CN1880411A - Process for preparing fuel oil by using coal tar - Google Patents
Process for preparing fuel oil by using coal tar Download PDFInfo
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- CN1880411A CN1880411A CN 200610018476 CN200610018476A CN1880411A CN 1880411 A CN1880411 A CN 1880411A CN 200610018476 CN200610018476 CN 200610018476 CN 200610018476 A CN200610018476 A CN 200610018476A CN 1880411 A CN1880411 A CN 1880411A
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Abstract
This invention relates to a process for producing fuel oil from coal oil, comprising: 1. vacuum dehydrate the coal oil; 2. distill the dehydrated coal oil to produce <=360Deg C fraction and >=360Deg C fraction; (1) dephenolize and denaphthalenize the <=360Deg C fraction, then add hydrogen for refining and modification, and lastly distill to produce superior benzin naphtha and diesel fuel fractions; (2) perform complete cycle of the charring wax oil produced by delayed carbonization of the >=360Deg C fraction to produce the <=360Deg C fraction, then add hydrogen for refining and modification, and lastly distill to produce superior benzin naphtha and diesel fuel fractions. The invention is characterized of broad range of raw material, rational process, easy industrial production, and flexible operation.
Description
Technical field: the present invention relates to the method that a kind of liquid hydrocarbon that the dry distillation of coal and/or coal generating gas are obtained carries out hydrofining, the hydrogenation transformation of the way.More particularly, be a kind of from coal tar the method for production high-quality petroleum naphtha, diesel component and coke.
Technical background: the producing fuel oil from coal tar method though sophisticated Technology is arranged both at home and abroad, exists stock oil is required height and originates wideless, the gained liquid product yield is low, and lightweight oil is on the low side, and the course of processing is loaded down with trivial details, resource is disperseed, and process scale is little, and environmental problem can not get basic solution.Metallurgical Research Institute, Department of Architecture environmental protection institute, coalification institute of Institutes Of Technology Of Taiyuan with coalite tar, be raw material, adopt the atmospheric depressurized fractionating method, cut corresponding cut, through acid-alkali washing, carclazyte adsorption bleaching, add additive compound and combine.Its impact of performance is the same with the ordinary diesel oil component, closes national standard; Factory of real company of Harbin Gas Works section has carried out the hydrofining test to coalite tar, promptly carries out catalytic hydrofinishing with the FH-98 new catalyst.Its stock oil is the cut before 370 ℃ of the coalite tars.In depress production diesel component after adding agent, can satisfy the index request of No. 0 diesel component of GB; Beijing Coal Chemistry Inst., Coal Sciences General Inst., to gasification tar, hydrofined gasoline, diesel component have carried out systematic study, at gasification tar content of impurities height, the characteristics that heteroatoms is many, the condensed ring aromatic hydrocarbon content is high, proposed the hydrogenation technique of stock oil pre-treatment, presaturated hydrogenation, hydrofining, hydrocracking, vapour, diesel component product all meet national standard.3822 catalyzer are used in hydrofining, and 3823 catalyzer are used in hydrocracking, reaction pressure 14.7MPa, and temperature is relative with hydrogen-oil ratio higher.Still too busy to get away traditional acid-alkali refining scope with the introduction of patents such as CN92110407.3, CN93107496.7; Though the CN200410012455.1 patent is advanced hydrogenation technique, the diesel component cetane value of producing is low slightly, and will add inhibitor in hydrogenated oil.
Summary of the invention:
Purpose of the present invention be exactly provide 1 at the existing above-mentioned deficiency of producing fuel oil from coal tar method, a kind of production technique of producing fuel oil from coal tar, its production craft step is:
One, vacuum hydro-extraction: coal tar is carried out vacuum hydro-extraction;
Two, distillation cutting: dehydrated coal tar is distilled, make≤360 ℃ of cuts and 〉=360 ℃ of cuts;
(1) ,≤360 ℃ of cuts are carried out dephenolize, take off naphthalene, repeated hydrogenation is refining, the hydrogenation transformation of the way, and distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last;
(2), cuts that will 〉=360 ℃ carry out delayed coking, make≤360 ℃ of cuts and wax tailings;
(1), cuts that will 〉=360 ℃ carry out making after the delayed coking≤360 ℃ of refining, hydrogenation transformations of the way of cut fraction hydrogenation, distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last;
(2), cuts that will 〉=360 ℃ wax tailings that carries out making after the delayed coking follows also entirely, makes≤360 ℃ of cuts, repeated hydrogenation is refining, the hydrogenation transformation of the way, distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last.
Vacuum hydro-extraction is the vacuum hydro-extraction of 3-4 level, and vacuum tightness is-0.082-0.095MPa that temperature is 70-80 ℃.
Hydrofining, hydrogenation transformation of the way temperature of reaction are 350-400 ℃, and pressure is 8.0-15.0MPa, and liquid hourly space velocity is 0.2-3.0/h
-1, hydrogen to oil volume ratio is 800-1200: 1.
The coking temperature of delayed coking is 490-520 ℃, and pressure is 0.1-0.5MPa, water injection rate accounts for 〉=and the 2-3% of 360 ℃ cut weight.
Hydrofining, hydrogenation transformation of the way reaction are used two reactors in series together, and the catalyzer that reacts used is made up of catalyst for refining, protective material and modifying catalyst; Adorn catalyst for refining and/or protective material in a reactor therein, protective material is contained in the upper strata, and catalyst for refining is contained in lower floor, loads modifying catalyst in another reactor; Protective material, catalyst for refining, the admission space of transformation of the way catalyzer is than being 1-2: 4-6: 3-5.
Catalyst for refining is RCT-1, and protective material is RG-10A, and modifying catalyst is RIC-1.
Advantage of the present invention is: 1, wide to the ingredient requirement scope, and the processing of applicable middle low temperature and coal-tar heavy oil.2, technology is reasonable, easy suitability for industrialized production, flexible operation.3, the specific surface area of catalyst of selecting for use is big, and pore capacities is big, and is active high, good stability, and test is 1000 hours non-inactivations of operation continuously, long service life, stable, the catalyzer cost is low, is convenient to commercially produce and industrial application.
Embodiment
At first with used feed coal tar through filtering, the content of impurity such as sulphur, nitrogen, metal, colloid is high more in the raw material, and is big more to the influence in Hydrobon catalyst life-span.Nitrogen content is not more than 2.0 weight % in the raw material, preferably is not more than 1.2 weight %, and sulphur content is not more than 1.0 weight %.
One, vacuum hydro-extraction: the coal tar after will filtering carries out vacuum hydro-extraction 3-4 time by vacuum hydroextractor, and vacuum tightness is-0.082-0.095MPa that temperature is 70-80 ℃.Dehydration back tar water content≤0.2%.
Two, distillation cutting: dehydrated coal tar is distilled by distillation tower, make≤360 ℃ of cuts and 〉=360 ℃ of cuts;
(1), will≤360 ℃ after cuts carry out dephenolize, take off naphthalene by ordinary method, on the fixed bed hydrogenation device, carry out hydrofining, the hydrogenation transformation of the way again, use two reactors in series together, i.e. " two anti-one-stage serial " Technology; (trade names, the weight percent of its physical and chemical index: WO3 are that the weight percent of 23-36%, NiO is that the weight percent of 2.5-4.3%, MgO is that the unformed aluminum oxide or the silica-alumina supports of 0.1-2.1% and surplus constitutes to adopt RCT-1.Pore volume be 0.32-0.40ml/g, specific surface＞150m2/g, bulk density be 94-99g/100ml, intensity greater than 26N/mm, be shaped as trifolium, diameter is that 11-13mm, length are 3-8mm) be 4 catalyst for refining; adopt RG-10A (trade names are made up of the γ-Al2O3 carrier with diplopore distribution of the heavy % NiO of 1.0-5.0, the heavy %MoO3 of 5.5-10.0 and surplus) to be protective material; adopting RIC-1 (trade names) is modifying catalyst, and RG-10A, RCT-1, RIC-1 produce by Sinopec Chang Ling catalyst plant.Dress protective material and/or finishing agent in reactor 1, protective material is contained in the upper strata of reactor 1, and finishing agent is contained in protectant lower floor, loads modification agent in reactor 2; The admission space ratio of RG-10A, RCT-1, RIC-1 is 1: 5: 4.The hydrogenation reaction temperature is 350-400 ℃, is preferably 360-380 ℃, and pressure is 8.0-15.0MPa, and optimum pressure is 10.0-12.0MPa, and liquid hourly space velocity is 0.2-3.0/h
-1, the best also is air speed position 0.5-0.8h
-1, hydrogen to oil volume ratio is 800-1200: 1, and best hydrogen to oil volume ratio is 1000: 1V/V.Distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last;
(2), the cut of inciting somebody to action 〉=360 ℃ carries out delayed coking, adopting " single-furnace double-tower " technology is that a process furnace is two coking tower heating processes simultaneously, coking temperature is that 490-520 ℃, optimum temps are 500-510 ℃, and pressure is that 0.1-0.5MPa, optimum pressure are 0.2-0.3MPa; Water injection rate accounts for 〉=360 ℃ of tar (weight) 2-3%; Make≤360 ℃ of cuts and wax tailings;
(1), cuts that will 〉=360 ℃ carry out making after the delayed coking≤and 360 ℃ of cuts make with the distillation of above-mentioned distillation tower≤360 ℃ of cuts mix hydrofining, the hydrogenation transformation of the way, distill at last, make high-quality petroleum naphtha and fine-quality diesel oil component;
(2), the wax tailings that cut that will 〉=360 ℃ carries out making after the delayed coking follows also entirely, make≤distillation of 360 ℃ of cuts and above-mentioned distillation tower makes≤360 ℃ of cuts mix hydrofining, the hydrogenation transformation of the way, distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last.
Concrete result of experiment sees Table 1, table 2.
Table 1≤360 ℃ hydropyrolysis experiment result
| Hydropyrolysis experiment condition and product distribute | ||
| Test conditions | Pressure MPa | 10.0-14.0 |
| Temperature ℃ | 360-370 | |
| Air speed h-1 | 0.5-1.0 | |
| Hydrogen/oily V/V | 1200 | |
| Product distributes *％ | Gas | 0.3 |
| Generate oil | 98.7 | |
| Petroleum naphtha | 3.0 | |
| The diesel component cut | 97.0 | |
| Loss ** | 1.0 | |
Product distributes and all is as the criterion (down together) with charging; * generates oily normal temperature gas and proposes loss.
The main character of table 2 test products
| Project | Petroleum naphtha | Diesel component | 0# diesel oil salable product leading indicator |
| Boiling range scope ℃ | ＜180 | 180-360 | - |
| Close flash point ℃ | - | 70 | Be not less than 65 |
| Density g/cm3 | 0.7450 | 0.8428 | Actual measurement |
| Sulphur content μ g/g | 70 | 326 | -(top grade is not more than 0.01%) |
| Nitrogen content μ g/g | 45 | 69 | - |
| Octane value RON | 76 | - | - |
| Cetane value | 45 | Be not less than 45 | |
| Condensation point ℃ | -3 | Be not more than 0 |
Claims (6)
1, a kind of production technique of producing fuel oil from coal tar is characterized in that its production craft step is:
One, vacuum hydro-extraction: coal tar is carried out vacuum hydro-extraction;
Two, distillation cutting: dehydrated coal tar is distilled, make≤360 ℃ of cuts and 〉=360 ℃ of cuts;
(1) ,≤360 ℃ of cuts are carried out dephenolize, take off naphthalene, repeated hydrogenation is refining, the hydrogenation transformation of the way, and distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last;
(2), cuts that will 〉=360 ℃ carry out delayed coking, make≤360 ℃ of cuts and wax tailings;
(1), cuts that will 〉=360 ℃ carry out making after the delayed coking≤360 ℃ of refining, hydrogenation transformations of the way of cut fraction hydrogenation, distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last;
(2), cuts that will 〉=360 ℃ wax tailings that carries out making after the delayed coking carries out recycle to extinction, makes≤360 ℃ of cuts, repeated hydrogenation is refining, the hydrogenation transformation of the way, distillation makes high-quality petroleum naphtha and fine-quality diesel oil component at last.
2, the production technique of producing fuel oil from coal tar according to claim 1 is characterized in that vacuum hydro-extraction is the vacuum hydro-extraction of 3-4 level, and vacuum tightness is-0.082--0.095MPa that temperature is 70-80 ℃.
3, the production technique of producing fuel oil from coal tar according to claim 1 and 2 is characterized in that hydrofining, hydrogenation transformation of the way temperature of reaction are 350-400 ℃, and pressure is 8.0-15.0MPa, and liquid hourly space velocity is 0.2-3.0/h
-1, hydrogen to oil volume ratio is 800-1200: 1.
4, the production technique of producing fuel oil from coal tar according to claim 1 and 2, the coking temperature that it is characterized in that delayed coking is 490-520 ℃, and pressure is 0.1-0.5MPa, and water injection rate accounts for 〉=2-3% of 360 ℃ cut weight.
5, according to the production technique of claim 1,2 or 4 described producing fuel oil from coal tar, it is characterized in that hydrofining, two reactors in series of hydrogenation transformation of the way reaction use together, the catalyzer that reacts used is made up of catalyst for refining, protective material and modifying catalyst; Adorn catalyst for refining and/or protective material in a reactor therein, protective material is contained in the upper strata, and catalyst for refining is contained in lower floor, loads modifying catalyst in another reactor; The admission space of protective material, catalyst for refining, transformation of the way catalyzer is than being 1-2: 4-6: 3-5.
6, the production technique of producing fuel oil from coal tar according to claim 5 is characterized in that catalyst for refining is RCT-1, and protective material is RG-10A, and modifying catalyst is RIC-1.
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| CN101747925A (en) * | 2009-12-26 | 2010-06-23 | 何巨堂 | Method for coking heavy oil of coal tar |
| CN101967395A (en) * | 2010-10-18 | 2011-02-09 | 李湘平 | Method for producing clean fuel by hydrogenation of mixed oil |
| CN101979469A (en) * | 2010-11-17 | 2011-02-23 | 湖南长岭石化科技开发有限公司 | Method for removing free oxygen from inferior hydrogenation raw oil |
| CN101979470A (en) * | 2010-11-17 | 2011-02-23 | 湖南长岭石化科技开发有限公司 | Method for removing free oxygen from inferior hydrogenated feedstock oil |
| CN102161901A (en) * | 2011-03-19 | 2011-08-24 | 宝钢工程技术集团有限公司 | Coal tar alkali-free normal/reduced-pressure distillation process and device |
| CN102161909A (en) * | 2011-03-04 | 2011-08-24 | 中国科学院过程工程研究所 | Method for filling catalyst in production of fuel oil by hydrogenation of coal tar |
| CN101429456B (en) * | 2008-11-28 | 2012-04-25 | 王守峰 | Delay coking hydrogenation combined process for coal oil |
| CN102465033A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
| CN101307257B (en) * | 2007-05-16 | 2012-06-27 | 中国石油化工股份有限公司 | Coal tar hydrogenating modified method by two-stage method |
| CN102533332A (en) * | 2012-01-11 | 2012-07-04 | 中国科学院过程工程研究所 | Method for comprehensively using all fractions produced through hydrogenation combined with delayed coking on coal tar |
| CN101724461B (en) * | 2009-12-07 | 2012-10-03 | 中国科学院山西煤炭化学研究所 | Method for processing coal tar of productive, lightweight and clean fuel oil though catalytic hydrogenation |
| CN101475817B (en) * | 2008-12-18 | 2012-11-28 | 中冶焦耐工程技术有限公司 | Distillate dephenolizing process and apparatus thereof |
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| CN101429456B (en) * | 2008-11-28 | 2012-04-25 | 王守峰 | Delay coking hydrogenation combined process for coal oil |
| CN101475817B (en) * | 2008-12-18 | 2012-11-28 | 中冶焦耐工程技术有限公司 | Distillate dephenolizing process and apparatus thereof |
| CN101724461B (en) * | 2009-12-07 | 2012-10-03 | 中国科学院山西煤炭化学研究所 | Method for processing coal tar of productive, lightweight and clean fuel oil though catalytic hydrogenation |
| CN101747925A (en) * | 2009-12-26 | 2010-06-23 | 何巨堂 | Method for coking heavy oil of coal tar |
| CN101967395A (en) * | 2010-10-18 | 2011-02-09 | 李湘平 | Method for producing clean fuel by hydrogenation of mixed oil |
| CN102465033B (en) * | 2010-11-04 | 2015-02-18 | 中国石油化工股份有限公司 | Processing method of medium-low temperature coal tar |
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| CN101979469B (en) * | 2010-11-17 | 2013-05-15 | 湖南长岭石化科技开发有限公司 | Method for removing free oxygen from inferior hydrogenation raw oil |
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| CN102533332A (en) * | 2012-01-11 | 2012-07-04 | 中国科学院过程工程研究所 | Method for comprehensively using all fractions produced through hydrogenation combined with delayed coking on coal tar |
| CN102863986A (en) * | 2012-09-27 | 2013-01-09 | 大连理工大学 | Coal tar hydrogenation upgrading method |
| CN102876376A (en) * | 2012-09-27 | 2013-01-16 | 大连理工大学 | Method for improving hydrogenation production of gasoline and diesel oil by coal tar |
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