CN102732295B - 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
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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 obtained by this preparation method and this coal oil mixture thereof refine altogether at oily coal hydrogenation.
Background technology
In recent years, world petroleum resource worsening shortages, and the heaviness of petroleum resources and in poor quality problem are more and more obvious, but along with the quick growth of economy, society grows with each passing day to the demand of petroleum products.Heavy oil deep process technology not only effectively can utilize petroleum resources, and can improve the economic benefit of oil-processing enterprises.Meanwhile, China is the country of a rich coal resources, how rich reserves and cheap coal resources is changed into the important development direction that liquid product becomes coal resources clean utilization.
It is process coal and the common hydrocracking of heavy oil that oil coal hydrogenation refines altogether.Owing to presenting the synergy promoting heavy oil modification and gelatin liquefaction between coal and heavy oil, heavy oil ~ coal hydrogenation refines altogether than coal or oil processing separately, and liquid yield improves, and hydrogen consumption reduces.Simultaneously coal also promotes removing of metallic element in heavy oil, and high, the unmanageable heavy oil of heavy metal content is utilized.
Catalyzer is oily coal one of core technology of refining process altogether, for reduction reaction severity, improves reaction efficiency, thus reduces oily coal and be smelt this altogether, and improving its economic competitiveness has very important effect.The catalyzer that coal liquefaction known at present uses can be divided three classes, and the first kind is metal catalyst, as cobalt, molybdenum, nickel, tungsten catalyst.Equations of The Second Kind is metal halide catalyst, as zinc chloride and tin chloride etc.; Metal halide catalyst is strongly acidic catalyst, has stronger katalysis to scission reaction, but to liquefaction device seriously corroded, is difficult to industrialization.3rd class is iron system abandoning property catalyzer, as natural mineral, the industrial residue and synthesis iron containing compounds etc. of iron content.
Fe-series catalyst is due to wide material sources, cheap, can single use and not reclaiming, discharge with liquefied residue, additional effect is not formed to environment, become the focus of research at present, but still there is active and that oily productive rate is not high problem, the size reducing catalyzer is one of important means of the activity improving Fe-series catalyst, and as CN1778871A discloses a kind of high-dispersion iron catalyst of coal Direct Hydrogenation liquefaction, preparation method adopts FeSO
4solution joins in carrier coal, adds the basic solution of hydroxyl-containing ion after stirring, and makes it to generate Fe (OH)
2be deposited on coal dust, then active ingredient γ-FeOOH is oxidized to air or oxygen at 20 ~ 50 DEG C, again after filtration, finished catalyst is made in drying, active ingredient γ-FeOOH is in strip, long 60-200nm, wide 20-100nm, the addition for being suitable for during DCL/Direct coal liquefaction is 0.5 ~ 1.0 % by weight of butt coal, weak point is that active ingredient size is large, and product oil yield is low.
Summary of the invention
The object of the invention is to provide a kind of oily coal hydrogenation to refine oil the preparation method of coal slurry altogether on prior art basis, the coal oil mixture obtained by this preparation method, and the application method that this coal oil mixture refines altogether at oily coal hydrogenation.
The oily coal hydrogenation provided refines oil the preparation method of coal slurry altogether, comprising:
(1) the Primary Catalysts presoma containing ferro element is made the aqueous solution, add dispersion aids, stir;
(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, pass into oxygen-containing gas, hydrous iron oxide is solidificated in coal dust surface;
(4) step (3) gained mixture after filtration, washing after, obtain the coal dust being loaded with hydrous iron oxide, then 90 ~ 120 DEG C of dryings;
(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 described Primary Catalysts presoma containing ferro element is selected from one or more in ferric sulfate, ferrous sulfate, Iron diacetate, iron nitrate, iron protochloride.
Described dispersion aids is selected from one or more in quadrol, L-glutamic acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), tartrate, Secondary ammonium phosphate, citric acid; The mol ratio of dispersion aids add-on and Fe is 1: 500 ~ 1: 100.Preferably, described dispersion aids is selected from ethylenediamine tetraacetic acid (EDTA) (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 Fe wherein, for 0.2 % by weight ~ 5.0 % by weight of coal dust (butt), be preferably 0.5 % by weight ~ 3.0 % by weight of coal dust (butt), described auxiliary agent is SULPHUR POWDER or sulfocompound, be preferably SULPHUR POWDER, described sulfocompound is be selected from the one in sodium sulphite, hydrogen sulfide, dithiocarbonic anhydride, dimethyl thioether, Methyl disulfide or butyl mercaptan.Promoter addition, makes the molar ratio of S/Fe be 1 ~ 4, preferably makes the molar ratio of S/Fe be 1.5 ~ 2.5.
Can also add secondary catalyst precursor in step (5) described coal oil mixture, described secondary catalyst precursor is selected from one or more in oil-soluble molybdenum carbonyl, molybdenum naphthenate, isocaprylic acid molybdenum, and the mol ratio of Mo and Fe is 1: 50 ~ 1: 200.Now, promoter addition, makes the molar ratio of S/ (Fe+Mo) be 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, sodium carbonate solution, and the mol ratio of basic cpd and Fe is 1.8 ~ 2.5.
Described oxygen-containing gas is the gas of air or oxygen level 20% ~ 100%, and it is 5 ~ 60 minutes that oxygen-containing gas passes into the time.
The temperature of described step (1) ~ (3) is 15 ~ 40 DEG C.
Described coal dust is selected from one or more in brown coal, sub-bituminous coal, bituminous coal, and coal powder size is less than 150 microns.Be conducive to coal and refine oil dispersing and mixing together evenly, fully liquefy, improve liquiefied product yield.
Dry coal dust described in step (5) comprises the coal dust of the load hydrous iron oxide of step (4) gained and the coal dust of non-load hydrous iron oxide, with dry coal dust for benchmark, by weight, the coal dust proportion of load hydrous iron oxide is 20% ~ 100%.The coal dust of non-load hydrous iron oxide, from the part being partly or entirely less than 150 microns in pulverized coal preparation process, is preferably less than the part of 100 microns.When calculating catalyst precursor add-on, be for benchmark calculates with the coal dust of all refinings altogether.
Described altogether oil refining is selected from natural ground crude oil, oil-refining chemical process, oily coal one or more heavy hydrocarbons of obtaining of the process of refining altogether; Described natural ground crude oil is one or more in viscous crude, special thick oil and super-viscous oil, the heavy hydrocarbon obtained in described oil-refining chemical process is one or more in long residuum, vacuum residuum, heavy catalytic cycle oil, catalytically cracked oil, Aromatics Extractive Project oil, visbreaker tar, coking heavy oil and oil fuel, and the heavy hydrocarbon obtained in described oily coal refining process is altogether heavy oil.
The weight ratio that described 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 described surface being loaded with the coal dust of hydrous iron oxide, described hydrous iron oxide is bar-shaped, diameter 10 ~ 30nm, long 50 ~ 150nm.Described hydrous iron oxide refers to one or more of alpha-feooh, β-FeOOH, γ-FeOOH.The present invention is solidified at Primary Catalysts presoma introduce dispersion aids in coal dust surface process, can promote that Primary Catalysts presoma is in the dispersion on coal dust surface, suppresses Primary Catalysts crystal grain to increase, and makes resulting procatalyst in the state of coal dust surface dispersion in nanoscale heights.
A kind of oily coal hydrogenation smelting method altogether, react in presence of hydrogen with the coal oil mixture of any one method gained above-mentioned, described coal oil mixture hydrogenation refines reaction altogether and is divided into two stages, first stage is decomposition, vulcanization reaction stage of catalyzer (comprising Primary Catalysts and secondary catalyzer), and catalyzer is through decomposition in situ, the active ingredient generating metallic sulfide with auxiliary agent sulfuration.First stage reaction conditions: temperature 300 ~ 410 DEG C, 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: temperature 380 ~ 470 DEG C, pressure 8 ~ 22MPa, 30 ~ 120 minutes reaction times; Preferable temperature 420 ~ 460 DEG C, pressure 12 ~ 20MPa, 30 ~ 90 minutes reaction times.
Primary Catalysts presoma of the present invention is highly dispersed at coal dust surface in advance under the effect of dispersion aids, and the hydrous iron oxide of formation is in nano level on coal dust, and preserve at the effect Absorbable organic halogens of coal surface functional group and oil refining altogether, preparation method is relatively simple.Described hydrous iron oxide refines altogether at oily coal that process situ decomposes, sulfuration generates the active ingredient of nascent state, and coal oil mixture of the present invention and altogether smelting method have that transformation efficiency is high and oily yield is high, the advantage that catalyst levels is few.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but therefore do not make the present invention be subject to any restriction.
A kind of brown coal and a kind of sub-bituminous coal are pulverized respectively, through screening, gets the coal dust that granularity is less than 150 microns and test.M in table 1
adwater content, A
dash content, V
dafit is volatile matter.Ad represents air dried basis; D represents dry base; Daf represents dry ash-free basis.The analytical results of two kinds of coal dusts is as shown in table 1.
In embodiment, oil refining is a kind of viscous crude and a kind of catalytically cracked oil altogether, and two kinds refining oil properties is as shown in table 2 altogether.
Embodiment 1
The coal dust that the present embodiment adopts is brown coal, and the common oil refining of employing is viscous crude.Primary Catalysts presoma is the add-on of water miscible ferrous sulfate, Primary Catalysts presoma, by Fe wherein, is 0.5 % by weight of coal dust (butt); Auxiliary agent is SULPHUR POWDER, and the molar ratio of S/Fe is 2; Dispersion aids is the mol ratio of EDTA, EDTA/Fe is 1: 200.
Oil coal hydrogenation is refined oil the concrete steps of preparation method of coal slurry altogether and is: at room temperature, 5.0g iron vitriol and 0.026gEDTA are dissolved in 100g water, 200g brown coal powder (butt), stirs, and makes ferrous sulfate impregnated on coal dust, make coal slurry, separately get 4.2g ammoniacal liquor and be added dropwise to above-mentioned coal slurry, pass into air and continue to stir 20min, then carrying out suction filtration, obtain filter cake in 105 DEG C of dryings 2 hours, obtained supporting agent coal sample.Supporting agent coal sample, add 1.15g SULPHUR POWDER and 300g heavy oil is mixed and made into coal oil mixture.
Use the oily coal hydrogenation of above-mentioned coal oil mixture altogether smelting method be: coal oil mixture is imported 2L autoclave, after displacement gas reactor, fills hydrogen and close to 9.5MPa.Rise to 400 DEG C, stop 15min, then lower the temperature after rising to 450 DEG C of reaction 60min, collect gas reactor and analyze, in still, product adopts the method stage treatment of soxhlet type.
Acquired results is in table 3, transformation efficiency in table and oily yield data are all refine oil sum together for Calculation Basis with daf base coal, transformation efficiency=(tetrahydrofuran insoluble SOLID ORGANIC matter in 1-product/(daf base coal and common oil refining)) × 100%, oily yield is be dissolved in the percentage ratio that normal hexane part accounts for daf base coal and oil refining altogether in product.
Comparative example 1
Comparative example 1 is different from embodiment 1 be in, do not add dispersion aids.
Prepare in coal oil mixture process and oily coal refining process altogether and do not add any one described dispersion aids, other conditions are all identical with embodiment 1.Acquired results is in table 3.
Embodiment 2
Prepare coal oil mixture according to the method identical with embodiment 1 and carry out oily coal hydrogenation and refine reaction altogether, unlike EDTA dispersion aids addition in the mol ratio of EDTA/Fe for 1: 100, other conditions are constant.Acquired results is in table 3.
Embodiment 3
Preparing coal oil mixture according to method substantially the same manner as Example 1 and carry out oily coal hydrogenation and refine reaction altogether, is L-glutamic acid unlike dispersion aids, and consumption is in the mol ratio of L-glutamic acid/Fe for 1: 400, and logical purity oxygen, other conditions are constant.Acquired results is in table 3.
Embodiment 4
Preparing coal oil mixture according to method substantially the same manner as Example 1 and carry out oily coal hydrogenation and refine reaction altogether, is tartrate unlike dispersion aids, consumption in the mol ratio of tartrate/Fe for 1: 300, other conditions are constant.Acquired results is in table 3.
Embodiment 5
Prepare coal oil mixture according to the method identical with embodiment 1 and carry out oily coal hydrogenation and refine reaction altogether, adopt bituminous coal unlike coal dust, dispersion aids is Secondary ammonium phosphate, and consumption is in the mol ratio of Secondary ammonium phosphate/Fe for 1: 200, and other conditions are constant.Acquired results is in table 3.
Embodiment 6
The coal dust that the present embodiment adopts is bituminous coal, and the common oil refining of employing is catalytically cracked oil.Primary Catalysts presoma is the add-on of water miscible ferrous sulfate, Primary Catalysts presoma, by Fe wherein, is 0.5 % by weight of coal dust (butt); Auxiliary agent is SULPHUR POWDER, and the molar ratio of S/Fe is 2; Dispersion aids is the mol ratio of EDTA, EDTA/Fe is 1: 100.Prepare coal oil mixture according to the method identical with embodiment 1 and carry out oily coal hydrogenation and refine reaction altogether, other conditions are constant.Acquired results is in table 3.
Comparative example 2
Comparative example 2 is different from embodiment 6 be in, do not add dispersion aids.
Prepare in coal oil mixture process and oily coal refining process altogether and do not add any one described dispersion aids, other conditions are all identical with embodiment 6.Acquired results is in table 3.
Embodiment 7
Prepare coal oil mixture according to the method identical with embodiment 2 and carry out oily coal hydrogenation and refine reaction altogether, bituminous coal is adopted unlike coal dust, oil refining adopts catalytically cracked oil altogether, and add the isocaprylic acid molybdenum 0.15g that molybdenum content is 15 % by weight before hydrogenation refines altogether, other conditions are constant.Acquired results is in table 3.
Table 1
| Project | Brown coal | Sub-bituminous coal |
| Technical analysis, % by weight | ||
| Mad | 18.08 | 10.49 |
| Aad | 16.36 | 6.68 |
| Vdaf | 47.85 | 36.69 |
| Ultimate analysis daf, % by 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 DEG C)/(g/cm 3) | 0.996 | 1.005 |
| Ultimate analysis/% by 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/DEG C | ||
| IBP | 98 | 200 |
| 5％ | 260 | 295 |
| 10％ | 325 | 389 |
| 30％ | 452 | 420 |
| 50％ | 541 | 510 |
| Four composition/% by weight | ||
| Saturated point | 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/% by weight | Oil productive rate/% by 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 example 1 | 91.30 | 60.85 |
| Comparative example 2 | 93.92 | 73.54 |
By embodiment 1-4 in table 3 compared with comparative example 1, can find out, carry out for raw material with a kind of heavy oil and brown coal, use coal oil mixture of the present invention and oily coal thereof to face hydrogen smelting method altogether, transformation efficiency height 1.5%-4.0%, oily yield height 0.7%-5.5%.Embodiment 6 with bituminous coal and catalytically cracked oil for raw material carry out facing hydrogen refine altogether time, compare with comparative example 2, use coal oil mixture of the present invention and altogether smelting method make transformation efficiency and oily yield improve nearly 4%.
Claims (17)
1. oily coal hydrogenation refines oil a preparation method for coal slurry altogether, comprising:
(1) the Primary Catalysts presoma containing ferro element is made the aqueous solution, add dispersion aids, stir; Described dispersion aids is selected from one or more in quadrol, L-glutamic acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), tartrate, Secondary ammonium phosphate, citric acid; The mol ratio of dispersion aids and Fe is 1: 500 ~ 1: 100;
(2) coal dust joins in the mixing solutions that step (1) obtains, and after being uniformly dispersed, adds basic cpd; Described coal dust is selected from one or more in brown coal, sub-bituminous coal, bituminous coal, and coal powder size is less than 150 microns;
(3) in step (2) gained mixture, pass into oxygen-containing gas, hydrous iron oxide is solidificated in coal dust surface;
(4) step (3) gained mixture after filtration, washing after, obtain the coal dust being loaded with hydrous iron oxide, then 90 ~ 120 DEG C of dryings;
(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. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that the described Primary Catalysts presoma containing ferro element is selected from ferric sulfate, ferrous sulfate, Iron diacetate, iron nitrate, iron protochloride one or more.
3. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that described dispersion aids is selected from ethylenediamine tetraacetic acid (EDTA) (EDTA) and/or Secondary ammonium phosphate; The mol ratio of dispersion aids and Fe is 1: 300 ~ 1: 100.
4. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that, the add-on of described Primary Catalysts presoma is by Fe wherein, for 0.2 % by weight ~ 5.0 % by weight of coal dust butt, described auxiliary agent is SULPHUR POWDER or sulfocompound, promoter addition, makes the molar ratio of S/Fe be 1 ~ 4.
5. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that, the add-on of described Primary Catalysts presoma is by Fe wherein, for 0.5 % by weight ~ 3.0 % by weight of coal dust butt, described auxiliary agent is SULPHUR POWDER, promoter addition, makes the molar ratio of S/Fe be 1.5 ~ 2.5.
6. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that, secondary catalyst precursor is added in step (5) described coal oil mixture, described secondary catalyst precursor is selected from one or more in oil-soluble molybdenum carbonyl, molybdenum naphthenate, isocaprylic acid molybdenum, and the mol ratio of Mo and Fe is 1: 50 ~ 1: 200.
7. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 6, 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.
8. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that one or more that described basic cpd is selected from ammoniacal liquor, ammonia, sodium hydroxide solution, sodium carbonate solution, the mol ratio of basic cpd and Fe is 1.8 ~ 2.5.
9. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that described oxygen-containing gas to be air or oxygen volume content be the gas of 20% ~ 100%, it is 5 ~ 60 minutes that oxygen-containing gas passes into the time.
10. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that the temperature of described step (1) ~ (3) is 15 ~ 40 DEG C.
11. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that the dry coal dust described in step (5) comprises the coal dust of the load hydrous iron oxide of step (4) gained and the coal dust of non-load hydrous iron oxide, with dry coal dust for benchmark, by weight, the coal dust proportion of load hydrous iron oxide is 20% ~ 100%.
12. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that described oil refining is altogether selected from natural ground crude oil, oil-refining chemical process, oily coal one or more heavy hydrocarbons of obtaining of the process of refining altogether; Described natural ground crude oil is one or more in viscous crude, special thick oil and super-viscous oil, the heavy hydrocarbon obtained in described oil-refining chemical process is one or more in long residuum, vacuum residuum, heavy catalytic cycle oil, catalytically cracked oil, Aromatics Extractive Project oil, visbreaker tar, coking heavy oil and oil fuel, and the heavy hydrocarbon obtained in described oily coal refining process is altogether heavy oil.
13. refine oil coal slurry preparation method altogether according to the oily coal hydrogenation of one according to claim 1, it is characterized in that the weight ratio that described dry coal dust is refined oil together is 20: 80 ~ 60: 40.
14. 1 kinds with the coal oil mixture of any one method gained of claim 1 ~ 13.
15., according to coal oil mixture according to claim 14, is characterized in that, on the described surface being loaded with the coal dust of hydrous iron oxide, described hydrous iron oxide is bar-shaped, diameter 10 ~ 30nm, long 50 ~ 150nm.
16. 1 kinds of oily coal hydrogenations smelting method altogether, it is characterized in that, react in presence of hydrogen with the coal oil mixture of any one method gained of claim 1 ~ 13, described coal oil mixture hydrogenation refines reaction altogether and is divided into two stages, first stage reaction conditions: temperature 300 ~ 410 DEG C, pressure 8 ~ 20MPa, 10 ~ 60 minutes reaction times; Subordinate phase reaction conditions: temperature 380 ~ 470 DEG C, pressure 8 ~ 22MPa, 30 ~ 120 minutes reaction times.
17., according to oily coal hydrogenation according to claim 16 smelting method altogether, is characterized in that first stage reaction conditions: 10 ~ 30 minutes reaction times; Subordinate phase reaction conditions: temperature 420 ~ 460 DEG C, pressure 12 ~ 20MPa, 30 ~ 90 minutes reaction times.
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