CN101462078B - Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst - Google Patents
Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst Download PDFInfo
- Publication number
- CN101462078B CN101462078B CN 200710179765 CN200710179765A CN101462078B CN 101462078 B CN101462078 B CN 101462078B CN 200710179765 CN200710179765 CN 200710179765 CN 200710179765 A CN200710179765 A CN 200710179765A CN 101462078 B CN101462078 B CN 101462078B
- Authority
- CN
- China
- Prior art keywords
- acid
- catalyst
- hydrogenation
- pka value
- metal compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a hydrogenation catalyst soaking solution composition, which comprises a precursor of a hydrogenation active ingredient, a soaking additive and water, wherein the soaking additive has similar pKa value with that of the precursor of the hydrogenation active ingredient and comprises carbon-carbon double bond and/or carbon-carbon triple bond substances in molecular structure. The invention also provides a method for preparing a hydrogenation catalyst, which comprises: using the soaking solution to soak a catalyst carrier, and drying and roasting the catalyst carrier, wherein the soaking solution is the hydrogenation catalyst soaking solution composition. The hydrogenation catalyst prepared from the hydrogenation catalyst soaking solution composition has higher hydrogenation activity and higher cracking activity at the same reaction temperature compared with a hydrogenation catalyst prepared by the prior art.
Description
Technical field
The invention relates to a kind of hydrogenation catalyst steeping fluid composition and hydrogenization catalyst preparation method.
Background technology
In recent years, crude oil heavy and poor qualityization tendency are obvious day by day in the world wide, meanwhile, demand to premium, kerosene and diesel oil but constantly increases, this impels with heavy hydrocarbon oil is that raw material production premium, kerosene and diesel oil are that the hydrocracking technology of purpose is developed rapidly, and hydrofinishing and hydrocracking catalyst are one of the most important and The key factor of hydrocracking technology development.
Hydrocracking catalyst is a kind of bifunctional catalyst, and it has lytic activity and hydrogenation activity simultaneously, promptly contains acidic components and hydrogenation activity component simultaneously, and its acidity is mainly provided by heat-resistant inorganic oxide that constitutes carrier and/or various zeolite; The hydrogenation activity component generally is selected from metal, metal oxide and/or the metal sulfide of group vib and VIII family in the periodic table of elements.For reaching different requirements, need carry out adaptive modulation to acidic components in the catalyst and hydrogenation activity component to the hydrocracking product.
Silica-alumina material is the acidic components of using always, can be divided into molecular sieve and amorphous aluminum silicide two classes according to crystallization degree.Molecular sieve is used for the catalyst of the more acid site of needs, high reaction activity.Compare with molecular sieve, the amorphous aluminum silicide preparation method is simple, cost is low, bigger aperture is arranged, bigger silica alumina ratio adjusting range and lower sour density, is particularly suitable for handling big molecular raw material, as heavy oil and residual oil etc.; The catalyst that is usually used in the low sour density of needs is as distillate between senior middle school optionally hydrocracking catalyst and hydroisomerization catalyst.Amorphous aluminum silicide is the acid carrier of a lot of industrial amorphous catalysts, also is the important component part of many molecular sieve type catalysts, but the common disadvantage that the amorphous silicon aluminum exists is that cracking activity is lower.
For hydrocracking catalyst, the raising of catalyst performance requires the hydrogenation performance further to improve on the one hand; Cracking or isomery performance require suitable acidic components on the other hand, so that can be complementary with the purpose product.By selecting different molecular sieves or mesoporous material even solid super-strong acid, can adjust the character of acidic components in the larger context, thus the acid function of optimization catalyst.Yet the space of adjusting the hydrogenation performance by the selection hydrogenation component is limited, though noble metal can be used as hydrogenation component, but generally can not process the sulfur-bearing raw material, therefore the hydrogenation component of industrial hydrocracking catalyst generally selects base metal as hydrogenation component, yet non-noble metal hydrogenation activity is lower than noble metal, often can't meet the demands.Therefore, the hydrogenation performance that how to improve catalyst becomes the problem that the partial hydrogenation Cracking catalyst need solve.
Adopt non-noble metal components as hydrogenation component, the microscopic property of hydrogenation component is very big to the influence of catalyst performance, and the patent of Preparation of Catalyst aspect is a lot of both at home and abroad.By selecting different metal components, can improve the hydrogenation performance of catalyst, select the Ni-W component such as metal component, its hydrogenation activity can be higher than Ni-Mo and the (contact catalysis of Co-Mo type catalyst, preparation of industrial catalyst principle and application thereof, J.F. work such as Le Bari, Li Xuanwen, Huang Zhiyuan translates, petroleum industry publishing house, Beijing, 1984, p207).
Only actually changes metal component, and the amplitude that the catalyst hydrogenation performance improves is still not enough.Because the microscopic appearance of catalyst does not reach optimization.It is best that the hydrogenation component of optimizing should all reach on geometrical factor and electronic factor.The optimization of electronic factor can obtain in various degree optimization by selecting obstructed auxiliary agent and carrier, and the optimization difficulty of geometrical factor is bigger.The key of how much patterns of control is in catalyst preparation process, and wherein the catalyst soakage process is particularly important, and method commonly used is to add the dipping auxiliary agent in maceration extract.
CN 1249327A discloses the preparation method of the used dipping solution of a kind of hydrogenation catalyst, this method is for containing the salt of group vib metal or group VIII metal earlier with ammonia solvent, perhaps the mixture of the two after making it to dissolve fully, adds citric acid so that solution-stabilized.
CN 1325942A has proposed a kind of Preparation of catalysts method, and this patent has proposed a kind of metal impregnation liquid, is containing on the basis of reactive metal, adds organic carboxyl acid, polyalcohol and auxiliary agent B, it is said that this method is applicable to hydrodenitrogeneration.Described organic carboxyl acid comprises aminotriacetic acid, ethylenediamine tetra-acetic acid, citric acid, tartaric acid, and described polyalcohol comprises sweet mellow wine, ethylene glycol and glycerine.The content of described organic carboxyl acid is that the content of 5-30 weight %, described polyalcohol is that the content of 1-10 weight %, described auxiliary agent B is counted 0.5-10 weight % with boron oxide.
CN 1362467A provides a kind of multicomponent solution as catalyst impregnating solution, this solution contains 0.01-0.5 grams per milliliter vib metal oxide, 0.001-0.2 grams per milliliter VIII family metal oxide, 0.005-0.1 grams per milliliter hydrogen peroxide, and the pH value is 8-13.
Above patent application document has proposed the preparation method of maceration extract, helps improving the stability of maceration extract, and catalytic performance also increases, but is not the hydrogenation performance that improves catalyst targetedly.In fact hydrogenation catalyst generally adopts aluminium oxide or silica to make carrier, silica is different with the adsorption property of aluminium oxide in solution, the most important thing is that tungstates and molybdate also have nothing in common with each other at the absorption behavior of carrier surface, if different metal is adopted identical processing mode, obviously be to obtain optimized result.
Summary of the invention
The objective of the invention is provides a kind of hydrogenation activity is high when being used for the hydrocarbon hydrogenation reaction hydrogenation catalyst steeping fluid composition and hydrogenization catalyst preparation method in order to overcome existing catalyst hydrogenation activity shortcoming on the low side when being used for the hydrocarbon hydrogenation reaction.
Hydrogenation catalyst steeping fluid composition provided by the invention contains predecessor, dipping auxiliary agent and the water of hydrogenation activity component, wherein, described dipping auxiliary agent has the material that contains carbon-carbon double bond and/or carbon-carbon triple bond in close pKa value and the molecular structure for the predecessor with the hydrogenation activity component.
Hydrogenization catalyst preparation method provided by the invention comprises with maceration extract impregnation catalyst agent carrier, dry, roasting, and wherein, described maceration extract is a hydrogenation catalyst steeping fluid composition provided by the invention.
Adopt the hydrogenation catalyst of hydrogenation catalyst steeping fluid composition preparation provided by the invention, under same reaction temperature, have higher hydrogenation activity and the cracking activity of hydrogenation catalyst that makes than prior art.
The specific embodiment
The pKa that the present invention mentions is according to " the define method that Lan Shi chemistry handbook provides.The pKa value is the negative logarithm of acid dissociation constant, promptly-and logKa=pKa.For general Proton-Transfer Reactions:
HB＝H
++B
Ka＝[H
+][B]/[HB]
The pKa of wolframic acid or metatungstic acid is 2.2, and the pKa of molybdic acid is 2.54.
According to the present invention, described close pKa value preferably is illustrated in the scope of pKa value ± 2.2 of predecessor of hydrogenation activity component, more preferably in the scope of pKa value ± 1.2 of the predecessor of hydrogenation activity component, further preferably in the scope of pKa value ± 1.0 of the predecessor of hydrogenation activity component.That is to say, the pKa value of dipping auxiliary agent of the present invention is preferably pKa value ± 2.2 of the predecessor of hydrogenation activity component, more preferably pKa value ± 1.2 of the predecessor of hydrogenation activity component, more preferably pKa value ± 1.0 of the predecessor of hydrogenation activity component.
The pKa numerical value that the present invention mentions all take from " Lan Shi chemistry handbook (and Chinese second edition, in May, 2003 front page, the first impression, Science Press, Beijing, 8.19-8.71) in.
The dipping auxiliary agent that the present invention mentions can be an inorganic matter, also can be organic matter, can be high molecular polymer, also can be micromolecular compound, as long as pKa is in above-mentioned scope.Can be monoacid, also can be polyacid.Wherein for polyacid, as long as its arbitrary number of level dissociation constant scope according to the invention.
According to the present invention, although a spot of dipping auxiliary agent can be realized purpose of the present invention, but under the preferable case, total amount with maceration extract is a benchmark, and the content of described dipping auxiliary agent is 0.5-45 weight %, is preferably 1-15 weight %, the content of the predecessor of described hydrogenation activity component is 5-50 weight %, be preferably 15-35 weight %, the content of water is 20-85 weight %, is preferably 50-80 weight %.
Among the present invention, described dipping auxiliary agent can be one or more, and the ratio of multiple dipping auxiliary agent and consumption all can be arbitrarily, as long as the pKa value of any one in this multiple dipping auxiliary agent satisfies above-mentioned scope of the present invention.
The predecessor of described hydrogenation activity component can be a various predecessor that can the hydrogenation activity component well known in the art, for example, can be group VIII metal and/or group vib metal, be preferably at least a soluble metal compound in iron content, cobalt, nickel, molybdenum and the tungsten.The mixture of the soluble metal compound of the soluble metal compound of nickel and molybdenum and/or tungsten more preferably, in oxide, the weight ratio of the total amount of the soluble metal compound of described molybdenum and/or tungsten and the soluble metal compound of nickel is 0.5-40, more preferably 1.25-36.Described soluble metal compound can be acid and/or salt.When described soluble metal compound was salt, the pKa value of the predecessor of the component of hydrogenation activity described in the present invention was the pKa value of the acid corresponding with this salt.The soluble metal compound of described molybdenum and/or tungsten is one or more in molybdic acid, para-molybdic acid, wolframic acid, metatungstic acid, ethyl metatungstic acid and molybdate, paramolybdate, tungstates, metatungstate, the ethyl metatungstate, and the soluble metal compound of described nickel is one or more in the nitrate, acetate, chloride, soluble complexes of nickel.When the predecessor of described hydrogenation activity component is the mixture of soluble metal compound of the soluble metal compound of nickel and molybdenum and/or tungsten, described dipping auxiliary agent is preferably acrylic acid (the pKa value is 4.26), butene dioic acid (the pKa value is 1.92), methylmaleic acid (the pKa value is 2.29), phenyl propiolic acid (the pKa value is 2.58), 2-propiolic acid (the pKa value is 1.887), 2-butine-1,4 diacid (the pKa value is 1.75), tetrolic acid (the pKa value is 2.62), two perfluoroalkyl acrylates (the pKa value is 1.79), 3,3-two perfluoroalkyl acrylates (the pKa value is 3.17), chlorallylene acid (the pKa value is 3.65), 4-cyclohexene-1,2-dicarboxylic acids (the pKa value is 3.95), anti-glutaconate (the pKa value is 3.77), 3-perfluoroalkyl acrylate (the pKa value is 2.55), mesaconic acid (the pKa value is 3.09), 3-methyl cyclopentene base-1,1-oxalic acid (the pKa value is 3.79), propargyl chloride acid (the pKa value is 1.854), 4-hydroxyl-3-penetenoic acid (the pKa value is 4.3), 4-cyclohexene-1,2-dicarboxylic acids (the pKa value is 3.89), in the bromo propiolic acid (the pKa value is 1.855) one or more.
According to hydrogenation catalyst steeping fluid composition provided by the invention,, can also contain other auxiliary agent in the described hydrogenation catalyst steeping fluid composition based on different purposes.For example, in order to obtain to have the more hydrogenation catalyst steeping fluid composition of high stability, can also contain phosphoric acid in the described steeping fluid composition.Dispersion for the predecessor that helps the hydrogenation activity component, hydrogenation catalyst steeping fluid composition of the present invention can also contain various surfactants and other various organic solvents, and described surfactant for example can be among polyvinylpyrrolidone, neopelex and polyvinyl alcohol such as PET400 or the PET 2000 one or more; Described organic solvent can be ethanol and/or acetone.The content of described other auxiliary agent generally can be 0-20 weight %.
According to hydrogenization catalyst preparation method provided by the invention, the temperature of described dipping is not particularly limited, can be all temps that maceration extract can reach.Time to dipping is not particularly limited, as long as can make the hydrogenation activity component predecessor of aequum in the catalyst carrier load, it is 60-95 weight % that the degree of preferred described dipping makes the content of catalyst carrier in the dried hydrogenation catalyst, preferred 60-90 weight %.Generally speaking, dipping temperature is high more, and impregnation concentration is big more, and it is short more to reach the required time of same pickup (being catalyst carrier dipping back and the preceding weight difference of dipping); Vice versa.After required pickup and immersion condition were determined, those skilled in the art's instruction according to the present invention was easy to select suitable dip time.The present invention does not have special requirement to dipping method, and described dipping can be saturated dipping, can be the supersaturation dipping yet.
There is no particular limitation to the environment of described dipping, can also can carry out in open environment under air-proof condition, can be in dipping process the aqueous solvent of replenish lost, can not replenish yet.In dipping process, all gases can be fed,, also any new component can be do not fed such as air, nitrogen, steam etc.
According to hydrogenization catalyst preparation method provided by the invention, described carrier can be hydrogenation catalyst various carriers commonly used in the prior art, and for example, described catalyst carrier can be one or more in heat-resistant inorganic oxide and the molecular sieve.Described heat-resistant inorganic oxide plays binding agent, catalyst carrier simultaneously in catalyst, it can improve the intensity of catalyst, and can improve and reconcile the physico-chemical property of catalyst, as improving the pore structure of catalyst.Described heat-resistant inorganic oxide is selected from catalyst carrier for hydrgenating heat-resistant inorganic oxide commonly used, as in silica, aluminium oxide, amorphous aluminosilicate, zirconia, titanium oxide, magnesia, thorium oxide, beryllium oxide, boron oxide, the cadmium oxide one or more.In the preferred silica of described heat-resistant inorganic oxide, aluminium oxide, the amorphous aluminosilicate one or more.Described aluminium oxide comprises gibbsite such as gibbsite, bayerite nordstrandite and a diaspore such as boehmite, diaspor, pseudoboehmite.Total amount with catalyst is a benchmark, and the content of described heat-resistant inorganic oxide is 5-70 weight %, is preferably 10-50 weight %.
Described molecular sieve comprises usually said molecular sieve or zeolite, and it constitutes skeleton by the sial element, also can comprise other element, as: P, Ti, Ge, Ga etc.Described molecular sieve be preferably have 10 yuan of rings, the molecular sieve of 12 yuan of rings, 14 yuan of rings, 18 yuan of rings, the present invention does not limit the aperture size and the aperture of institute's use molecular sieve.Described molecular sieve can be ZRP, Y type, β, modenite, ZSM-5, MCM-41, Ω, ZSM-12, MCM-22 type molecular sieve.Described molecular sieve can be a kind of, also can be two or more, also can be mixed crystal, twin or the molecular sieve presoma of complete crystallization not of two kinds of molecular sieves.Wherein the usage ratio of two kinds of molecular sieves can be 10: 1-1: 10.
Shape to described carrier does not have special requirement, can be bar shaped or sphere, the bulk etc. of sphere, bar shaped, hollow, and the bar shaped carrier can be leafy careless shape and their deformable bodys such as cloverleaf pattern, bunge bedstraw herb shape.
According to method provided by the invention, there is no particular limitation to the condition of described drying and roasting, can be this area various dryings and roasting condition commonly used, and for example, the temperature of described drying can be 80-200 ℃, and the dry time can be 0.5-12 hour; The temperature of roasting can be 120-800 ℃, and the time of roasting can be 0.2-12 hour.
According to hydrogenization catalyst preparation method provided by the invention, dry weight with the gained catalyst is a benchmark, in oxide, contain at least a molybdenum of group vib or at least a iron, cobalt or the nickel that is selected from group VIII of tungsten and 1-10 weight % of being selected from of 5-40 weight % in the preferred gained hydrogenation catalyst.At least a molybdenum of group vib or at least a iron, cobalt or the nickel that is selected from group VIII of tungsten and 1-8 weight % of being selected from that more preferably contains 10-36 weight %.
Hydrogenization catalyst preparation method provided by the invention comprises the catalyst carrier after handling under the condition that is enough to iron, cobalt or the nickel of at least a group VIII and at least a molybdenum that is selected from group vib or tungsten metal component be deposited on the catalyst carrier, the solution of described catalyst carrier and the iron that contains at least a group VIII, cobalt or nickel and at least a molybdenum that is selected from group vib or tungsten metallization compound is contacted and prepares.
According to the conventional method in this area, hydrogenization catalyst preparation method provided by the invention preferably also is included in before the use, 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 also can original position vulcanizing in device outside device, is translated into sulfide type.
The hydrogenation catalyst that adopts hydrogenization catalyst preparation method provided by the invention to make is applicable to hydrocarbon raw material carried out hydrocracking, has hydrocarbon fraction than low boiling and lower molecular weight with production.Described hydrocarbon raw material can be various heavy mineral oils or artificial oil or their mixed fraction oil, as straight run gas oil (straight run gas oil), vacuum gas oil (VGO) (vacuum gas oil), metal removal oil (demetallizedoils), reduced crude (atmospheric residue), depitching decompression residuum (deasphalted vacuumresidue), coker distillate (coker distillates), catalytic cracking distillate oil (cat craker distillates), shale oil (shale oil), asphalt sand oil (tar sand oil), liquefied coal coil (coal liquid) etc.
When the hydrogenation catalyst that adopts hydrogenization catalyst preparation method provided by the invention to make is used for the hydrocarbon raw material hydrocracking, can under the hydrocracking process condition of routine, use, as reaction temperature 200-650 ℃, preferred 300-510 ℃, reaction pressure 3-24 MPa, preferred 4-15 MPa, liquid hourly space velocity (LHSV) 0.1-10 hour
-1Preferred 0.2-5 hour
-1, hydrogen to oil volume ratio 100-5000, preferred 200-1000.
The following examples will the present invention is described further.Agents useful for same in the example except that specifying, is chemically pure reagent.
Reference example 1
This embodiment is used to prepare catalyst carrier.
251.0 gram SB powder (from Sasol company), 375.3 are restrained Siral 40 (from Sasol company, SiO
239.6 weight %, Al
2O
360.3 weight %) mix, add the dilute nitric acid solution that 585 ml concns are 3 weight %, mix the back extruded moulding, 650 ℃ of following roastings 3 hours, obtain catalyst carrier a after 120 ℃ oven dry is spent the night down.
Reference example 2
This embodiment is used to prepare catalyst carrier.
493.0 gram CL powder (from the Chang Ling catalyst plant), 125.8 are restrained Siral 40 (from Sasol company, SiO
2Content is 39.6 weight %, Al
2O
3Content is 60.3 weight %) and 69.5 gram USY molecular sieve (SiO
2/ Al
2O
3=4.3 (weight ratios), Na
2The content of O is 0.18 weight %, from the Chang Ling catalyst plant) mix, add the dilute nitric acid solution that 725 ml concns are 3 weight %, mix the back extruded moulding, 550 ℃ of following roastings 2 hours, obtain catalyst carrier b after 120 ℃ oven dry is spent the night down.
Embodiment 1
This embodiment is used to illustrate hydrogenation catalyst steeping fluid composition provided by the invention and hydrogenization catalyst preparation method.
(the pKa value is 2.29 with 13.9 gram ammonium molybdates, 8.16 gram nickel nitrates and 10 gram methylmaleic acids, contain two carboxyls and a carbon-carbon double bond) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier a, dried 2 hours down at 105 ℃ then, be warming up to 300 ℃ of roastings 1 hour, obtain 119.6 gram catalyst S 1.
Embodiment 2
This embodiment is used to illustrate hydrogenation catalyst steeping fluid composition provided by the invention and hydrogenization catalyst preparation method.
(the pKa value is 4.26 with 41.6 gram ammonium metatungstates, 39.6 gram nickel nitrates and 6 gram acrylic acid, contain a carboxyl and a carbon-carbon double bond) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier b, dried 2 hours down at 105 ℃ then, be warming up to 150 ℃ of roastings 4 hours, obtain 149.8 gram catalyst S 2.
Embodiment 3
This embodiment is used to illustrate hydrogenation catalyst steeping fluid composition provided by the invention and hydrogenization catalyst preparation method.
(the pKa value is 3.65 with 41.6 gram ammonium metatungstates, 39.6 gram nickel nitrates and 6 gram chlorallylene acid, contain a carboxyl and a carbon-carbon triple bond) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier b, dried 2 hours down at 105 ℃ then, be warming up to 150 ℃ of roastings 4 hours, obtain 149.8 gram catalyst S 3.
Embodiment 4
This embodiment is used to illustrate hydrogenation catalyst steeping fluid composition provided by the invention and hydrogenization catalyst preparation method.
41.6 gram ammonium metatungstates, 39.6 gram nickel nitrates, 3 are restrained the chlorallylene acid, and (the pKa value is 3.65, contain a carboxyl and a carbon-carbon double bond) and 3 gram phenyl propiolic acids (the pKa value is 2.58, contain a carboxyl and a carbon-carbon triple bond) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier b, dried 2 hours down at 105 ℃ then, be warming up to 150 ℃ of roastings 4 hours, obtain 149.8 gram catalyst S 4.
Embodiment 5
This embodiment is used to illustrate hydrogenation catalyst steeping fluid composition provided by the invention and hydrogenization catalyst preparation method.
(the pKa value is 1.92 with 39.3 gram ammonium metatungstates, 14.8 gram nickel nitrates and 6 gram butene dioic acids, contain carbon-carbon double bond and carboxyl) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier a, dried 2 hours down at 105 ℃ then, be warming up to 350 ℃ of roastings 2 hours, obtain 140.8 gram catalyst S 5.
Comparative Examples 1
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
39.3 gram ammonium metatungstates and 14.8 are restrained the nickel nitrates mixing and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier a, then 105 ℃ of oven dry 2 hours down, be warming up to 350 ℃ of roastings 2 hours, obtain 140.8 gram reference catalyst CJ1.
Comparative Examples 2
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
(pKa 3.04 with 22.53 gram ammonium molybdates, 13.0 gram nickel nitrates and 6 gram tartaric acid, contain two carboxyls and two hydroxyls) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier b, dried 2 hours down at 105 ℃ then, be warming up to 200 ℃ of roastings 8 hours, obtain 125.7 gram reference catalyst CJ2.
Comparative Examples 3
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
(pKa 2.03 with 30.4 gram ammonium metatungstates, 28.7 gram nickel nitrates and 10 gram thiocarbamides, contain two keys of charcoal sulphur and amido) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier b, dried 2 hours down at 105 ℃ then, be warming up to 150 ℃ of roastings 10 hours, obtain 138.4 gram reference catalyst CJ3.
Comparative Examples 4
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
(pKa 2.36 with 13 gram ammonium metatungstates, 12.2 gram nickel nitrates and 8 gram glycine, contain carboxyl and amido) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier a, dried 2 hours down at 105 ℃ then, be warming up to 250 ℃ of roastings 6 hours, obtain 122.7 gram reference catalyst CJ4.
Comparative Examples 5
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
With 12.7 gram ammonium metatungstates, 4.9 gram nickel nitrates and 2 gram mandelic acid (pKa3.4, contain hydroxyl and carboxyl) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier b, dried 2 hours down at 105 ℃ then, be warming up to 400 ℃ of roastings 1 hour, obtain 115.1 gram reference catalyst CJ5.
Comparative Examples 6
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
With 21 gram ammonium metatungstates, 19.6 gram nickel nitrates and 8 gram cyanoacetic acid (pKa2.46, contain a carboxyl and a charcoal nitrogen key) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier b, dried 2 hours down at 105 ℃ then, be warming up to 200 ℃ of roastings 8 hours, obtain 125.5 gram reference catalyst CJ6.
Comparative Examples 7
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
With 23.5 gram ammonium molybdates, 31.8 gram nickel nitrates and 2 gram malic acid (pKa3.4, contain two carboxyls and a hydroxyl) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier a, dried 2 hours down at 105 ℃ then, be warming up to 250 ℃ of roastings 2 hours, obtain 130.0 gram reference catalyst CJ7.
Comparative Examples 8
This Comparative Examples is used to illustrate the hydrogenation catalyst steeping fluid composition and the hydrogenization catalyst preparation method of prior art.
(pKa 2.85 with 6.5 gram ammonium molybdates, 3.7 gram nickel nitrates and 4 gram malonic acid, contain two carboxyls) mix and add water to 78 milliliters, after dissolving finishes, adopt hole saturation dipping 100 gram said catalyst carrier a, dried 2 hours down at 105 ℃ then, be warming up to 200 ℃ of roastings 6 hours, obtain 106.6 gram reference catalyst CJ8.
Embodiment 6-10
Following examples are used to estimate the catalytic activity of hydrogenation catalyst.
Adopt microreactor to estimate the catalytic activity of hydrogenation catalyst.The catalyst that 0.5 gram is made by the foregoing description 1-5 adopts to contain 5 weight %CS respectively under 300 ℃, 4.0MPa
2N-hexane in air speed 36 hours
-1Under vulcanized 3 hours, after the sulfuration, adopt n-decane+10 volume % toluene as reaction oil, in 4.0 MPas, volume space velocity 12 hours
-1, 300,360 ℃ of cracking and hydrogenation activities of investigating catalyst down of hydrogen to oil volume ratio.The make a comment or criticism conversion ratio of decane of cracking activity; The conversion ratio of hydrogenation activity nail benzene.The result is as shown in table 1 below.
Comparative Examples 9-16
This Comparative Examples is used to estimate the catalytic activity of hydrogenation catalyst.
According to the catalytic activity of the evaluation of the method shown in the foregoing description 6-10 hydrogenation catalyst, different is to be changed into the reference catalyst CS1-CS8 that is made by Comparative Examples 1-8 by the catalyst that the foregoing description makes.The result is as shown in table 1 below.
Table 1 catalyst performance relatively
| The catalyst source | Catalyst | The auxiliary agent kind | Cracking activity % | Hydrogenation activity % | Functional group in the auxiliary agent |
| Embodiment 1 | S1 | Butene dioic acid | 48.3 | 38.2 | Carbon-carbon double bond and carboxyl |
| Embodiment 2 | S2 | Acrylic acid | 56.7 | 36.2 | Carbon-carbon double bond and carboxyl |
| Embodiment 3 | S3 | Olefin(e) acid in the 3-chlorine | 46.7 | 33.5 | Carbon-carbon triple bond and carboxyl |
| Embodiment 4 | S4 | Methylmaleic acid | 47.7 | 39.1 | Carbon-carbon double bond and carboxyl |
| Embodiment 5 | S5 | The phenyl propiolic acid | 49.7 | 40.1 | Carbon-carbon triple bond and carboxyl |
| Comparative Examples 1 | CJ1 | Do not have | 24.4 | 23.6 | Do not have |
| Comparative Examples 2 | CJ2 | Tartaric acid | 38.7 | 26.4 | Two carboxyls and two hydroxyls |
| Comparative Examples 3 | CJ3 | Thiocarbamide | 30.1 | 34.2 | Two keys of carbon sulphur and amido |
| Comparative Examples 4 | CJ4 | Glycine | 32.7 | 33.7 | Carboxyl and amido |
| Comparative Examples 5 | CJ5 | Mandelic acid | 44.4 | 32.8 | Hydroxyl and carboxyl |
| Comparative Examples 6 | CJ6 | Cyanoacetic acid | 29.8 | 27.0 | Carboxyl and carbonnitrogen bond |
| Comparative Examples 7 | CJ7 | Malic acid | 41.2 | 34.8 | Two carboxyls and a hydroxyl |
| Comparative Examples 8 | CJ8 | Malonic acid | 26.4 | 31.3 | Two carboxyls |
The result of last table 1 shows, adopts the catalyst of method preparation provided by the invention to compare with contrast medium, under same reaction temperature, has higher hydrogenation activity and cracking activity.
Claims (11)
1. hydrogenation catalyst steeping fluid composition, said composition contains predecessor, dipping auxiliary agent and the water of hydrogenation activity component, it is characterized in that, described dipping auxiliary agent is for having the material that contains carbon-carbon double bond and/or carbon-carbon triple bond in close pKa value and the molecular structure with the predecessor of hydrogenation activity component, and the pKa value of the described close described dipping auxiliary agent of pKa value representation is pKa value ± 2.2 of the predecessor of hydrogenation activity component; The predecessor of described hydrogenation activity component is the soluble metal compound of group VIII metal and/or group vib metal; Described soluble metal compound is acid and/or salt; And when described soluble metal compound was salt, the pKa value of the predecessor of described hydrogenation activity component was the pKa value of the acid corresponding with this salt.
2. composition according to claim 1 wherein, is a benchmark with the total amount of maceration extract, and the content of the predecessor of described hydrogenation activity component is 5-50 weight %, and the content of described dipping auxiliary agent is 0.5-45 weight %, and the content of described water is 20-85 weight %.
3. composition according to claim 1, wherein, the pKa value of described dipping auxiliary agent is pKa value ± 1.2 of the predecessor of hydrogenation activity component.
4. composition according to claim 1, wherein, the predecessor of described hydrogenation activity component is the soluble metal compound of nickel and the soluble metal compound of molybdenum and/or tungsten, in oxide, the weight ratio of the total amount of the soluble metal compound of described molybdenum and/or tungsten and the soluble metal compound of nickel is 0.5-40, described dipping auxiliary agent is an acrylic acid, butene dioic acid, methylmaleic acid, the phenyl propiolic acid, the 2-propiolic acid, 2-butine-1, the 4-diacid, tetrolic acid, two perfluoroalkyl acrylates, chlorallylene acid, 4-cyclohexene-1, the 2-dicarboxylic acids, anti-glutaconate, the 3-perfluoroalkyl acrylate, mesaconic acid, 3-methyl cyclopentene base-1, the 1-oxalic acid, propargyl chloride acid, 4-hydroxyl-3-penetenoic acid, in the bromo propiolic acid one or more.
5. composition according to claim 4, wherein, the weight ratio of the total amount of the soluble metal compound of described molybdenum and/or tungsten and the soluble metal compound of nickel is 1.25-36.
6. according to claim 4 or 5 described compositions, wherein, the soluble metal compound of described molybdenum and/or tungsten is one or more in molybdic acid, para-molybdic acid, wolframic acid, metatungstic acid, ethyl metatungstic acid and molybdate, paramolybdate, tungstates, metatungstate, the ethyl metatungstate, and the soluble metal compound of described nickel is one or more in the nitrate, acetate, chloride of nickel.
7. hydrogenization catalyst preparation method, this method comprise that dry and roasting is characterized in that described maceration extract is any described hydrogenation catalyst steeping fluid composition among the claim 1-6 with maceration extract impregnation catalyst agent carrier.
8. method according to claim 7, wherein, described catalyst carrier is one or more in heat-resistant inorganic oxide and the molecular sieve.
9. method according to claim 8, wherein, described heat-resistant inorganic oxide is selected from one or more in aluminium oxide, silica, the amorphous aluminum silicide.
10. method according to claim 7, wherein, it is 60-95 weight % that the degree of described dipping makes the content of catalyst carrier in the dried hydrogenation catalyst.
11. method according to claim 7, wherein, the temperature of described drying is 80-200 ℃; The temperature of roasting is greater than 200 ℃ and smaller or equal to 500 ℃, and the time of roasting is 0.2-12 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710179765 CN101462078B (en) | 2007-12-18 | 2007-12-18 | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710179765 CN101462078B (en) | 2007-12-18 | 2007-12-18 | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101462078A CN101462078A (en) | 2009-06-24 |
| CN101462078B true CN101462078B (en) | 2011-08-10 |
Family
ID=40803008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710179765 Active CN101462078B (en) | 2007-12-18 | 2007-12-18 | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101462078B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3035601B1 (en) * | 2015-04-30 | 2017-04-21 | Ifp Energies Now | A CATALYST BASED ON Y-VALEROLACTONE AND / OR ITS HYDROLYSIS PRODUCTS AND ITS USE IN A HYDROTREATMENT AND / OR HYDROCRACKING PROCESS |
| CN109833915A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | Molybdenum loaded catalyst and preparation method thereof for 1- butylene self disproportionation reaction |
| CN111151271B (en) * | 2018-11-08 | 2022-08-12 | 中国石油化工股份有限公司 | Preparation method of hydrodesulfurization catalyst |
| CN110801841A (en) * | 2019-11-27 | 2020-02-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing 2, 2' -bipyridine by coupling synthesis of pyridine and preparation method and application thereof |
| CN113019429B (en) * | 2019-12-25 | 2022-09-09 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN114733577B (en) * | 2021-01-07 | 2023-10-10 | 中国石油化工股份有限公司 | Sulfuration type hydrogenation catalyst, preparation method and application thereof |
| CN112973714B (en) * | 2021-03-24 | 2023-04-07 | 甘肃农业大学 | Catalyst for preparing cyclopentene, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175481A (en) * | 1996-09-04 | 1998-03-11 | 中国石油化工总公司抚顺石油化工研究院 | Co-impregnation liquid for preparing hydrocracking catalyst |
| CN1769381A (en) * | 2005-10-26 | 2006-05-10 | 长春惠工催化剂有限责任公司 | Refined hydrogenation catalyst and its preparation method |
-
2007
- 2007-12-18 CN CN 200710179765 patent/CN101462078B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175481A (en) * | 1996-09-04 | 1998-03-11 | 中国石油化工总公司抚顺石油化工研究院 | Co-impregnation liquid for preparing hydrocracking catalyst |
| CN1769381A (en) * | 2005-10-26 | 2006-05-10 | 长春惠工催化剂有限责任公司 | Refined hydrogenation catalyst and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| JP昭56-123923A 1981.09.29 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101462078A (en) | 2009-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101462078B (en) | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst | |
| US11097258B2 (en) | Catalyst made from an organic compound and use thereof in a hydroprocessing and/or hydrocracking method | |
| CN101757931B (en) | Hydrogenation catalyst, preparation method thereof and hydrocracking method | |
| CN100496729C (en) | Hydrogenating and condensation point depressing catalyst and its preparing method | |
| US9683180B2 (en) | Vacuum distillate hydrotreatment process employing a concatenation of catalysts | |
| JP2018520842A (en) | Catalysts based on γ-valerolactone and / or its hydrolysis products and their use in hydroprocessing and / or hydrocracking processes | |
| CN102247864A (en) | Preparation method of catalyst for hydrogenation desulfurization and denitrification of light-weight oil | |
| CN101157056A (en) | Hydrogenation catalysts carrier with nickel and cobalt, hydro-catalyst and its preparing method | |
| CN103551162A (en) | Diesel hydrodesulfurization and denitrification catalyst and preparation method thereof | |
| BR112015029993B1 (en) | HYDROPROCESSING CATALYTIC COMPOSITION CONTAINING A POLAR HETEROCYCLIC COMPOUND, METHOD FOR MANUFACTURING SUCH COMPOSITION AND PROCESS FOR HYDROTREATMENT OF A RAW MATERIAL OF HYDROCARBIDE | |
| US9404053B2 (en) | Low-pressure process utilizing a stacked-bed system of specific catalysts for the hydrotreating of a gas oil feedstock | |
| CN101468317B (en) | Hydrocracking catalyst and its preparing process | |
| US20210354118A1 (en) | In situ bifunctional catalyst for deep desulfurization and increasing octane number of gasoline and preparation method thereof | |
| CN101590424A (en) | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof | |
| CN104437518A (en) | Selective hydrodesulfurization catalyst, and preparation and application thereof | |
| CN1872962B (en) | Hydrotreating catalyst of containing molecular sieve, and preparation method | |
| CN103372457A (en) | Catalytic cracking diesel oil hydro-upgrading catalyst and application thereof | |
| JP5537781B2 (en) | Kerosene composition | |
| US20150144533A1 (en) | Process for the hydrotreatment of diesel employing a concatenation of catalysts | |
| CN103386327B (en) | A kind of catalyst for selectively hydrodesulfurizing and Synthesis and applications thereof | |
| CN102851061A (en) | Hydrofining method of low-grade gasoline/diesel oil | |
| JP5537780B2 (en) | Light oil composition | |
| CN101733149B (en) | Hydrocracking catalyst and method for preparing same | |
| US10828627B2 (en) | Catalyst containing 2-acetylbutyrolactone and/or the hydrolysis products thereof, and use thereof in a hydrotreatment and/or hydrocracking process | |
| JP5364438B2 (en) | Heavy oil composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |