CN101429456B - Delay coking hydrogenation combined process for coal oil - Google Patents
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- CN101429456B CN101429456B CN2008102095585A CN200810209558A CN101429456B CN 101429456 B CN101429456 B CN 101429456B CN 2008102095585 A CN2008102095585 A CN 2008102095585A CN 200810209558 A CN200810209558 A CN 200810209558A CN 101429456 B CN101429456 B CN 101429456B
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Abstract
The invention provides a combined technique for delayed coking and hydrogenation of coal tar. The combined technique adopts the delayed coking and hydrogenation method to perform delayed coking, hydrogenation and final refining on the coal tar, wherein the hydrogenation process comprises hydrotreating, hydrorefining and hydrocracking; and liquefied gas, fuel oil and lube base oil are finally obtained. The key point of the combined technique is to utilize the combined technique of delayed coking and hydrogenation to adjust the technological conditions of the delayed coking technology and the hydrogenation technology, so as to realize final aim of modification of the coal tar. The combined technique converts the coal tar with low value and high pollution into clean and superior liquefied gas, gasoline, diesel fuel, lube and so on, improves the added value of products, and reduces environmental pollution.
Description
(1) technical field
What the present invention relates to is coal chemical technology, the combination process of specifically a kind of delay coking of coal tar and hydrogenation.
(2) background technology
Coal tar is one of product of coal coking and gas maked coal, and coal tar is produced the research of oil fuel products such as gasoline, diesel oil through deep processing method, once receives much attention and drops into substantial contribution and manpower studies in the twentieth century 50-60 age.Because China is in grand celebration, ground such as Xinjiang are found and the recovery of subterranean oil, the motor spirit that petroleum products has replaced gelatin liquefaction, gasification and coking to produce as main energy sources very soon.From twentieth century seventies; China produces the research of oil fuel products such as the gasoline, diesel oil of high-quality environment-friendly type and almost nobody shows any interest in to coal tar deep processing; Until twentieth century end of the nineties, since the raising of environmental consciousness, the raising of oil Refining Technologies; People are to the raising of the understanding of petroleum resources, and the comprehensive utilization of coal and coal tar is just paid attention to by the knowledgeable people again.
At present; The needed coke major part of domestic steel-making enterprise is from the coal coking plant; Process of coking can produce a large amount of tar; The domestic in addition coking plant that many gasification plants and production semicoke are arranged, but also different according to the different by-product coal tar of the tar content oil mass of coal, coal tar output is more in the factory below 50,000 tons/year.The coal tar part of these coking plants and gasification plant by-product is directly burnt as low-quality fuel oil behind acid-alkali refining at present; Or directly burn as emulsion fuel after the emulsification; Impurity such as institute's sulfur-bearing, nitrogen become sulphur and nitrogen oxides and discharge into the atmosphere and cause topsoil in combustion processes; And produce large amount of sewage in the acid-alkali refining process again, and a part is behind acid-alkali refining, and extraction separation is burnt or is used as heating and culinary art after going out chemical substances such as phenol, naphthalene.So wherein impurity such as institute's sulfur-bearing, nitrogen become sulphur and nitrogen oxides is discharged into the atmosphere in combustion processes, cause topsoil, and coal combustion process also causes dust pollution.With the coal is that the raw material production town gas is increasingly high as the ratio of domestic fuel; The coal tar oil mass of association simultaneously also rolls up, and the China's oil inadequate resource, and the crude oil import ratio increases year by year; With coal tar is raw oil; Adopt suitable processing means production clean fuel or the petroleum products suitable, not only have remarkable economic efficiency, also have obvious social simultaneously with petroleum products.
(3) summary of the invention
The object of the present invention is to provide and a kind ofly can the coal tar of low value, high pollution be changed into cleaning, fine liquefied gas, gasoline, diesel oil, lubricated wet goods; Improve value-added content of product, reduced the delay coking hydrogenation combined process for coal oil of environmental pollution.
The objective of the invention is to realize like this: the method that coal tar is adopted delayed coking and hydrogenation; It is refining to carry out delayed coking, hydrogenation and back; Hydrogenation comprises hydrotreatment, unifining and hydrogen cracking, obtains liquefied gas, oil fuel and lubricant base at last.
The present invention also has some technical characterictics like this:
1, described coal tar is meant that coal is in gasification, coking or produce low temperature 500-700 ℃ of producing in the semicoke process, middle temperature 700-900 ℃ and high temperature 900-1100 ℃ coal tar;
2, described coal tar is the coal tar heavy duty fraction greater than a certain temperature section of 300 ℃ or 350 ℃ as the delayed coking charging, or without the full fraction of coal tar of any processing;
3, the reaction pressure of described delayed coking is at 0.1--3.0Mpa, and temperature is between 450--550 ℃;
4, the pressure of described hydrogenation reaction is at 6.0--20.0Mpa, and temperature is between 300--450 ℃;
5, described hydrogenation comprise coker gasoline, coker gas oil and wax tailings that the delayed coking of coal tar obtains mix the back as the raw material of hydrogenation or coker gasoline, coker gas oil and wax tailings separately respectively as the raw material of hydrogenation;
6, described hydrocracking process is single pass or part circulation or recycle to extinction, or one-part form or two-part hydrocracking process;
7, described delay coking hydrogenation combined process for coal oil step is: the coal tar that will be preheating to 300-400 ℃ is sent into process furnace; After process furnace is heated to 450-550 ℃, get into coke drum, under the pressure of 0.1-3.0Mpa, carry out pyrogenic reaction, obtain refinery coke as product; Obtain coker gasoline, coker gas oil and wax tailings simultaneously; Then coker gasoline, coker gas oil and wax tailings are mixed the back or respectively separately as the raw material of hydrogenation, will mixed or respectively independent hydrogenating materials introducing process furnace and mix with hydrogen, then under 6.0-20.0MPa, 300-450 ℃; Single pass successively; Or tail oil partly circulates or whole circulation of tail oil is equipped with hydrotreatment, unifining and the hydrocracking reactor of catalyzer, obtains hydrogenated oil, gets into separation column and stabilizer tower again; Obtain liquefied gas, oil fuel and lubricant base through fractionation, stabilizing technical processes.
The present invention is to provide the combination process of a kind of delay coking of coal tar and hydrogenation, obtain oil fuel and lubricant bases such as liquefied gas, gasoline, diesel oil at last.The present invention changes into cleaning, fine liquefied gas, gasoline, diesel oil, lubricated wet goods with the coal tar of low value, high pollution, has improved value-added content of product, has reduced environmental pollution.
The present invention is a target with resource comprehensive utilization rationally and environmental protection, utilizes petroleum refining industry's modern technologies to the transplanting of the coal chemical technology property improved, and yields products of quality with coal tar, improves the utility value of coal tar, the protection environment.Key of the present invention is to utilize delayed coking and hydrogenation combination technique technology, the processing condition of adjustment delayed coking and hydrogenation technique, the final purpose of realization coal tar upgrading.
Because coal tar comes from coal coking and gasification retort section, is the thermally splitting product.The coal tar oil properties is very complicated, and their chemical constitution mainly is an aromatics, and alkane and olefin(e) centent are less, and aromatic hydrocarbons, colloid, bituminous matter, heavy metal content height also contain a certain amount of oxygen, nitrogenous, sulfocompound of containing.Oxygenatedchemicals mainly is to have weakly acidic various corresponding phenolic, and nitrogenous compound mainly is to have weakly alkaline pyridine, and quinoline and their verivate, sulfocompound mainly are thiophene, mercaptan, thiophenol, thioether, thia indenes etc.
According to above coal tar oil properties, the present invention carries out delayed coking with coal tar earlier, and two types of reactions mainly take place: one type is scission reaction, and another kind of is condensation reaction.Alkane is under heating condition, and principal reaction is a scission reaction, the at first less C-C key place fracture of bond energy in molecule, and its reaction product is less an alkane and olefin hydrocarbon molecules of molecular weight.Naphthenic hydrocarbon and aromatic hydrocarbon thermally-stabilised higher, temperature reaches 500 ℃ under normal pressure--and in the time of 600 ℃, five members, six membered rings are broken into two olefin hydrocarbon molecules, and benzene begins to take place cracking and condensation reaction, and product mainly is biphenyl, gas and coke.Polycyclic aromatic hydrocarbons, similar with benzene like the thermal conversion reaction of naphthalene, anthracene etc., at high temperature generating with hydrogen is main gas, polymer condenses and coke.Alkyl group side chain on naphthenic hydrocarbon and the aromatic hydrocarbon generation alkene that at high temperature ruptures.The coal tar pyrolytic reaction is except that following general hydrocarbon reaction mechanism; The response characteristic that also has self; The polycondensation under the effect of heat of bituminous matter in the coal tar is converted into coke, when generating coke, with the most heavy metal depositions in the coal tar in coke; Coking behind the final process delayed coking reaction generates oil difference by the cut temperature in coking fractional distillation column and is cut into coker gasoline, coker gas oil and wax tailings; These three kinds oil mix the raw oil of back as hydrogenation, and its character has been compared with coal tar and improved significantly, but the content of non-hydrocarbons materials such as sulfide wherein, nitride, oxide compound can't satisfy the requirement of processed oil; Carry out unifining and hydrogen cracking so again; Under temperature, pressure, catalyzer and hydro condition, the sulfide in the coking generation oil, nitride, oxide compound react with hydrogen respectively and generate hydrogen sulfide, ammonia and water, and the macromolecule hydrocarbon of aromatic hydrocarbons and long-chain is then distinguished micromolecular hydro carbons saturated and cracking generation naphthenic hydrocarbon and short chain; In separation column, fractionate out cleaning, fine gasoline and diesel product at last, finally reach the purpose of upgrading.
Delay coking of coal tar hydrogenation combination technique of the present invention is the important technology of tar resource comprehensive utilization technique; The tar resource comprehensive utilization that is not merely China provides new working method and thinking; And make the processing tar resource have remarkable economic efficiency; Simultaneously environment protection is also had great importance, coal tar of the present invention is meant low temperature, middle temperature and the coal-tar heavy oil that coal produces in gasification, coking or production semicoke process.
The contriver is with for many years in the working experience of coal chemical technology and responsive technological consciousness; Domestic and international present situation is carried out analysis-by-synthesis; After carrying out scientific forecasting future; Delay coking of coal tar and hydrogenation production environmentally friendly machine are carried out integrated technology exploitation, the patented technology of having invented delay coking of coal tar and hydrogenation combination technique.The present invention relates to delay coking of coal tar and hydrogenation technique; Comprehensive utilization to tar resource is especially significant to environment protection; Its essence is with delayed coking and hydrocracking process and be the basis; Through engineering development, suitable delayed coking of research and hydrocracking condition are realized removing the component of environmental pollutions such as coal tar oxide compound, sulfide, nitride, colloid, bituminous matter and heavy metal; The liquefied gas of production high-quality simultaneously, environmental protection, oil fuel and lubricant bases such as gasoline, diesel oil.
(4) description of drawings
Fig. 1 is a process flow diagram of the present invention.
(5) embodiment
For example the present invention is further described below:
In conjunction with Fig. 1; After will being preheated to 300-400 ℃ coal tar 13 delayed coking heaters 1 and being heated to 450-550 ℃, present embodiment gets into coke drum 2; Generation oil after pyrogenic reaction gets into delayed coker fractionator 3, fractionates out coker gasoline 15, coker gas oil 16, the middle mixing tank 4 of wax tailings 17 entering.In operation the pressure-controlling of coke drum is at 0.28Mpa, and temperature is controlled between 450--550 ℃, and two coke drums be the one-period blocked operation by 18 hours or 24 hours, and during a normal charging, another is removed charcoal and grasps 19.Simultaneously isolate fuel gas 14, after desulfurization, get into the fuel gas pipe net, isolate the inlet that turning oil 18 turns back to delay coking heating furnace 1 in the bottom of coking fractional distillation column 3 on the top of coking fractional distillation column 3.
Coker gasoline 15, coker gas oil 16, wax tailings 17 mix the raw material 20 of back as hydrogenation in middle mixing tank 4; Through unifining process furnace 5 heating and with entering hydrofining reactor 6 after fresh hydrogen 21 is mixed; In hydrofining reactor 6, Hydrobon catalyst is housed, and control reaction stagnation pressure 15.0Mpa, 350 ℃ of average reaction temperature; Hydrogen to oil volume ratio 800:1, volume space velocity 1.2h
-1Sulfide, nitride and oxide compound in the hydrogenating materials oil 20 generates hydrogen sulfide, ammonia and water after heat exchange gets into unifining HP separator 7 with hydrogen reaction respectively like this; Isolate circulating hydrogen 22 Returning reactors; Isolate and generate oil entering hydrogenation refining fractionation tower 8, isolate gasoline 24, diesel oil 25 and refining tail oil according to the difference of cut temperature.
Refining tail oil through 9 heating of hydrogen cracking process furnace and with entering hydrocracking reactor 10 after fresh hydrogen 21 is mixed; In hydrocracking reactor 10, hydrocracking catalyst is housed, and control reaction stagnation pressure 15.0Mpa, 370 ℃ of average reaction temperature; Hydrogen to oil volume ratio 1000:1, volume space velocity 1.8h
-1The macromolecule hydrocarbon compound of the long-chain in the refining like this tail oil and arene compounds are under the effect of hydrocracking catalyst; The macromolecule hydrocarbon compound of long-chain becomes the micromolecular compound of short chain, and arene compounds is further saturated and open loop also, has so all become micromolecular gasoline and diesel oil; After heat exchange, get into hydrogen cracking HP separator 11 then; Isolate circulating hydrogen 22 Returning reactors, isolate and generate oil entering hydrogen cracking separation column 12, isolate gasoline 24, diesel oil 25 and circulation tail oil 26 according to the difference of cut temperature.Unconverted circulation tail oil 26 turns back to hydrocracking reactor 10 further crackings again, finally all is converted into gasoline and diesel oil.Different with the production purpose for example the main character of certain coal tar is seen table 1 to delayed coking hydrogenation combination technique of the present invention and different according to raw material, and the purpose product is gasoline and diesel oil.Processing condition are seen table 2, and the product main character is seen table 3.
Table 1 coal tar main character
Table 2 processing condition
Table 3 product main character
| Analysis project | Gasoline | Diesel oil |
| The cut scope, ℃ | <180 | 180～360 |
| Density, g/cm 3(20℃) | 0.7520 | 0.8537 |
| Boiling range, ℃ | ||
| IBP/10％ | 68/102 | 185/228 |
| 30％/50％ | 115/125 | 246/281 |
| 70％/90％ | 139/164 | 312/336 |
| 95％/EBP | 173/182 | 344/351 |
| Flash-point, ℃ | 80 | |
| Condensation point, ℃ | -15 | |
| Carbon residue, m% | <0.01 | |
| Octane value (MON) | 80.6 | |
| Cetane value | 44.5 | |
| Cetane index | 46.5 | |
| Mass spectrum is formed, % | ||
| Alkane | 9.4 | 30.6 |
| Naphthenic hydrocarbon | 80.0 | 26.6 |
| Aromatic hydrocarbons | 10.6 | 42.8 |
| Virtue is dived | 82.6 |
Claims (4)
1. delay coking hydrogenation combined process for coal oil; It is characterized in that process method is coal tar to be adopted the method for delayed coking and hydrogenation; It is refining to carry out delayed coking, hydrogenation and back; Hydrogenation comprises unifining and hydrogen cracking, obtains liquefied gas, oil fuel and lubricant base at last, and described hydrogenation comprises that coker gasoline, coker gas oil and wax tailings that the delayed coking of coal tar obtains mix the raw material of back as hydrogenation.
2. a kind of delay coking hydrogenation combined process for coal oil according to claim 1 is characterized in that described coal tar is meant that coal is in gasification or produce low temperature 500-700 ℃ of producing in the semicoke process, middle temperature 700-900 ℃ and high temperature 900-1100 ℃ coal tar.
3. a kind of delay coking hydrogenation combined process for coal oil according to claim 1; It is characterized in that described coal tar is the full fraction of coal tar without any processing as the delayed coking charging; The reaction pressure of described delayed coking is at 0.1-3.0Mpa, and temperature is between 450--550 ℃.
4. a kind of delay coking hydrogenation combined process for coal oil according to claim 1; It is characterized in that described delay coking hydrogenation combined process for coal oil step is: the coal tar that will be preheating to 300-400 ℃ is sent into process furnace; After process furnace is heated to 450-550 ℃, get into coke drum, under the pressure of 0.1-3.0Mpa, carry out pyrogenic reaction, obtain refinery coke as product; Obtain coker gasoline, coker gas oil and wax tailings simultaneously; Then coker gasoline, coker gas oil and wax tailings are mixed the back and introduce process furnace and mix with hydrogen, then under 6.0-20.0MPa, 300-450 ℃, unifining and hydrocracking reactor successively through catalyzer is housed; Obtain hydrogenated oil; Get into separation column and stabilizer tower again, obtain liquefied gas, oil fuel and lubricant base through fractionation, stabilizing technical processes.
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Cited By (1)
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| CN102863988B (en) * | 2011-07-07 | 2014-10-22 | 中国石油化工股份有限公司 | Coal tar combined machining method |
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| CN101691928B (en) * | 2009-10-14 | 2012-11-07 | 洛阳香江万基铝业有限公司 | Method for using coal tar as starting ignition fuel of pulverized coal firing boiler |
| CN102337144A (en) * | 2010-07-20 | 2012-02-01 | 陕西煤业化工集团神木天元化工有限公司 | Method for preparing light fuel from medium and low-temperature coal tar generated by carbonizing lump coal |
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| CN102863986A (en) * | 2012-09-27 | 2013-01-09 | 大连理工大学 | Coal tar hydrogenation upgrading method |
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| CN105713630A (en) * | 2016-03-31 | 2016-06-29 | 陕西煤业化工集团神木天元化工有限公司 | Coal carbonization, oil-gas washing separation and delayed coking combined technology and device |
| CN106362789A (en) * | 2016-09-30 | 2017-02-01 | 过冬 | Delayed-coking, hydrofining and catalytic-cracking combined technology |
| CN111718738B (en) * | 2020-06-30 | 2021-06-29 | 葛霖 | Coke oven hydrogen utilization method and system |
| CN117844525A (en) * | 2024-03-07 | 2024-04-09 | 陕西煤业化工集团神木天元化工有限公司 | Method for preparing chemicals and special fuel from medium-temperature coal tar |
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Effective date of registration: 20150619 Address after: 719319 Shenmu Tianyuan Chemical Industry Co., Ltd., Shaanxi coal chemical industry group, Shenmu Industrial Zone, Shenmu City, Shaanxi, Yulin Patentee after: Shaanxi Coal and Chemical Industry Group Shenmu Tianyuan Chemical Industry Co., Ltd. Address before: 719319 brocade Industrial Zone, Shenmu county, Shaanxi Province Patentee before: Wang Shoufeng Patentee before: Qiao Chui Patentee before: Qi Xiangpu Patentee before: Zhang Xiaodong Patentee before: Guan Jintao |