CN104998696B - A kind of dipping solution and its preparation and application - Google Patents
A kind of dipping solution and its preparation and application Download PDFInfo
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Abstract
A kind of dipping solution and its preparation and application, the solution contains cobalt compound, molybdate compound, phosphorus-containing compound and citric acid, the concentration for the cobalt compound counted in the solution using cobalt is 0.01 0.1g/mL, the concentration for the molybdate compound counted using molybdenum is 0.05 0.4g/mL, the concentration for the phosphorus-containing compound counted using phosphorus is 0.005 0.10g/mL, the concentration of citric acid is 0.05 0.5g/mL, with uv-vis spectra analysis and characterization, λ≤1 of the dipping solution, λ are spectral peak at 517 ± 10nm in uv-vis spectra and the ratio of spectral peak peak height at 772 ± 10nm.Compared with prior art, the catalyst for providing dipping solution preparation using the present invention has more preferable Hydrogenation.
Description
Technical field
The present invention relates to a kind of dipping solution and its preparation and application.
Background technology
Prepared by hydrogenation catalyst generally use infusion process, i.e., using containing required active component (such as Ni, Mo, Co, W etc.)
It is prepared by the method for solution impregnating carrier.Such as：
CN201010276669.5 discloses a kind of maceration extract and the method for preparing catalyst using the maceration extract, the leaching
Stain liquid contains compound, the acylate containing group VIII metal, inorganic acid and the organic additive of the metal containing group vib, wherein, institute
The concentration for stating organic additive in maceration extract is 1-150g/L, and in terms of compound, the concentration of the compound of the metal containing group vib is 100-
1100g/L, the concentration of the acylate containing group VIII metal is 10-800g/L, and the concentration of inorganic acid is 1-100g/L.
CN96109048.0 discloses a kind of high metal concentration, high stability contains Mo, Ni (Co) P solution and its preparation side
The compound method of method, particularly a kind of dipping solution for catalyst preparation.The solution contains MoO3Concentration 45-80g/100mL,
NiO concentration 8-20g/100mL, CoO concentration 0-15g/100mL.P/MoO3Weight ratio is 0.08-0.18.PH value of solution is 0-3.8.
CN201210452002.5 discloses a kind of compound method of reformed pre-hydrogenated catalyst impregnating solution, and its feature exists
In；The solution contains Mo, Ni, Co, W, Mg, P and auxiliary agent, contains MoO3Concentration 10-16g/100ml, NiO concentration 5-9g/
100mL, CoO concentration 3-5g/100mL, WO3Concentration 20-28g/100mL, MgO concentration 0.5-2g/100mL, P/MoO3Mol ratio
0.3-0.5, auxiliary agent 5-15g/100mL；Its process for preparation is：Phosphate aqueous solution is heated to 70-80 DEG C, molybdenum trioxide is added and adds
Solution is cooled to 70-80 DEG C, is slowly added to basic nickel carbonate ebuillition of heated stirring and dissolving by heat boiling stirring to dissolving, and is concentrated
To required volume, concentrate cooling down to room temperature, cobalt nitrate stirring and dissolving is added, add ammonium metatungstate stirring and dissolving, added
Magnesium compound stirring and dissolving, auxiliary agent stirring and dissolving is added, constant volume, obtains maceration extract.
CN200710179765.6 discloses a kind of hydrogenation catalyst steeping fluid composition, and said composition contains hydrogenation activity
Predecessor, impregnation aids and the water of component, wherein, the impregnation aids are with similar with the predecessor of hydrogenation active component
Material containing carbon-carbon double bond and/or carbon-carbon triple bond in pKa value and molecular structure.
CN201110317245.3 discloses a kind of maceration extract of hydrogenation catalyst and preparation method thereof, and this method includes,
Group VIII metallic compound and the first organic complexing agent are configured to water solution A；Vib metals compound is configured to water
Solution B；The water solution A and aqueous solution B are mixed；Wherein, at least contain in the ligand of first organic complexing agent and match somebody with somebody
Position atom N.
When preparing catalyst using the prior art including above-mentioned, the performance of catalyst can all have to varying degrees
Improved.But prior art is specially urged being prepared using Co and Mo as the maceration extract of active metal component and by the maceration extract
Agent research deficiency.Therefore, the Co -- Mo catalyst performance prepared using prior art is still relatively low.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of system containing cobalt and the dipping solution of molybdenum and the dipping solution
Preparation Method and application.
Content of the present invention includes：
1. a kind of dipping solution, containing cobalt compound, molybdate compound, phosphorus-containing compound and citric acid, the solution
In the concentration of cobalt compound counted using cobalt as 0.01-0.1g/mL, the concentration for the molybdate compound counted using molybdenum is 0.05-0.4g/
ML, the concentration for the phosphorus-containing compound counted using phosphorus is 0.005-0.10g/mL, and the concentration of citric acid is 0.05-0.5g/mL, with purple
Outside-visible diffusing reflection spectrum analysis and characterization, λ≤1 of the dipping solution, λ are 517 ± 10nm places spectrum in ultraviolet-visible spectrum
The ratio of spectral peak peak height at peak and 772 ± 10nm.
2. the dipping solution according to 1, it is characterised in that the concentration of the cobalt compound in the solution in terms of cobalt is
0.02-0.09g/mL, the concentration for the molybdate compound counted using molybdenum as 0.08-0.35g/mL, phosphorus-containing compound in terms of phosphorus it is dense
To spend for 0.007-0.08g/mL, the concentration of citric acid is 0.1-0.4g/mL, with ultraviolet-visible spectrum analysis and characterization, the dipping
λ=0-0.95 of solution.
3. the dipping solution according to 1, it is characterised in that the solution is described with ultraviolet-visible spectrum analysis and characterization
λ=0-0.80 of dipping solution.
4. according to the preparation method of 1 maceration extract, including：(1) by cobalt compound, molybdate compound, phosphorous chemical combination
Thing and citric acid are mixed with water, and dissolving is reacted into dipping solution；(2) dipping solution for obtaining step (1) is at 60 DEG C -300 DEG C
At a temperature of react -200 hours 0.5 hour；
Wherein, the dosage of each component makes the concentration of the cobalt compound in terms of cobalt in the final dipping solution be
0.01-0.1g/mL, the concentration for the molybdate compound counted using molybdenum is 0.05-0.4g/mL, the concentration of the phosphorus-containing compound in terms of phosphorus
For 0.005-0.1g/mL, the concentration of citric acid is 0.05-0.5g/mL, is analysed and characterized with UV-Vis DRS spectrum analysis,
λ≤1 of the dipping solution, λ are spectral peak at 517 ± 10nm in ultraviolet-visible spectrum and the ratio of spectral peak peak height at 772 ± 10nm
Value.
5. the method according to 4, it is characterised in that the dosage of each component makes in the final dipping solution with cobalt
The concentration of the cobalt compound of meter is 0.02-0.09g/mL, the concentration for the molybdate compound counted using molybdenum as 0.08-0.35g/mL,
For the concentration for the phosphorus-containing compound counted using phosphorus as 0.007-0.08g/mL, the concentration of citric acid is 0.1-0.4g/mL, with it is ultraviolet-can
See that spectrum analysis characterizes, λ=0-0.95 of the dipping solution；Step (2) reaction temperature is 75 DEG C -180 DEG C, during reaction
Between be -100 hours 1 hour.
6. the method according to 5, it is characterised in that the solution is with ultraviolet-visible spectrum analysis and characterization, the dipping
λ=0-0.80 of solution.
7. the method according to 5, it is characterised in that the step (2) to the cobalt molybdenum solution that routinely prepares 80 DEG C-
Handled -50 hours 2 hours at 150 DEG C.
8. application of the dipping solution in hydrogenation catalyst is prepared according to 1-3.
In the present invention, the cobalt compound is selected from water miscible cobalt compound, but water solubility refers to that the compound can
Be directly dissolved in water, or in the presence of cosolvent it is water-soluble, cosolvent can be ammoniacal liquor, phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid
The ammonium of hydrogen two, citric acid etc..The example of such compound such as, salt, oxide and the hydroxide of the metal component containing cobalt.They can
With the nitrate selected from cobalt, chloride, sulfate, formates, acetate, phosphate, citrate, oxalates, carbonate, alkali
One kind in formula carbonate, hydroxide, phosphate, phosphide, sulfide, aluminate, molybdate, tungstates, oxide or
It is several.Oxalates, carbonate, subcarbonate, hydroxide, phosphate, molybdate, tungstates, oxide preferably wherein
In one or more, be more highly preferred to subcarbonate and carbonate therein.
The molybdate compound is selected from water miscible molybdate compound, but water solubility refers to that the compound can be directly dissolved in
Water, or in the presence of cosolvent it is water-soluble, cosolvent can be ammoniacal liquor, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
Citric acid etc..The example of such compound such as, salt, the oxide of the component containing molybdenum.They can be selected from ammonium molybdate, miscellaneous more
One or more in hydrochlorate, molybdenum oxide.
The phosphorus-containing compound can be selected from phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid hydrogen two
One or more in sodium, phosphoric acid preferably wherein.
In the present invention, the concentration of the cobalt compound in the dipping solution in terms of cobalt is：0.01-0.1g/mL, it is excellent
Elect 0.02-0.09g/mL, more preferably 0.03-0.08g/mL as；The concentration of the molybdate compound in terms of molybdenum is：
0.05-0.4g/mL, preferably 0.08-0.35g/mL, more preferably 0.10-0.3g/mL；The phosphorous chemical combination in terms of phosphorus
The concentration of thing is 0.005-0.1g/mL, preferably 0.007-0.05g/mL, more preferably 0.01-0.03g/mL；Described lemon
The concentration of lemon acid is 0.05-0.5g/mL, preferably 0.10-0.4g/mL, more preferably 0.15-0.3g/mL.
Cobalt-molybdenum-phosphorus-citric acid dipping solution is conventionally prepared (for example, being separately added into phosphorus in deionized water
After acid, citric acid, basic cobaltous carbonate and molybdenum trioxide, by the suspension be heated to 80 DEG C it is agitated be easily dissolved, obtain cobalt
Molybdenum solution), inventor is had found, the solution is further being heated at a temperature of 60 DEG C -300 DEG C, and the property of solution occurs
Change.Characterized using UV-Vis DRS spectrum analysis, when λ≤1 for controlling the dipping solution, preferably λ=0-0.95,
(λ is spectral peak at 517 ± 10nm in ultraviolet-visible spectrum and the ratio of spectral peak peak height at 772 ± 10nm to more preferably λ=0-0.80.
Cobalt-molybdenum-phosphorus-the citric acid solution directly configured, without the λ ＞ 1 during further heat；During through further heating,
Spectral peak dies down (peak height reduction) until disappearing at 517 ± 10nm；When spectral peak disappears at 517 ± 10nm, corresponding λ=0), by
The Hydrogenation of this catalyst prepared significantly improves.
It is described at a temperature of 60 DEG C -300 DEG C at heating according to the preparation method of the dipping solution provided by the invention
Reason, preferable temperature are 75 DEG C -200 DEG C, and more preferably 80 DEG C -150 DEG C, the time of heating is at least 0.5 hour.
Premised on meeting application claims, the time of heating is preferably -200 hours 0.5 hour, more preferably 1 hour -
100 hours；More preferably -50 hours 2 hours.Described heating can be carried out in the container situ for preparing solution,
It can not also carry out in the original location.The heating can be carried out under static (such as not stirring), can also (example in a dynamic state
Such as stirring) carry out.
The process of the heating can be carried out in closed container (such as autoclave) also can be in open body
Carried out in system, afterwards, can be to be diluted with water to final required volume in resulting solution.
Dipping solution stability provided by the invention is high, available for direct impregnation catalyst carrier to prepare hydrogenation catalyst
Agent.Wherein, the carrier can be the arbitrary carrier that can be used for preparing hydrogenation catalyst that prior art provides.For example, oxygen
Change aluminium, silica, silica-alumina.
Compared with catalyst prepared by conventional method, catalyst prepared by cobalt molybdenum solution provided by the present invention is with higher
Hydrogenation activity.
Embodiment
The present invention is described further for the following examples.
UV-Vis DRS spectrum analysis (UV-Vis), using the Lambda35 types of Perkin-Elmer companies of the U.S.
Multi-functional spectrophotometry instrument, in light neon source, measurement wavelength 286nm, slit width 1.0nm, sample detection time
4.5min, detection step-length 2.0s experiment condition under determine ultra-violet absorption spectrum of the solution in the range of 450-900nm.
Comparative example 1
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids are weighed respectively is put into 55mL
In deionized water, it is heated to 80 DEG C and is stirred dissolving 1 hour, obtains clarifying dipping solution, add water to 85mL, obtain solution
L1.Dipping solution L1 λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and rubbing for molybdenum
You are than (nP/nMo), the mol ratio (n of molybdenum and cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Comparative example 2
28.2 grams of molybdenum trioxides, 9.5 grams of basic cobaltous carbonates, 11.4 grams of phosphoric acid are weighed respectively to be put into 55mL deionized waters,
It is heated to 80 DEG C and is stirred dissolving 1 hour, obtains clarifying dipping solution, add water to 85mL, obtain solution L2.Dipping solution L2
λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the mol ratio (n of molybdenumP/nMo)、
Mol ratio (the n of molybdenum and cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Comparative example 3
11.5 grams of molybdenum trioxides, 3.5 grams of basic cobaltous carbonates, 5.8 grams of citric acids are weighed respectively to be put into 55mL deionized waters,
It is heated to 80 DEG C and is stirred dissolving 1 hour, obtains clarifying dipping solution, add water to 85mL, obtain solution L3.Dipping solution L3
λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the mol ratio (n of molybdenumP/nMo)、
Mol ratio (the n of molybdenum and cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 1
Cobalt molybdenum solution provided by the invention：
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids are weighed respectively is put into 55mL
In deionized water, it is heated to 80 DEG C and is stirred dissolving, be changed into brownish red settled solution after about 1 hour.The solution is put into burning
In cup, 90 DEG C and under agitation constant temperature 8 hours are heated to, add water to 85mL, obtain clarifying dipping solution S1.Dipping solution S1's
λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the mol ratio (n of molybdenumP/nMo), molybdenum
With the mol ratio (n of cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 2
Cobalt molybdenum solution provided by the invention：
20 grams of molybdenum trioxides, 14.5 grams of basic cobaltous carbonates, 8.7 grams of phosphoric acid, 18 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, be changed into brownish red settled solution after about 1 hour.The solution is put into closed
In container, 100 DEG C of simultaneously constant temperature 1 hours are heated to, add water to 85mL, obtain clarifying dipping solution S2.Dipping solution S2 λ value,
Cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the mol ratio (n of molybdenumP/nMo), molybdenum and cobalt
Mol ratio (nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 3
Cobalt molybdenum solution provided by the invention：
38 grams of molybdenum trioxides, 8.6 grams of basic cobaltous carbonates, 4.7 grams of phosphoric acid, 10.7 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, be changed into brownish red settled solution after about 1 hour.The solution is put into beaker
In, 70 DEG C and under agitation constant temperature 18 hours are heated to, add water to 85mL, obtain clarifying dipping solution S3.Dipping solution S3 λ
Value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the mol ratio (n of molybdenumP/nMo), molybdenum with
Mol ratio (the n of cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 4
Cobalt molybdenum solution provided by the invention：
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 6.5 grams of phosphoric acid, 15 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, be changed into brownish red settled solution after about 1 hour.The solution is put into closed
In container, 120 DEG C of simultaneously constant temperature 12 hours are heated to, add water to 85mL, obtain clarifying dipping solution S4.Dipping solution S4 λ value,
Cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the mol ratio (n of molybdenumP/nMo), molybdenum and cobalt
Mol ratio (nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 5
Cobalt molybdenum solution provided by the invention：
Weigh respectively 24 grams of molybdenum trioxides, 10 grams of basic cobaltous carbonates, 6.5 grams of phosphoric acid, 8.4 grams of citric acids be put into 55mL go from
In sub- water, it is heated to 80 DEG C and is stirred dissolving, be changed into brownish red settled solution after about 1 hour.The solution is put into closed appearance
In device, 120 DEG C of simultaneously constant temperature 2 hours are heated to, add water to 85mL, obtain clarifying dipping solution S5.Dipping solution S5 λ value, cobalt
(Co), the concentration (g/mL) and the mol ratio (n of phosphorus and molybdenum of molybdenum (Mo), phosphorus (P) and citric acid (CTA)P/nMo), molybdenum and cobalt
Mol ratio (nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 6
Cobalt molybdenum solution provided by the invention：
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 19 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, be changed into brownish red settled solution after about 1 hour.The solution is put into closed
In container, 140 DEG C of simultaneously constant temperature 10 hours are heated to, add water to 85mL, obtain clarifying dipping solution S6.Dipping solution S6 λ value,
Cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the mol ratio (n of molybdenumP/nMo), molybdenum and cobalt
Mol ratio (nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Table 1
Note：With ultraviolet-visible spectrum analysis and characterization, if only occurring spectral peak at 517nm in the spectrogram of solution, but do not occur
772nm spectral peaks, solution λ=∞ now.
2000 grams of aluminium hydrate powders (dry glue powder of Chang Ling branch company catalyst plant production, the weight % of butt 72) are weighed, are used
Banded extruder is extruded into the butterfly bar that circumscribed circle diameter is 1.3 millimeters, and roasting 3 is small under the conditions of wet bar is dried 4 hours, 600 DEG C in 120 DEG C
When, carrier Z1 is made.Z1 water absorption rate is 0.85.
Comparative example 4
Using L1 solution 85ml saturations 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 200 DEG C of dryings 3
Hour, catalyst C1 is obtained, its composition is shown in Table 2.The content composition of catalyst components is determined using X-fluorescence method, similarly hereinafter.
Comparative example 5
Using L2 solution 85ml saturations 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 200 DEG C of dryings 3
Hour, catalyst C2 is obtained, its composition is shown in Table 2.
Comparative example 6
Using L3 solution 85ml saturations 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 200 DEG C of dryings 3
Hour, catalyst C3 is obtained, its composition is shown in Table 2.
Embodiment 7
Using S1 solution 85ml saturations 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 200 DEG C of dryings 3
Hour, catalyst D1 is obtained, its composition is shown in Table 2.
Table 2
Embodiment 8
This example illustrates that the present invention provides the diesel oil hydrofining performance that cobalt molybdenum dipping prepares hydrogenation catalyst.
Catalyst D1 is evaluated respectively on 30 milliliters of diesel hydrotreating units, is as a result shown in table 3.
Raw materials used is Middle East straight-run diesel oil, and its property is as follows：
S contents：9700wppm
N content：97wppm
Density (20 DEG C)：0.8321g/cm3
Refraction index (20 DEG C)：1.4658
Use following process operating condition：
Volume space velocity during liquid：2.0h-1；Hydrogen to oil volume ratio：300；Reaction pressure：3.2MPa；Reaction temperature：330℃
The hydrodesulfurization activity of catalyst is evaluated using relative hydrodesulfurization activity, computational methods are that hydrodesulfurization is anti-
The processing of 1.65 order reactions is should be used as, catalyst X reaction rate constant k (X) is calculated as followsHDS：
In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction.
On the basis of catalyst C1 hydrodesulfurization activity (being designated as k (C1) HDS), the relative of catalyst X is calculated as follows
Hydrodesulfurization activity：
In following examples and comparative example, the hydrodenitrogenationactivity activity of catalyst is evaluated using relative hydrodenitrogenationactivity activity,
Computational methods are to be handled using hydrodenitrogeneration reaction as 1 order reaction, and catalyst X reaction rate constant k is calculated as follows
(X)HDN：
In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction,
On the basis of the catalyst C1 prepared by comparative example 2 hydrodenitrogenationactivity activity (being designated as k (C1) HDN), it is calculated as follows
Catalyst X relative hydrodenitrogenationactivity activity：
Comparative example 7-9
Catalyst C1-C3 is evaluated according to the same procedure of embodiment 8, is as a result shown in table 3.
Table 3
The result of table 3 shows that the catalyst prepared according to present invention configuration solution is in the hydrofinishing for hydrocarbon ils, tool
There is higher catalytic activity.
Claims (8)
1. a kind of dipping solution, containing cobalt compound, molybdate compound, phosphorus-containing compound and citric acid, in the solution with
The concentration of the cobalt compound of cobalt meter is 0.01-0.1g/mL, the concentration for the molybdate compound counted using molybdenum as 0.05-0.4 g/mL,
The concentration for the phosphorus-containing compound counted using phosphorus is 0.005-0.10 g/mL, and the concentration of citric acid is 0.05-0.5 g/mL, with purple
Outside-visible diffusing reflection spectrum analysis and characterization, λ≤1 of the dipping solution, λ are 517 ± 10nm places spectrum in ultraviolet-visible spectrum
The ratio of spectral peak peak height at peak and 772 ± 10nm.
2. dipping solution according to claim 1, it is characterised in that cobalt compound in the solution in terms of cobalt it is dense
The concentration for the molybdate compound for 0.02-0.09g/mL, counted using molybdenum is spent as 0.08-0.35 g/mL, the phosphorus-containing compound in terms of phosphorus
Concentration be 0.007-0.08 g/mL, the concentration of citric acid is 0.1-0.4 g/mL, with ultraviolet-visible spectrum analysis and characterization, institute
State λ=0-0.95 of dipping solution.
3. dipping solution according to claim 1, it is characterised in that the solution with ultraviolet-visible spectrum analysis and characterization,
λ=0-0.80 of the dipping solution.
4. the preparation method of dipping solution described in claim 1, including：（1）By cobalt compound, molybdate compound, containing phosphatization
Compound and citric acid are mixed with water, and dissolving is reacted into dipping solution；（2）By step（1）Obtained dipping solution is at 60 DEG C -300
Reacted -200 hours 0.5 hour at a temperature of DEG C；
Wherein, the concentration for the cobalt compound that the dosage of each component makes to count using cobalt in the final dipping solution is 0.01-0.1g/
ML, the concentration for the molybdate compound counted using molybdenum is 0.05-0.4 g/mL, and the concentration for the phosphorus-containing compound counted using phosphorus is 0.005-
0.1 g/mL, the concentration of citric acid is 0.05-0.5 g/mL, is characterized with UV-Vis DRS spectrum analysis, the dipping
λ≤1 of solution, λ are spectral peak at 517 ± 10nm in ultraviolet-visible spectrum and the ratio of spectral peak peak height at 772 ± 10nm.
5. according to the method for claim 4, it is characterised in that the dosage of each component makes in the final dipping solution with cobalt
The concentration of the cobalt compound of meter is 0.02-0.09g/mL, the concentration for the molybdate compound counted using molybdenum as 0.08-0.35 g/mL,
For the concentration for the phosphorus-containing compound counted using phosphorus as 0.007-0.08 g/mL, the concentration of citric acid is 0.1-0.4 g/mL, with it is ultraviolet-
Visible Spectra Analysis on Edge Recycling characterizes, λ=0-0.95 of the dipping solution；The step（2）Reaction temperature is 75 DEG C -180 DEG C, reaction
Time is -100 hours 1 hour.
6. according to the method for claim 5, it is characterised in that the solution is described with ultraviolet-visible spectrum analysis and characterization
λ=0-0.80 of dipping solution.
7. according to the method for claim 5, it is characterised in that the step（2）Reaction temperature is 80 DEG C -150 DEG C, instead
It is -50 hours 2 hours between seasonable.
8. application of the dipping solution in hydrogenation catalyst is prepared described in claim 1-3.
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| CN107486251B (en) * | 2016-06-12 | 2019-12-27 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst and hydrogenation catalyst prepared by same |
| CN114682265B (en) * | 2020-12-31 | 2024-02-13 | 中国石油化工股份有限公司 | Deactivated Co-Mo type hydrogenation catalyst regeneration liquid and regeneration method |
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| CN1552794A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Dipping solution and preparing method thereof |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
| CN102950003A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1552794A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Dipping solution and preparing method thereof |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
| CN102950003A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof |
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