CN102732295A - Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method - Google Patents
Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method Download PDFInfo
- Publication number
- CN102732295A CN102732295A CN201110093245XA CN201110093245A CN102732295A CN 102732295 A CN102732295 A CN 102732295A CN 201110093245X A CN201110093245X A CN 201110093245XA CN 201110093245 A CN201110093245 A CN 201110093245A CN 102732295 A CN102732295 A CN 102732295A
- Authority
- CN
- China
- Prior art keywords
- coal
- oil
- coal dust
- described preparation
- altogether
- 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.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a preparation method of a coal-oil slurry coprocessed by coal-oil hydrogenation, the coal-oil slurry and its coprocessing method. The preparation method of the coal-oil slurry comprises the following steps of: predispersing FeOOH in a nanometer dimension onto coprocessed coal dust in the presence of an iron-containing main catalyst precursor under the action of a dispersing aid, and mixing the coprocessed coal dust, a sulfur containing auxiliary agent and coprocessed oil to prepare the coal-oil slurry. During the coal-oil coprocessing process, FeOOH undergoes in-situ decomposition and sulfuration to generate a nascent active component. The coal-oil slurry and the coprocessing method have advantages of high conversion rate, high oil yield, small catalyst amount and the like.
Description
Technical field
The present invention relates to a kind of oily coal hydrogenation and refine oil the preparation method of coal slurry altogether, the application method that the coal oil mixture that obtains with this preparation method and this coal oil mixture thereof refine at oily coal hydrogenation altogether.
Background technology
In recent years, the world petroleum resource worsening shortages, and also the heaviness of petroleum resources and inferiorization problem are more and more obvious, but along with rapid growth of economy, society grows with each passing day to the demand of petroleum products.The heavy oil deep process technology not only can effectively be utilized petroleum resources, and can improve the refining of petroleum economic benefit of enterprises.Simultaneously, China is the country of a rich coal resources, and how abundant and cheap coal resources change into the important development direction that liquid product becomes the coal resources clean utilization with reserves.
It is the process coal and the common hydrocracking of heavy oil that the oil coal hydrogenation refines altogether.Owing to present the synergy that promotes heavy oil modification and gelatin liquefaction between coal and the heavy oil, heavy oil～coal hydrogenation refines than coal or oil processing separately altogether, and liquid yield improves, and the hydrogen consumption reduces.Simultaneously coal also promotes removing of metallic element in the heavy oil, makes that heavy metal content is high, unmanageable heavy oil obtains utilizing.
Catalyzer is one of oily coal core technology of refining process altogether, for reducing the reaction severity, improves reaction efficiency, is smelt this altogether thereby reduce oily coal, and improving its economic competitiveness has important effect.The employed catalyzer of present known gelatin liquefaction process can be divided three classes, and the first kind is a metal catalyst, like cobalt, molybdenum, nickel, tungsten catalyst.Second type is metal halide catalyst, like zinc chloride and tin chloride etc.; Metal halide catalyst is a strongly acidic catalyst, and scission reaction is had stronger katalysis, but to the liquefaction device seriously corroded, is difficult to industriallization.The 3rd type for iron system abandoning property catalyzer, like ferruginous natural mineral, industrial residue and synthetic iron containing compounds etc.
Fe-series catalyst is because wide material sources, and is cheap, can disposable use and do not reclaim; Discharge with liquefied residue, environment is not constituted additional effect, become the focus of present research; But still there are active and the not high problem of oily productive rate; Reducing size of catalyst is one of active important means that improves Fe-series catalyst, discloses a kind of high-dispersion iron catalyst of coal Direct Hydrogenation liquefaction like CN1778871A, and the preparation method adopts FeSO
4Solution joins in the carrier coal, and the back that stirs adds the basic soln of hydroxyl-containing ion, makes it to generate Fe (OH)
2Be deposited on the coal dust, be oxidized to active ingredient γ-FeOOH with air or oxygen at 20～50 ℃ then, process the catalyzer finished product through filtration, drying again; Active ingredient γ-FeOOH is strip; Long 60-200nm, wide 20-100nm, addition suitable when being used for DCL/Direct coal liquefaction is 0.5～1.0 weight % of butt coal; Weak point is that the active ingredient size is big, and product oil yield is low.
Summary of the invention
The objective of the invention is on the prior art basis, to provide a kind of oily coal hydrogenation to refine oil the preparation method of coal slurry altogether, the coal oil mixture that obtains with this preparation method, and the application method that refines altogether at oily coal hydrogenation of this coal oil mixture.
The oily coal hydrogenation that is provided is refined oil the preparation method of coal slurry altogether, comprising:
The Primary Catalysts presoma that (1) will contain ferro element is processed the aqueous solution, adds dispersion aids, stirs;
(2) coal dust joins in the mixing solutions that step (1) obtains, and after being uniformly dispersed, adds basic cpd;
(3) in step (2) gained mixture, feed oxygen-containing gas, hydrous iron oxide is solidificated in the coal dust surface;
(4) step (3) gained mixture obtains being loaded with the coal dust of hydrous iron oxide, then 90～120 ℃ of dryings after filtering, washing;
(5) the dry coal dust of step (4) gained, sulfur-bearing auxiliary agent are refined oil together and are mixed and made into coal oil mixture.
The said Primary Catalysts presoma that contains ferro element is selected from one or more in ferric sulfate, ferrous sulfate, Iron diacetate, iron nitrate, the iron protochloride.
Said dispersion aids is selected from one or more in quadrol, L-glutamic acid, YD 30 (EDTA), tartrate, Secondary ammonium phosphate, the Hydrocerol A; The mol ratio of dispersion aids add-on and Fe is 1: 500～1: 100.Preferably, said dispersion aids is selected from YD 30 (EDTA) and/or Secondary ammonium phosphate; The mol ratio of dispersion aids add-on and Fe is 1: 300～1: 100.
The add-on of Primary Catalysts presoma is by wherein Fe; 0.2 weight %～5.0 weight % for coal dust (butt); Be preferably the 0.5 weight %～3.0 weight % of coal dust (butt); Described auxiliary agent is SULPHUR POWDER or sulfocompound, is preferably SULPHUR POWDER, and described sulfocompound is to be selected from a kind of in sodium sulphite, hydrogen sulfide, dithiocarbonic anhydride, dimethyl thioether, DMDS or the normal-butyl mercaptan.Promoter addition, the molar ratio that makes S/Fe is 1～4, the molar ratio that preferably makes S/Fe is 1.5～2.5.
In the said coal oil mixture of step (5), can also add secondary catalyst precursor, said secondary catalyst precursor is selected from one or more in oil-soluble molybdenum carbonyl, molybdenum naphthenate, the isocaprylic acid molybdenum, and the mol ratio of Mo and Fe is 1: 50～1: 200.At this moment, promoter addition, the molar ratio that makes S/ (Fe+Mo) is 1.5～2.5.Described auxiliary agent is SULPHUR POWDER or sulfocompound.
Described basic cpd is selected from one or more in ammoniacal liquor, ammonia, sodium hydroxide solution, the sodium carbonate solution, and the mol ratio of basic cpd and Fe is 1.8～2.5.
Said oxygen-containing gas is the gas of air or oxygen level 20%～100%, and the oxygen-containing gas feeding time is 5～60 minutes.
The temperature of said step (1)～(3) is 15～40 ℃.
Said coal dust is selected from one or more in brown coal, sub-bituminous coal, the bituminous coal, and coal powder size is less than 150 microns.Helping coal, to refine oil dispersing and mixing together even, and fully liquefaction improves the liquiefied product yield.
The described dry coal dust of step (5) comprises the coal dust and the coal dust of load hydrous iron oxide not of the load hydrous iron oxide of step (4) gained, is benchmark with dry coal dust, and by weight, the coal dust proportion of load hydrous iron oxide is 20%～100%.Not the coal dust of load hydrous iron oxide from the pulverized coal preparation process partly or entirely less than 150 microns part, preferably less than 100 microns part.When calculating the catalyst precursor add-on, be with all altogether coal dusts of refining be that benchmark calculates.
Said altogether oil refining is selected from one or more heavy hydrocarbons that natural heavy crude, oil-refining chemical process, oily coal refining process altogether obtain; Described natural heavy crude is one or more in viscous crude, special viscous crude and the ultra viscous crude; The heavy hydrocarbon that obtains in the described oil-refining chemical process is one or more in long residuum, vacuum residuum, heavy catalytic cycle oil, catalytically cracked oil, aromatic hydrocarbons extract oil, visbreaker tar, coking heavy oil and the oil fuel, and the heavy hydrocarbon that obtains in the described oily coal refining process altogether is a heavy oil.
The weight ratio that said dry coal dust is refined oil together is 20: 80～60: 40.
More than one state the coal oil mixture of any one method gained.
On the surface of the said coal dust that is loaded with hydrous iron oxide, said hydrous iron oxide is bar-shaped, diameter 10～30nm, long 50～150nm.Said hydrous iron oxide is meant one or more of alpha-feooh, β-FeOOH, γ-FeOOH.The present invention is solidified in the coal dust surface process at the Primary Catalysts presoma and is introduced dispersion aids, can promote the dispersion of Primary Catalysts presoma on the coal dust surface, suppresses the Primary Catalysts grain growth, makes Primary Catalysts be the state of nano level high dispersing on the coal dust surface.
A kind of oily coal hydrogenation is smelting method altogether; Coal oil mixture with above-mentioned any one method gained reacts in the presence of hydrogen; Said coal oil mixture hydrogenation refines reaction altogether and is divided into two stages; Fs is catalyzer decomposition, the vulcanization reaction stage of (comprising Primary Catalysts and secondary catalyzer), and catalyzer is through decomposition in situ, generate the active ingredient of metallic sulfide with auxiliary agent sulfuration.Fs reaction conditions: 300～410 ℃ of temperature, pressure 8～20MPa, 10～60 minutes reaction times; 10～30 minutes preferred reaction time.Subordinate phase is the hydrocracking step of reaction that oily coal refines altogether, its reaction conditions: 380～470 ℃ of temperature, pressure 8～22MPa, 30～120 minutes reaction times; 420～460 ℃ of preferred temperature, pressure 12～20MPa, 30～90 minutes reaction times.
High dispersing is on the coal dust surface in advance under the effect of dispersion aids for Primary Catalysts presoma of the present invention, and the hydrous iron oxide of formation is nano level on coal dust, can stablize preservation in the coal surface functional group and the effect of oil refining altogether, and the preparation method is simple relatively.Said hydrous iron oxide decomposition in situ, sulfuration in oily coal refining process altogether generate the active ingredient of nascent state, and coal oil mixture of the present invention has the high and oily yield height of transformation efficiency, the advantage that catalyst levels is few with smelting method altogether.
Embodiment
Below in conjunction with embodiment the present invention is further described, but does not therefore make the present invention receive any restriction.
With a kind of brown coal and a kind of sub-bituminous coal pulverize separately,, get granularity and make an experiment less than 150 microns coal dust through screening.M in the table 1
AdBe water cut, A
dBe ash content, V
DafIt is volatile matter.Ad representes air dried basis; D representes dry base; Daf representes dry ash-free basis.The analytical results of two kinds of coal dusts is as shown in table 1.
Refining oil altogether among the embodiment is a kind of viscous crude and a kind of catalytically cracked oil, and two kinds of character of refining oil altogether are as shown in table 2.
Embodiment 1
The coal dust that present embodiment adopts is brown coal, and the common oil refining of employing is viscous crude.The Primary Catalysts presoma is water miscible ferrous sulfate, and the add-on of Primary Catalysts presoma by Fe wherein, is 0.5 weight % of coal dust (butt); Auxiliary agent is a SULPHUR POWDER, and the molar ratio of S/Fe is 2; Dispersion aids is EDTA, and the mol ratio of EDTA/Fe is 1: 200.
The oil coal hydrogenation is refined oil preparing method's the concrete steps of coal slurry altogether and is: at room temperature, 5.0g iron vitriol and 0.026gEDTA are dissolved in the 100g water 200g brown coal powder (butt); Stir, ferrous sulfate impregnated on the coal dust, process coal slurry; Other gets 4.2g ammoniacal liquor and is added dropwise to above-mentioned coal slurry, and bubbling air also continues to stir 20min, carries out suction filtration then; Obtain filter cake in 105 ℃ of dryings 2 hours, make the supporting agent coal sample.Be mixed and made into coal oil mixture to supporting agent coal sample, adding 1.15g SULPHUR POWDER and 300g heavy oil.
The oily coal hydrogenation that uses above-mentioned coal oil mixture altogether smelting method is: coal oil mixture is imported the 2L autoclave, behind the displacement gas reactor, fill hydrogen and seal to 9.5MPa.Rise to 400 ℃, stop 15min, lower the temperature after rising to 450 ℃ of reaction 60min again, collect gas reactor and analyze, product adopts the extractive method stage treatment of Suo Shi in the still.
The gained result sees table 3; Transformation efficiency in the table and oily productive rate data all are that to refine oil sum together with daf base coal serve as to calculate benchmark; Transformation efficiency=(tetrahydrofuran insoluble SOLID ORGANIC matter in the 1-product/(daf base coal and common oil refining)) * 100%, oily yield are to be dissolved in normal hexane in the product partly to account for daf base coal and the percentage ratio of refining oil altogether.
Comparative Examples 1
Comparative Examples 1 and embodiment 1 be different be in, do not add dispersion aids.
Do not add described any dispersion aids in preparation coal oil mixture process and the oily coal refining process altogether, other conditions are all identical with embodiment 1.The gained result sees table 3.
Embodiment 2
According to preparing coal oil mixture with embodiment 1 identical method and carry out oily coal hydrogenation and refine reaction altogether, different is EDTA dispersion aids addition is 1: 100 in the mol ratio of EDTA/Fe, and other conditions are constant.The gained result sees table 3.
Embodiment 3
According to preparing coal oil mixture with embodiment 1 essentially identical method and carrying out oily coal hydrogenation and refine reaction altogether, different is that dispersion aids is a L-glutamic acid, and consumption is 1: 400 in the mol ratio of L-glutamic acid/Fe, logical purity oxygen, and other conditions are constant.The gained result sees table 3.
Embodiment 4
According to preparing coal oil mixture with embodiment 1 essentially identical method and carrying out oily coal hydrogenation and refine reaction altogether, different is that dispersion aids is a tartrate, and consumption is 1: 300 in the mol ratio of tartrate/Fe,, other conditions are constant.The gained result sees table 3.
Embodiment 5
According to preparing coal oil mixture with embodiment 1 identical method and carrying out oily coal hydrogenation and refine reaction altogether, different is that coal dust adopts bituminous coal, and dispersion aids is a Secondary ammonium phosphate, and consumption is 1: 200 in the mol ratio of Secondary ammonium phosphate/Fe, and other conditions are constant.The gained result sees table 3.
Embodiment 6
The coal dust that present embodiment adopts is a bituminous coal, and the common oil refining of employing is catalytically cracked oil.The Primary Catalysts presoma is water miscible ferrous sulfate, and the add-on of Primary Catalysts presoma by Fe wherein, is 0.5 weight % of coal dust (butt); Auxiliary agent is a SULPHUR POWDER, and the molar ratio of S/Fe is 2; Dispersion aids is EDTA, and the mol ratio of EDTA/Fe is 1: 100.According to preparing coal oil mixture with embodiment 1 identical method and carrying out oily coal hydrogenation and refine reaction altogether, other conditions are constant.The gained result sees table 3.
Comparative Examples 2
Comparative Examples 2 and embodiment 6 be different be in, do not add dispersion aids.
Do not add described any dispersion aids in preparation coal oil mixture process and the oily coal refining process altogether, other conditions are all identical with embodiment 6.The gained result sees table 3.
Embodiment 7
According to preparing coal oil mixture with embodiment 2 identical methods and carrying out oily coal hydrogenation and refine reaction altogether; Different is that coal dust adopts bituminous coal; Catalytically cracked oil is adopted in oil refining altogether, and adding molybdenum content before hydrogenation refines altogether is the isocaprylic acid molybdenum 0.15g of 15 weight %, and other conditions are constant.The gained result sees table 3.
Table 1
| Project | Brown coal | Sub-bituminous coal |
| Technical analysis, weight % | ||
| Mad | 18.08 | 10.49 |
| Aad | 16.36 | 6.68 |
| Vdaf | 47.85 | 36.69 |
| Ultimate analysis daf, weight % | ||
| C | 73.13 | 81.80 |
| H | 5.13 | 4.58 |
| S | 1.27 | 0.82 |
| N | 2.54 | 1.46 |
| O | 17.93 | 11.33 |
Table 2
| Analysis project | Viscous crude | Catalytically cracked oil |
| Density (20 ℃)/(g/cm 3) | 0.996 | 1.005 |
| Ultimate analysis/weight % | ||
| C | 84.98 | 88.06 |
| H | 11.66 | 9.84 |
| N | 1.04 | 0.39 |
| S | 2.00 | 1.50 |
| O | 1.54 | 0.21 |
| Boiling range/℃ | ||
| IBP | 98 | 200 |
| 5％ | 260 | 295 |
| 10％ | 325 | 389 |
| 30％ | 452 | 420 |
| 50％ | 541 | 510 |
| Four components/weight % | ||
| Saturated branch | 32.4 | 35.9 |
| Aromatic hydrocarbons | 26.7 | 46.6 |
| Colloid | 29.2 | 10.0 |
| Bituminous matter | 11.7 | 7.5 |
Table 3
| Project | Transformation efficiency/weight % | Oil productive rate/weight % |
| Embodiment 1 | 93.81 | 61.61 |
| Embodiment 2 | 92.85 | 65.32 |
| Embodiment 3 | 95.30 | 66.41 |
| Embodiment 4 | 93.61 | 62.24 |
| Embodiment 5 | 95.30 | 68.75 |
| Embodiment 6 | 97.85 | 77.98 |
| Embodiment 7 | 97.72 | 78.26 |
| Comparative Examples 1 | 91.30 | 60.85 |
| Comparative Examples 2 | 93.92 | 73.54 |
Embodiment 1-4 in the table 3 being compared with Comparative Examples 1, can find out, is that raw material carries out with a kind of heavy oil and brown coal, uses coal oil mixture of the present invention and oily coal thereof to face hydrogen smelting method altogether, the high 1.5%-4.0% of transformation efficiency, the high 0.7%-5.5% of oily yield.Embodiment 6 is a raw material when facing hydrogen and refining altogether with bituminous coal and catalytically cracked oil, with Comparative Examples 2 relatively, use coal oil mixture according to the invention and altogether smelting method make transformation efficiency and oily yield improve nearly 4%.
Claims (19)
1. an oily coal hydrogenation is refined oil the preparation method of coal slurry altogether, comprising:
The Primary Catalysts presoma that (1) will contain ferro element is processed the aqueous solution, adds dispersion aids, stirs;
(2) coal dust joins in the mixing solutions that step (1) obtains, and after being uniformly dispersed, adds basic cpd;
(3) in step (2) gained mixture, feed oxygen-containing gas, hydrous iron oxide is solidificated in the coal dust surface;
(4) step (3) gained mixture obtains being loaded with the coal dust of hydrous iron oxide, then 90～120 ℃ of dryings after filtering, washing;
(5) the dry coal dust of step (4) gained, sulfur-bearing auxiliary agent are refined oil together and are mixed and made into coal oil mixture.
2. according to the described preparation method of claim 1, it is characterized in that the said Primary Catalysts presoma that contains ferro element is selected from one or more in ferric sulfate, ferrous sulfate, Iron diacetate, iron nitrate, the iron protochloride.
3. according to the described preparation method of claim 1, it is characterized in that said dispersion aids is selected from one or more in quadrol, L-glutamic acid, YD 30 (EDTA), tartrate, Secondary ammonium phosphate, the Hydrocerol A; The mol ratio of dispersion aids and Fe is 1: 500～1: 100.
4. according to the described preparation method of claim 1, it is characterized in that said dispersion aids is selected from YD 30 (EDTA) and/or Secondary ammonium phosphate; The mol ratio of dispersion aids and Fe is 1: 300～1: 100.
5. according to the described preparation method of claim 1; It is characterized in that; The add-on of said Primary Catalysts presoma is the 0.2 weight %～5.0 weight % of coal dust (butt) by wherein Fe, and described auxiliary agent is SULPHUR POWDER or sulfocompound; Promoter addition, the molar ratio that makes S/Fe is 1～4.
6. according to the described preparation method of claim 1, it is characterized in that the add-on of said Primary Catalysts presoma is by wherein Fe; 0.5 weight %～3.0 weight % for coal dust (butt); Described auxiliary agent is a SULPHUR POWDER, promoter addition, and the molar ratio that makes S/Fe is 1.5～2.5.
7. according to the described preparation method of claim 1; It is characterized in that; In the said coal oil mixture of step (5), add secondary catalyst precursor; Said secondary catalyst precursor is selected from one or more in oil-soluble molybdenum carbonyl, molybdenum naphthenate, the isocaprylic acid molybdenum, and the mol ratio of Mo and Fe is 1: 50～1: 200.
8. according to the described preparation method of claim 7, it is characterized in that described auxiliary agent is SULPHUR POWDER or sulfocompound, promoter addition, the molar ratio of S/ (Fe+Mo) is 1.5～2.5.
9. according to the described preparation method of claim 1, it is characterized in that described basic cpd is selected from one or more in ammoniacal liquor, ammonia, sodium hydroxide solution, the sodium carbonate solution, the mol ratio of basic cpd and Fe is 1.8～2.5.
10. according to the described preparation method of claim 1, it is characterized in that said oxygen-containing gas is the gas of air or oxygen level 20%～100%, the oxygen-containing gas feeding time is 5～60 minutes.
11. according to the described preparation method of claim 1, the temperature that it is characterized in that said step (1)～(3) is 15～40 ℃.
12. according to the described preparation method of claim 1, it is characterized in that said coal dust is selected from one or more in brown coal, sub-bituminous coal, the bituminous coal, coal powder size is less than 150 microns.
13. according to the described preparation method of claim 1; It is characterized in that the described dry coal dust of step (5) comprises the coal dust and the coal dust of load hydrous iron oxide not of the load hydrous iron oxide of step (4) gained; With dry coal dust is benchmark; By weight, the coal dust proportion of load hydrous iron oxide is 20%～100%.
14., it is characterized in that said altogether oil refining is selected from one or more heavy hydrocarbons that natural heavy crude, oil-refining chemical process, oily coal refining process altogether obtain according to the described preparation method of claim 1; Described natural heavy crude is one or more in viscous crude, special viscous crude and the ultra viscous crude; The heavy hydrocarbon that obtains in the described oil-refining chemical process is one or more in long residuum, vacuum residuum, heavy catalytic cycle oil, catalytically cracked oil, aromatic hydrocarbons extract oil, visbreaker tar, coking heavy oil and the oil fuel, and the heavy hydrocarbon that obtains in the described oily coal refining process altogether is a heavy oil.
15., it is characterized in that the weight ratio that said dry coal dust is refined oil together is 20: 80～60: 40 according to the described preparation method of claim 1.
16. coal oil mixture with any one method gained of claim 1～15.
17., it is characterized in that on the surface of the said coal dust that is loaded with hydrous iron oxide, said hydrous iron oxide is bar-shaped according to the described coal oil mixture of claim 16, diameter 10～30nm, long 50～150nm.
18. an oily coal hydrogenation is total to smelting method; It is characterized in that; Coal oil mixture with any one method gained of claim 1～15 reacts in the presence of hydrogen, and said coal oil mixture hydrogenation refines reaction altogether and is divided into two stages, fs reaction conditions: 300～410 ℃ of temperature; Pressure 8～20MPa, 10～60 minutes reaction times; Subordinate phase reaction conditions: 380～470 ℃ of temperature, pressure 8～22MPa, 30～120 minutes reaction times.
19. be total to smelting method according to the described oily coal hydrogenation of claim 18, it is characterized in that the fs reaction conditions: 10～30 minutes reaction times; Subordinate phase reaction conditions: 420～460 ℃ of temperature, pressure 12～20MPa, 30～90 minutes reaction times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110093245.XA CN102732295B (en) | 2011-04-14 | 2011-04-14 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110093245.XA CN102732295B (en) | 2011-04-14 | 2011-04-14 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102732295A true CN102732295A (en) | 2012-10-17 |
| CN102732295B CN102732295B (en) | 2015-03-18 |
Family
ID=46988605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110093245.XA Active CN102732295B (en) | 2011-04-14 | 2011-04-14 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102732295B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549278A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Dual-functional catalyst applied to residual oil, preparation and application of catalyst |
| CN104549276A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof |
| CN104588016A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for hydrogenation catalyst |
| CN104588109A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Coal tar hydrogenation catalyst, and preparation method and application thereof |
| CN104785272A (en) * | 2015-04-20 | 2015-07-22 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| CN105349163A (en) * | 2015-10-23 | 2016-02-24 | 北京中科诚毅科技发展有限公司 | On-line detection and control method and apparatus thereof for swelling degree of coal |
| WO2016176947A1 (en) * | 2015-05-06 | 2016-11-10 | 北京中科诚毅科技发展有限公司 | Iron-based catalyst, and preparation method therefor and use thereof |
| CN104588015B (en) * | 2013-11-03 | 2017-02-01 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN107159271A (en) * | 2017-05-31 | 2017-09-15 | 中国石油大学(华东) | The common artificial coal loaded catalyst of kerosene hydrogenation, preparation method and applications |
| CN108587678A (en) * | 2018-04-12 | 2018-09-28 | 深圳市广昌达石油添加剂有限公司 | The removal methods of catalyst granules in catalytic cracked oil pulp sedimentation agent and catalytic cracked oil pulp |
| CN108772064A (en) * | 2018-02-11 | 2018-11-09 | 国家能源投资集团有限责任公司 | The preparation method of Fe-series catalyst |
| CN109207183A (en) * | 2017-06-30 | 2019-01-15 | 昆山超优清洁能源有限公司 | A kind of composite oil-soluble catalyst is total to the application method in sweetening process in oily coal |
| CN109622030A (en) * | 2019-01-08 | 2019-04-16 | 黑龙江工业学院 | A kind of catalyst and preparation method for Coal Liquefaction |
| CN110257117A (en) * | 2019-07-10 | 2019-09-20 | 中国神华煤制油化工有限公司 | A kind of liquefied coal coil coal slurry preparation method of supported catalyst |
| CN110743526A (en) * | 2019-11-07 | 2020-02-04 | 陕西师范大学 | Resource utilization process for kerosene co-refining residue |
| CN110804456A (en) * | 2018-08-06 | 2020-02-18 | 中国石油化工股份有限公司 | Method and system for oil-coal co-refining |
| CN114768833A (en) * | 2022-03-31 | 2022-07-22 | 中国神华煤制油化工有限公司 | Catalyst oil coal slurry and preparation method thereof, and method for directly liquefying coal and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054504A (en) * | 1975-10-02 | 1977-10-18 | Hydrocarbon Research, Inc. | Catalytic hydrogenation of blended coal and residual oil feeds |
| US5120429A (en) * | 1987-07-10 | 1992-06-09 | Lummus Crest Inc. | Co-processing of carbonaceous solids and petroleum oil |
| CN1778871A (en) * | 2004-11-22 | 2006-05-31 | 煤炭科学研究总院 | High-dispersion iron catalyst by direct coal hydrogenation liquefaction |
| CN101220287A (en) * | 2007-12-13 | 2008-07-16 | 神华集团有限责任公司 | Coal and stone oil joint processing method for producing high quality engine fuel |
-
2011
- 2011-04-14 CN CN201110093245.XA patent/CN102732295B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054504A (en) * | 1975-10-02 | 1977-10-18 | Hydrocarbon Research, Inc. | Catalytic hydrogenation of blended coal and residual oil feeds |
| US5120429A (en) * | 1987-07-10 | 1992-06-09 | Lummus Crest Inc. | Co-processing of carbonaceous solids and petroleum oil |
| CN1778871A (en) * | 2004-11-22 | 2006-05-31 | 煤炭科学研究总院 | High-dispersion iron catalyst by direct coal hydrogenation liquefaction |
| CN101220287A (en) * | 2007-12-13 | 2008-07-16 | 神华集团有限责任公司 | Coal and stone oil joint processing method for producing high quality engine fuel |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549278A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Dual-functional catalyst applied to residual oil, preparation and application of catalyst |
| CN104549276A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof |
| CN104549276B (en) * | 2013-10-28 | 2017-04-26 | 中国石油化工股份有限公司 | Thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof |
| CN104549278B (en) * | 2013-10-28 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of residual oil bifunctional catalyst and its preparation and application |
| CN104588016A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for hydrogenation catalyst |
| CN104588109A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Coal tar hydrogenation catalyst, and preparation method and application thereof |
| CN104588109B (en) * | 2013-11-03 | 2017-01-11 | 中国石油化工股份有限公司 | Coal tar hydrogenation catalyst, and preparation method and application thereof |
| CN104588016B (en) * | 2013-11-03 | 2017-01-25 | 中国石油化工股份有限公司 | Preparation method for hydrogenation catalyst |
| CN104588015B (en) * | 2013-11-03 | 2017-02-01 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN104785272A (en) * | 2015-04-20 | 2015-07-22 | 神华集团有限责任公司 | Iron-based catalyst and preparation method thereof |
| WO2016176947A1 (en) * | 2015-05-06 | 2016-11-10 | 北京中科诚毅科技发展有限公司 | Iron-based catalyst, and preparation method therefor and use thereof |
| CN105349163A (en) * | 2015-10-23 | 2016-02-24 | 北京中科诚毅科技发展有限公司 | On-line detection and control method and apparatus thereof for swelling degree of coal |
| CN107159271A (en) * | 2017-05-31 | 2017-09-15 | 中国石油大学(华东) | The common artificial coal loaded catalyst of kerosene hydrogenation, preparation method and applications |
| CN109207183A (en) * | 2017-06-30 | 2019-01-15 | 昆山超优清洁能源有限公司 | A kind of composite oil-soluble catalyst is total to the application method in sweetening process in oily coal |
| CN108772064A (en) * | 2018-02-11 | 2018-11-09 | 国家能源投资集团有限责任公司 | The preparation method of Fe-series catalyst |
| CN108772064B (en) * | 2018-02-11 | 2021-03-23 | 国家能源投资集团有限责任公司 | Preparation method of iron-based catalyst |
| CN108587678A (en) * | 2018-04-12 | 2018-09-28 | 深圳市广昌达石油添加剂有限公司 | The removal methods of catalyst granules in catalytic cracked oil pulp sedimentation agent and catalytic cracked oil pulp |
| CN108587678B (en) * | 2018-04-12 | 2020-09-11 | 深圳市广昌达石油添加剂有限公司 | Catalytic cracking slurry oil settling agent and method for removing catalyst particles in slurry oil |
| CN110804456A (en) * | 2018-08-06 | 2020-02-18 | 中国石油化工股份有限公司 | Method and system for oil-coal co-refining |
| CN110804456B (en) * | 2018-08-06 | 2021-11-16 | 中国石油化工股份有限公司 | Method and system for oil-coal co-refining |
| CN109622030A (en) * | 2019-01-08 | 2019-04-16 | 黑龙江工业学院 | A kind of catalyst and preparation method for Coal Liquefaction |
| CN110257117A (en) * | 2019-07-10 | 2019-09-20 | 中国神华煤制油化工有限公司 | A kind of liquefied coal coil coal slurry preparation method of supported catalyst |
| CN110743526A (en) * | 2019-11-07 | 2020-02-04 | 陕西师范大学 | Resource utilization process for kerosene co-refining residue |
| CN114768833A (en) * | 2022-03-31 | 2022-07-22 | 中国神华煤制油化工有限公司 | Catalyst oil coal slurry and preparation method thereof, and method for directly liquefying coal and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102732295B (en) | 2015-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102732295B (en) | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method | |
| CN102309972B (en) | Oil coal hydrogenation mixing catalyst and mixing method thereof | |
| CN102380396B (en) | Bimetal or multi-metal high-dispersion composite coal tar hydrogenation catalyst and preparation method thereof | |
| CN107866278A (en) | A kind of hydrocracking heavy oil catalyst and preparation method thereof | |
| WO2016176947A1 (en) | Iron-based catalyst, and preparation method therefor and use thereof | |
| CN103769196B (en) | A kind of residual oil hydrocatalyst, its preparation method and application thereof | |
| CN105013505A (en) | Iron-based catalyst and preparation method thereof | |
| CN100432186C (en) | Directly hydrogenating liquifying process for mixed coal | |
| CN106423142A (en) | Catalyst for suspension bed hydrocracking of inferior heavy oil and preparation method thereof | |
| CN107867993A (en) | A kind of organic-molybdenum salt composite and preparation method thereof | |
| CN101940936B (en) | Coal tar hydrogenation protective agent and preparation method thereof | |
| CN1579623A (en) | Method for preparing high dispersion iron-base catalyst for coal direct liquefication | |
| CN107868108B (en) | Organic molybdenum salt and preparation method thereof | |
| CN102527432B (en) | High-activity iron-based catalysts for coal direct liquefaction and preparation methods for high-activity iron-based catalysts | |
| Guan et al. | MoS2 catalysts with adjustable size and layer structure derived from polyoxometalates-ionic liquids complexes for hydrogen production and hydrogenation | |
| CN111686735A (en) | Hydrogenation co-refining catalyst for preparing high-dispersion briquette/heavy oil by modifying carrier coal | |
| CN103877999B (en) | A kind of coal tar heavy duty oil hydrogenation catalysts and preparation method thereof | |
| CN1778871A (en) | High-dispersion iron catalyst by direct coal hydrogenation liquefaction | |
| CN1107705C (en) | Heavy oil and residual oil treating process | |
| CN111111771A (en) | Recycling method and application of catalytic cracking waste catalyst | |
| CN103059915A (en) | Poor-quality heavy oil hydro-upgrading method | |
| CN104549278B (en) | A kind of residual oil bifunctional catalyst and its preparation and application | |
| CN102311750B (en) | Method for co-refining oil and coal by taking ferrous acetate as catalyst precursor | |
| CN106513049A (en) | Heavy oil hydrofining nano-catalyst with ultrahigh coke inhibiting performance and preparation method and application of heavy oil hydrofining nano-catalyst | |
| CN104549277B (en) | A kind of Residual catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |