CN102266760B - Heavy-oil hydrogenating catalyst and application thereof - Google Patents
Heavy-oil hydrogenating catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to a heavy-oil hydrogenating catalyst and application thereof. The heavy-oil hydrogenating catalyst contains a carrier and a hydrogenating active metal component, wherein the carrier is prepared by the step of roasting a boric pseudoboehmite; based on the dry basis of the pseudoboehmite, the content of boron (boron oxide) in the pseudoboehmite is 1-10wt%; the pseudoboehmite contains at least one pseudoboehmite P1 meeting the relation that n is more than or equal to 1.1 but less than or equal to 2.5; n is equal to D(031)/D(120); the D(031) represents a grain size of a crystal surface represented by peak 031 in an XRD (X-Ray Diffraction) spectrogram of pseudoboehmite grains; the D(120) represents the grain size of the crystal surface represented by peak 120 in the XRD spectrogram of pseudoboehmite grains; the peak 031 is a peak with a 2theta being 34-43 degrees in the XRD spectrogram; the peak 120 is the peak with the 2theta being 23-33 degrees in the XRD spectrogram; D is equal to K Lambda/(Bcos theta); K is Scherrer constant; Lambda is a diffraction wavelength of a target material; B is a half-peak width of a refraction peak; and 2theta is the position of the refraction peak.
Description
Invention field
The present invention relates to a kind of hydrotreating catalyst and application thereof, particularly relate to a kind of heavy oil hydrogenating treatment catalyst and application thereof.
Background technology
Day by day scarcity along with petroleum resources, the contradiction of crude oil heaviness and product lighting is becoming increasingly acute, the countries in the world oil refining enterprise is all mixed refining or is entirely refined catalytic cracking (RFCC) technology of residual oil and the thermal cracking technology such as coking greatly developing, and wherein RFCC technique becomes the most effectively technique of light materialization of heavy oil.But the impurity of high-load in the residual oil has larger impact such as sulphur, nitrogen, metal and carbon residue etc. to the stable operation of RFCC process unit.In order to increase resid feed to the adaptability of RFCC device, as the raw material preprocessing device of RFCC device, taking off percentage of admixture, particularly desulfurization degree, demetallization per and taking off carbon yield of residue fixed-bed hydrotreater beds just seems particularly important.
Alumina support is the carrier of this type of catalyst of preparation, the pore structure that can reach optimization of catalysts by selection and modification to alumina support, and then improve the purpose of catalyst performance.For example:
CN101332430A discloses a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof.Catalyst contains at least a VIII family and at least a metal component that is selected from VI B of being selected from of carrier and effective dose.Wherein said carrier is a kind of alumina support that meets of boracic, in element, take the total amount of described carrier as benchmark, the content of boron is the 0.3-5 % by weight in the described carrier, described carrier acid amount is 0.2～0.5mmol/g, wherein, the weak acid amount that is lower than 250 ℃ accounts for the 50-100% of total acid content, and is higher than the 0-5% that 450 ℃ strong acid accounts for total acid content.This invention provides catalyst when keeping high hydrotreatment activity, the anti-carbon performance be improved significantly.
Summary of the invention
The technical problem to be solved in the present invention provides that a kind of new, performance is improved to be particularly suitable for catalyst and the application thereof that heavy-oil hydrogenation is processed.
The invention provides a kind of heavy oil hydrogenating treatment catalyst, this catalyst contains carrier and hydrogenation active metals component, it is characterized in that, described carrier is obtained through roasting by a kind of boehmite of boracic, in oxide, and take the butt of described boehmite as benchmark, the content of boron is the 1-10 % by weight in the described boehmite, and described boehmite is the boehmite P1 that comprises at least a 1.1≤n≤2.5; Wherein, its 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 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 shaped material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
The invention provides a kind of heavy oil hydrogenation treatment method, be included under the heavy-oil hydrogenation processing reaction condition heavy raw oil is contacted with hydrotreating catalyst, described catalyst is aforementioned catalyst provided by the invention.
The performance that the invention provides catalyst obviously improves.For example, in the identical situation of hydrogenation active metals content, the preparation condition of catalyst, adopt the catalyst of carrier preparation provided by the invention when being used for residuum hydrogenating and metal-eliminating, removing than reference catalyst of its (Ni+V) can improve 10%.
The specific embodiment
According to catalyst provided by the invention, in oxide, and take the butt of described boehmite as benchmark, the content of boron is preferably the 1-8 % by weight in the described boehmite, 2-6 % by weight more preferably, wherein said P1 is preferably the boehmite of 1.2≤n≤2.2.Butt described here refers to described boehmite percentage of the ratio of weight before the weight of 600 ℃ of roastings after 4 hours and the roasting under air atmosphere.
Under the prerequisite that boron content in being enough to make the boehmite of described boracic meets the demands, the introducing method of described boron is not particularly limited.For example, can be in the process of the boehmite P1 for preparing described 1.1≤n≤2.5, to introduce boron-containing compound, also can be the boehmite P1 that at first prepares described 1.1≤n≤2.5, the method for afterwards it being mixed with boron-containing compound is introduced.
Described boron-containing compound can be water miscible such as boric acid, boron oxide or borate, also can be non-water-soluble boride, such as halogenation boron etc.
Wherein, 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; Hydrated alumina obtained above 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 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, 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 the selective hydrolysis reaction; The consumption of grain growth conditioning agent is the inorganic 0.5-10 % by weight that contains al reactant weight in the described precipitation reaction, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In the 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, among 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.Also be, in aluminium oxide, in the 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 the 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 the described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 % by 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 after the two kinds or more of mixing.Described aluminate solution is aluminate solution arbitrarily, such 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, the oxalic acid, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, the 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, and the concentration of preferred H+ is 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, 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/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 the 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, in the aluminum alkoxide of generation aqua oxidation aluminum precipitation one or more for example can be one or more in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the 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 the 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 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, then under suitable temperature, wear out.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 such as the method for filtration or centrifugation or evaporation.
In boracic 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 boracic boehmite of the present invention, a preferred embodiment 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; The hydrated alumina slurries that also 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.
When introducing described boracic add the compound of component in the process of boehmite P1 of preparation described 1.1≤n≤2.5, described boracic adds the compound of component can be introduced in above-mentioned step (1), (2), (3) or (4) any one or several step.
According to catalyst provided by the invention, wherein said 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 contained P2, 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 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 preparation.
According to catalyst provided by the invention, optionally can be made into the arbitrarily article shaped of convenient operation, catalyst provided by the invention can adopt the usual method preparation of the art, for example the preparation method of preformed catalyst comprises: the preparation shaping carrier, and at least a VIII family and at least a metal component that is selected from VI B family of being selected from of carrier introducing.Described moulding can be carried out according to a conventional method, all can such as methods such as compressing tablet, spin, extrusions.For guaranteeing carrying out smoothly of moulding, when moulding, usually need in material (being boehmite), introduce auxiliary agent and water etc. herein, for example, when adopting the moulding of extrusion method, comprise described boehmite and an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the cellulose one or more) are mixed then extrusion molding.Article shaped drying, roasting obtain carrier.Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-6 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-2 hour drying time.The method of described roasting is conventional method, carries out roasting as adopting mesh-belt kiln, vertical examination stove and converter, and preferred roasting condition comprises: temperature is 350-1200 ℃, and roasting time 1-12 hour, preferred sintering temperature was 600-1100 ℃, time 2-8 hour.Afterwards, described at least a group VIB and at least a metal component of group VIII of being selected from is carried under the prerequisite on the described aluminium oxide being enough to, can adopts any known hydrogenation class method for preparing catalyst preparation.For example, under the condition that is enough to the nickel that is selected from VIII family of effective dose and/or cobalt metal component be deposited on the described carrier, the solution of described carrier with the compound that contains the nickel that is selected from VIII family containing of effective dose and/or cobalt metal component is contacted, such as the method by dipping, carry out afterwards the method preparation of drying, roasting or not roasting.The condition of described drying is 80～350 ℃ for the habitual condition of this type of catalyst of preparation such as baking temperature, is preferably 100～300 ℃, and be 1～24 hour drying time, is preferably 2～12 hours.When described catalyst need to carry out roasting, described temperature was preferably 100-700 ℃, and roasting time is 1-6 hour, and further preferred temperature is preferably 200-500 ℃, and roasting time is 2-4 hour.
Described group VIII metal compound is selected from one or more in the group VIII metal soluble compound, such as in the nitrate of cobalt and/or nickel metal, acetate, soluble carbonate salt, chloride, the soluble complexes one or more.
Described group VIB metallic compound is selected from one or more in the group VIB metal soluble compound, such as in molybdate, tungstates, metatungstate, the ethyl metatungstate one or more.
According to catalyst provided by the invention, can also contain the material that any material that does not affect the catalytic performance that the invention provides catalyst maybe can improve the catalytic performance of catalyst provided by the invention.As introducing in the components such as phosphorus or silicon one or both, in element and take catalyst as benchmark, the introducing amount of above-mentioned auxiliary agent is the 0-10 % by weight, is preferably the 0.5-5 % by weight.
During one or both components in also containing components such as being selected from phosphorus or silicon in the described catalyst, its introducing method can be that the compound that will contain described auxiliary agent directly mixes with boehmite, moulding and roasting; Can be the compound that to contain described auxiliary agent and contact with described alumina support after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be to contact and roasting with described alumina support behind the independent obtain solution of the compound that contains auxiliary agent.When auxiliary agent and hydrogenation active metals are introduced described alumina support respectively, preferably at first auxiliary compound solution contacts with described alumina support and roasting with containing, contact with the solution of the compound that contains the hydrogenation active metals component more afterwards, for example pass through the method for dipping, described sintering temperature is 250-600 ℃, be preferably 350-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to heavy oil hydrogenation treatment method provided by the present invention, described heavy-oil hydrogenation processing reaction condition is not particularly limited, in preferred embodiment, described HDM reaction condition is: reaction temperature 300-550 ℃, further preferred 330-480 ℃, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 hour
-1, further preferred 0.15-2 hour
-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of described hydrogenation reaction can be enough to make described feedstock oil to carry out under the hydrotreatment reaction condition with in the catalytic reaction dress of the described catalyst device any, for example, at described fixed bed reactors, carries out in moving-burden bed reactor or the fluidized bed reactor.
According to the conventional method in this area, described hydrotreating catalyst is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.
Catalyst provided by the invention can use separately, also can use with other catalyst combination, this catalyst be particularly suitable for heavy oil particularly poor residuum carry out HDM, in order to provide qualified feedstock oil for subsequent technique (such as catalytic cracking process).
The below will illustrate the present invention by example.Agents useful for same in the example except specifying, is chemically pure reagent.
Embodiment 1-6 explanation is suitable for preparing the boehmite that the invention provides catalyst and use, aluminium oxide and preparation method thereof.
Embodiment 1
(1) boracic boehmite
In one 2 liters retort and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum sulfate solution of 3.6 gram ribitol and the ammonia spirit that concentration is 8 % by weight and carry 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 ammoniacal liquor in slurries, to make the pH value of slurries be 8.5, slurries filter after 55 ℃ of lower wearing out 60 minutes, filter cake washs 2 times with the deionized water making beating, filter cake obtains hydrated alumina through 120 ℃ of dryings 24 hours.With the hydrated alumina that obtains and 60mL concentration be 19.2 gram diboron trioxides/liter boric acid aqueous solution mix, 120 ℃ of dryings 12 hours obtain boracic hydrated alumina P1-1, adopt XRD to characterize, P1-1 has structure of similar to thin diaspore.
XRD measures 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 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 calculate n=D (031)/D (120), characterize the n value that calculates P1-1 through XRD and list in the table 1.
(2) boron-containing alumina
With (1) obtain 200 the gram P1-1, after adding respectively 4 gram nitric acid and 200 gram deionized waters mixing, beginning is kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 1000 ℃ of lower roastings 4 hours, obtain boron-containing alumina carrier Z1, the character of Z1 is listed in table 2, and wherein the content of boron is calculated value (lower same).
Comparative Examples 1-7 explanation reference boehmite, aluminium oxide and preparation method thereof.
Comparative Examples 1
(1) boracic boehmite
Method according to embodiment 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, also be not contain ribitol in the aluminum sulfate solution, obtain hydrated alumina P2-1.Method according to embodiment 1 adopts XRD to characterize, 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.
(2) boron-containing alumina
Get 200 gram P2-1, add respectively after 4 gram nitric acid and 200 gram deionized waters mix kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 1000 ℃ of lower roastings 4 hours, obtain alumina support DZ1.The character of DZ1 is listed in table 2.
Embodiment 2
(1) boracic boehmite
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 the NaAlO that gluconic acid sodium salt 16.3 grams obtain containing gluconic acid sodium salt
2Then solution be transferred in the one-tenth glue reactor of cumulative volume 8L, and the reactor ratio of height to diameter is 8, bottom band CO
2Gas distributor.The control solution temperature is 25 ± 5 ℃, passes into the CO of concentration 90 volume % from reactor bottom
2Gas becomes the glue reaction, becomes the glue temperature to be 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 into the glue reaction.With the gained slurries be heated to 70 ℃ aging 4 hours, then filter with vacuum filter, to be filtered complete after, replenish at filter cake and to add 20 liters of deionized waters (temperature 70 C) flush cake approximately 30 minutes.With the washing qualified filter cake join 1.5 liters of concentration be 4 the gram diboron trioxides/liter boric acid aqueous solution in stir into slurries, slurries carry out drying with being pumped into spray dryer, obtain hydrated alumina P1-2.Method according to embodiment 1 adopts XRD to characterize, 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.
(2) boron-containing alumina
With (1) obtain 200 the gram P1-2, after adding respectively 4 gram nitric acid and 200 gram deionized waters mixing, kneading on kneading machine, kneading 1 hour, then be squeezed into diameter and be 0.8 millimeter, the column of long 3-5 millimeter, wet bar is through 120 ℃ of dryings after 4 hours, 950 ℃ of lower roastings 4 hours, obtain boron-containing alumina carrier Z2, the character of Z2 is listed in table 2.
Comparative Examples 2
(1) boracic boehmite
Method according to embodiment 2 prepares boehmite, and different is, does not contain gluconic acid sodium salt in the sodium aluminate solution, obtains hydrated alumina P2-2.Method according to embodiment 1 adopts XRD to characterize, and P2-2 has structure of similar to thin diaspore, characterizes the n value that calculates P2-2 through XRD and lists in the table 1.
(2) boron-containing alumina
Get 200 gram P2-2, add respectively after 4 gram nitric acid and 200 gram deionized waters mix kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 950 ℃ of lower roastings 4 hours, obtain alumina support DZ2.The character of DZ2 is listed in table 2.
Embodiment 3
(1) boracic boehmite
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 be 80 ℃, conditioned reaction logistics capacity so that in and the pH value be 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 to add 20 liters of deionized waters (80 ℃ of temperature) flush cake approximately 30 minutes at filter cake.With the washing qualified filter cake join 200mL concentration be 21.6 the gram diboron trioxides/liter boric acid aqueous solution in stir into slurries, slurries carry out drying with being pumped into spray dryer, control spray dryer outlet temperature is 100-110 ℃ of scope, approximately 2 minutes dry materials time, obtain hydrated alumina P1-3 after the drying.Method according to embodiment 1 adopts XRD to characterize, and P1-3 has structure of similar to thin diaspore, characterizes the n value that calculates P1-3 through XRD and lists in the table 1.
(2) boron-containing alumina
With (1) obtain 200 the gram P1-3, after adding respectively 4 gram nitric acid and 200 gram deionized waters mixing, kneading on kneading machine, kneading 1 hour, then be squeezed into diameter and be 0.8 millimeter, the column of long 3-5 millimeter, wet bar is through 120 ℃ of dryings after 4 hours, 900 ℃ of lower roastings 4 hours, obtain boron-containing alumina carrier Z3, the character of Z3 is listed in table 2.
Comparative Examples 3
(1) boracic boehmite
Method according to embodiment 3 prepares boehmite, and different is, aluminum sulfate solution change into concentration be 48 gram aluminium oxide/liter aluminum trichloride solution, and do not contain D-sorbite in the sodium aluminate solution, obtain hydrated alumina P2-3.Method according to embodiment 1 adopts XRD to characterize, and P2-3 has structure of similar to thin diaspore, characterizes the n value that calculates P2-3 through XRD and lists in the table 1.
(2) boron-containing alumina
Get 200 gram P2-3, add respectively after 4 gram nitric acid and 200 gram deionized waters mix kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 900 ℃ of lower roastings 4 hours, obtain alumina support DZ3.The character of DZ3 is listed in table 2.
Embodiment 4
(1) boracic boehmite
In one 2 liters retort and stream add 800 ml concns be 60 gram aluminium oxide/liter, gluconic acid content be the aluminum nitrate solution of 3.9 grams per liters and 300 milliliters contain 200 gram aluminium oxide/liter, concentration be 18 the gram diboron trioxides/liter boric acid aqueous solution, the causticity coefficient is that 1.58 sodium aluminate solution carries out precipitation reaction, reaction temperature is 55 ℃, the conditioned reaction logistics capacity so that in and the pH value be 7.0, reaction stops after 15 minutes and filters, the gained solid is pulled an oar with deionized water, then adding concentration in the gained slurries is the sodium bicarbonate solution of 150 grams per liters, regulate slurries pH to 9.0, and be warming up to 65 ℃, aging 5 hours, then filter with vacuum filter, to be filtered complete after, replenish to add 20 liters of deionized waters (65 ℃ of temperature) flush cake approximately 30 minutes at filter cake.Filter cake obtains hydrated alumina P1-4 through 120 ℃ of dryings 24 hours.Method according to embodiment 1 adopts XRD to characterize, and P1-4 has structure of similar to thin diaspore, characterizes the n value that calculates P1-4 through XRD and lists in the table 1.
(2) boron-containing alumina
With (1) obtain 200 the gram P1-4, after adding respectively 4 gram nitric acid and 200 gram deionized waters mixing, kneading on kneading machine, kneading 1 hour, then be squeezed into diameter and be 0.8 millimeter, the column of long 3-5 millimeter, wet bar is through 120 ℃ of dryings after 4 hours, 800 ℃ of lower roastings 4 hours, obtain boron-containing alumina carrier Z4, the character of Z4 is listed in table 2.
Comparative Examples 4
(1) boracic boehmite
Method according to embodiment 4 prepares boehmite, and different is, the aluminum sulfate solution that contains glucose change into concentration be 60 gram aluminium oxide/liter aluminum nitrate solution, obtain hydrated alumina P2-4.Method according to embodiment 1 adopts XRD to characterize, and P2-4 has structure of similar to thin diaspore, characterizes the n value that calculates P2-4 through XRD and lists in the table 1.
(2) boron-containing alumina
Get 200 gram P2-4, after adding respectively 4 gram nitric acid and 200 gram deionized waters mixing, begin to mediate, kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 800 ℃ of lower roastings 4 hours, obtain alumina support DZ4.The character of DZ4 is listed in table 2.
Embodiment 5
(1) boracic boehmite
In 2 liters of there-necked flasks of band stirring and reflux condensing tube, adding the ribonic acid sodium content is azeotropic mixture (water content is 15 % by weight) 1000 grams of the isopropanol-water of 0.5 % by weight, be heated to 90 ℃, slowly be added dropwise in flask by separatory funnel 500 gram fusing aluminium isopropoxides, after the back flow reaction 24 hours, steam the dehydration isopropyl alcohol, then divide 1.5 liters of deionized waters that add ribonic acid sodium content 0.5 % by weight for 3 times, 90 ℃ were worn out 4 hours, in aging, steam aqueous isopropanol, after hydrated alumina after aging filters, through 120 ℃ of dryings 24 hours, obtain hydrated alumina.With the hydrated alumina that obtains and 100mL concentration be 74.1 gram diboron trioxides/liter boric acid aqueous solution mix, 120 ℃ of dryings 12 hours obtain boracic hydrated alumina P1-5.Method according to embodiment 1 adopts XRD to characterize, and P1-5 has structure of similar to thin diaspore, characterizes the n value that calculates P1-5 through XRD and lists in the table 1.
(2) boron-containing alumina
With (1) obtain 200 the gram P1-5, after adding respectively 4 gram nitric acid and 200 gram deionized waters mixing, kneading on kneading machine, kneading 1 hour, then be squeezed into diameter and be 0.8 millimeter, the column of long 3-5 millimeter, wet bar is through 120 ℃ of dryings after 4 hours, 700 ℃ of lower roastings 4 hours, obtain boron-containing alumina carrier Z5, the character of Z5 is listed in table 2.
Comparative Examples 5-
(1) boracic boehmite
Method according to embodiment 5 prepares boehmite, and different is, does not add ribonic acid sodium in the azeotropic mixture of isopropanol-water (water content is 15 % by weight) and the deionized water, obtains hydrated alumina P2-5.Method according to embodiment 1 adopts XRD to characterize, and P2-5 has structure of similar to thin diaspore, characterizes the n value that calculates P2-5 through XRD and lists in the table 1.
(2) boron-containing alumina
Get 200 gram P2-5, add respectively after 4 gram nitric acid and 200 gram deionized waters mix kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 700 ℃ of lower roastings 4 hours, obtain alumina support DZ5.The character of DZ5 is listed in table 2.
Embodiment 6
(1) boracic boehmite
The boehmite P1-2 that the laboratories of 280 grams are synthetic and 20 restrains P2-2 kneading 10 minutes on double screw banded extruder, obtains a kind of compound boehmite P1-2/P2-2.
(2) boron-containing alumina
The sesbania powder of above-mentioned compound boehmite P1-2/P2-2 and 10 grams is mixed, it at room temperature is 1% aqueous solution of nitric acid with the concentration of this mixture and 300 milliliters, mix, after double screw banded extruder continuation kneading is plastic, be extruded into the butterfly bar of 1.1 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain carrier Z6, the character of Z6 is listed in table 2.
Comparative Examples 6
(1) boracic boehmite not
P2-6 is the commercial boehmite product SB powder that Sasol company sells, and according to the method employing XRD sign of embodiment 1, it has structure of similar to thin diaspore, characterizes the n value that calculates this P2-6 powder through XRD and lists in the table 1.
(2) boron-containing alumina not
Get 200 gram P2-6, add respectively after 4 gram nitric acid and 200 gram deionized waters mix kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 900 ℃ of lower roastings 4 hours, obtain alumina support DZ6.The character of DZ6 is listed in table 2.
Comparative Examples 7
(1) boracic boehmite not
P2-7 is the commercial boehmite product SD powder that mountain aluminium company of Chalco joint-stock company sells, and according to the method employing XRD sign of embodiment 1, it has structure of similar to thin diaspore, characterizes the n value that calculates this P2-7 through XRD and lists in the table 1.
(2) boron-containing alumina not
Get 200 gram P2-7, add respectively after 4 gram nitric acid and 200 gram deionized waters mix kneading on kneading machine, then kneading 1 hour is squeezed into diameter and is 0.8 millimeter, the column of long 3-5 millimeter, and wet bar is through 120 ℃ of dryings after 4 hours, 900 ℃ of lower roastings 4 hours, obtain alumina support DZ7.The character of DZ7 is listed in table 2.
Table 1
From the results shown in Table 1, adopt the boracic boehmite of method preparation provided by the invention to have the feature of 1.1≤n≤2.5, preferred 1.2≤n≤2.2, and adopt the method for prior art and the n value of the various boehmites that are obtained commercially at present all less than 1.1.In addition, take the commercial SB powder of Condea company as benchmark, adopting the degree of crystallinity of the boehmite of method preparation provided by the invention is in the 50-80% scope.
Table 2
| Embodiment | The sample title | Pore volume ml/g | Specific area rice 2/ gram | Most probable bore dia nanometer |
| 1 | Z-1 | 0.70 | 110 | 19.3 |
| Comparative Examples 1 | DZ-1 | 0.68 | 125 | 17.3 |
| 2 | Z-2 | 0.75 | 135 | 16.2 |
| Comparative Examples 2 | DZ-2 | 0.70 | 145 | 15.2 |
| Example 3 | Z-3 | 0.80 | 170 | 13.7 |
| Comparative Examples 3 | DZ-3 | 0.75 | 190 | 12.1 |
| 4 | Z-4 | 0.83 | 200 | 12.3 |
| Comparative Examples 4 | DZ-4 | 0.78 | 212 | 12.1 |
| 5 | Z-5 | 0.88 | 244 | 8.7 |
| Comparative Examples 5 | DZ-5 | 0.86 | 261 | 8.1 |
| 6 | Z-6 | 0.82 | 256 | 7.5 |
| Comparative Examples 6 | DZ-6 | 0.65 | 180 | 12.2 |
| Comparative Examples 7 | DZ-7 | 0.6 | 190 | 12.2 |
Data from table 2 can find out, all in 0.6-1.2 ml/g of scope, BET nitrogen adsorption method specific area is in 100-300 meters squared per gram scope for the nitrogen adsorption method pore volume of boron-containing alumina, and the most probable bore dia is in the 8-25 nanometer range.
Embodiment 7～12 explanations are provided the catalyst of boron-containing alumina preparation by embodiment 1-6.
The boron-containing alumina carrier that embodiment 1-6 is obtained is used respectively the mixed solution of seven Ammonium paramolybdate tetrahydrates, ammoniacal liquor and nickel nitrate, carry out saturated dipping, preparation contains the catalyst of the nickel oxide of the molybdenum oxide of 8.0 % by weight and 1.8 % by weight, wet bar behind the dipping is through 120 ℃ of dryings after 4 hours, 450 ℃ of roastings 3 hours, obtain catalyst C1, C2, C3, C4, C5 and C6.
Comparative Examples 8～14
The carrier that adopts Comparative Examples 1～7 to obtain, according to embodiment 7 same procedure Kaolinite Preparation of Catalyst DC1, DC2, DC3, DC4, DC5, DC6 and DC7.
Embodiment 13～18 explanations the invention provides application and the effect thereof of catalyst.
Employing is feedstock oil by the invention provides boron-containing alumina Kaolinite Preparation of Catalyst processing branch Witter reduced crude, and in the feedstock oil (Ni+V 112.3 microgram/grams, S 4.7%, MCR 15.1%).
Catalyst is respectively: C1, C2, C3, C4, C5 and C6.
Reaction is carried out in fixed bed reactors, and reaction condition is: 380 ℃ of reaction temperatures, LHSV 0.50 hour, hydrogen dividing potential drop 14.0 MPas.
(Ni+V) content in the analytical reactions product the results are shown in such as table 3.
Application and the effect thereof of Comparative Examples 15～21 explanation Comparative Examples catalyst.
Operation carries out according to embodiment 13 supplying methods.
Catalyst is respectively: DC1, DC2, DC3, DC4, DC5, DC6 and DC7.
(Ni+V) content in the analytical reactions product the results are shown in such as table 3.
Table 3
| Embodiment | The sample title | (Ni+V) content in the product, % |
| 13 | C1 | 25.3 |
| Comparative Examples 15 | DC1 | 35.1 |
| 14 | C2 | 22.4 |
| Comparative Examples 16 | DC2 | 31.5 |
| 15 | C3 | 26.3 |
| Comparative Examples 17 | DC3 | 34.2 |
| 16 | C4 | 27.5 |
| Comparative Examples 18 | DC4 | 36.2 |
| 17 | C5 | 31.9 |
| Comparative Examples 19 | DC5 | 39.5 |
| 18 | C6 | 26.4 |
| Comparative Examples 20 | DC6 | 33.2 |
| Comparative Examples 21 | DC7 | 34.7 |
As can be seen from Table 3, when adopting the aluminium oxide that makes after the boracic boehmite provided by the invention roasting as catalyst carrier, this catalyst has a better demetalization performance in the situation that other condition is identical.
Claims (9)
1. heavy oil hydrogenating treatment catalyst, contain carrier and hydrogenation active metals component, described hydrogenation active metals component is selected from least a VIII of being selected from family and at least a metal component that is selected from group vib, in oxide and take catalyst as benchmark, the content of described VIII family metal component is the 0.6-6 % by weight, the content of described group vib metal component is the 1-10 % by weight, it is characterized in that, described carrier is obtained through roasting by a kind of boehmite of boracic, in oxide and take the butt of described boehmite as benchmark, the content of boron is the 1-10 % by weight in the described boehmite, and described boehmite comprises the boehmite P1 of at least a 1.1≤n≤2.5; Wherein, 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 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 shaped 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, described P1 is the boehmite of 1.2≤n≤2.2; In oxide and take the butt of described boehmite as benchmark, the content of boron is the 1-8 % by weight in the described boehmite.
3. catalyst according to claim 1 is characterized in that, in oxide, and take the butt of described boehmite as benchmark, the content of boron is the 2-6 % by weight in the described boehmite.
4. catalyst according to claim 1 is characterized in that, described roasting condition comprises: sintering temperature is 350-1200 ℃, and roasting time is 1-12 hour.
5. catalyst according to claim 4 is characterized in that, described roasting condition comprises: sintering temperature is 600-1000 ℃, and roasting time is 2-8 hour.
6. catalyst according to claim 1 is characterized in that, in oxide and take catalyst as benchmark, the content of described VIII family metal component is the 0.8-4 % by weight, and the content of described group vib metal component is the 2-8 % by weight.
7. catalyst according to claim 1 is characterized in that, described boehmite comprises the boehmite P2 of 0.8＜n＜1.1, and take described boehmite total amount as benchmark, the content of described P2 is not more than 50 % by weight.
8. catalyst according to claim 7 is characterized in that, described P2 is the boehmite of 0.85≤n≤1.05, and take described boehmite total amount as benchmark, the content of described P2 is not more than 30 % by weight.
9. heavy oil hydrogenation treatment method is included under the heavy-oil hydrogenation processing reaction condition heavy raw oil is contacted with hydrotreating catalyst, and described catalyst is the described catalyst of each claim of aforementioned claim 1-8.
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| CN114522693B (en) * | 2020-10-30 | 2023-07-14 | 中国石油化工股份有限公司 | Boron-containing heavy oil hydrotreating catalyst and heavy oil hydrotreating method |
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| CN85101162A (en) * | 1984-06-22 | 1987-01-10 | 飞力士石油公司 | The hydrofinishing process of hydrocarbon containing feed stream |
| CN1351115A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Demetalating and desulfurizing hydrocatalyst and its preparing process |
| CN101618326A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Heavy oil hydrogenation processing catalyst and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN85101162A (en) * | 1984-06-22 | 1987-01-10 | 飞力士石油公司 | The hydrofinishing process of hydrocarbon containing feed stream |
| CN1351115A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Demetalating and desulfurizing hydrocatalyst and its preparing process |
| CN101618326A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Heavy oil hydrogenation processing catalyst and method for preparing same |
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