CN108714434A - A kind of light oil type hydrogen cracking catalyst and preparation method thereof - Google Patents
A kind of light oil type hydrogen cracking catalyst and preparation method thereof Download PDFInfo
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- CN108714434A CN108714434A CN201810565969.1A CN201810565969A CN108714434A CN 108714434 A CN108714434 A CN 108714434A CN 201810565969 A CN201810565969 A CN 201810565969A CN 108714434 A CN108714434 A CN 108714434A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention discloses a kind of light oil type hydrogen cracking catalyst and preparation method thereof, which is made of the compound of the element containing group VIII metal, the compound of the metallic element containing group vib, boehmite, molecular sieve, the alkyl substituted siloxanes containing modified group of raw material.Light oil selectivity greatly improved in gained light oil type hydrogen cracking catalyst on the basis of improving catalyst activity, and the yield of fluid product also improves therewith, and gaseous hydrocarbon, which generates, to be reduced, and the output benefit of production light oil type hydrogen cracking device can be significantly improved.
Description
Technical field
Present invention relates particularly to a kind of light oil type hydrogen cracking catalysts and preparation method thereof.
Background technology
Hydrocracking process is a kind of oil refining work that higher boiling raw material is transformed into low-boiling naphtha and diesel oil distillate
Skill.Compared with catalytic cracking, the adaptability to raw material of hydrocracking process is high, and the yield height of diesel oil distillate, quality are good, but stone brain
The octane number of oil is relatively low.Demand with society to clean traffic fuel oil is continuously increased, and hydrocracking process becomes existing
For one of the core process of refinery.
Hydrocracking catalyst is the core of entire hydrocracking process, generally includes difunctional center：One is acidity
Center is provided by carrier, determines the activity of catalyst substantially, acidic components were once adopted in hydrocracking catalyst evolution
With such as halogenated（Chlorine or fluorine）The materials such as aluminium oxide, amorphous silicon aluminium and molecular sieve, since the seventies in last century, with
The development of molecular sieve technology of preparing, Si-Al molecular sieve are increasingly becoming hydrocracking catalyst since its structure is clear, acid adjustable
The mainstream component of middle acid centre.Second is metal center, plays the role of hydrogenation/dehydrogenation during the reaction, for acidity
Center provides reaction raw materials, and is saturated acid centre product in time, prevents drastic cracking.Metal center is generally by group vib metal
Or group vib is formed with group VIIIB binary metal system, and real hydrogenation/dehydrogenation activity is provided with oxide morphology.Acid centre
It is combined with hydrogenation/dehydrogenation close centre and the two coordinative role is the key that hydrocracking catalyst successful operation.
In order to meet society to the ever-increasing demand of clean traffic fuel oil, abundant profit is needed in hydrocracking process
With high boiling raw material to produce more naphthas and diesel product, and reduce production low value gaseous product (C1-C4).Simultaneously
In order to reduce production operation expense, industrial production is desirable for higher active catalyst, to reduce reaction temperature.Specific to urging
Agent then wishes the synchronous acid centre performance and metal center performance for improving catalyst when designing；The performance of acid centre can be with
By increasing acid material（Such as molecular sieve）Acid strength or its usage amount be improved；And metal center performance then due to by
The limitation of effective ratio area and metal self character that carrier can be provided cannot be obtained simply by usage amount is increased
It improves.Therefore, the hot spot that metal center performance is always the area research how is improved.
Inorganic oxide（Such as aluminium oxide）Surface have a large amount of hydroxyl, the type of hydroxyl is with aluminium atom coordination environment
Difference can be divided into five types（Bibliography：Catal Rev. Sci. Eng. 17(1), 31-70, 1978）.These hydroxyls
It is the key that strong effect original is formed between group vib metal and alumina support that base forms Al-O-M chemical bonds by condensation
Cause.The present invention carries out surface modifying and decorating to the carrier of hydrocracking catalyst that inorganic oxide forms, by the strong hydroxyl on its surface
Base completely or partially replaces with other functional groups, so that it is formed weak interaction between VI B metals, or even directly participate in
Into the sulfidation of VI B metal oxides, to change phase interaction between transition metal and inorganic carrier surface in itself
With, be conducive to the abundant presulfurization of transition metal oxide, to play best plus/dehydrogenation in hydrocracking reaction,
Especially during being hydrocracked production light oil, be conducive to being rapidly saturated for alkene intermediates, reduce drastic cracking, reduces
The generation of C1 ~ C4 gaseous hydrocarbons, and then improve liquid product yield.
Invention content
To solve the problems, such as that the light oil selectivity of current hydrocracking catalyst is not high, liquid product yield is relatively low, this hair
Bright to provide a kind of novel light oil type hydrogen cracking catalyst and preparation method thereof, which has high activity, high light oil
The characteristics of selective and high liquid yield.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of light oil type hydrogen cracking catalyst is made of following raw material：
（a）The compound of the element containing group VIII metal；
（b）The compound of the metallic element containing group vib；
（c）Boehmite；
（d）Molecular sieve；
（e）Alkyl substituted siloxanes containing modified group；
In above-mentioned technical proposal, in terms of parts by weight, raw material（a）Dosage is preferably 0.1 ~ 35 part, more preferable 15 ~ 25 parts；Raw material
（b）Dosage is preferably 0.1 ~ 15 part, more preferable 4 ~ 8 parts；Raw material（c）Dosage is preferably 1 ~ 95 part, more preferable 20 ~ 60 parts；Raw material
（d）Dosage is preferably 1 ~ 80 part, more preferable 10 ~ 40 parts；Raw material（e）Dosage is preferably 0.1 ~ 20 part, more preferable 1 ~ 10 part.
In above-mentioned technical proposal, the group VIII metal element is selected from least one of Co and Ni；
The group vib metallic element is selected from least one of Mo and W；
The structural formula of the alkyl substituted siloxanes containing modified group is：X-R1-Si(OR2)3, wherein R1And R2It is independently selected from
Alkyl, aromatic radical or substituted aromatic base, X are-H ,-F ,-NH2,-SH ,-CHO ,-OH or-C (O) NH2, preferably-SH.
The molecular sieve is hydrogen type molecular sieve, is specially USY molecular sieve, Beta molecular sieves, ZSM-5 molecular sieve, SSZ-
At least one of 32 molecular sieves, preferably USY molecular sieve, specific surface area are 400 ~ 1000 m2/ g, preferably 600 ~ 800
m2/g；Total pore volume is 0.45 ~ 1.00 cm3/ g, preferably 0.50 ~ 0.80 ml/g；0.10 ~ 0.50 mL/g of mesoporous Kong Rongwei,
Preferably 0.20 ~ 0.40 mL/g；Si/Al molar ratios are 2 ~ 30, preferably 3 ~ 10；Unit cell dimension is 24.30 ~ 24.60, excellent
It is selected as 24.40 ~ 24.55。
The preparation method of the light oil type hydrogen cracking catalyst includes the following steps：
（1）Boehmite and molecular sieve are uniformly mixed, acid solution is then added, fully kneaded and formed rear dry, roasting obtains
To catalyst carrier；
（2）By alkyl substituted siloxanes and step containing modified group（1）Obtained catalyst carrier reaction, then crosses diafiltration
It washs, then is dried in vacuo to obtain modified catalyst supports；
（3）The compound of the compound of the metallic element containing group vib and the element containing group VIII metal is scattered in solvent, for soaking
Stain step（2）Obtained modified catalyst supports, then dry, roasting, obtain the light oil type hydrogen cracking catalyst.
In above-mentioned technical proposal, step（1）A concentration of 0.5wt% ~ 5wt% of the acid solution, preferably 1wt% ~ 3wt%,
Acid used can be the inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, can also be the organic acids such as formic acid, acetic acid, citric acid, preferably nitric acid.
Step（1）In kneaded and formed extrudate a diameter of 1.5 ~ 3.5 mm, long 3 ~ 12 mm, section be it is round or
Cloverleaf pattern.
Step（1）The temperature of middle drying is 80 ~ 200 DEG C, and the time is 2 ~ 24 h.
Step（1）The temperature of middle roasting is 400 ~ 650 DEG C, and the time is 2 ~ 10 h.Boehmite is through 500 DEG C of 4 h of roasting
Afterwards, aluminium oxide is obtained, specific surface area is 150 ~ 400 m2/ g, preferably 200 ~ 320 m2/g；0.2 ~ 0.8 cm of Kong Rongwei3/ g,
Preferably 0.40 ~ 0.65 cm3/g；In terms of weight fraction, wherein Na constituent content≤0.1%, preferably≤0.05%.
Step（2）In the reaction conditions of alkyl substituted siloxanes and catalyst carrier containing modified group do not limit especially
System, those skilled in the art can reasonably select.
Step（2）In vacuum drying temperature be 60 ~ 150 DEG C, the time be 2 ~ 36 h.
Step（3）Described in the compound of the metallic element containing group vib and the compound of the element containing group VIII metal without spy
It does not limit, as long as the negative of group vib metallic element, group VIII metal element or its oxide can be realized on modified catalyst supports
Load, those skilled in the art can reasonably select.As long as used solvent is it is not also specifically limited, can realize that dipping is negative
The operation of load can be single solvent, or mixed solvent can directly be dissolved, or pass through and adjust pH
Dissolving can also be to form colloid or form the solvent that colloid realizes dissolving by adjusting pH.
Step（3）The temperature of middle drying is 80 ~ 200 DEG C, and the time is 2 ~ 24 h.
Reaction when using light oil type hydrogen cracking catalyst hydrocracked, treated VGO of the present invention or being hydrocracked recycle oil
Condition is：In the presence of hydrogen, 12 ~ 18MPa of reaction pressure, 300 ~ 420 DEG C of reaction temperature, hydrogen to oil volume ratio 450 ~ 1500, when liquid
0.5 ~ 8.0 h of volume space velocity-1。
Compared to existing hydrocracking catalyst, the light oil type hydrogen cracking provided by the invention prepared using modified support
Light oil selectivity greatly improved in catalyst on the basis of improving catalyst activity, and the yield of fluid product also carries therewith
Height, gaseous hydrocarbon, which generates, to be reduced, and output benefit can be significantly improved.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
Enough aluminium oxide can be provided USY molecular sieve powder and in the final catalyst（Al2O3）Boehmite powder it is mixed
It closes uniformly, the salpeter solution of 1.5wt% is then added, the cylindrical grain of 3-10 mm long, 2 mm of diameter are extruded into after fully mediating
Son, it is 12 hours dry under the conditions of 120 DEG C, it is then roasted 8 hours under the conditions of 550 DEG C, obtains catalyst carrier S-0,
Middle Al2O3:The weight ratio of USY molecular sieve is 60:40.
Embodiment 2
（1）The 3- mercaptopropyltriethoxysilanes of enough modified groups can be provided in the final catalyst by weighing, and be added to quality
In the ethanol solution that score is 95%, it is stirred at room temperature and is allowed within 30 minutes fully dissolve.Then embodiment 1 is added in the solution to obtain
The carrier S -0 arrived is heated to 80 DEG C after being stored at room temperature 12 hours, react 4 hours, then filter, absolute ethyl alcohol washing, 70 DEG C
24 h are dried in vacuo, obtained modified catalyst supports S-1.
（2）The nickel nitrate of enough NiO will be provided in the final catalyst（Ni(NO3)2·6H2O）With enough three oxygen of offer
Change tungsten WO3Ammonium metatungstate（(NH4)10W12O41·xH2O）It is scattered in deionized water, is used for impregnation steps（1）Obtained modification
Catalyst carrier S-1, then roasted 5 hours under the conditions of drying 10 hours, 520 DEG C under the conditions of 100 DEG C, obtain catalyst C-1.
In terms of parts by weight, NiO in the catalyst:WO3:The ratio of modified support S-1 is 5:20:75.
Embodiment 3
（1）The 2- mercaptoethyltriethoxysilanes of enough modified groups can be provided in the final catalyst by weighing, and be added to quality
In the ethanol solution that score is 95%, it is stirred at room temperature and is allowed within 30 minutes fully dissolve.Then embodiment 1 is added in the solution to obtain
The carrier S -0 arrived is heated to 80 DEG C after being stored at room temperature 12 hours, react 4 hours, then filter, absolute ethyl alcohol washing, 70 DEG C
24 h are dried in vacuo, obtained modified catalyst supports S-2.
（3）The nickel nitrate of enough NiO will be provided in the final catalyst（Ni(NO3)2·6H2O）With enough three oxygen of offer
Change tungsten WO3Ammonium metatungstate（(NH4)10W12O41·xH2O）It is scattered in deionized water, is used for impregnation steps（1）Obtained modification
Catalyst carrier S-2, then roasted 5 hours under the conditions of drying 10 hours, 520 DEG C under the conditions of 100 DEG C, obtain catalyst C-2.
In terms of parts by weight, NiO in the catalyst:WO3:The ratio of modified support S-2 is 5:20:75.
Embodiment 4
（1）The 3- mercaptopropyl trimethoxysilanes of enough modified groups can be provided in the final catalyst by weighing, and be added to quality
In the ethanol solution that score is 95%, it is stirred at room temperature and is allowed within 30 minutes fully dissolve.Then embodiment 1 is added in the solution to obtain
The carrier S -0 arrived is heated to 80 DEG C after being stored at room temperature 12 hours, react 4 hours, then filter, absolute ethyl alcohol washing, 70 DEG C
24 h are dried in vacuo, obtained modified catalyst supports S-3.
（2）The nickel nitrate of enough NiO will be provided in the final catalyst（Ni(NO3)2·6H2O）With enough three oxygen of offer
Change tungsten WO3Ammonium metatungstate（(NH4)10W12O41·xH2O）It is scattered in deionized water, is used for impregnation steps（1）Obtained modification
Catalyst carrier S-3, then drying 10 hours under the conditions of 100 DEG C, roast 5 hours under the conditions of 520 DEG C, obtain catalyst C-
3.In terms of parts by weight, NiO in the catalyst:WO3:The ratio of modified support S-3 is 5:20:75.
Embodiment 5
（1）The methyltriethoxysilane of enough modified groups can be provided in the final catalyst by weighing, and be added to mass fraction
It is allowed within 30 minutes fully dissolve in 95% ethanol solution, to be stirred at room temperature.Then it is added what embodiment 1 obtained in the solution
Carrier S -0 is heated to 80 DEG C after being stored at room temperature 15 hours, react 6 hours, then filter, absolute ethyl alcohol washing, 70 DEG C of vacuum
Dry 24 h, obtained modified catalyst supports S-4.
（2）The nickel nitrate of enough NiO will be provided in the final catalyst（Ni(NO3)2·6H2O）With enough three oxygen of offer
Change tungsten WO3Ammonium metatungstate（(NH4)10W12O41·xH2O）It is scattered in deionized water, is used for impregnation steps（1）Obtained modification
Catalyst carrier S-4, then drying 10 hours under the conditions of 100 DEG C, roast 5 hours under the conditions of 520 DEG C, obtain catalyst C-
4.In terms of parts by weight, NiO in the catalyst:WO3:The ratio of modified support S-4 is 5:20:75.
Embodiment 6
（1）The 3- aminopropyl triethoxysilanes of enough modified groups can be provided in the final catalyst by weighing, and be added to quality
In the ethanol solution that score is 95%, it is stirred at room temperature and is allowed within 30 minutes fully dissolve.Then embodiment 1 is added in the solution to obtain
The carrier S -0 arrived is heated to 80 DEG C after being stored at room temperature 15 hours, react 6 hours, then filter, absolute ethyl alcohol washing, 70 DEG C
24 h are dried in vacuo, obtained modified catalyst supports S-5.
（2）The nickel nitrate of enough NiO will be provided in the final catalyst（Ni(NO3)2·6H2O）With enough three oxygen of offer
Change tungsten WO3Ammonium metatungstate（(NH4)10W12O41·xH2O）It is scattered in deionized water, is used for impregnation steps（1）Obtained modification
Catalyst carrier S-5, then drying 10 hours under the conditions of 100 DEG C, roast 5 hours under the conditions of 520 DEG C, obtain catalyst C-
5.In terms of parts by weight, NiO in the catalyst:WO3:The ratio of modified support S-5 is 5:20:75.
Comparative example 1
The nickel nitrate of enough NiO will be provided in the final catalyst（Ni(NO3)2·6H2O）With the enough tungstic acid WO of offer3
Ammonium metatungstate（(NH4)10W12O41·xH2O）It is scattered in deionized water, the carrier S -0 obtained for impregnating embodiment 1, then
It is 10 hours dry under the conditions of 100 DEG C, it is roasted 5 hours under the conditions of 520 DEG C, obtains catalyst C-0.In terms of parts by weight,
NiO in the catalyst:WO3:The ratio of carrier S -0 is 5:20:75.
Hydrogen evaluating apparatus is added to carry out catalyst performance evaluation using one-pass 100 mL is small-sized.Use is by body before evaluation
The H of fraction 5%2The H of S and 95%2The gaseous mixture of composition carries out presulfurization to catalyst.Evaluate that catalyst performance is raw materials used to be
It is hydrocracked recycle oil, property and reaction process condition are shown in Tables 1 and 2 respectively.Reaction temperature is adjusted on demand to ensure 100
Net conversion ratio is maintained at 80% by percentage to the quality in hour.The calculation formula of net conversion ratio is as follows：
。
1 raw material oil nature of table
2 reaction process condition of table
The reactivity worth comparing result of each catalyst is shown in Table 3.
3 evaluating catalyst result of table
By table 3, the result shows that, compared with catalyst C-0, catalyst C-1, C-2 and the C-3 of the modified group containing-SH reach 80% only
The reaction temperature of conversion ratio is at least 3 DEG C low, the light oil of C5 ~ 175 DEG C selectively raising at least two percentage point in product, and gaseous state
Hydrocarbon-selective reduces at least 2 percentage points, and the liquid product yield of C5 or more is also improved.It proves to pass through organosiloxane pair
Carrier is modified, and can be improved the activity and selectivity of the wax oil hydrogenation cracking light oil of catalyst, be reduced gaseous hydrocarbon
It generates, improves liquid product yield.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of light oil type hydrogen cracking catalyst, it is characterised in that：It is made of following raw material：
（a）The compound of the element containing group VIII metal；
（b）The compound of the metallic element containing group vib；
（c）Boehmite；
（d）Molecular sieve；
（e）Alkyl substituted siloxanes containing modified group；
The group VIII metal element is selected from least one of Co and Ni；
The group vib metallic element is selected from least one of Mo and W；
The structural formula of the alkyl substituted siloxanes containing modified group is：X-R1-Si(OR2)3, wherein R1And R2It is independently selected from
Alkyl, aromatic radical or substituted aromatic base, X are-H ,-F ,-NH2,-SH ,-CHO ,-OH or-C (O) NH2。
2. light oil type hydrogen cracking catalyst according to claim 1, it is characterised in that：Each raw material used is in parts by weight
It is calculated as：0.1 ~ 35 parts of the compound of the element containing group VIII metal, intends thin water at 0.1 ~ 15 parts of the compound of the metallic element containing group vib
1 ~ 95 part of aluminium stone, 1 ~ 80 part of molecular sieve, 0.1 ~ 20 part of the alkyl substituted siloxanes containing modified group.
3. light oil type hydrogen cracking catalyst according to claim 1, it is characterised in that：Each raw material used is in parts by weight
It is calculated as：15 ~ 25 parts of the compound of the element containing group VIII metal, 4 ~ 8 parts of the compound of the metallic element containing group vib, boehmite
20 ~ 60 parts, 10 ~ 40 parts of molecular sieve, 1 ~ 10 part of the alkyl substituted siloxanes containing modified group.
4. according to the light oil type hydrogen cracking catalyst described in any one of claim 1-3, it is characterised in that：The molecule
Sieve be hydrogen type molecular sieve, be specially in USY molecular sieve, Beta molecular sieves, ZSM-5 molecular sieve, SSZ-32 molecular sieves at least
It is a kind of.
5. a kind of preparation method of light oil type hydrogen cracking catalyst as described in any one of claim 1-4, feature
It is：Include the following steps：
（1）Boehmite and molecular sieve are uniformly mixed, acid solution is then added, fully kneaded and formed rear dry, roasting obtains
To catalyst carrier；
（2）By alkyl substituted siloxanes and step containing modified group（1）Obtained catalyst carrier reaction, then crosses diafiltration
It washs, then is dried in vacuo to obtain modified catalyst supports；
（3）The compound of the compound of the metallic element containing group vib and the element containing group VIII metal is scattered in solvent, for soaking
Stain step（2）Obtained modified catalyst supports, then dry, roasting, obtain the light oil type hydrogen cracking catalyst.
6. the preparation method of light oil type hydrogen cracking catalyst according to claim 5, it is characterised in that：Step（1）Middle institute
With a concentration of 0.5wt% ~ 5wt% of acid solution, the acid is inorganic acid or organic acid；
A diameter of 1.5 ~ 3.5 mm of kneaded and formed extrudate, long 3 ~ 12 mm, section are round or cloverleaf pattern；
Dry temperature is 80 ~ 200 DEG C, and the time is 2 ~ 24 h；
The temperature of roasting is 400 ~ 650 DEG C, and the time is 2 ~ 10 h.
7. the preparation method of light oil type hydrogen cracking catalyst according to claim 5, it is characterised in that：Step（2）Vacuum
Dry temperature is 60 ~ 150 DEG C, and the time is 2 ~ 36 h.
8. the preparation method of light oil type hydrogen cracking catalyst according to claim 5, it is characterised in that：Step（3）It is dry
Temperature be 80 ~ 200 DEG C, the time be 2 ~ 24 h.
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| CN110252390A (en) * | 2019-07-08 | 2019-09-20 | 中化泉州石化有限公司 | A kind of hydrocracking catalyst and preparation method thereof producing high-quality tail oil |
| CN111318312A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Hydrogenation modified catalyst carrier, preparation method and application thereof |
| CN111632620A (en) * | 2020-06-16 | 2020-09-08 | 中化泉州石化有限公司 | Medium oil type hydrocracking catalyst |
| CN111889133A (en) * | 2020-08-06 | 2020-11-06 | 中化泉州石化有限公司 | Preparation method of vulcanization type hydrocracking catalyst |
| CN112221535A (en) * | 2020-10-27 | 2021-01-15 | 中化泉州石化有限公司 | Medium oil type hydrocracking catalyst and preparation method thereof |
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