CN107952432A - A kind of preparation method of heavy oil hydrogenating treatment catalyst - Google Patents
A kind of preparation method of heavy oil hydrogenating treatment catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
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Abstract
The present invention provides a kind of preparation method of heavy oil hydrogenating treatment catalyst, this method is：Dust carrier is added in ruthenium precursor water solution, hydrogen peroxide solution is added dropwise to after being sufficiently stirred, after mixing heating heating, then solution ph is adjusted with alkali, solid-liquid separation treatment is carried out afterwards, and isolated solid is dried, obtains heavy oil hydrogenating treatment catalyst.Heavy oil hydrogenating treatment catalyst prepared by the present invention can solve current heavy oil hydrogenating treatment catalyst preparation method high energy consumption, water consumption is big, step is numerous and diverse, is not easy the shortcomings such as prepared by industry amplification, noble ruthenium utilization ratio is low, and processing step is few, water consumption is few, energy consumption is low, the cycle is short, yield is high.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of preparation method of heavy oil hydrogenating treatment catalyst.
Background technology
Catalytic oxidation of hydrogen chloride for preparing chlorine gas (2HCl (g)+1/2O2→H2O+Cl2), Deacon processes are also known as, by Henry
Deacon was proposed in 1868.Industrial by-products hydrogen chloride can be converted into chlorine by Deacon processes, realize chlorine resources circulation
Utilize, be to solve hydrogen chloride discharge and recycle most effective, most economical environmentally friendly method.Deacon reactions are exothermic reactions,
Equilibrium conversion is raised and reduced with reaction temperature, therefore catalyst must possess extraordinary low temperature active.Have numerous
In the catalyst of chloration hydro-oxidation activity, load ruthenium catalyst is the best catalyst system and catalyzing of low temperature active.It is well known that catalysis
The preparation method of agent not only influences its catalytic performance, has an effect on the cost of industrial catalyst.
Preparation catalyst is difficult to control the size of active component particles, causes active component dispersiveness poor, drop
Low catalyst activity.The Ru/SiO for chloration hydro-oxidation is described in GB10463132Catalyst, with RuCl3For presoma
SiO is loaded to using equi-volume impregnating2Carrier surface.CN101663092 discloses the ruthenium catalyst containing different accelerating agents,
Its preparation method also uses infusion process, although accelerating agent can improve the stability of catalyst, preparation method causes RuO2
The problem of bad dispersibility, is still unresolved.CN12457738 reports the ruthenium catalyst of some chloration hydro-oxidations, and which part is implemented
Using excessive infusion process in example, but excessive infusion process needs to evaporate excessive solvent, not only increases energy consumption, and evaporate
During dipping solution concentration change can also reduce active component dispersiveness.
Precipitation sedimentation and coprecipitation are also used for the preparation of heavy oil hydrogenating treatment catalyst.CN1145328 reports use
In the ruthenium catalyst of chloration hydro-oxidation, its preparation method is by RuCl3After solution and alkali precipitation, then mix with freshly prepared carrier
Close and complete loading process.CN101448735 reports a kind of load ruthenium catalyst, and carrier is rutile crystal type stannic oxide,
Its preparation method is precipitation sedimentation, i.e., ruthenium halide is deposited to SnO by alkali2Surface.CN101722019 is deposited using precipitation
Method is prepared for a kind of catalyst containing the carrier loaded ruthenium compound of magnesium fluoride.In CN1145328 embodiments, partial catalyst is adopted
With coprecipitation, i.e. support precursor forms precipitation together with active component presoma, and catalysis then is made by post-processing
Agent.The salt that precipitation solution, rear cleaning produce in precipitation sedimentation preparation process is required to substantial amounts of water, consumes more water money
Source, and this method prepares catalyst and is not easy to amplify, and manufacturing cost is higher.And coprecipitation has the above-mentioned of precipitation sedimentation
Outside shortcoming, since co-precipitation causes the embedding of active component, the utilization rate of active component is reduced, is not suitable for precious metal
The preparation of catalyst.
Traditional method for preparing catalyst shortcoming for more than, the ruthenium catalyst of CN1245773 reports employ one kind and change
Into hydrogen chloride method for preparing catalyst.On the basis of traditional infusion process, pass through the reduction treatment under alkaline condition, and alkali
Metal chloride is handled to improve the activity of catalyst.But this method includes load, alkali process, reduction, washing, alkali metal
The complicated procedures of forming such as chloride treatment, drying, roasting, washing, drying, are not suitable for industry amplification and prepare.A kind of use of document report
In the high dispersancy nano RuO of chloration hydro-oxidation2/TiO2Catalyst (Catal.Sci.Technol., 2013,3,2555), first
A nanometer RuO is synthesized by nanometer preparation method first2Solution, then falls excess solution by excessive impregnated carrier, rotary evaporation
.But such representative nanometer synthetic method is used to prepare industrial catalyst that there is be much difficult to overcome to lack
Point, for example, the protective agent added during synthesizing nano-particle needs post processing, solvent dosage is big, yield is relatively low, and nanometer
The loading process of particle needs rotary evaporation to fall excessive solvent, not only increases energy consumption, is also difficult to prepare the catalysis of heavy load amount
Agent.It can be seen from the above that nanometer preparation method is of high cost, low output, step is more, is not easy industrial amplification.
The content of the invention
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, there is provided a kind of chloration hydro-oxidation
The preparation method of catalyst, this method can solve that current heavy oil hydrogenating treatment catalyst preparation method high energy consumption, water consumption be big, step
It is rapid it is numerous and diverse, be not easy the shortcomings such as prepared by industry amplification, noble ruthenium utilization ratio is low.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of preparation of heavy oil hydrogenating treatment catalyst
Method, it is characterised in that this method is：It is first according to ruthenium presoma:Hydrogen peroxide:Dust carrier=(0.3~3) ﹕ (0.5~
10) the molar ratio of ﹕ 100 weighs ruthenium precursor water solution, hydrogen peroxide solution and dust carrier respectively, then adds dust carrier
Enter into ruthenium precursor water solution, hydrogen peroxide solution is added dropwise to after being sufficiently stirred, be warming up to 80 DEG C~100 DEG C guarantors after mixing
Warm 1h~10h, it is 6~12 to adjust solution ph using alkali afterwards, solid-liquid separation treatment is finally carried out, by isolated solid
Drying, obtains heavy oil hydrogenating treatment catalyst.
The preparation method of above-mentioned a kind of heavy oil hydrogenating treatment catalyst, it is characterised in that the ruthenium presoma is anhydrous three
Ruthenic chloride or hydrate ruthenium trichloride；The mass concentration of ruthenium is 0.1%~5% in the ruthenium precursor water solution.Present invention research
It was found that if the mass concentration of Ru (III) is less than 0.1%, the water consumed is excessive, the rise of catalyst cost；If Ru
(III) mass concentration is more than 5%, then can reduce RuO2In the dispersion degree of carrier surface.Therefore the mass concentration of Ru (III) exists
0.1~5% is suitable, is more preferably 0.2~2%.
A kind of preparation method of above-mentioned heavy oil hydrogenating treatment catalyst, it is characterised in that the quality of the hydrogen peroxide solution
Concentration is 10%~50%.Present invention research finds that, if the concentration of hydrogen peroxide is less than 10%, the water consumed is excessive, urges
Agent cost raises；If the concentration of hydrogen peroxide be more than 50%, the price of hydrogen peroxide can be raised significantly, increase catalyst into
This.Therefore hydrogen peroxide concentration is suitable 10~50%, is more preferably 20%~30%.
The preparation method of above-mentioned a kind of heavy oil hydrogenating treatment catalyst, it is characterised in that the dust carrier is three oxidations
At least one of two lanthanums, ceria, alundum (Al2O3), silica, nickel sesquioxide and cobaltosic oxide and titanium dioxide
The compound of titanium composition, or titanium dioxide or/and stannic oxide.
The preparation method of above-mentioned a kind of heavy oil hydrogenating treatment catalyst, it is characterised in that the alkali is waterglass, metasilicic acid
In sodium and sodium metaaluminate any one or it is two or more.
A kind of preparation method of above-mentioned heavy oil hydrogenating treatment catalyst, it is characterised in that the heavy oil hydrogenating treatment catalyst
In active component be ruthenic oxide, the mass ratio of the ruthenic oxide and carrier is (0.1~1) ﹕ 20.In the present invention, if
Ruthenic oxide is more than 5% relative to the load capacity of carrier, noble metal utilisation can be caused to reduce, and increases catalyst cost；If
Ruthenic oxide is less than 0.5% relative to the load capacity of carrier, then unit mass catalyst is active relatively low, and not reaching industry will
Ask.Therefore ruthenic oxide is suitable for 0.5%~5% relative to the load capacity of carrier.
In the present invention, the addition sequence of ruthenium precursor water solution and hydrogen peroxide solution can be exchanged, i.e.,：By dust carrier plus
Enter in hydrogen peroxide solution, ruthenium precursor water solution is added dropwise to after being sufficiently stirred.Product of the present invention can equally be generated.
In the present invention, Solid separate can it is fired (temperature be 250 DEG C~450 DEG C under conditions of roast 2~10h) obtain
Final product is obtained, also can not be fired, it can equally obtain final product.
In the present invention, outlet chlorine growing amount is analyzed using iodometric titrationiodimetry titration, the conversion ratio and unit mole ruthenium of HCl
Space-time yield computational methods it is as follows：
Wherein, it is mol/min to export chlorine generating rate and the unit of HCl feed rates.
Wherein, the unit for exporting chlorine generating rate is mol/min, and the unit of the mole of Ru is mol in 0.1g catalyst.
The present invention has the following advantages compared with prior art：
(1) preparation method of the invention is suitable for preparing industrial catalyst, and step is few, water consumption is few, energy consumption is low, the cycle
It is short, yield is high；
(2) method using the present invention is prepared in catalyst process, and dust carrier obtains fully dispersed, Ke Yichong in solution
Divide the outer surface using carrier, improve load capacity；
(3) method using the present invention is prepared in catalyst process, and ruthenic oxide load capacity is in the range of 0.5%~5%
When, ruthenic oxide can uniform deposition to carrier surface, so as to improve the dispersiveness of ruthenic oxide particle, increase noble ruthenium
Utilization ratio；
(4) method using the present invention is prepared in catalyst process, and the addition of alkali not only makes support powder pass through precipitation point
From, but also unreacted ruthenium presoma can be made to deposit to carrier surface, improve catalyst preparation yield.
(5) method using the present invention is prepared in catalyst process, it may not be necessary to which roasting can obtain ruthenic oxide work
Property component, the shortcomings that overcoming energy consumption and pollution during traditional preparation methods.
The present invention is described in further detail with reference to embodiment.
Embodiment
Embodiment 1
A kind of preparation method of heavy oil hydrogenating treatment catalyst is present embodiments provided, this method comprises the following steps：
Step 1: by the commercially available RuCl of 0.14g3.nH2O (Ru mass contents>37%) add in 50g distilled water, obtain ruthenium
Mass content is 0.1% solution, is named as solution one；
Step 2: commercially available 30% hydrogen peroxide of 20g is added in 20g distilled water, obtain hydrogen peroxide content be 15% it is molten
Liquid, is named as solution two；
Step 3: it is 0.3 according to the molar ratio of ruthenium presoma, hydrogen peroxide, titanium dioxide:0.5:100, by powder titanium dioxide
Titanium carrier (rutile-type, Aladdin reagent) is added in solution one, is sufficiently stirred, is obtained solution three；Then solution two is added dropwise
Enter solution three, obtain solution four；
Step 4: solution four is warming up to 80 DEG C, 4h is kept, obtains solution five；
Step 5: solution five is adjusted to 6 by pH with sodium metasilicate, then separation of solid and liquid is carried out by the way of filtering；
Step 6: the solid material body obtained in step 5 after solid-liquid separation treatment is obtained into chlorination in 60 DEG C of dryings
Hydro-oxidation catalyst finished product.
Catalyst manufactured in the present embodiment is denoted as catalyst 1.On the basis of carrier quality, ruthenic oxide phase in the catalyst
Load capacity for carrier is 0.5%.
Embodiment 2
A kind of preparation method of heavy oil hydrogenating treatment catalyst is present embodiments provided, this method comprises the following steps：
Step 1: the commercially available RuCl of 0.68g3.nH2O (Ru mass contents>37%) add in 50g distilled water, obtain ruthenium matter
The solution that content is 0.5% is measured, is named as solution one；
Step 2: commercially available 50% hydrogen peroxide of 20g adds 20g distilled water, the solution that hydrogen peroxide content is 25%, life are obtained
Entitled solution two；
Step 3: it is 0.6 according to the molar ratio of ruthenium presoma, hydrogen peroxide, titanium dioxide:2:100, by powdered titanium dioxide
Carrier (rutile-type, Aladdin reagent) is added in solution one, is sufficiently stirred, is obtained solution three；Then solution two is added dropwise to
Solution three, obtains solution four；
Step 4: solution four is warming up to 90 DEG C, 2h is kept, obtains solution five；
Step 5: solution five is adjusted to more than 6 by pH with sodium metasilicate, solid-liquid point is then carried out by the way of filtering
From；
Step 6: the solid material body obtained in step 5 after solid-liquid separation treatment is obtained into chlorination in 80 DEG C of dryings
Hydro-oxidation catalyst finished product.
Catalyst manufactured in the present embodiment is denoted as catalyst 2.On the basis of carrier quality, ruthenic oxide phase in the catalyst
Load capacity for carrier is 1%.
Embodiment 3
A kind of preparation method of heavy oil hydrogenating treatment catalyst is present embodiments provided, this method comprises the following steps：
Step 1: the commercially available RuCl of 7.81g3.nH2O (Ru mass contents>37%) add in 50g distilled water, obtain ruthenium matter
The solution that content is 5% is measured, is named as solution one；
Step 2: commercially available hydrogen peroxide content is 35% solution, solution two is named as；
Step 3: it is 3 according to the molar ratio of ruthenium presoma, hydrogen peroxide, titanium dioxide:10:100, by powdered titanium dioxide
Carrier (rutile-type, Aladdin reagent) is added in solution one, is sufficiently stirred, is obtained solution three；Then solution two is added dropwise to
Solution three, obtains solution four；
Step 4: solution four is warming up to 90 DEG C, 2h is kept, obtains solution five；
Step 5: solution five is adjusted to more than 6 by pH with sodium metasilicate, solid-liquid point is then carried out by the way of filtering
From；
Step 6: the solid material body obtained in step 5 after solid-liquid separation treatment is obtained into chlorination in 80 DEG C of dryings
Hydro-oxidation catalyst finished product.
Catalyst manufactured in the present embodiment is denoted as catalyst 3.On the basis of carrier quality, ruthenic oxide phase in the catalyst
Load capacity for carrier is 5%.
Embodiment 4
A kind of preparation method of heavy oil hydrogenating treatment catalyst is present embodiments provided, this method comprises the following steps：
Step 1: the commercially available RuCl of 2.86g3.nH2O (Ru mass contents>37%) add in 50g distilled water, obtain ruthenium matter
The solution that content is 2% is measured, is named as solution one；
Step 2: commercially available hydrogen peroxide content is 35% solution, solution two is named as；
Step 3: it is 1.2 according to the molar ratio of ruthenium presoma, hydrogen peroxide, titanium dioxide:5:100, by powdered titanium dioxide
Carrier (rutile-type, Aladdin reagent) is added in solution two, is sufficiently stirred, is obtained solution three；Then solution one is added dropwise to
Solution three, obtains solution four；
Step 4: solution four is warming up to 90 DEG C, 2h is kept, obtains solution five；
Step 5: solution five is adjusted to more than 6 by pH with sodium metasilicate, solid-liquid point is then carried out by the way of filtering
From；
Step 6: by the solid material body obtained in step 5 after solid-liquid separation treatment in 80 DEG C of dryings, then at 250 DEG C
4h is roasted, that is, obtains heavy oil hydrogenating treatment catalyst finished product.
Catalyst manufactured in the present embodiment is denoted as catalyst 4.On the basis of carrier quality, ruthenic oxide phase in the catalyst
Load capacity for carrier is 2%.
Embodiment 5
A kind of preparation method of heavy oil hydrogenating treatment catalyst is present embodiments provided, this method comprises the following steps：
Step 1: the commercially available RuCl of 2.86g3.nH2O (Ru mass contents>37%) add in 50g distilled water, obtain ruthenium matter
The solution that content is 2% is measured, is named as solution one；
Step 2: commercially available hydrogen peroxide content is 35% solution, solution two is named as；
Step 3: it is 1.13 according to the molar ratio of ruthenium presoma, hydrogen peroxide, stannic oxide:5:100, by powder titanium dioxide
Tin carrier (traditional Chinese medicines reagent) is added in solution two, is sufficiently stirred, is obtained solution three；Then solution one is added dropwise to solution three, obtained
To solution four；
Step 4: solution four is warming up to 100 DEG C, 2h is kept, obtains solution five；
Step 5: solution five is adjusted to more than 6 by pH with sodium metaaluminate, solid-liquid point is then carried out by the way of filtering
From；
Step 6: the solid material body obtained in step 5 after solid-liquid separation treatment is obtained into chlorination in 80 DEG C of dryings
Hydro-oxidation catalyst finished product.
Catalyst manufactured in the present embodiment is denoted as catalyst 5.On the basis of carrier quality, ruthenic oxide phase in the catalyst
Load capacity for carrier is 1%.
Embodiment 6
A kind of preparation method of heavy oil hydrogenating treatment catalyst is present embodiments provided, this method comprises the following steps：
Step 1: the commercially available RuCl of 2.86g3.nH2O (Ru mass contents>37%) add in 50g distilled water, obtain ruthenium matter
The solution that content is 2% is measured, is named as solution one；
Step 2: commercially available hydrogen peroxide content is 35% solution, solution two is named as；
Step 3: it is 2.26 according to the molar ratio of ruthenium presoma, hydrogen peroxide, stannic oxide:5:100, by powder titanium dioxide
Tin carrier (traditional Chinese medicines reagent) is added in solution two, is sufficiently stirred, is obtained solution three；Then solution one is added dropwise to solution three, obtained
To solution four；
Step 4: solution four is warming up to 90 DEG C, 2h is kept, obtains solution five；
Step 5: solution five is adjusted to more than 8 by pH with waterglass, then separation of solid and liquid is carried out by the way of filtering；
Step 6: the solid material body obtained in step 5 after solid-liquid separation treatment is obtained into chlorination in 80 DEG C of dryings
Hydro-oxidation catalyst finished product.
Catalyst manufactured in the present embodiment is denoted as catalyst 6.On the basis of carrier quality, ruthenic oxide phase in the catalyst
Load capacity for carrier is 2%.
Comparative example 1
This comparative example provides a kind of preparation method of heavy oil hydrogenating treatment catalyst, and this method is：It is first that 0.82g is commercially available
RuCl3.nH2O (Ru mass contents>37%) it is added in 5.48g distilled water, obtains the solution that ruthenium mass content is 4.8%.
Next by above-mentioned solution incipient impregnation to 20g powdered titanium dioxides carrier (rutile-type, Aladdin reagent), static mistake
Night.Then by the solid after dipping in 100 DEG C of dry 10h, then 300 DEG C of roasting 5h in Muffle furnace, that is, obtain finished catalyst.
Catalyst prepared by this comparative example is denoted as comparative catalyst 1, and ruthenic oxide is relative to the negative of carrier in the catalyst
Carrying capacity is 2%.
Following evaluation test is carried out to the performance of above-mentioned catalyst：
1 tabletting of embodiment catalyst 1-6 and comparative catalyst, broken granulation are obtained into 40~60 mesh catalyst granules.So
Take the quartz sand of 40~60 mesh catalyst of 0.1g mesh number same with 0.6g to be uniformly mixed afterwards, be loaded into the fixed bed that internal diameter is 6mm
In quartz reactor.
Reaction condition is as follows：Reactor feed gas is HCl/O2=2 gaseous mixture, 320 DEG C of reaction temperature, reaction pressure
0.1MPa, gas phase air speed 36000ml/h.g-cat。
After reaction 2h reaches and stablizes, with the KI solution absorbing reaction device exit gas that mass concentration is 20%.Then use
The NaS of 0.14mol/L2O3Solution titrates absorbing liquid, calculates the growing amount of chlorine.Formula according to this specification description calculates
The space-time yield of HCl conversion ratios and unit mole ruthenium is obtained, the results are shown in Table 1.
1 different catalysts hydrogen chloride oxidation reaction performance of table
As shown in Table 1, the catalyst synthesized using the method for the present invention, its ruthenic oxide load capacity is in 0.5~5% scope
Interior, the utilization ratio of ruthenium keeps higher level.Catalyst 4 is compared with comparative catalyst 1, although the two load capacity is identical,
It is that the space-time yield of 4 unit mole ruthenium of catalyst significantly improves, illustrates that the method for the present invention can be conducive to increase noble ruthenium
Utilization ratio.
The above, is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions.It is every according to invention skill
Any simple modification, change and equivalence change that art substantially makees above example, still fall within technical solution of the present invention
Protection domain in.
Claims (6)
1. a kind of preparation method of heavy oil hydrogenating treatment catalyst, it is characterised in that this method is：It is first according to ruthenium presoma:It is double
Oxygen water:Dust carrier=((molar ratio of 0.5~10) ﹕ 100 weighs ruthenium precursor water solution, hydrogen peroxide to 0.3~3) ﹕ respectively
Dust carrier, is then added in ruthenium precursor water solution by solution and dust carrier, and it is water-soluble to be added dropwise to dioxygen after being sufficiently stirred
Liquid, is warming up to 80 DEG C~100 DEG C insulation 1h~10h after mixing, and it is 6~12 to adjust solution ph using alkali afterwards, finally
Solid-liquid separation treatment is carried out, isolated solid is dried, obtains heavy oil hydrogenating treatment catalyst.
A kind of 2. preparation method of heavy oil hydrogenating treatment catalyst according to claim 1, it is characterised in that the ruthenium forerunner
Body is anhydrous ruthenium trichloride or hydrate ruthenium trichloride；The mass concentration of ruthenium is 0.1%~5% in the ruthenium precursor water solution.
A kind of 3. preparation method of heavy oil hydrogenating treatment catalyst according to claim 1, it is characterised in that the hydrogen peroxide
The mass concentration of solution is 10%~50%.
4. the preparation method of a kind of heavy oil hydrogenating treatment catalyst according to claim 1, it is characterised in that the powder carries
Body is at least one in lanthanum sesquioxide, ceria, alundum (Al2O3), silica, nickel sesquioxide and cobaltosic oxide
Kind and the compound of titanium dioxide composition, or titanium dioxide or/and stannic oxide.
5. the preparation method of a kind of heavy oil hydrogenating treatment catalyst according to claim 1, it is characterised in that the alkali is water
In glass, sodium metasilicate and sodium metaaluminate any one or it is two or more.
A kind of 6. preparation method of heavy oil hydrogenating treatment catalyst according to claim 1, it is characterised in that the hydrogen chloride
Active component in oxidation catalyst is ruthenic oxide, and the mass ratio of the ruthenic oxide and carrier is (0.1~1) ﹕ 20.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821571A (en) * | 2019-03-15 | 2019-05-31 | 西安近代化学研究所 | A kind of preparation method of high activity heavy oil hydrogenating treatment catalyst |
| CN112536032A (en) * | 2020-12-04 | 2021-03-23 | 浙江师范大学 | High-temperature-resistant sintering catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof |
| CN115155558A (en) * | 2022-06-24 | 2022-10-11 | 西安近代化学研究所 | Solid solution carrier and preparation method of ruthenium-based catalyst |
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| CN115155558A (en) * | 2022-06-24 | 2022-10-11 | 西安近代化学研究所 | Solid solution carrier and preparation method of ruthenium-based catalyst |
| CN115155558B (en) * | 2022-06-24 | 2024-05-28 | 西安近代化学研究所 | Solid solution carrier and preparation method of ruthenium-based catalyst |
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