CN102311750B - Method for co-refining oil and coal by taking ferrous acetate as catalyst precursor - Google Patents
Method for co-refining oil and coal by taking ferrous acetate as catalyst precursor Download PDFInfo
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Abstract
The invention provides a method for co-refining oil and coal by taking ferrous acetate as a catalyst precursor. The method comprises the following steps of: adding coal powder into a saturated solution of ferrous acetate and agitating uniformly; and then soaking and drying to prepare a liquefied coal sample; pulping the treated coal sample, co-refined oil and an addition agent; and then reacting under the conditions of hydrogenation and pressurization, and separating to obtain the product. The method provided by the invention has the advantages as follows: the loading method of the catalyst precursor is simple, the catalyst precursor does not need to be treated by the steps of precipitating, filtering and pre-vulcanizing, the use amount of the catalyst precursor is less, and the yield of the product oil is high.
Description
Technical field
The present invention relates to a kind of method that oily coal refines hydrogenation liquefaction altogether, more specifically say that a kind of oily coal using ferrous acetate as catalyst precursor refines the method for hydrogenation liquefaction altogether.
Background technology
In recent years, world petroleum resource worsening shortages, and the heaviness of petroleum resources and in poor quality problem more and more obvious, but along with economic rapid growth, society the demand of petroleum products is grown with each passing day.Heavy oil deep process technology not only can effectively be utilized petroleum resources, and can improve the economic benefit of refining of petroleum enterprise.Meanwhile, China is the country of a rich coal resources, and how abundant reserves and cheap coal resources being changed into liquid product becomes an important development direction of coal resources clean utilization.
It is the process coal and the common hydrocracking of heavy oil that oil coal hydrogenation refines altogether.Owing to presenting a kind of promote heavy oil modification and the collaborative interaction of gelatin liquefaction between coal and heavy oil, heavy oil-coal hydrogenation refine altogether than coal or in have independent processing, liquid yield improves, 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 one of oily coal core technology of refining altogether process, for reducing reaction severity, improves reaction efficiency, thereby reduce oily coal, is smelt altogether this, and improving its economic competitiveness has very important effect.The catalyzer that known gelatin liquefaction process is used at present can be divided three classes, and the first kind is noble 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, and scission reaction is had to stronger katalysis, but to liquefaction device seriously corroded, is difficult to industrialization.The 3rd class is iron system abandoning property catalyzer, as the natural mineral of iron content, industrial residue and synthetic iron containing compounds etc.
Fe-series catalyst is due to wide material sources, cheap, can disposable use and do not reclaim, with liquefied residue, discharge, and environment is not formed to additional effect, in gelatin liquefaction, occupy an leading position.Fe-series catalyst can be divided into two classes, and a class is waste residue or natural ferrous mineral, and another kind of is the Fe-series catalyst of ultrafine particulate, and the former is owing to being difficult to dispersion, and granularity is many at micron order, and catalytic activity is not high, large usage quantity; The latter's granules of catalyst is little, and high dispersive, in system, fully contacts with coal in system, and active high, catalyst levels is few.
A kind of iron-base coal liquidation catalyst that CN100457261C provides, grinds at least 2h with the iron compounds such as ferric sulfate, iron(ic) chloride, ironic oxalate and coal, waste lubricating oil, makes a kind of slurried catalyst.The method adopts the method for mechanical mill, is difficult to the particle diameter of catalyzer to be down to below micron, active limited.
CN1778871A discloses a kind of high-dispersion iron catalyst of coal Direct Hydrogenation liquefaction, preparation method adopts FeSO4 solution is joined in carrier coal, after stirring, add the basic solution of hydroxyl-containing ion, making it to generate Fe (OH) 2 is deposited on coal dust, then also must at 20-50 ℃, be oxidized to active ingredient γ-FeOOH with air or oxygen, again after filtration, the dry catalyzer finished product of making, active ingredient γ-FeOOH is strip, long 60-200nm, wide 20-100nm, during for DCL/Direct coal liquefaction, suitable addition is the 0.5-1.0 % by weight of butt coal, the weak point of the method is that preparation section is many, method complexity.
Summary of the invention
A kind of method that provides oily coal using ferrous acetate as catalyst precursor to refine altogether hydrogenation liquefaction on prior art basis is provided.
Method provided by the invention, comprises the steps:
In coal dust, add printer's liquor, stir, and place 0.5-48 hour;
By step (1) gained mixture dry 2-12 hour at 80-120 ℃, obtain being loaded with the coal dust of ferrous acetate;
The coal dust that is loaded with ferrous acetate of step (2) gained is refined oil together, auxiliary agent mixes making beating, obtains coal oil mixture;
The coal oil mixture of step (3) gained imports reactor, under hydrogen existence condition, reacts, and reaction product separates and obtains liquiefied product.
The add-on of described ferrous acetate, by iron wherein, is 0.2 % by weight-5.0 % by weight of butt coal; Preferably 0.5 % by weight-2.0 % by weight.
Described auxiliary agent is sulphur or sulfocompound, and it is 1-4 that add-on makes the molar ratio of sulphur/iron.Described sulfocompound is the one being selected from sodium sulphite, hydrogen sulfide, dithiocarbonic anhydride, dimethyl thioether, Methyl disulfide or normal-butyl mercaptan.Preferably described auxiliary agent is sulphur, and it is 1-2 that preferred add-on makes the molar ratio of sulphur/iron.
Described coal dust is selected from brown coal, sub-bituminous coal, bituminous coal or its mixture, and coal powder size is less than 150 microns.
Described 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 super viscous crude, the heavy hydrocarbon obtaining 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 obtaining in described oily coal refining process is altogether middle oil and/or heavy oil.
The weight ratio that described coal dust is refined oil is together 20: 80-60: 40.
The reaction of coal oil mixture described in step (4) is divided into two stages, and the first stage is decomposition, the vulcanization reaction of catalyst precursor, its reaction conditions: temperature 300-410 ℃, pressure 8-20MPa, reaction times 10-60 minute, preferably 10-30 minute; Subordinate phase is the hydrocracking reaction of oily coal, its reaction conditions: temperature 380-470 ℃, pressure 8-22MPa, reaction times 0.5-2 hour, preferably temperature 420-460 ℃, pressure 12-20MPa, reaction times 0.5-1.5 hour.
Compared with prior art, the present invention has the following advantages: (1) catalyst precursor is introduced only needs dipping, drying step, does not need to add precipitation agent or oxygenant, and step of the present invention is simple, and auxiliary reagent consumption is few; (2) catalyst precursor in advance high dispersing on common artificial coal surface, utilize the resolution characteristic of ferrous acetate, in common refining process, carry out decomposition in situ, sulfuration generates the active ingredient of nascent state, active ingredient is of a size of nano level, active high; (3) sulfidation completes at reaction process situ, and without independent vulcanisation step, equipment is few, and method is simple.
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, got the coal dust that granularity is less than 150 microns and test.The analytical results of two kinds of coal dusts is as shown in table 1.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.
In embodiment, altogether oil refining is a kind of viscous crude and a kind of catalytically cracked oil, and two kinds to refine altogether oil properties as shown in table 2.
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/% by weight, daf | ||
| 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 | 0.955 |
| Ultimate analysis/% by weight | ||
| C | 85.09 | 86.96 |
| H | 11.04 | 11.02 |
| S | 2.25 | 1.50 |
| N | 0.68 | 0.31 |
| O | 0.94 | 0.21 |
| Boiling range/℃ | ||
| IBP | 98 | 187 |
| 5％ | 260 | 235 |
| 10％ | 325 | 280 |
| 30％ | 452 | 377 |
| 50％ | 541 | 495 |
Embodiment 1
The coal dust that the present embodiment adopts is brown coal, and the common oil refining of employing is viscous crude.
Concrete steps are: 8.6g tetra-water ferrous acetates (purity 95%) are dissolved in 50g water, add 160g brown coal powder (butt), stir, make it impregnated on coal dust, through infiltrating 30min, in 105 ℃ of dry 2h, make dipping coal sample.Dipping coal sample, 1.35g SULPHUR POWDER and 240g viscous crude are mixed and made into coal oil mixture, import 2L autoclave, after displacement gas reactor, fill hydrogen to 8MPa, sealing.Rise to 400 ℃, stop 15min, then lower the temperature after rising to 450 ℃ of reaction 60min, collect gas reactor and analyze, in still, product adopts the method stage treatment of Soxhlet extracting.
The amount that transformation efficiency is defined as tetrahydrofuran (THF) solvend accounts for moisture-and-ash-free basis coal and refines oil altogether the per-cent of total amount, and oily productive rate is defined as and by distillation, obtains being less than 500 ℃ of oily amounts and account for moisture-and-ash-free basis coal and refine oil altogether the per-cent of total amount.Acquired results is in Table 3.
Comparative example 1
Comparative example 1 is different from embodiment 1 to be in, catalyst precursor iron vitriol, and other conditions are identical, the results are shown in Table 3.
Embodiment 2
According to the method Kaolinite Preparation of Catalyst identical with embodiment 1 and react, different is that four water ferrous acetate consumptions are 5g, and other conditions are constant.The results are shown in Table 3.
Embodiment 3
According to the method Kaolinite Preparation of Catalyst identical with embodiment 1 and react, different is that four water ferrous acetate consumptions are 15g, and other conditions are constant.The results are shown in Table 3.
Embodiment 4
According to the method Kaolinite Preparation of Catalyst identical with embodiment 1 and react, different is to rise to 360 ℃, stops 15min, then rises to 450 ℃ of reaction 60min, and other conditions are constant.The results are shown in Table 3.
Embodiment 5
According to the method Kaolinite Preparation of Catalyst identical with embodiment 1 and react, different is that coal dust adopts sub-bituminous coal, and other conditions are constant.The results are shown in Table 3.
Embodiment 6
According to the method Kaolinite Preparation of Catalyst identical with embodiment 1 and react, different is that common oil refining adopts catalytically cracked oil, and other conditions are constant.The results are shown in Table 3.
Table 3
| Project | Transformation efficiency/% by weight | Oil productive rate/% by weight |
| Embodiment 1 | 94.26 | 66.91 |
| Embodiment 2 | 93.51 | 64.52 |
| Embodiment 3 | 98.06 | 68.46 |
| Embodiment 4 | 95.47 | 65.27 |
| Embodiment 5 | 96.30 | 70.03 |
| Embodiment 6 | 94.30 | 71.03 |
| Comparative example 1 | 89.56 | 63.21 |
Above embodiment result shows, when in comparative example 1, catalyst precursor is used ferrous sulfate, transformation efficiency and oily productive rate are respectively 89.56 % by weight and 63.21 % by weight, while using catalyst precursor of the present invention and preparation method to refine altogether for oily coal, transformation efficiency and oily productive rate all increase, improve respectively 1 % by weight-8.5 % by weight and 1.3 % by weight-7.8 % by weight, and catalyst precursor of the present invention introducing step is simple, auxiliary reagent consumption is few.
Claims (9)
1. the smelting method altogether of the oily coal take ferrous acetate as catalyst precursor, comprises the following steps:
(1) in coal dust, add printer's liquor, stir, and place 0.5-48 hour;
(2), by step (1) gained mixture dry 2-12 hour at 80-120 ℃, obtain being loaded with the coal dust of ferrous acetate;
(3) coal dust that is loaded with ferrous acetate of step (2) gained refine oil together, auxiliary agent mix making beating, obtain coal oil mixture;
(4) coal oil mixture of step (3) gained imports reactor, under hydrogen existence condition, reacts, and reaction product separates and obtains liquiefied product;
Described auxiliary agent is sulphur or sulfocompound, and it is 1-4 that add-on makes the molar ratio of sulphur/iron.
2. in accordance with the method for claim 1, it is characterized in that the add-on of described ferrous acetate, by iron wherein, is 0.2 % by weight-5.0 % by weight of butt coal.
3. in accordance with the method for claim 2, it is characterized in that the add-on of described ferrous acetate, by iron wherein, is 0.5 % by weight-2.0 % by weight of butt coal.
4. in accordance with the method for claim 1, it is characterized in that described auxiliary agent is sulphur, it is 1-2 that add-on makes the molar ratio of sulphur/iron.
5. in accordance with the method for claim 1, it is characterized in that described coal dust is selected from brown coal, sub-bituminous coal, bituminous coal or its mixture, coal powder size is less than 150 microns.
6. in accordance with the method for claim 1, it is characterized in that described altogether oil refining be selected from natural heavy crude, oil-refining chemical process one or more heavy hydrocarbons that obtain, one or more heavy hydrocarbons that oily coal refining process altogether obtains; Described natural heavy crude is one or more in viscous crude, special viscous crude and super viscous crude, and the heavy hydrocarbon obtaining 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.
7. in accordance with the method for claim 1, it is characterized in that the weight ratio that described coal dust is refined oil is together 20: 80-60: 40.
8. in accordance with the method for claim 1, it is characterized in that being divided into two stages, first stage reaction conditions: temperature 300-410 ℃, pressure 8-20MPa, reaction times 10-60 minute in the reaction of coal oil mixture described in step (4); Subordinate phase reaction conditions: temperature 380-470 ℃, pressure 8-22MPa, reaction times 0.5-2 hour.
9. in accordance with the method for claim 8, it is characterized in that first stage reaction conditions: reaction times 10-30 minute; Subordinate phase reaction conditions: temperature 420-460 ℃, pressure 12-20MPa, reaction times 0.5-1.5 hour.
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| CN104549277B (en) * | 2013-10-28 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of Residual catalyst and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2083999C (en) * | 1992-01-08 | 1995-11-28 | Michio Ikura | Incorporation of a coprocessing additive into coal/oil agglomerates |
| RU2131904C1 (en) * | 1998-03-10 | 1999-06-20 | Институт химии и химической технологии СО РАН | Coal hydrogenation process |
| CN1853776A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Iron-based coal liquefied catalyst and production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59109588A (en) * | 1982-12-15 | 1984-06-25 | Kobe Steel Ltd | Liquefaction of brown coal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2083999C (en) * | 1992-01-08 | 1995-11-28 | Michio Ikura | Incorporation of a coprocessing additive into coal/oil agglomerates |
| RU2131904C1 (en) * | 1998-03-10 | 1999-06-20 | Институт химии и химической технологии СО РАН | Coal hydrogenation process |
| CN1853776A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Iron-based coal liquefied catalyst and production thereof |
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