that is selected from cobalt, nickel, iron on silica-alumina carriers, described silica-alumina carrier has
29Si NMR spectrum, wherein-50ppm to-maximum main peak that 100ppm observes be positioned at-80ppm is to-100ppm, in carrier, the content of silica is 1-20%, and mixes with alumina source and sneak into carbon monoxide-olefin polymeric with the organo-silicon compound form that is selected from alkyl silane, alkoxy silane and straight chain or modified silicon oil.
ZL200510064753 discloses a kind of preparation method of the hydrogenation catalyst of containing phosphor take silica-alumina as carrier, the method comprises in described silica-alumina carrier introduces phosphorus, molybdenum, nickel and tungsten, the preparation method of described silica-alumina carrier comprise with the precursor of aluminium oxide and/or aluminium oxide and silica and or the precursor of silica mixes also roasting, obtain the silica-alumina carrier, this carrier contains the silica of 2-45% and the aluminium oxide of 55-98%.
Wherein, adopt hydrated alumina such as boehmite directly mixes with silicon-containing compound, the method for roasting prepares silica-alumina, be used more and more because it is simple to operate.
Boehmite of the prior art generally is prepared by the following method: (1) alkaline precipitation, i.e. acidifying aluminium salt and alkali neutralization.Be settled out monohydrate alumina with alkali from the acidifying aluminum salt solution, then obtain the boehmite product by processes such as aging, washing, dryings, this method often is called as alkali precipitation (acid system), as the method for ammonia neutralization alchlor; (2) acid precipitation method is namely in the aluminium salt of strong acid or strong acid and aluminate.First be settled out monohydrate alumina with acid from aluminate solution, then obtain the boehmite product by processes such as aging, washing, dryings, often be called as acid precipitation (alkaline process), common method comprises the most at present: CO
2In gas and in the method for sodium metaaluminate, aluminum sulfate and the method for sodium metaaluminate; (3) aluminum alkoxide Hydrolyze method generates monohydrate alumina with aluminum alkoxide and the reaction of steeping in water for reconstitution unboiled water solution, then obtains the boehmite product through aging, filtration, drying.Preparation process at boehmite generally all is comprised of processes such as crystal grain generation (neutralization precipitation or hydrolytic process), grain growth (ageing process), washing, dryings.Therefore, crystal grain generates, the process conditions of grain growth can exert an influence to quantity and the speed of growth that crystal grain generates, the preparation technology of various boehmites has proposed process conditions separately, control grain size, the degree of crystallinity of product, to reach the purpose of physical propertys such as controlling product pore volume and specific area.For example:
ZL200410024185 discloses a kind of preparation method of boehmite, the method comprises that sodium aluminate solution is carried out carbonating to be decomposed, reacting slurry is separated, fractional crystallization is obtained product through washing, dry post processing, what described sodium aluminate solution carbonating was decomposed is controlled to be: add sodium aluminate solution in the water that passes into carbon dioxide, the pH value of controlling solution by the throughput of controlling carbon dioxide is 10-13, add complete after, increase rapidly the throughput of carbon dioxide, make the pH value of solution be reduced to rapidly 9.5-10.5, obtain reacting slurry.
ZL200510068393 discloses a kind of preparation method of boehmite, the method comprises in the process of producing boehmite take acid or aluminate as precipitating reagent, adds 6-18 gram melamine (CA) for after the expanding agent dissolution filter and contain the acidifying aluminum salt solution plastic of alchlor 20-40 grams per liter in the sodium aluminate solution that contains alchlor 60-180 grams per liter; The plastic temperature is 50-90 ℃, and plastic pH value is 6.5-8.5, Separation of Solid and Liquid, and filtration washing obtains filter cake, and the water that oven dry is adhered to turns brilliant 4-10 hour 320-350 ℃ of lower roasting, pulverizes namely to get the boehmite finished product.
ZL02120772 discloses a kind of preparation method of gama-alumina, the method comprises sodium metaaluminate or sodium aluminate solution is contacted with carbonated gas, with intermittence or continuous mode plastic, the aging boehmite that obtains, isolate solid product, washing is also dry, the terminal point pH of described plastic or process pH are controlled in the scope of 6-9.5, time or the time of staying of plastic reaction are less than 40 minutes, 10-100 ℃ of plastic reaction temperature, after finishing, the plastic reaction adds rapidly alkaline matter, make the pH value of slurries rise to 9.5-11.5 or carry out rapidly Separation of Solid and Liquid and washing.
USP4019978 discloses a kind of method of producing aluminium oxide, and the method is by pressing Al
2O
3Meter concentration is at least in 2% aluminum sulfate solution introduces sodium aluminate solution, by controlling the concentration of sodium aluminate and aluminum sulfate solution, the control sodium aluminate joins speed and the mixing speed in aluminum sulfate solution, to guarantee that absolutely large section hydrated alumina precipitates generation under acid condition, control mixture temperature and be 12-35 ℃ or 45-70 ℃, control alkaline ageing time, the low-density aluminium oxide that forms to produce boehmite.Hydrated alumina after filtration, washing, then dry.Low-density aluminium oxide useful as catalysts carrier, particularly hydrodesulfurization catalyst support.
Although prior art has the multiple different method for preparing boehmite, and the performance of the boehmite that obtains is more excellent in some aspects, yet, they and silicon-containing compound are being mixed with the silica-alumina carrier, again with these carriers for the preparation of catalyst, when particularly preparing hydrogenation class catalyst, the performance of catalyst, as still on the low side in aromatic saturation performance, hydrodesulfurization activity.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new boehmite and composition and the silica-alumina prepared therefrom of silicon-containing compound.
The present inventor finds under study for action, the n value of the boehmite that prior art provides (being generally 0.85-1.05) on the low side, be cause this type of boehmite and the silicon-containing compound composition for the preparation of hydrogenation catalyst the time, one of reason of catalyst performance deviation.
The invention provides the composition of a kind of boehmite and silicon-containing compound, wherein, described boehmite is the boehmite P1 that comprises at least a 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 XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of diffraction maximum, 2 θ are the position of diffraction maximum.
The present invention further provides a kind of silica-alumina, this silica-alumina is obtained through roasting by the composition of aforementioned boehmite provided by the invention and silicon-containing compound.
Compared with prior art, in the composition of boehmite provided by the invention and silicon-containing compound, the boehmite P1 that comprises at least a 1.1≤n≤2.5, said composition obtains the silica-alumina carrier through roasting, when adopting this carrier to prepare hydrogenation catalyst, catalyst performance be improved significantly.for example, hydrogenation active metals content at catalyst, in the identical situation of preparation condition, employing the invention provides the silica-alumina carrier, and (precursor is boehmite and the silicon-containing compound of a kind of n=1.8, in oxide, in described composition, the content of aluminium oxide is 70 % by weight, the content of silica is 30 % by weight) preparation hydrogenation catalyst, (precursor is boehmite and the silicon-containing compound of a kind of n=0.98 than reference silica-alumina carrier, in oxide, in described composition, the content of aluminium oxide is 70 % by weight, the content of silica is 30 % by weight) the relative arene saturating activity of the hydrogenation catalyst of preparation improves 30%.
The specific embodiment
According to the composition of boehmite provided by the invention and silicon-containing compound, wherein, described P1 is preferably the boehmite of 1.2≤n≤2.2.described n=D (031)/D (120), 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 XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, the D value is obtained by following formula, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of this diffraction maximum, 2 θ are the position of this diffraction maximum, for different diffraction maximums, the value that B and 2 θ all get peak correspondingly, for example, when calculating D (031), D (031)=K λ/(Bcos θ), wherein B is the half-peak breadth of 031 diffraction maximum, 2 θ are the position of 031 diffraction maximum, when calculating D (120), D (120)=K λ/(Bcos θ), wherein B is the half-peak breadth of 120 diffraction maximums, 2 θ are the position of 120 diffraction maximums.
Described silicon-containing compound, it can be organic silicon-containing compound, as one or more in esters of silicon acis, silanol, silicon ether, silicone and silicone oil, can be also inorganic silicon-containing compound, for example be selected from a kind of in silica gel (hydrated SiO 2), Ludox, silicic acid, waterglass, amorphous aluminum silicide, zeolite molecular sieve.Preferred silica gel, silicic acid and the Ludox that adopts in inorganic silicon-containing compound.
Composition according to boehmite provided by the invention and silicon-containing compound, wherein, content to described boehmite and silicon-containing compound is not particularly limited, and namely they can be usual content, in oxide, the content of preferred boehmite is the 65-99 % by weight, more preferably the 75-97 % by weight, be more preferably 80-95% weight, and the content of silicon-containing compound is the 1-35% % by weight, more preferably the 3-25% % by weight, be more preferably 5-20% weight.
The preparation method of the boehmite P1 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; Carry out hydrated alumina obtained above aging, 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 carry out under the grain growth conditioning agent exists, 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 carry out realizing purpose of the present invention under the grain growth conditioning agent exists, but under preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out under the grain growth conditioning agent exists, and can make like this n of gained boehmite in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growth conditioning agent, in selective hydrolysis reaction, the consumption of grain growth conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight to be hydrolyzed, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In described precipitation reaction, the consumption of grain growth conditioning agent is the inorganic 0.5-10 % by weight that contains al reactant weight, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In described ageing process, the consumption of grain growth conditioning agent can be preferably the 1-8.5 % by weight for the 0.5-10 % by weight of hydrated alumina weight, further preferred 5-8.5 % by weight.Unless stated otherwise, in the present invention, the consumption of described grain growth conditioning agent respectively in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina weight of corresponding aluminium oxide calculate as benchmark.Be also, in aluminium oxide, in described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of inorganic aluminum contained compound weight, in described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight, and in described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of hydrated alumina weight.
In 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 one or more in D-sorbite, glucose, gluconic acid, gluconate, ribitol, ribonic acid, ribose hydrochlorate.Described gluconate and ribose hydrochlorate can be their soluble-salt separately, for example, can be one or more in sylvite, sodium salt and lithium salts.
In boehmite preparation process of the present invention, the mode that adds 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, can be for example one or more the aqueous solution in aluminum sulfate, aluminium chloride, aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use after two kinds or more of mixing.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/L with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be one or more in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, oxalic acid, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, hydrochloric acid.Described carbonic acid can original position produce by pass into carbon dioxide in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, preferred H
+Concentration be the 0.2-2 mol/L.
Described aqueous slkali can be hydrolyzed for hydroxide or in aqueous medium the salt that makes the aqueous solution be alkalescence, and preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, 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, potash.Concentration to described aqueous slkali is not particularly limited, preferred OH
-Concentration be the 0.2-4 mol/L.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 potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can the reaction with steeping in water for reconstitution unboiled water solution, one or more in the aluminum alkoxide of generation aqua oxidation aluminum precipitation can be for example one or more in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and isooctanol aluminium.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 reactant or acid.
Condition to described hydrolysis is not particularly limited, as long as water contacts with aluminum alkoxide, hydrolysis generation hydrated alumina occurs, and the concrete condition that hydrolysis occurs is conventionally known to one of skill in the art.
Wherein, can add the compound of crystal grain growth regulating effect in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, also can add aqueous slkali or acid solution suitably to regulate the pH value to 7-10, then carry out aging at suitable temperature.Then separate, 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, also comprise the washing and the dry step that often comprise in preparation boehmite process after aging, 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, a preferred embodiment comprises the following 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 reaction vessel, obtain the hydrated alumina slurries; Perhaps add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide in deionized water, obtain the hydrated alumina slurries;
(2) filter cake after 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; The hydrated alumina slurries that also above-mentioned steps (1) can be obtained are without filtering in the existence of grain growth conditioning agent or being under 7-10 at pH not, 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.
Composition according to boehmite provided by the invention and silicon-containing compound, wherein 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 contained P2, in oxide and take the boehmite total amount as benchmark, the content of described P2 was not more than 70 % by weight, further preferably was not more than 50 % by weight, more preferably was not more than 30 % by weight.
Described composition can adopt any prior art that described boehmite and described silicon-containing compound are mixed to get.Wherein, described mixing can be the simple accumulation that described boehmite and described silicon-containing compound are placed in a place, can be also to adopt any one prior art, for example, can directly boehmite be mixed by the mode that stirs with silicon-containing compound in mixer, grinder, can boehmite, silicon-containing compound and water be mixed being enough under the condition of pulp, filter afterwards, dry or moist method mixes.When adopting any one prior art to mix, those skilled in the art optionally can control the uniformity that described mixing should reach, to this present invention to being not particularly limited.
During the consumption of each component makes final composition in described mixed process, in oxide, the content of preferred boehmite is the 65-99 % by weight, 75-97 % by weight more preferably, be more preferably 80-95% weight, the content of silicon-containing compound is the 1-35% % by weight, and more preferably the 3-25% % by weight, be more preferably 5-20% weight.Said composition obtains silica-alumina provided by the invention through roasting.
According to silica-alumina provided by the present invention, wherein, described method of roasting and condition can be that this area prepares examples of such carriers customary way and condition.Preferred roasting condition comprises: 400～900 ℃ of temperature are carried out, and further preferred 500～750 ℃, roasting time is 1-12 hour, more preferably 2-8 hour.
According to silica-alumina provided by the invention, optionally can be made into the article shaped of convenient operation arbitrarily, as spherical, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.
One preferred embodiment in, the article shaped preparation method of described silica-alumina comprises:
(1) the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1, silicon-containing compound and water are mixed being enough under the condition of pulp, filter afterwards, dry or moist, obtain described composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (2) step of introducing appropriate water, peptizing agent (as in being selected from nitric acid, acetic acid and citric acid one or more), extrusion aid (as being one or more in sesbania powder, cellulose) in the described composition and mixing.Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln, converter and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, 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 the roasting temperature 1-12 of 400-900 ℃ hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.
Another preferred embodiment in, the article shaped preparation method of described silica-alumina comprises:
(1) on kneading machine or grinder, the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1 are mixed with silicon-containing compound, obtain described composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (1) and introduce appropriate water, peptizing agent (as in being selected from nitric acid, acetic acid and citric acid one or more), extrusion aid (as being one or more in sesbania powder, cellulose).Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln, converter and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, 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 the roasting temperature 1-12 of 400-900 ℃ hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.
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.
Silica-alumina carrier provided by the invention has following physico-chemical property, and pore volume is 0.5-1.1 ml/g, and specific surface is 100-400 rice
2/ gram can several bore dias be the 5-20 nanometer, and the pore volume of bore dia 4-10 nanometer is greater than 70% of total pore volume.Further preferred, the pore volume of described silica-alumina carrier is 0.55-0.90 ml/g, and specific surface is 150-350 rice
2/ gram can several bore dias be the 6-15 nanometer, and the pore volume of bore dia 4-10 nanometer is greater than 75% of total pore volume.
Silica-alumina provided by the invention can be used as the matrix of various adsorbents, catalyst carrier and catalyst and uses.
The present invention will be further described for following example, but therefore do not limit content of the present invention.
Agents useful for same in example except specifying, is chemically pure reagent.In catalyst, each constituent content except specifying, all adopts x-ray fluorescence spectrometry.
In example of the present invention, the n value of all boehmites all adopts XRD method to measure.The XRD test is carried out on 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 shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) calculation of parameter at ° peak goes out (120) take 2 θ as 23-33 respectively grain size is D (031) as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size, and by formula n=D (031)/D (120) calculates the n value.
The boehmite P2 of boehmite P1, the n of the 1.1≤n that uses in the embodiment of the present invention≤2.5＜1.1, preparation method and originate as follows:
P1-1 (comprising P1-1a and P1-1b), adopt following method preparation:
In the retort of 2 liters and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum sulfate solution of 3.6 gram ribitol and ammonia spirit that concentration is 8 % by weight carries out precipitation reaction, reaction temperature is 40 ℃, reaction time is 10 minutes, it is 7 that the flow of control ammonia spirit makes the pH of reaction system, after precipitation reaction finishes, adding proper ammonia to make the pH value of slurries in slurries is 8.5, slurries filtered after under 55 ℃ aging 60 minutes, filter cake washs 2 times with the deionized water making beating, and drying does not obtain hydrated alumina P1-1a; Through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-1b.XRD characterizes and shows that P1-1a and P1-1b have structure of similar to thin diaspore.
Characterizing through XRD the n value that calculates P1-1a and P1-1b lists in 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, then adds gluconic acid sodium salt 16.3 grams to obtain containing the NaAlO of gluconic acid sodium salt
2Then solution be transferred in the plastic reactor of cumulative volume 8L, and the reactor ratio of height to diameter is 8, bottom band CO
2Gas distributor.Controlling solution temperature is 25 ± 5 ℃, passes into the CO of concentration 90 volume % from reactor bottom
2Gas carries out the plastic reaction, and the plastic temperature is controlled at 20-40 ℃, regulates CO
2Gas flow is 15 ± 2 liter/mins of clocks, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes the plastic reaction.With the gained slurries be heated to 70 ℃ aging 4 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (temperature 70 C) flush cake approximately 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 through XRD the n value that calculates P1-2 and lists in table 1.
P1-3, adopt following method preparation:
In the retort of 2 liters 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 % by weight, and be warming up to 80 ℃, aging 3 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (80 ℃ of temperature) flush cake approximately 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, control the spray dryer outlet temperature 100-110 ℃ of scope, approximately 2 minutes dry materials time, obtain hydrated alumina P1-3 after drying.Adopt XRD to characterize, P1-3 has structure of similar to thin diaspore.The n value that adopts XRD method to calculate P1-3 is listed in table 1.
P2-1 (comprising P2-1a and P2-1b), adopt following method preparation:
Method according to P1-1 prepares boehmite, and different is, the aluminum sulfate solution that contains ribitol by concentration be 96 gram aluminium oxide/liter aluminum sulfate solution replace, be also not contain ribitol in aluminum sulfate solution.Filtration product not drying obtains hydrated alumina P2-1a; Drying obtains hydrated alumina P2-1b.XRD characterizes demonstration, and P2-1a and P2-1b have structure of similar to thin diaspore, characterizes through XRD the n value and the degree of crystallinity that calculate P2-1a and P2-1b and lists in table 1.
P2-2 is the business 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 table 1.
P2-3, adopt following method preparation:
Method according to P1-3 prepares boehmite, and different is, does not contain D-sorbite in sodium aluminate solution, and drying obtains hydrated alumina P2-3.Method according to embodiment 1 adopts XRD to characterize, and P2-3 has structure of similar to thin diaspore, characterizes through XRD the n value that calculates P2-3 and lists in table 1.
P1-1a and P2-1a sample all carry out the XRD test again after 12 hours through 120 ℃ of dryings, obtain the n value.
Repeatedly prepare according to the method described above, to obtain enough for the boehmite raw material in example.
From the results shown in Table 1, boehmite P1-1a, P1-1b, P1-2 and P1-3 have the feature of 1.1≤n≤2.5; The n of boehmite P2-1a, P2-1b, P2-2 and P2-3＜1.1.In addition, take the degree of crystallinity of the business SB powder of Condea company as 100%, adopt the degree of crystallinity of boehmite of method preparation provided by the invention in the 60-80% scope.
Table 1
Embodiment 1～4 explanation described composition provided by the invention, silica-alumina carrier and preparation method thereof.
Embodiment 1
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
At room temperature the 1600 gram synthetic boehmite P1-1a (butt 22%) in laboratory are added 3000 ml water making beating, stir after 30 minutes, (Silica Gel 955, U.S. Davison Chemical company product contains SiO under agitation to add business silica gel
299.8% weight) 62 grams continue to stir after 150 minutes, filtered, and filter cake 120 ℃ of dryings 10 hours, is obtained composition Z H-1 of the present invention (butt 77%).Adopt x-ray fluorescence method to record the composition of ZH-1, in oxide and with butt, silica content is 15 % by weight, and alumina content is 85% weight.
(2) silica-alumina provided by the invention and preparation thereof:
420 gram ZH-1 are mixed with sesbania powder 4 grams, afterwards with this mixture and 13.5 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 530 ml waters mix, and on double screw banded extruder kneading, be extruded into the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-1 through 120 ℃ of dryings.The silica content of SA-1, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 2
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First 400 synthetic boehmite P1-1b (butt 70%) and the Ludox in gram laboratory (are contained SiO
230% weight, the production of Beijing flying dragon horse company) after 295 grams, sesbania powder 11 grams mix, again with 8.2 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west) and 310 milliliters of mixing of water, afterwards this mixture is continued kneading on double screw banded extruder, obtain composition Z H-2 of the present invention.ZH-2 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-2, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 24 % by weight, and alumina content is 76% weight.
(2) silica-alumina provided by the invention and preparation thereof:
Continue whole aforementioned ZH-2 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-2 through 120 ℃ of dryings.The silica content of SA-2, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 3
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First (Beijing chemical reagents corporation contains SiO for the boehmite P1-2 (butt 69%) that 450 gram laboratories are synthetic and ethyl orthosilicate
228% weight is analyzed pure) 46 grams, 12.5 gram sesbania powder mix, then with this mixture and 8.2 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west), 400 ml waters mix, and continue afterwards kneading equal on double screw banded extruder, obtain composition Z H-3 of the present invention.ZH-3 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-3, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 4 % by weight, and alumina content is 96% weight.
(2) silica-alumina provided by the invention and preparation thereof:
Continue whole aforementioned ZH-3 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-3 through 120 ℃ of dryings.The silica content of SA-3, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 4
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First (Siral 40, contain SiO for the boehmite P1-3 (butt 71%) that 400 gram laboratories are synthetic and amorphous aluminum silicide
240% weight, Germany Condea company product) 304 grams, sesbania powder 19 grams mix, again with this mixture and 12 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 413 ml waters mix, after kneading on double screw banded extruder is even, obtain composition Z H-4 of the present invention afterwards.ZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-4, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 30%, and alumina content is 70%.
(2) silica-alumina provided by the invention and preparation thereof:
Continue whole aforementioned ZH-4 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-4 through 120 ℃ of dryings.The silica content of SA-4, specific area, pore volume and pore size distribution data are listed in table 2.
Embodiment 5
(1) composition of boehmite provided by the invention and silicon-containing compound and preparation thereof:
First 300 synthetic boehmite P1-3 (butt 71%), business boehmite (Shandong Aluminium Industrial Corp produces, butt 67% weight, n value 1.02) 212 grams, the Ludox in gram laboratory (are contained SiO
230% weight, the production of Beijing flying dragon horse company) 131 grams, sesbania powder 13 grams mix, again with 11 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 210 ml waters mix, after continuation kneading on double screw banded extruder is even, obtain composition Z H-5 of the present invention afterwards.ZH-5 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-5, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 10% weight, and alumina content is 90% weight.
(2) silica-alumina provided by the invention and preparation thereof:
Whole aforementioned ZH-5 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-5 through 120 ℃ of dryings.The silica content of SA-5, specific area, pore volume and pore size distribution data are listed in table 2.The aluminium oxide that is provided by P1-3 accounts in carrier all 60% of alumina contents.
Comparative Examples 1-5 explanation reference composition, silica-alumina and preparation method thereof.
Comparative Examples 1
(1) reference composition and preparation thereof
At room temperature the 1600 gram synthetic boehmite P2-1a (butt 21%) in laboratory are added 3000 ml water making beating, stir after 30 minutes, (Silica Gel 955, U.S. Davison Chemical company product contains SiO under agitation to add business silica gel
299.8% weight) 60 grams continue to stir after 150 minutes, filtered, and filter cake 120 ℃ of dryings 10 hours, is obtained composition CZH-1 of the present invention (butt 78%).Adopt x-ray fluorescence method to record the composition of CZH-1, in oxide and with butt, silica content is 15 % by weight, and alumina content is 85% weight.
(2) reference silica-alumina and preparation thereof
420 gram CZH-1 are mixed with sesbania powder 4.2 grams, afterwards with this mixture and 13.5 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 530 ml waters mix, on double screw banded extruder kneading, be extruded into the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-1 through 120 ℃ of dryings.The silica content of CSA-1, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 2
(1) reference composition and preparation thereof:
First the 400 gram synthetic boehmite P2-1b (butt 68%) in laboratory (are contained SiO with Ludox
230% weight, the production of Beijing flying dragon horse company) 287 grams, sesbania powder 11.3 grams mix, again with this mixture and 8.8 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 313 ml waters mix, continue afterwards kneading on double screw banded extruder, obtain reference silica-alumina CZH-2.CZH-2 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-2, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 24 % by weight, and alumina content is 76% weight.
(2) reference silica-alumina and preparation thereof:
Whole aforementioned CZH-2 are continued to be extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-2 through 120 ℃ of dryings.The silica content of CSA-2, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 3
(1) reference composition and preparation thereof:
First (Beijing chemical reagents corporation contains SiO with 450 gram business boehmite P2-2 (the SB powder that German Condea company produces, butt 75%) and ethyl orthosilicate
228% weight is analyzed pure) 49.5 grams, 9 gram sesbania powder mix, then this mixture is mixed with 9 milliliters of nitric acid, 390 ml waters, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-3.CZH-3 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-3, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 4 % by weight, and alumina content is 96% weight.
(2) reference silica-alumina and preparation thereof:
Continue whole aforementioned CZH-3 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-3 through 120 ℃ of dryings.The silica content of CSA-3, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 4
(1) reference composition and preparation thereof:
First (Siral 40, contain SiO for the boehmite P2-3 (butt 68%) that 400 gram laboratories are synthetic and amorphous aluminum silicide
240% weight, Germany Condea company product) 291 grams, sesbania powder 18.7 grams mix, again with this mixture and 12 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 446 ml waters mix, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-4.CZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-4, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 30 % by weight, and alumina content is 70% weight.
(2) reference silica-alumina and preparation thereof:
Continue whole aforementioned CZH-4 are extruded into the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-4 through 120 ℃ of dryings.The silica content of CSA-4, specific area, pore volume and pore size distribution data are listed in table 2.
Comparative Examples 5
(1) reference composition and preparation thereof:
First 300 synthetic boehmite P2-3 (butt 68%), business boehmite (Shandong Aluminium Industrial Corp produces, butt 67% weight, n value 1.02) 202 grams, the Ludox in gram laboratory (are contained SiO
230% weight, Beijing flying dragon horse company produces) 126 grams, sesbania powder 13 grams mix, then this mixture is mixed with 11 milliliters of nitric acid, 265 ml waters, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-5.CZH-5 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-5, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 10 % by weight, and alumina content is 90% weight.
(2) reference silica-alumina and preparation thereof:
Continue on double screw banded extruder to say that whole aforementioned CZH-5 are extruded into the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-5 through 120 ℃ of dryings.The silica content of CSA-5, specific area, pore volume and pore size distribution data are listed in table 2.The aluminium oxide that is provided by P2-3 accounts in carrier all 60% of alumina contents.
PV in table 2 (4-10)/PV is always the pore volume of 4-10 nanometer shared ratio in total pore volume for bore dia.
Table 2
As can be seen from Table 2, the invention provides that silica-alumina PV (4-10)/the PV total value is all greater than 75%, and the PV of Comparative Examples silica-alumina (4-10)/PV is all below 75%.Therefore, silica-alumina of the present invention has more concentrated pore size distribution.
Embodiment 6-10 explanation is adopted and be the invention provides the catalyst that silica-alumina is the carrier preparation.
The catalyst of reference carrier preparation is adopted in Comparative Examples 6-10 explanation.
The raw material sources that Kaolinite Preparation of Catalyst uses are as follows: ammonium molybdate, Anqing moon metallurgy of copper chemical industry Co., Ltd product, technical grade; Ammonium metatungstate, Zhuzhou diamond tungsten product Co., Ltd product, technical grade; Nickel nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product is analyzed pure; Basic nickel carbonate, Yixing Xu Chi chemical industry Co., Ltd product, chemical pure; Cobalt nitrate, Beijing Yili Fine Chemicals Co., Ltd. analyzes pure; Phosphoric acid, Beijing Chemical Plant's product, analyze pure, 85% concentration; Ammoniacal liquor, 25% concentration, Beijing Chemical Plant's product is analyzed pure; Citric Acid Mono, Beijing Chemical Plant's product is analyzed pure; Ammonium fluoride, chemical plant, Jinan product is analyzed pure.
Embodiment 6
Get silica-alumina SA-1 200 grams, with 190 milliliters of aqueous solution dippings that contain ammonium molybdate 36 grams, nickel nitrate 29 grams, phosphatase 11 1.9 grams 2 hours, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours obtained catalyst C-1.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst C1, measurement result is as shown in table 3.
Comparative Examples 6
Get reference silica-alumina CSA-1 200 grams, contain ammonium molybdate (Anqing moon metallurgy of copper chemical industry Co., Ltd product with 205 milliliters, technical grade) 36 grams, nickel nitrate (Beijing Yili Fine Chemicals Co., Ltd.'s product, analyze pure) 29 grams, phosphoric acid (Beijing Chemical Plant's product, analyze pure, concentration 85%) aqueous solution dipping 2 hours of 11.9 grams, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours obtain catalyst DC-1.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst DC1, measurement result is as shown in table 3.
Embodiment 7
Get silica-alumina SA-2 200 grams, with 160 milliliters of dilute ammonia solutions (10% concentration) dippings that contain ammonium molybdate 28 grams, cobalt nitrate 18 grams 2 hours, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst C-2.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst C-2, measurement result is as shown in table 3.
Comparative Examples 7
Get reference silica-alumina CSA-2 200 grams, with 164 milliliters of dilute ammonia solutions (10% concentration) dippings that contain ammonium molybdate 28 grams, cobalt nitrate 18 grams 2 hours, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst DC-2.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst DC-2, measurement result is as shown in table 3.
Embodiment 8
Get silica-alumina SA-3 200 grams, with 170 milliliters of the aqueous solution dipping that contains molybdenum oxide 57 grams, basic nickel carbonate 28 grams, phosphoric acid 23 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyst C-3.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst C-3, measurement result is as shown in table 3.
Comparative Examples 8
Get reference silica-alumina CSA-3 200 grams, with 182 milliliters of the aqueous solution dipping that contains molybdenum oxide 57 grams, basic nickel carbonate 28 grams, phosphoric acid 23 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyst DC-3.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst DC-3, measurement result is as shown in table 3.
Embodiment 9
Get silica-alumina SA-4 200 grams, with the aqueous solution of 172 milliliters of fluorinated ammonium 19 grams dipping 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst fluorine bar F-1.
Get fluorine bar F-1 200 grams, with 158 milliliters of aqueous solution dipping fluorine bars that contain ammonium metatungstate 109 grams, nickel nitrate 45 grams 2 hours, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst C-4.Take catalyst weight as benchmark, adopt the chemical composition in XRF light measurement catalyst C-4, measurement result is as shown in table 3.
Comparative Examples 9
Get reference silica-alumina CSA-4 200 grams, with the aqueous solution of 156 milliliters of fluorinated ammonium 19 grams dipping 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst fluorine bar CF-1.
Get fluorine bar CF-1 200 grams, with 140 milliliters of aqueous solution dipping fluorine bars that contain ammonium metatungstate 109 grams, nickel nitrate 45 grams 2 hours, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst DC-4.Take catalyst weight as benchmark, adopt the chemical composition in XRF light method mensuration catalyst DC-4, measurement result is as shown in table 3.
Embodiment 10
Get silica-alumina SA-5 200 grams, with the 148 milliliters of impregnated carriers of the aqueous solution 2 hours that contain ammonium molybdate 20 grams, phosphatase 11 6 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained containing molybdenum carrier 225 grams.
Contained the molybdenum carrier 2 hours with the 110 milliliters of dippings of the aqueous solution that contain ammonium metatungstate 45 grams, basic nickel carbonate 14 grams, Citric Acid Mono 32 grams, in 120 ℃ of dryings 4 hours, 200 ℃ of dryings 4 hours obtained catalyst C-5.Take catalyst weight as benchmark, adopt the chemical composition in XRF light method mensuration catalyst C-5, measurement result is as shown in table 3.
Comparative Examples 10
Get reference silica-alumina CSA-5 200 grams, with the 161 milliliters of impregnated carriers of the aqueous solution 2 hours that contain ammonium molybdate 20 grams, phosphatase 11 6 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained containing molybdenum carrier 226 grams.
Contained the molybdenum carrier 2 hours with the 120 milliliters of dippings of the aqueous solution that contain ammonium metatungstate 45 grams, basic nickel carbonate 14 grams, Citric Acid Mono 32 grams, in 120 ℃ of dryings 4 hours, 200 ℃ of dryings 4 hours obtained catalyst DC-5.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst DC-5, measurement result is as shown in table 3.
Table 3
Embodiment 11-15 explanation method provided by the invention and effect thereof.
Reference method and effect thereof are adopted in Comparative Examples 11-15 explanation.
Embodiment 11
4 of the present embodiment explanation catalyst C-1 of the present invention, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) hydrodesulfurization reaction performance.
Reaction is carried out on the little inverse spectral apparatus of continuous-flow, and feedstock oil is for containing the n-decane solution of 4,6-DMDBT, 0.45 % by weight, and the catalyst loading amount is 150 milligrams.
Before formal charging, be first that sulfurized oil carries out presulfurization to catalyst with the mixed solution that contains 5 % by weight carbon disulfide and cyclohexane, conditions of vulcanization is: pressure 4.1 MPas, 360 ℃ of temperature, 4 hours time, sulfurized oil feed rate 0.4 ml/min, H
2Flow velocity 400 ml/min; Cut afterwards feedstock oil and react, reaction condition is: pressure 4.1 MPas, and feedstock oil input 0.2 ml/min, volume of hydrogen oil ratio are 2000, temperature is 280 ℃, reacts the online gas chromatographic analysis of sampling after 3 hours.
Comparative Examples 11
4 of this Comparative Examples explanation reference catalyst DC-1,6-DMDBT hydrodesulfurization reaction performance, evaluation method is with example 7.
4,6-DMDBT hydrodesulfurization activity is calculated as follows;
In formula, x is 4,6-DMDBT desulfurization degree, and the activity of getting catalyst DC-1 is 100,4 of catalyst C-1 of the present invention, and 6-DMDBT is relative, and hydrodesulfurization activity can be represented by the formula: relative activity=A
C-1/ A
DC-1* 100%.A in formula
C-1Be the activity of catalyst C-1 of the present invention, A
DC-1Activity for Comparative Examples catalyst DC-1.
4 of catalyst C-1 and DC-1, the 6-DMDBT hydrodesulfurization activity is listed in table 4.
Table 4
| Catalyst | Relative hydrodesulfurization activity, % | |
| Embodiment 11 | C-1 | 114 |
| Comparative Examples 11 | DC-1 | 100 |
Embodiment 12
The decompressed wax oil hydrotreatment performance of the present embodiment explanation catalyst C-2 of the present invention.
Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-2 on 250 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 5, and reaction result sees Table 6.
The assay method of sulphur is SH/T 0253-92, and the nitrogen determination method is SH/T 0657-1998.The hydrodesulfurization activity of catalyst calculates by 1.5 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and related computing formula is as follows, and in formula, LHSV is liquid hourly space velocity (LHSV).
Table 5
| Feedstock oil character | Decompressed wax oil |
| Density (20 ℃), g/cm 3 | 0.9113 |
| S，ppm | 20000 |
| N，ppm | 1100 |
| Index of refraction (70C) | 1.4875 |
| Boiling range (D1160), ℃ | |
| Initial boiling point | 258 |
| 50% point | 452 |
| 95% point | 515 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 8.0 |
| Catalyst volume, ml | 100 |
| Temperature, ℃ | 375 |
| Volume space velocity, h -1 | 1.4 |
| Hydrogen-oil ratio, v/v | 800 |
Comparative Examples 12
The decompressed wax oil hydrotreatment performance of this Comparative Examples explanation reference catalyst DC-2.
According to the method evaluation comparative catalyst DC-2 of embodiment 12, reaction result sees Table 6, take the activity of DC-2 catalyst as 100.
Table 6
Embodiment 13
The straight-run diesel oil hydrofinishing performance of the present embodiment explanation catalyst C-3 of the present invention.
Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-3 on 30 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 7, and reaction result sees Table 8.The hydrodesulfurization activity of catalyst calculates by 1.65 order reactions, and related computing formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and computing formula is seen embodiment 12.
Table 7
| Feedstock oil character | Straight-run diesel oil |
| Density (20 ℃), g/cm 3 | 0.8456 |
| S，ppm | 8000 |
| N，ppm | 144 |
| Index of refraction (20 ℃) | 1.4723 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 3.2 |
| Catalyst volume, ml | 30 |
| Temperature, ℃ | 350 |
| Volume space velocity, h -1 | 2.0 |
| Hydrogen-oil ratio, v/v | 300 |
Comparative Examples 13
The straight-run diesel oil hydrofinishing performance of this Comparative Examples explanation reference catalyst DC-3.
According to the method evaluation reference catalyst DC-3 of embodiment 13, reaction result is listed in table 8, take the activity of DC-3 catalyst as 100.
Table 8
Embodiment 14
The saturated performance of catalytic diesel oil aromatic hydrogenation of the present embodiment explanation catalyst C-4 of the present invention.
Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-4 on 30 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 9, and reaction result sees Table 10.The arene saturating activity of catalyst calculates by first order reaction, and related computing formula is as follows.Arene content adopts the application of gas chromatorgraphy/mass method to measure.
Comparative Examples 14
The saturated performance of catalytic diesel oil aromatic hydrogenation of this Comparative Examples explanation reference catalyst DC-4.
According to the catalytic diesel oil arene saturating activity of the method evaluation reference catalyst DC-4 of embodiment 14, reaction result is listed in table 10, take the toluene hydrogenation activity of DC-4 as 100.
Table 9
| Feedstock oil character | Catalytic diesel oil |
| Density (20 ℃), g/cm 3 | 0.9026 |
| S，ppm | 4500 |
| N，ppm | 833 |
| Total aromatic hydrocarbons, % | 64.5 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 6.0 |
| Catalyst volume, ml | 30 |
| Temperature, ℃ | 350 |
| Volume space velocity, h -1 | 1.5 |
| Hydrogen-oil ratio, v/v | 500 |
Table 10
| Catalyst | Relative arene saturating activity, % | |
| Embodiment 14 | C-4 | 130 |
| Comparative Examples 14 | DC-4 | 100 |
Embodiment 15
This illustrates the hydrotreatment performance of the liquefied coal coil simulated oil of catalyst C-5 of the present invention to embodiment.
Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-5 on 250 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 11, and reaction result sees Table 12.Hydrodenitrogenationactivity activity is calculated by 1 order reaction, and computing formula is seen embodiment 12.
Comparative Examples 15
The hydrotreatment performance of the liquefied coal coil simulated oil of this Comparative Examples explanation reference catalyst DC-5.
According to the method evaluation reference catalyst DC-5 of embodiment 15, result is provided by table 12, take the hydrodenitrogenationactivity activity of DC-5 as 100.
Table 11
| Feedstock oil character | The liquefied coal coil simulated oil |
| Density (20 ℃), g/cm 3 | 0.8814 |
| S，ppm | 2500 |
| N，ppm | 5100 |
| O，％ | 1.95 |
| Index of refraction (20 ℃) | 1.4808 |
| Reaction condition | |
| The hydrogen dividing potential drop, MPa | 10 |
| Catalyst volume, ml | 30 |
| Temperature, ℃ | 380 |
| Volume space velocity, h -1 | 2.5 |
| Hydrogen-oil ratio, v/v | 500 |
Table 12
| Catalyst | Relative denitrification activity, % | |
| Embodiment 15 | C-5 | 117 |
| Comparative Examples 15 | DC-5 | 100 |
By the result in table 4～table 12 as can be known, the hydrogenation catalyst of the silica-alumina preparation that provides than prior art of the hydrogenation catalyst of silica-alumina provided by the invention preparation has better hydrocarbons hydrogenation handling property.
Claims (18)
1. the composition of a boehmite and silicon-containing compound, is characterized in that, described boehmite comprises the boehmite P1 of at least a 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 XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of diffraction maximum, 2 θ are the position of diffraction maximum.
2. composition according to claim 1, is characterized in that, described P1 is the boehmite of 1.2≤n≤2.2.
3. composition according to claim 1, is characterized in that, in oxide, in the composition of described boehmite and silicon-containing compound, the content of boehmite is the 65-99 % by weight, and the content of silicon-containing compound is the 1-35% % by weight.
4. composition according to claim 3, is characterized in that, in oxide, in the composition of described boehmite and silicon-containing compound, the content of boehmite is the 75-97 % by weight, and the content of silicon-containing compound is the 3-25% % by weight.
5. composition according to claim 4, is characterized in that, in oxide, in the composition of described boehmite and silicon-containing compound, the content of boehmite is the 80-95% % by weight, and the content of silicon-containing compound is the 5-20% % by weight.
6. according to claim 1,3, the 4 or 5 described compositions of any one, it is characterized in that, described silicon-containing compound is selected from one or more in organic silicon-containing compound.
7. composition according to claim 6, described silicon-containing compound is selected from one or more in esters of silicon acis, silanol, silicon ether, silicone, silicone oil.
8. according to claim 1,3, the 4 or 5 described compositions of any one, it is characterized in that, described silicon-containing compound is selected from one or more in inorganic silicon-containing compound.
9. composition according to claim 8, is characterized in that, described inorganic silicon-containing compound is selected from one or more in silica gel, Ludox, silicic acid, waterglass.
10. composition according to claim 1, is characterized in that, contains the boehmite P2 of 0.8＜n＜1.1 in described composition, and in oxide and take the boehmite total amount as benchmark, the content of described P2 is not more than 70 % by weight.
11. composition according to claim 10 is characterized in that, described P2 is the boehmite of 0.85≤n≤1.05, and in oxide and take the boehmite total amount as benchmark, the content of described P2 is not more than 50 % by weight.
12. composition according to claim 11 is characterized in that, in oxide and take the boehmite total amount as benchmark, the content of described P2 is not more than 30 % by weight.
13. silica-alumina, this silica-alumina is obtained by the composition roasting of boehmite and silicon-containing compound, it is characterized in that, the composition of described boehmite and silicon-containing compound is the described composition of any one in claim 1-12.
14. silica-alumina according to claim 13 is characterized in that, described silica-alumina is the moulding silica-alumina.
15. silica-alumina according to claim 14 is characterized in that, described moulding silica-alumina is bar shaped, and the preparation method of described bar shaped silica-alumina comprises:
(1) the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1, silicon-containing compound and water are mixed being enough under the condition of pulp, filter afterwards, dry or moist, obtain described composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
16. silica-alumina according to claim 14 is characterized in that, described moulding silica-alumina is bar shaped, and the preparation method of described bar shaped silica-alumina comprises:
(1) on kneading machine or grinder, the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1 are mixed with silicon-containing compound, obtain described composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
17. the 15 or 16 described silica-aluminas of any one according to claim 13,, it is characterized in that, the dry also condition of roasting of described extrusion molding thing comprises: baking temperature is 50-200 ℃, 0.3-12 hour drying time, sintering temperature is 400-900 ℃, roasting time 1-12 hour.
18. silica-alumina according to claim 17 is characterized in that, the dry also condition of roasting of described extrusion molding thing comprises: baking temperature is 60-150 ℃, and 0.5-8 hour drying time, sintering temperature is 500-750 ℃, roasting time 2-8 hour.
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| CN1597092A (en) * | 2003-09-17 | 2005-03-23 | 中国石油化工股份有限公司 | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method |
| WO2006054447A1 (en) * | 2004-11-22 | 2006-05-26 | Idemitsu Kosan Co., Ltd. | Iron-containing crystalline aluminosilicate, hydrocracking catalyst comprising the aluminosilicate, and method of hydrocracking with the catalyst |
| CN102189002A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Pseudo-boehmite and molecular sieve composition and carrier prepared from same |
| CN102205249A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Catalytic de-waxing catalyst and its application |
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| CN1597092A (en) * | 2003-09-17 | 2005-03-23 | 中国石油化工股份有限公司 | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method |
| WO2006054447A1 (en) * | 2004-11-22 | 2006-05-26 | Idemitsu Kosan Co., Ltd. | Iron-containing crystalline aluminosilicate, hydrocracking catalyst comprising the aluminosilicate, and method of hydrocracking with the catalyst |
| CN102189002A (en) * | 2010-03-04 | 2011-09-21 | 中国石油化工股份有限公司 | Pseudo-boehmite and molecular sieve composition and carrier prepared from same |
| CN102205249A (en) * | 2010-03-31 | 2011-10-05 | 中国石油化工股份有限公司 | Catalytic de-waxing catalyst and its application |
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