CN104475148B - Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof - Google Patents
Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof Download PDFInfo
- Publication number
- CN104475148B CN104475148B CN201410775438.7A CN201410775438A CN104475148B CN 104475148 B CN104475148 B CN 104475148B CN 201410775438 A CN201410775438 A CN 201410775438A CN 104475148 B CN104475148 B CN 104475148B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- coal
- preparation
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a coal-oil hydrogenation co-processing catalyst as well as a preparation method and an application method thereof. The catalyst consists of a carrier, an active component and an additive, wherein the specific surface area of the carrier is 300 to 600 m＜2＞/g, the pore volume of the carrier is 0.5 to 1.0 cm＜3＞/g, the carrier is one or more of gamma zeolite, beta zeolite, ZSM-5 and KIT-6 powder with the particle size less than 200 micrometers, the active component is iron and nickel, and the additive is one or more of zinc chloride and tin chloride. The preparation method comprises the following steps of preparing the carrier, preparing the active component and preparing the additive. According to the application method of the catalyst, the catalyst and raw material coal powder are mixed and then added into a high pressure reaction kettle together with heavy oil, the addition amount of the catalyst is 0.5 to 5 parts by weight of the total mass of the coal and heavy oil, and the mass ratio of the coal to the oil is 1: 1. The catalyst is large in specific surface area, reasonable in preparation process, little in consumption, high in oil yield after the coal-oil hydrogenation co-processing and safe and convenient to use.
Description
Technical field
The present invention relates to coalification industrial technical field, especially a kind of kerosene hydrogenation refine altogether catalyst and preparation method thereof and
Application process.
Background technology
In recent years, the development with science and technology and economic rapid growth, society is increasing to the dependence of oil product.But
It is that world today's petroleum resources worsening shortages, the heaviness and in poor quality problem of petroleum resources is more and more obvious, and urgent need will be found
The energy and exploitation efficient utilization oil new technology of petroleum replacing.Heavy oil deep process technology not only can be provided with effectively utilizes oil
Source, and the economic benefit of oil-processing enterprises can be improved.China is the country of rich coal oil starvation, how by rich reserves and
Cheap coal resources change into fluid product becomes an important development direction of coal resources clean utilization, this
Under situation, coal liquefaction, kerosene hydrogenation are refined altogether etc., and technology is arisen at the historic moment.
It is process the common hydrocracking under catalyst action of coal and heavy oil that kerosene hydrogenation is refined altogether.Due to coal and heavy oil
Between the interaction of a kind of promotion heavy oil modification and coal liquefaction collaboration is presented, coal-heavy-oil hydrogenation refines altogether more independent than coal or heavy oil
Plus man-hour liquid is received and improved, hydrogen consumption is reduced.Meanwhile, coal also promotes the removing of metallic element in heavy oil, adds content of beary metal height, hardly possible
The heavy oil of work is obtained by.
Catalyst is that kerosene hydrogenation refines altogether one of core technology of process, for reaction severity is reduced, improves reaction effect
Rate, so as to reduce kerosene hydrogenation this is smelt altogether, and improving its economic competitiveness has very important effect.Fe-series catalyst due to
Wide material sources, it is cheap, can single use and do not reclaim, with liquefied residue discharge, additional effect is not constituted to environment,
Become the focus of current research.
Patent publication No. is that CN102311750B is entitled《A kind of oily coal with ferrous acetate as catalyst precursor is refined altogether
Method》Chinese invention patent application disclose a kind of oily coal with ferrous acetate as catalyst precursor altogether smelting method, second
Sour ferrous saturated solution adds coal dust, infiltrated, dry that liquefaction coal sample is obtained after stirring.Coal sample, refining altogether after process
Oil, auxiliary agent be beaten together, then hydrogenation pressurized conditions under reacted, isolated product.The complex catalyst precursor of the invention
Body carrying method is simple, is not required to precipitate, filters and pre-sulfiding step, and catalyst precursor consumption is few, and product oil yield is higher.But
Product oil yield need further raising.Patent publication No. is that CN102309972B is entitled《A kind of oily coal hydrogenation is refined altogether urges
Agent and its common smelting method》Chinese invention patent application disclose a kind of oily coal hydrogenation and refine catalyst and its common smelting method altogether.
The catalyst is made up of major catalyst, secondary catalyst and auxiliary agent.The presoma of major catalyst be water miscible molysite, secondary catalyst
Presoma be water-soluble and/or oil-soluble molybdenum salt, the mol ratio of Fe and Mo is 50: 1-200: 1；Described auxiliary agent is sulphur
Powder or sulfur-containing compound.The catalyst that the invention is provided is using the obtained catalysis of method of pre-dispersed, solidification, decomposition in situ
Agent, with particle size is little, consumption is few, is uniformly dispersed, the advantage that activity is high and product oil yield is high in system.But catalyst
Molybdenum is not easily recycled, and product oil yield need further raising.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of kerosene hydrogenation for above-mentioned state of the art
The altogether catalyst of refining, the catalyst carrier has that specific surface area is big, catalyst activity component is evenly distributed, and consumption is few, catalyst
Auxiliary agent is conducive to coal liquefaction, promotes kerosene hydrogenation to refine altogether.
The technical scheme that first technical problem to be solved by this invention is adopted for：This kerosene hydrogenation refines altogether catalyst,
The formula of the catalyst is made up of carrier, active component and auxiliary agent, it is characterised in that：The specific surface area of the carrier is 300
~600m2/ g, pore volume is 0.5~1.0cm3/ g, the carrier be particle diameter less than 200 microns γ zeolites, β zeolites, ZSM-5,
One or more in KIT-6 powder, the active component is iron and nickel, and the auxiliary agent is the one kind in zinc chloride, stannic chloride
Or it is various, it is above-mentioned for mass parts.
As improvement, 80~95 parts containing catalyst gross mass of the carrier, the active component gross mass containing catalyst
5~15 parts, the auxiliary agent is containing 1~5 part of catalyst gross mass.
Used as improvement, 5~10 parts containing catalyst gross mass of ferro element in the active component, nickel element is total containing catalyst
1~5 part of quality, it is above-mentioned for mass parts.
Second technical problem to be solved by this invention is to provide a kind of rational technology for above-mentioned state of the art,
Catalyst amount is few, and the high kerosene hydrogenation of oil productivity refines altogether the preparation method of catalyst after kerosene hydrogenation is refined altogether.
The technical scheme that second technical problem to be solved by this invention is adopted for：The preparation method of above-mentioned catalyst,
It is characterized in that：By following steps：
First, by the formula of carrier, carrier is added in the weakly acidic solution of the Containing Zinc Chloride of amount of calculation or stannic chloride,
Wash after stirring 1~4 hour in 30~90 DEG C, then by the carrier after washing, drying 1~6 is little in 80~150 DEG C of temperature
When, that is, carrier is obtained；
2nd, by molysite and the formula of nickel salt, molysite and nickel salt are mixedly configured into into the aqueous solution, carrier prepared by step one
Impregnate in the aqueous solution of the molysite that temperature is 30~90 DEG C with nickel salt 1~8 hour, then filter in the carrier after dipping, then
To add weakly alkaline solution in carrier after filtration, stir 1~4 hour, it is then placed in being dried in 80~150 DEG C of temperature 4~
18 hours, that is, make containing active component；
3rd, catalyst obtained in step 2 is carried out into sulfuration 1~4 hour under 100~300 DEG C of vulcanizing agent effects of temperature,
Obtain the finished catalyst with hydrogenation activity.
Used as improvement, the weakly acidic solution of the Containing Zinc Chloride or stannic chloride is preferably containing zinc chloride or stannic chloride
One or more in acetic acid, carbonic acid, hydrosulphuric acid solution, the pH value of the weakly acidic solution is preferably 5~7.
Used as improvement, described molysite may be selected to be in iron chloride, frerrous chloride, ferric sulfate, ferric nitrate, ferrous acetate
One or more, one or more in the nickel salt nickel nitrate, nickel sulfate, nickel acetate.
Used as improvement, the weakly alkaline solution may be selected to be sodium carbonate, sodium acid carbonate, sodium acetate, sodium citrate aqueous solution
In one or more, the pH value of the weakly alkaline solution is 8~10..
Used as improvement, the vulcanizing agent may be selected to be one kind in carbon disulfide, DMDS, dimethyl sulfide or many
Kind.
Improve again, in the step one, it is little that the carrier after washing is dried 1~6 in the baking oven that temperature is 80~150 DEG C
When, in the step 2, the carrier after stirring 1~4 hour is placed in the baking oven that temperature is 80~150 DEG C and is dried 4~18 hours,
Make the catalyst containing active component.
3rd technical problem to be solved by this invention be provide for above-mentioned state of the art it is a kind of it is simple to operate,
Prepare the application process of the catalyst of safety.
The technical scheme that 3rd technical problem to be solved by this invention is adopted for：The application process of above-mentioned catalyst,
It is characterized in that：The catalyst adds autoclave, the feed coal together with heavy oil after being well mixed with raw material coal dust
Powder is one or more in brown coal, jet coal, bottle coal, gas-rich coal, and the heavy oil is reduced crude, decompression residuum, tar drip
One or more in green grass or young crops, the addition of the catalyst is 0.5~5 part of coal and oily gross mass, the quality of the coal and oil
It is above-mentioned for mass parts than for 1: 1.
Compared with prior art, the advantage of catalyst of the present invention is：Carrier selects molecular sieve, and specific surface area is big, acidity
It is moderate, made by catalyst not only there is good hydrogenation cracking activity, and the easily separated recovery of catalyst；Selection of auxiliary chlorination
Zinc or stannic chloride, have using lique faction of coal is promoted, and improve the production rate of coal liquifaction；Active component selects the compound of iron and nickel,
Hydrogenation cracking activity is high, and consumption is few, and there is the catalyst excellent kerosene hydrogenation to refine the performance for generating light oil altogether.The present invention is urged
The preparation method of agent is first auxiliary agent zinc chloride or stannic chloride to be immersed on molecular sieve carrier under mildly acidic conditions, scrubbed
The presoma of active component iron and nickel is impregnated after drying, and iron and nickel are fixed on carrier with weakly alkaline solution, after drying
Obtain the catalyst containing active component, most after the finished catalyst with hydrogenation cracking activity is obtained Jing after vulcanizing treatment.Should
Method not only rational technology, and obtained catalyst activity is high, and consumption is few, and product oil yield is high after kerosene hydrogenation is refined altogether.This
Invention also provides a kind of application process simple to operate, catalyst that is preparing safety.
Specific embodiment
The present invention is described in further detail below；
The kerosene hydrogenation of the present embodiment refines altogether catalyst, and the formula of the catalyst is by carrier, active component and auxiliary agent group
Into the specific surface area of the carrier is 300~600m2/ g, pore volume is 0.5~1.0cm3/ g, the carrier is that particle diameter is less than 200
One or more in γ zeolites, β zeolites, ZSM-5, KIT-6 powder of micron, the active component is iron and nickel, described to help
Agent is one or more in zinc chloride, stannic chloride, and the carrier contains 80~95 parts of catalyst gross mass, the active component
Containing catalyst gross mass 5~15 parts, 1~5 part containing catalyst gross mass of the auxiliary agent, ferro element contains in the active component
5~10 parts of catalyst gross mass, 1~5 part containing catalyst gross mass of nickel element is above-mentioned for mass parts.The ratio of the carrier
Surface area refers to the surface area that unit mass carrier has, and the pore volume refers to that the pore that unit mass carrier has always holds
Product, the Y zeolites refer to a kind of Si-Al zeolite with three-dimensional supercage structure, cubic system, and the β zeolites refer to that one kind has
The silica-rich zeolite of three-dimensional twelve-ring pore structure, it is structurally characterized in that two four-membered rings and four pentacyclic pair of hexatomic ring units
Bug hole structure, the ZSM-5 powder refers to that a kind of composition is complicated and has the shape-selective zeolite molecular sieve of special crystalline form, is this technology
The known technology in field, it is industrial to be just this name.KIT-6 powder refers to a kind of porous silica material with nanostructured,
Also it is the known technology of the art, it is industrial to be just this name.
The preparation method of above-mentioned catalyst, by following steps：
First, by the formula of carrier, carrier is added in the weakly acidic solution of the Containing Zinc Chloride of amount of calculation or stannic chloride,
Wash after stirring 1~4 hour in 30~90 DEG C, then by the carrier after washing, drying 1~6 is little in 80~150 DEG C of temperature
When, that is, carrier is obtained；
2nd, by molysite and the formula of nickel salt, molysite and nickel salt are mixedly configured into into the aqueous solution, carrier prepared by step one
Impregnate in the aqueous solution of the molysite that temperature is 30~90 DEG C with nickel salt 1~8 hour, then filter in the carrier after dipping, then
To add weakly alkaline solution in carrier after filtration, stir 1~4 hour, it is then placed in being dried in 80~150 DEG C of temperature 4~
18 hours, that is, make the catalyst containing active component；
3rd, catalyst obtained in step 2 is carried out into sulfuration 1~4 hour under 100~300 DEG C of vulcanizing agent effects of temperature,
Obtain the finished catalyst with hydrogenation activity.The weakly acidic solution of the Containing Zinc Chloride or stannic chloride be containing zinc chloride or
One or more in acetic acid, carbonic acid, the hydrosulphuric acid solution of stannic chloride, the pH value of the weakly acidic solution is 5~7.Described
Molysite is one or more in iron chloride, frerrous chloride, ferric sulfate, ferric nitrate, ferrous acetate, the nickel salt nickel nitrate, sulphur
One or more in sour nickel, nickel acetate.The weakly alkaline solution is that sodium carbonate, sodium acid carbonate, sodium acetate, sodium citrate are water-soluble
One or more in liquid, the pH value of the weakly alkaline solution is 8~10.The vulcanizing agent be carbon disulfide, DMDS,
One or more in dimethyl sulfide, in the step one, the carrier after washing is done in the baking oven that temperature is 80~150 DEG C
Dry 1~6 hour, in the step 2, the carrier after stirring 1~4 hour was placed in the baking oven that temperature is 80~150 DEG C and is dried 4
~18 hours, that is, make the catalyst containing active component.
The application process of above-mentioned catalyst, the catalyst adds high pressure after being well mixed with raw material coal dust together with heavy oil
Reactor, the raw material coal dust is one or more in brown coal, jet coal, bottle coal, gas-rich coal, and the heavy oil is normal pressure slag
One or more in oil, decompression residuum, tar asphalt, the addition of the catalyst is the 0.5~5 of coal and oily gross mass
Part, the mass ratio of the coal and heavy oil is 1: 1, above-mentioned for mass parts.
The present invention is described in further detail with reference to embodiments.
Below in an example, catalyst C1~C4 is to refine catalyst altogether using the kerosene hydrogenation obtained by the present invention.
Embodiment 1~4 is the preparation of hydrocracking catalyst of the present invention, and embodiment 5 refines altogether performance evaluation for the kerosene hydrogenation of catalyst.
Embodiment 1
Amount of calculation γ zeolite is taken, (pH is 6.0) is added in the acetum of the Containing Zinc Chloride of amount of calculation, is stirred in 60 DEG C
Wash after mixing 2 hours, be put in 120 DEG C of baking ovens and be dried 2 hours, obtain the carrier containing auxiliary agent.
The iron chloride and nickel sulfate of amount of calculation are taken, the aqueous solution is mixedly configured into, by the carrier containing auxiliary agent of above-mentioned preparation,
Temperature is to impregnate 4 hours in 80 DEG C of iron chloride and the aqueous solution of nickel sulfate, adds a small amount of sodium carbonate liquor after filtration in carrier
(pH is 10.0), stirs 2 hours, is then placed in being dried 8 hours in 150 DEG C of baking ovens, that is, make the catalyst containing active component.
Catalyst obtained above is vulcanized under 200 DEG C of carbon disulfide effects of temperature, is finally given with hydrogenation
The finished catalyst C1 of activity.
Embodiment 2
Amount of calculation β zeolite is taken, (pH is 6.0) is added in the acetum of the Containing Zinc Chloride of amount of calculation, is stirred in 60 DEG C
Wash after mixing 3 hours, be put in 120 DEG C of baking ovens and be dried 3 hours, obtain the carrier containing auxiliary agent.
The frerrous chloride and nickel nitrate of amount of calculation are taken, the aqueous solution is mixedly configured into, by the carrier containing auxiliary agent of above-mentioned preparation,
Impregnate 4 hours in the aqueous solution of the frerrous chloride that temperature is 70 DEG C with nickel nitrate, add a small amount of sodium carbonate after filtration in carrier
Solution (pH is 10.0), stirs 3 hours, is then placed in being dried 12 hours in 150 DEG C of baking ovens, that is, make the catalysis containing active component
Agent.
Catalyst obtained above is vulcanized under the effect of 250 DEG C of DMDSs of temperature, finally give with plus
The finished catalyst C2 of hydrogen activity.
Embodiment 3
Amount of calculation KIT-6 powder is taken, is added to (pH is 5.0) in the acetum of the chloride containing tin of amount of calculation, at 60 DEG C
Middle stirring is washed after 2 hours, is put in 130 DEG C of baking ovens and is dried 3 hours, obtains the carrier containing auxiliary agent.
The ferric nitrate and nickel nitrate of amount of calculation are taken, the aqueous solution is mixedly configured into, by the carrier containing auxiliary agent of above-mentioned preparation,
Temperature is to impregnate 6 hours in 80 DEG C of ferric nitrate and the aqueous solution of nickel nitrate, adds a small amount of SAS after filtration in carrier
(pH is 10.0), stirs 4 hours, is then placed in being dried 12 hours in 150 DEG C of baking ovens, that is, make the catalyst containing active component.
Catalyst obtained above is vulcanized under 200 DEG C of carbon disulfide effects of temperature, is finally given with hydrogenation
The finished catalyst C3 of activity.
Embodiment 4
Amount of calculation γ zeolite and ZSM-5 are taken, (pH in the hydrosulphuric acid solution of the Containing Zinc Chloride of amount of calculation and stannic chloride is added to
5.0), to wash after stirring 2 hours in 80 DEG C, it is put in 120 DEG C of baking ovens and is dried 4 hours, obtains the carrier containing auxiliary agent.
The ferric sulfate and nickel sulfate of amount of calculation are taken, the aqueous solution is mixedly configured into, by the carrier containing auxiliary agent of above-mentioned preparation,
Temperature is to impregnate 4 hours in 80 DEG C of ferric sulfate and the aqueous solution of nickel sulfate, adds a small amount of SAS after filtration in carrier
(pH is 9.5), stirs 3 hours, is then placed in being dried 12 hours in 150 DEG C of baking ovens, that is, make the catalyst containing active component.
Catalyst obtained above is vulcanized under 250 DEG C of carbon disulfide effects of temperature, is finally given with hydrogenation
The finished catalyst C4 of activity.
The main physical and chemical of catalyst C1, C2, C3, C4 is shown in such as table 1 below in aforementioned four embodiment.
Kerosene hydrogenation refines altogether the main physical and chemical of catalyst in the embodiment of table 1
Embodiment 5
Kerosene hydrogenation of the present invention refines altogether the performance evaluation of catalyst, with autoclave as evaluating apparatus.Brown coal and to subtract
Pressure residual oil is raw material, and feedstock property is shown in Table 2, and coal and oily mass ratio are 1: 1, and catalyst charge is coal and oily gross mass
1%.The evaluation method that kerosene hydrogenation is refined altogether is：High pressure is imported together with decompression residuum after catalyst is well mixed with coal dust anti-
Kettle is answered, after displacement gas reactor, gas is flushed with hydrogen and is closed to 10.0MPa.Be warmed up to 450 DEG C reaction 2 hours after lower the temperature, collect kettle in gas
Body and liquid are simultaneously analyzed, and catalyst centrifuge washing is reclaimed in kettle, and using said method catalyst C1, C2, C3, C4 are evaluated respectively,
Evaluation result is shown in Table 3.Conversion ratio and oily yield data in table is to refine oil sum with coal and altogether as calculating benchmark.
Conversion ratio=(tetrahydrofuran insoluble SOLID ORGANIC matter/(coal+oil refining altogether) in 1- products) × 100%
N-hexane organic matter/(coal+oil refining altogether) × 100% is dissolved in oil yield=product
The feed coal of table 2 and property is refined oil altogether
| Analysis project | Brown coal | Decompression residuum |
| C, wt% | 71.3 | 81.5 |
| H, wt% | 6.8 | 11.8 |
| O, wt% | 18.5 | 3.2 |
| N, wt% | 2.4 | 1.3 |
| S, wt% | 1.0 | 2.1 |
| Density (20 DEG C), g/cm3 | 1.31 | 0.998 |
The kerosene hydrogenation of table 3 refines altogether evaluation result
| Catalyst | Conversion ratio, wt% | Oil yield, wt% |
| C1 | 95.6 | 75.4 |
| C2 | 94.5 | 72.3 |
| C3 | 98.7 | 79.6 |
| C4 | 97.2 | 77.5 |
From table 3 it can be seen that there is the catalyst of the present invention good kerosene hydrogenation to refine catalytic cracking activity altogether, product turns
Rate and oil yield are high.
Claims (8)
1. a kind of kerosene hydrogenation refines altogether catalyst, and the formula of the catalyst is made up of carrier, active component and auxiliary agent, its feature
It is：The specific surface area of the carrier is 300~600m2/ g, pore volume is 0.5~1.0cm3/ g, the carrier is less than for particle diameter
One or more in 200 microns of γ zeolites, β zeolites, ZSM-5, KIT-6 powder, the active component is iron and nickel, described
Auxiliary agent is one or more in zinc chloride, stannic chloride；80~95 parts containing catalyst gross mass of the carrier, the activearm
Divide 5~15 parts containing catalyst gross mass, 1~5 part containing catalyst gross mass of the auxiliary agent；Ferro element in the active component
Containing catalyst gross mass 5~10 parts, 1~5 part containing catalyst gross mass of nickel element is above-mentioned for mass parts.
2. the preparation method of catalyst described in a kind of claim 1, it is characterised in that：By following steps：
First, by the formula of catalyst, carrier is added in the weakly acidic solution of the Containing Zinc Chloride of amount of calculation or stannic chloride, 30
Wash after stirring 1~4 hour in~90 DEG C, be then dried the carrier after washing 1~6 hour in 80~150 DEG C of temperature,
Carrier is obtained；
2nd, by molysite and the formula of nickel salt, molysite and nickel salt are mixedly configured into into the aqueous solution, carrier prepared by step one is in temperature
Spend to impregnate in 30~90 DEG C of molysite and the aqueous solution of nickel salt 1~8 hour, then filter in the carrier after dipping, then incited somebody to action
Weakly alkaline solution is added in carrier after filter, is stirred 1~4 hour, be then placed in 80~150 DEG C of temperature dry 4~18 little
When, that is, make the catalyst containing active component；
3rd, catalyst obtained in step 2 is carried out into sulfuration 1~4 hour under 100~300 DEG C of vulcanizing agent effects of temperature, is obtained final product
To the finished catalyst with hydrogenation activity.
3. preparation method according to claim 2, it is characterised in that：The weakly acidic solution of the Containing Zinc Chloride or stannic chloride
It is one or more in the acetic acid containing zinc chloride or stannic chloride, carbonic acid, hydrosulphuric acid solution, the pH value of the weakly acidic solution
For 5~7.
4. preparation method according to claim 2, it is characterised in that：Described molysite is iron chloride, frerrous chloride, sulfuric acid
One or more in iron, ferric nitrate, ferrous acetate, the nickel salt is the one kind or many in nickel nitrate, nickel sulfate, nickel acetate
Kind.
5. preparation method according to claim 2, it is characterised in that：The weakly alkaline solution be sodium carbonate, sodium acid carbonate,
One or more in sodium acetate, sodium citrate aqueous solution, the pH value of the weakly alkaline solution is 8~10.
6. preparation method according to claim 2, it is characterised in that：The vulcanizing agent be carbon disulfide, DMDS,
One or more in dimethyl sulfide.
7. preparation method according to claim 2, it is characterised in that：In the step one, the carrier after washing is in temperature
To be dried 1~6 hour in 80~150 DEG C of baking ovens, in the step 2, the carrier after stirring 1~4 hour is placed on temperature for 80
It is dried 4~18 hours in~150 DEG C of baking oven, that is, makes the catalyst containing active component.
8. a kind of application process of catalyst according to claim 1, it is characterised in that：The catalyst is mixed with raw material coal dust
Autoclave is added after closing uniformly together with heavy oil, the raw material coal dust is in brown coal, jet coal, bottle coal, gas-rich coal
Plant or various, the heavy oil is one or more in reduced crude, decompression residuum, tar asphalt, the addition of the catalyst
The mass ratio for measuring 0.5~5 part for coal and oily gross mass, the coal and heavy oil is 1: 1, above-mentioned for mass parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410775438.7A CN104475148B (en) | 2014-12-12 | 2014-12-12 | Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410775438.7A CN104475148B (en) | 2014-12-12 | 2014-12-12 | Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104475148A CN104475148A (en) | 2015-04-01 |
| CN104475148B true CN104475148B (en) | 2017-05-17 |
Family
ID=52749829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410775438.7A Active CN104475148B (en) | 2014-12-12 | 2014-12-12 | Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104475148B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693975B (en) * | 2016-11-24 | 2020-03-27 | 中国石油大学(华东) | Oil-soluble Fe-Ni bimetallic catalyst and preparation method and application thereof |
| CN109294612A (en) * | 2018-10-12 | 2019-02-01 | 煤炭科学技术研究院有限公司 | A method of add hydrogen to prepare fuel oil altogether using sawdust and mink cell focus |
| CN112973718B (en) * | 2021-02-22 | 2022-10-25 | 安徽工业大学 | Kerosene co-hydrogenation catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03237193A (en) * | 1990-02-13 | 1991-10-23 | Osaka Gas Co Ltd | Catalytic hydrocracking of heavy oil |
| CN101607208A (en) * | 2008-06-18 | 2009-12-23 | 汉能科技有限公司 | A kind of catalyst, its preparation method and application thereof that is used for coal liquefaction |
| CN101649220A (en) * | 2009-09-15 | 2010-02-17 | 中国科学院山西煤炭化学研究所 | Method for simultaneously producing liquid fuel and asphalt paving materials by coprocessing coal and heavy oil |
| CN102029157A (en) * | 2010-11-25 | 2011-04-27 | 同济大学 | Catalyst used for coal tar pitch hydrocracking lightening reaction |
| CN103074097A (en) * | 2013-01-31 | 2013-05-01 | 煤炭科学研究总院 | Method and system for direct coal liquefaction |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CO5980161A1 (en) * | 2008-09-02 | 2008-11-28 | Univ Nac De Colombia | PREPARATION PROCESS OF USEFUL CATALYSTS IN DIRECT CARBON LICUEFACTION AND THE CATALYST SO OBTAINED |
-
2014
- 2014-12-12 CN CN201410775438.7A patent/CN104475148B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03237193A (en) * | 1990-02-13 | 1991-10-23 | Osaka Gas Co Ltd | Catalytic hydrocracking of heavy oil |
| CN101607208A (en) * | 2008-06-18 | 2009-12-23 | 汉能科技有限公司 | A kind of catalyst, its preparation method and application thereof that is used for coal liquefaction |
| CN101649220A (en) * | 2009-09-15 | 2010-02-17 | 中国科学院山西煤炭化学研究所 | Method for simultaneously producing liquid fuel and asphalt paving materials by coprocessing coal and heavy oil |
| CN102029157A (en) * | 2010-11-25 | 2011-04-27 | 同济大学 | Catalyst used for coal tar pitch hydrocracking lightening reaction |
| CN103074097A (en) * | 2013-01-31 | 2013-05-01 | 煤炭科学研究总院 | Method and system for direct coal liquefaction |
Non-Patent Citations (2)
| Title |
|---|
| Optimization of Two-Stage Liquefaction of Tanito Harum Coal with FeNi Catalyst Supported on Carbon Black;Unggul Priyanto等;《Energy & Fuels》;20010620;第15卷;摘要，第856页左栏第1行-第859页右栏倒数第10行，第861-862页"Discussion" * |
| 分散型镍、铁催化剂用于重油-煤的加氢共炼研究;戈军等;《中国石油大学学报(自然科学版)》;20110831;第35卷(第4期);第157页左栏第1行-第158页左栏第20行，第158页"1. 5 渣油、煤-油加氢共处理及其产物的分离分析"，第163页"3结论" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104475148A (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105778987B (en) | A kind of production method of biodiesel and bunker fuel oil | |
| CN103055933B (en) | A kind of hydrocracking catalyst and its preparation method and application | |
| CN101219396B (en) | Method for reliving FCC dead catalyst | |
| CN102309972B (en) | Oil coal hydrogenation mixing catalyst and mixing method thereof | |
| CN105289706B (en) | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN104907078B (en) | A kind of hydrogenation catalyst and its preparation method and application | |
| CN102463131B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN104475148B (en) | Coal-oil hydrogenation co-processing catalyst as well as preparation method and application method thereof | |
| CN103421594A (en) | Waste lubricating oil regeneration technology and preparation method for hydrogenation catalyst | |
| CN105733646B (en) | A kind of method of high-grade aliphatic ester Hydrogenation hydrocarbon | |
| CN102500403A (en) | Liquefied gas hydrogenating, olefin content decreasing and desulfurizing catalyst and preparation method thereof | |
| CN107867993A (en) | A kind of organic-molybdenum salt composite and preparation method thereof | |
| CN102784653B (en) | Catalyst for producing clean fuel oil by using coal tar and preparation method of catalyst | |
| CN104673382A (en) | Hydrogenation method for producing high-aromatic latent naphtha employing bad aromatics-rich fraction oil | |
| CN114574234A (en) | Production process of second-generation biodiesel | |
| CN105126899B (en) | A kind of inferior heavy oil suspension bed hydrogenation catalyst for being carried on molecular sieve and its preparation and application | |
| CN105289632B (en) | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil | |
| CN101905163A (en) | Coal tar hydrorefining catalyst and preparation method thereof | |
| CN109092315A (en) | A kind of catalyst and preparation method and application preparing naphthane for naphthalene selective catalytic hydrogenation | |
| CN104593063B (en) | A kind of middle coalite tar produces the method for rubber filling oil base oil | |
| Trisunaryanti et al. | Preparation of Mo-impregnated mordenite catalysts for the conversion of refined kernel palm oil into bioavtur | |
| CN102626635B (en) | Coal tar denitrification catalyst and its preparation method and use | |
| CN108219840A (en) | A kind of method converted heavy oils into using suspension bed hydrogenation process as light oil | |
| CN104987882A (en) | Method for preparing diesel through coal tar | |
| CN104593067A (en) | Method for producing white rubber filling oil base oil from catalytic slurry oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 8 / F, building e, Hefeng creative Plaza, 435 Jiangdong North Road, Yinzhou District, Ningbo City, Zhejiang Province Patentee after: Ningbo Antai Environmental Chemical Engineering Design Co.,Ltd. Address before: 315040 8/F, Building E, Hefeng Creative Plaza, 435 Jiangbei Road, Ningbo City, Zhejiang Province Patentee before: NINGBO RESEARCH & DESIGN INSTITUTE OF CHEMICAL INDUSTRY CO.,LTD. |