CN105689009B - Inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts and its preparation method and application - Google Patents
Inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts, which includes aluminium oxide and bar-shaped SBA 15.The present invention provides a kind of preparation method of inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts, this method includes：In the presence of acetic acid, boehmite is contacted with bar-shaped SBA 15.The present invention provides the inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts being prepared according to preparation method of the present invention.The present invention provides application of the inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts of the present invention in inferior feedstock oil hydrogenation desulfurization and denitrogenation.Using the carrier of the present invention, even if can also obtain higher desulfurization degree and denitrification percent as metal active constituent element only with Ni and W, it can be seen that, carrier using the present invention prepares catalyst, and not only activity is high, and cost is low.
Description
Technical field
The present invention relates to a kind of inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts, and a kind of inferior feedstock oil to add
The preparation method of hydrogen desulphurization and denitrification catalyst carrier, and the inferior feedstock oil hydrogenation desulfurization and denitrogenation catalyst of the present invention carry
The application of body.
Background technology
In recent years, as crude oil heaviness is on the rise, coking vapour increasingly stringent with clean fuel sulfur content statute of limitation
Oil, coker gas oil, the quality of catalytic cracking diesel oil and high-sulfur straight-run diesel oil can not meet the requirement of product oil, it is impossible to directly go out
Factory, it is necessary to which hydrofinishing is carried out to it can just produce the petrol and diesel oil of high quality.In fact, the core of Hydrofining Technology is to add
Hydrogen catalyst for refining.
Gasoline hydrogenation catalyst disclosed in CN85104438 is using high-purity alpha-alumina as carrier, using tungsten, nickel as active component,
Using fluorine as auxiliary agent.Fluorine in the catalyst is easily lost in industry park plan, and fluorine etching apparatus and pollution environment.
CN1872959A is disclosed using aluminium oxide as carrier, and nickel-loaded, molybdenum, tungsten are clean property component, introduces fluorine as auxiliary agent
Hydrogenation catalyst.Compared with the hydrogenation catalyst of traditional bimetallic component, its three metal component catalyst activity provided has
Improved, but due to reasons such as carrier properties, it improves limitation, and activity is still relatively low.Meanwhile the catalyst also faces fluorine and exists
Be easy to run off in industry park plan and fluorine etching apparatus and pollution environment the problems such as.
CN1040610A is disclosed to contain TiO2γ-A12O3For the Hydrobon catalyst of carrier, its carrier catalysis
Agent γ-A12O3The content of middle titanium oxide is 5-30%, using W, Mo, Ni as active component.With TiO2Modified A12O3For carrier
The performance of hydrogenation catalyst can be improved necessarily, and carrier acid amount is relatively low, and especially middle strong acidity center is less, is unfavorable for azepine
The open loop fracture of ring, denitrification effect unobvious.
A kind of hydrogenation catalyst with high activity is used in the petroleum hydrocarbon hydrotreating method that USP4880524 is proposed.
The catalyst is Ni-Mo/A12O3Type, specific surface area are more than 300m2/ g, the aperture less than 7nm are more than 70%.The catalyst for
Light fraction oil has the clean property of preferable hydrofinishing, but the active metal of its load is two kinds of components of Ni, Mo, with regard to the country at present
From the point of view of price, molybdenum oxide is higher than tungsten oxide price, therefore for domestic oil refining enterprises, using Ni-Mo/A12O3Type catalyst can increase
Add production cost.
In face of new clean fuel environmental regulation requirement, traditional Hydrofining Technology is faced with formidable challenges at present.Always
Since, hydrodesulfurization attention, but this situation is changing, on the one hand the processing of high nitrogen heavy oil is into trend of the times,
The presence of another aspect nitride suppresses catalyst depth hydrodesulfurization performance.The processing of the high nitrogen Crude oil from CNOOC in China is in China
Occupy considerable proportion in petroleum refining industry, it is therefore desirable to develop high nitrogen inferior distillate oil deep hydrodesulfurizationof catalyst.
CN102151582B discloses a kind of high nitrogen poor quality gasoline and diesel hydrogenation desulphurization catalyst, with A12O3-TiO2-SiO2Three
First oxide is complex carrier；Catalyst composition includes carrier, auxiliary agent, active metal；Active metal includes the oxygen of nickel, molybdenum and tungsten
Compound；Auxiliary agent is phosphorus；Carrier includes aluminium oxide and titanium oxide, silica；Percentage by weight of each component on the basis of catalyst
Content is：Nickel oxide accounts for 1-15wt%, molybdenum oxide 2-12wt%；Tungsten oxide accounts for 12-35wt%, and phosphorus pentoxide accounts for 2-
5wt%；Titanium oxide accounts for 2-15wt%；Silica accounts for 2-20wt%, remaining is aluminium oxide；Dissolving is prepared using room temperature complexing method
The W-Mo-Ni-P co-impregnation liquid that performance is stablized, then supports active metal using substep saturation dipping technique on above-mentioned carrier
Component W-Mo-Ni and auxiliary agent P.The catalyst hydrodesulfurization active and hydrodenitrogenationactivity activity can further improve.
The content of the invention
The high inferior feedstock oil hydrogenation desulfurization and denitrogenation of hydrodesulfurization activity is used to prepare the object of the present invention is to provide a kind of
The carrier of catalyst.
In order to realize object defined above, on the one hand, the present invention provides a kind of inferior feedstock oil hydrogenation desulfurization and denitrogenation catalyst
With carrier, which includes aluminium oxide and bar-shaped SBA-15.
Second aspect, the present invention provides a kind of preparation side of inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts
Method, wherein, this method includes：In the presence of acetic acid, boehmite is contacted with bar-shaped SBA-15.
The third aspect, the present invention provides the inferior feedstock oil hydrogenation being prepared according to preparation method of the present invention
Desulphurization and denitrification catalyst carrier.
Fourth aspect, the present invention provides inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts of the present invention to exist
Application in inferior feedstock oil hydrogenation desulfurization and denitrogenation.
Using the carrier of the present invention, even if can also obtain higher take off as metal active constituent element only with Ni and W
Sulphur rate and denitrification percent, it can be seen that, carrier using the present invention prepares catalyst, and not only activity is high, and cost is low.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
As it was previously stated, the present invention provides a kind of inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts, the carrier bag
Include aluminium oxide and bar-shaped SBA-15.
, according to the invention it is preferred to aluminium oxide and the weight ratio of bar-shaped SBA-15 are 0.1-100:1, more preferably 1-50:1,
More preferably 2-10:1.
It is described bar-shaped as long as ensureing that the carrier includes bar-shaped SBA-15 and can achieve the object of the present invention in the present invention
The pore size of SBA-15 can be pore size known to the technical staff in Zeolite synthesis field.It is preferably bar-shaped for the present invention
The most probable pore size of SBA-15 be 6-10 nanometer, pore volume be 0.5-1.5 mls/g, specific surface area be 600-700 square metres/
Gram when, enable to catalyst have higher catalytic activity.It is highly preferred that the most probable pore size of SBA-15 is 6-6.5 nanometers,
Pore volume is 0.8-1.2 mls/g, and specific surface area is 600-660 meters squared per grams.Further, the rod of the bar-shaped SBA-15
Length can select and change in a wider scope, for example, typically 30-100 microns.
Meet that the SBA-15 of above-mentioned condition is commercially available.Such as：Have commercially available from Changchun Jilin University high-tech share
The SBA-15 of limit company.
In the present invention, the carrier can be formed body, can also be directly to be powdered, specifically can be according to reaction formation
Determine.
Aluminium oxide and bar-shaped SBA-15 can be directly mixed to get by the aforementioned bearer of the present invention, then according to reaction formation
Determine its form, such as can also be molded to obtain formed body according to needs directly to be powdered.
For the present invention, preferably carrier of the invention is prepared as follows：In the presence of acetic acid, by boehmite with
Bar-shaped SBA-15 contacts.
, according to the invention it is preferred to acetic acid and the dosage weight ratio of bar-shaped SBA-15 are 5-20:100.
, according to the invention it is preferred to the condition of the contact includes：Temperature is 50-100 DEG C.
, according to the invention it is preferred to the condition of the contact further includes：Time is 1-5h.
, according to the invention it is preferred to boehmite is counted with the weight ratio of bar-shaped SBA-15 as 0.1-100 using aluminium oxide:1, it is excellent
Elect 1-50 as:1, more preferably 2-10:1.
The property of the bar-shaped SBA-15 is described in detail in the foregoing description to carrier, and details are not described herein.
With the method for the invention it is preferred to this method further includes：Material after contact is heat-treated, is preferably heat-treated
Condition include：Temperature is 300-400 DEG C, and the time being more preferably heat-treated is 3-4h.
The method according to the invention, can be according to needing the powder after heat treatment being molded, originally after Overheating Treatment
Invention to molding method without particular/special requirement, for the present invention, it is preferable that the solid powder after heat treatment is mixed with aqueous solution of nitric acid
Pinch, be molded after roast, wherein, the preferably concentration of aqueous solution of nitric acid is 40-50 weight %, and the weight ratio of nitric acid and solid powder is
1：1-2.
And molding shape can be according to needing to make choice molding mode, such as extruded moulding can be used, the present invention
It is not described one by one herein.
According to the present invention, the condition of the roasting can be preferably for the conventional selection of this area, such as the temperature of roasting
500-600 DEG C, the time is preferably 2-8h, can be more preferably dried before roasting, and dry temperature can be 100-150
DEG C, time 1-5h.
The present invention is to the source of the boehmite without particular/special requirement, for the present invention, preferably described boehmite
Alumina content be 60-80 weight %.
The present invention provides the inferior feedstock oil hydrogenation desulfurization and denitrogenation catalysis that a kind of the method according to the invention is prepared
Agent carrier.
The present invention provides a kind of inferior feedstock oil hydrogenation desulfurization and denitrogenation catalyst, which includes：Carrier and load
Hydrogenation active component element on this carrier, wherein, the carrier is carrier of the present invention.
According to the present invention, the catalyst that prepared by carrier using the present invention usually contains carrier of the present invention and bears
Hydrogenation active component element on the carrier is carried, wherein, the hydrogenation active component element can be the routine of this area
Selection, for the present invention, the one or more being preferably selected from group VIII metallic element and vib metals element.
, according to the invention it is preferred on the basis of the gross weight of catalyst, in terms of oxide, the content of hydrogenation active component is
10-50 weight %, are preferably 30-40 weight %；The content of carrier is 50-90 weight %, is preferably 60-70 weight %.
A kind of preferred embodiment according to the present invention, the hydrogenation active component element is Ni and W, more preferably to urge
On the basis of the gross weight of agent, in terms of oxide, the content of Ni is that the content of 2-10 weight %, W are 25-35 weight %.
The catalyst of the present invention can use conventional load dipping method such as saturation impregnation to obtain, the present invention
To this without particular/special requirement.
The present invention provides inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts of the present invention and original inferior
Application of the oily hydrogenation desulfurization and denitrogenation catalyst of material in inferior feedstock oil hydrogenation desulfurization and denitrogenation.
Wherein, hydrogenation active component element generally exists with oxidation states in catalyst, before use, can generally incite somebody to action
Catalyst carries out presulfurization, and the method for presulfurization is well known to those skilled in the art, and this is not described in detail here by the present invention.
The present invention provides a kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation, wherein, this method includes：It is de- in hydrogenation
Under the conditions of sulphur denitrogenation, inferior feedstock oil is contacted with hydrogen and catalyst, wherein, the catalyst includes：Carrier and it is supported on
Hydrogenation active component element on the carrier, wherein, the carrier is the foregoing carrier of the present invention.
According to the present invention, the condition of the hydrogenation desulfurization and denitrogenation condition can be the conventional selection of this area, for this hair
It is bright, preferably include：Pressure is 5-15MPa, and temperature is 300-450 DEG C, and volume space velocity is 0.5-3h during liquid-1, hydrogen to oil volume ratio is
500-1000。
According to the present invention, the inferior feedstock oil can be the conventional selection of this area, preferably inferior former for the present invention
Nitrogen content is 2000-3000wppm, sulfur content 2000-3000wppm in material oil, and more preferably described inferior feedstock oil is straight run
One or more in diesel oil, coker gasoline, coker gas oil and catalytic diesel oil.
Using the carrier of the present invention, even if can also obtain higher take off as metal active constituent element only with Ni and W
Sulphur rate and denitrification percent, it can be seen that, carrier using the present invention prepares catalyst, and not only activity is high, and cost is low.
Below by embodiment, the present invention will be described in detail, but the present invention is not limited to this.
With in embodiment, the bar-shaped SBA-15 is purchased from high-tech limited company of Changchun Jilin University, specific nature
It is shown in Table 1.
Table 1
Prepare embodiment 1
Boehmite (alumina content is 80 weight %), SBA-15 samples 1 are contacted with acetic acid, wherein, contact
Condition includes：The weight ratio of acetic acid and SBA-15 samples 1 is 5:100, boehmite in terms of aluminium oxide with SBA-15 samples 1
Weight ratio is 10:1, temperature is 60 DEG C, and time 3h, the material after contact is heat-treated, and the temperature of heat treatment is 300
DEG C, time 4h, then carries out kneading, institute by the solid powder being thermally treated resulting in and aqueous solution of nitric acid (concentration is 45 weight %)
It is 1 to add the part by weight of nitric acid and solid powder：1.6, extruded moulding, when 120 DEG C of dryings 2 are small, when 550 DEG C of roastings 4 are small, obtains
Carrier A.
Prepare embodiment 2
Boehmite (alumina content is 60 weight %), SBA-15 samples 2 are contacted with acetic acid, wherein, contact
Condition includes：The weight ratio of acetic acid and SBA-15 samples 1 is 10:100, boehmite in terms of aluminium oxide with SBA-15 samples 1
Weight ratio be 6:1, temperature is 80 DEG C, and time 2h, the material after contact is heat-treated, and the temperature of heat treatment is 400
DEG C, time 3h, then carries out kneading, institute by the solid powder being thermally treated resulting in and aqueous solution of nitric acid (concentration is 45 weight %)
It is 1 to add the part by weight of nitric acid and solid powder：1.6, extruded moulding, when 120 DEG C of dryings 2 are small, when 550 DEG C of roastings 4 are small, obtains
Carrier B.
Prepare embodiment 3
Boehmite (alumina content is 70 weight %), SBA-15 samples 3 are contacted with acetic acid, wherein, contact
Condition includes：The weight ratio of acetic acid and SBA-15 samples 1 is 20:100, boehmite in terms of aluminium oxide with SBA-15 samples 1
Weight ratio be 2:1, temperature is 100 DEG C, and time 1h, the material after contact is heat-treated, and the temperature of heat treatment is 350
DEG C, time 3.5h, subsequently heat-treated obtained solid powder carries out kneading, institute with aqueous solution of nitric acid (concentration is 45 weight %)
It is 1 to add the part by weight of nitric acid and solid powder：1.6, extruded moulding, when 120 DEG C of dryings 2 are small, when 550 DEG C of roastings 4 are small, obtains
Support C.
Prepare embodiment 4
According to the method for preparing embodiment 3, the difference is that, the weight ratio of acetic acid and SBA-15 samples 3 is 50:100, remaining
Condition all same, obtains carrier D.
Prepare embodiment 5
According to the method for preparing embodiment 3, the difference is that, weight of the boehmite in terms of aluminium oxide with SBA-15 samples 3
Amount is than being 0.1:1, remaining condition all same, obtains carrier E.
Prepare embodiment 6
According to prepare embodiment 3 method, unlike, by boehmite (alumina content is 70 weight %),
The temperature that SBA-15 samples 3 are contacted with acetic acid is 120 DEG C, remaining condition all same, obtains carrier F.
Prepare embodiment 7
According to the method for preparing embodiment 3, the difference is that, the temperature of heat treatment is 480 DEG C, remaining condition all same, obtains
To carrier G.
Prepare embodiment 8
According to the method for preparing embodiment 3, the difference is that, after boehmite is mixed with SBA-15 samples 3, dry
To solid powder, kneading, shaping etc. then are carried out according to the method for preparing embodiment 3, obtains carrier H.
Prepare embodiment 9
After alumina powder (SB powder, German CONDEA companies production) is mixed with SBA-15 samples 3, according to preparation embodiment
3 method carries out kneading, shaping etc., obtains carrier I.
Prepare embodiment 10
According to the method for preparing embodiment 3, the difference is that, boehmite is used into alumina powder (SB powder, Germany
CONDEA companies produce) replace, remaining condition all same, obtains carrier J.
Embodiment 1-10
When carrier A-J tungstenics, the maceration extract room temperature immersion 4 of nickel are small, when 120 DEG C of dryings 6 are small, when 450 DEG C of roastings 4 are small,
Obtaining catalyst C1-C10, (wherein, NiO contents are 5 weight %, WO3Content is 30 weight %, remaining is carrier).
Comparative example 1-2
Alumina powder and SBA-15 samples 3 are each obtained into shaped alumina according to the method kneading of preparation embodiment 3, shaping
Alumina supporter, is molded SBA-15 carriers；
Method according to embodiment 1-10 uses foregoing shaped alumina alumina supporter, and shaping SBA-15 carriers each prepare catalysis
(wherein, NiO contents are 5 weight %, WO to agent D1-D23Content is 30 weight %, remaining is carrier).
Test case
This test case illustrates hydrogenation reaction performance of the catalyst provided by the invention for high nitrogen inferior distillate oil.
Evaluation feedstock oil (sulfur content 2308.6wppm, nitrogen content 2739.3wppm, the bromine index used
It is 18200mgBr/100g) by the high nitrogen inferior distillate oil miscella of high-sulfur of CNOOC refinery offer.The feedstock oil belongs to high
The naphthene base crude oil of the high nitrogen of sulphur, is mixed by straight-run diesel oil, catalytic diesel oil, coker gasoline and coker gas oil.
Hydrogenation reaction performance is carried out to catalyst C1-C10 and D1-D2 using the fixed bed hydrogenation device of 200mL respectively
Evaluation.
Presulfiding of catalyst condition:Using containing 3wt%CS2Boat coal, with air speed 1.0h-1, hydrogen to oil volume ratio 500：1,
Under the operating pressure of 8.0MPa, presulfurization is carried out to catalyst.
Pre-vulcanization process is as follows：
It is oily into presulfurization at 120 DEG C, after oil inlet 2h, constant temperature vulcanization 2h；Start to warm up, 150 DEG C be warming up to 15 DEG C/h,
Constant temperature vulcanizes 4h；230 DEG C are warming up to 6 DEG C/h, constant temperature vulcanization 10h；290 DEG C are warming up to 6 DEG C/h, constant temperature vulcanization 6h；With 10
DEG C/h is warming up to 340 DEG C, constant temperature vulcanization 6h；200 DEG C are finally naturally cooling to, presulfurization terminates.
Hydrogenation reaction evaluation response condition is：Operating pressure 8.0MPa, 300 DEG C of reaction temperature, hydrogen to oil volume ratio 600：1,
Volume space velocity is 1.5h-1, evaluation result is shown in Table 2.
Table 2
| Catalyst source | Catalyst is numbered | Bearer number | Desulfurization degree, % | Denitrification percent, % |
| Embodiment 1 | C1 | A | 98.0 | 97.3 |
| Embodiment 2 | C2 | B | 97.3 | 97.5 |
| Embodiment 3 | C3 | C | 98.1 | 97.5 |
| Embodiment 4 | C4 | D | 95.5 | 95.5 |
| Embodiment 5 | C5 | E | 95.3 | 95.0 |
| Embodiment 6 | C6 | F | 94.6 | 95.0 |
| Embodiment 7 | C7 | G | 95.1 | 95.0 |
| Embodiment 8 | C8 | H | 94.0 | 94.5 |
| Embodiment 9 | C9 | I | 93.3 | 93.6 |
| Embodiment 10 | C10 | J | 92.6 | 92.4 |
| Comparative example 1 | D1 | Shaped alumina alumina supporter | 86.7 | 83.5 |
| Comparative example 2 | D2 | It is molded SBA-15 carriers | 52.4 | 53.6 |
Ni, W is used only as active metal component element in carrier using the present invention it can be seen from the result of table 2,
High desulfurization degree and denitrification percent can be obtained.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (8)
1. a kind of preparation method of inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts, wherein, this method includes：In acetic acid
In the presence of, boehmite is contacted with bar-shaped SBA-15, wherein, weight of the boehmite in terms of aluminium oxide with bar-shaped SBA-15
It is 1-50 to measure ratio:1.
2. preparation method according to claim 1, wherein, this method further includes, and the material after contact is heat-treated,
By the solid powder after heat treatment with being roasted after aqueous solution of nitric acid kneading, shaping, wherein, the condition of heat treatment includes：Temperature is
300-400 DEG C, time 3-4h；The concentration of aqueous solution of nitric acid is 40-50 weight %, and the weight ratio of nitric acid and solid powder is 1：
1-2。
3. preparation method according to claim 1, wherein, the condition of the contact includes：Acetic acid is with bar-shaped SBA-15's
Dosage weight ratio is 5-20:100, temperature is 50-100 DEG C, time 1-5h.
4. according to the preparation method described in any one in claim 1-3, wherein, boehmite in terms of aluminium oxide with it is bar-shaped
The weight ratio of SBA-15 is 2-10:1.
5. the inferior feedstock oil hydrogenation desulfurization and denitrogenation catalysis that the preparation method in claim 1-4 described in any one is prepared
Agent carrier.
6. the inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts described in claim 5 takes off in inferior feedstock oil hydrodesulfurization
Application in nitrogen.
7. application according to claim 6, wherein, nitrogen content is 2000-3000wppm in the inferior feedstock oil, and sulphur contains
Measure as 2000-3000wppm.
8. application according to claim 7, wherein, the inferior feedstock oil is straight-run diesel oil, coker gasoline, coker gas oil
With the one or more in catalytic diesel oil.
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Citations (3)
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|---|---|---|---|---|
| JP2002097015A (en) * | 2000-09-21 | 2002-04-02 | Mitsubishi Rayon Co Ltd | Method for producing hydrogen cyanide |
| CN101590424A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof |
| CN103285904A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
-
2014
- 2014-11-27 CN CN201410699465.0A patent/CN105689009B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097015A (en) * | 2000-09-21 | 2002-04-02 | Mitsubishi Rayon Co Ltd | Method for producing hydrogen cyanide |
| CN101590424A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof |
| CN103285904A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
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