CN104449843A - Step-by-step cracking and hydrogen-present coking process for coal tar - Google Patents
Step-by-step cracking and hydrogen-present coking process for coal tar Download PDFInfo
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- CN104449843A CN104449843A CN201310452684.4A CN201310452684A CN104449843A CN 104449843 A CN104449843 A CN 104449843A CN 201310452684 A CN201310452684 A CN 201310452684A CN 104449843 A CN104449843 A CN 104449843A
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- coal tar
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a technical method for optimal utilization for medium-temperature and low-temperature coal tar resources. The method is capable of remarkably improving a coal tar processing process and improving the liquid yield. The method disclosed by the invention aims at abundantly utilizing the characteristics of coal tar, carrying out differentiation treatment, and optimizing the coal tar processing process. The coal tar processing process disclosed by the invention comprises coal tar step-by-step cracking, light-component pre-separation and hydrogen-present coking. Coal tar is conveyed to the convection section of a heating furnace for heating at first, and then enters a cracking reactor for a preliminary cracking reaction, and components easy to crack are cracked to generate light components, and the light components enter a fractionation tower from the top of the reactor with light components in coal tar; heavy components in the reactor are mixed with oil generated at the bottom of the fractionation tower and then conveyed into the radiation section of the heating furnace by a pump for further heating, and then enters a coke tower for a hydrogen-present coking reaction, so as to generate oil gas and coke; hydrogen is injected in the inlet of the radiation section. The oil gas generated by the reaction enters the fractionation tower for separation, so as to obtain gasoline, diesel and wax oil components, the components are conveyed for hydrogenation, and a rich gas can be used for hydrogen production or used as a fuel for the heating furnace. The method is reasonable in process, high in liquid yield and low in energy consumption compared with the prior art.
Description
Technical field
The present invention relates to a kind of technological method of tar resource Optimum utilization.The method significantly can improve coal tar processing, improves liquid and receives.
Background technology
Traditional coal tar processing delayed coking pretreatment technology adopts conventional residual oil delayed coking complete processing.
Delay coking of coal tar pretreatment technology adopts conventional residual oil complete processing, does not utilize coal tar characteristic well, carries out differential process.Major defect has: 1. part easily cracking, condensation component first do not carry out low-temp reaction, together enter process furnace radiation section, easily cause tube coking, affect long-term operation; 2. light constituent is not separated and all enters process furnace, and energy consumption is high; 3. because coal tar is rich in oxygen, in cracking, condensation course, part becomes water, and hydrogen valuable in coal tar is reduced further; 4. adopt process furnace water filling (or steam) technique, because hydro-thermal enthalpy is higher, energy consumption is high; 5. in coal tar, light constituent component is not separated in advance and together enters process furnace and coke drum, and the at high temperature generating portion cracking of part light constituent produces rich gas, and hydrogen component natively little in coal tar is reduced further, reduces liquid simultaneously and receives;
Due to China's oil shortage of resources, degree of dependence on inport is high, and coal liquifaction, under soaring oil prices background, becomes new focus.In order to improve the utilising efficiency of coal tar, alleviate energy contradiction, coal tar processing improves and seems more and more urgent.For coal tar, find reasonable complete processing according to its characteristic, increase operation rate, energy-saving and cost-reducing particularly important.
Chinese patent CN1485404A is open introduces process furnace with coal tar being preheated to coalite tar in 300-380 DEG C, coke drum is entered after process furnace is heated to 480-550 DEG C, pyrogenic reaction is carried out under the pressure of 0.8-2.0Mpa, the coke generated in coke drum discharges coke drum, generation oil after coking enters extraction tower, alkaline solution is added in extraction tower, the aldehydes matter extracted goes out extraction tower, extract the fraction oil after aldehydes matter and enter separation column, isolate light hydrocarbon material, petroleum naphtha and diesel oil blending component that carbon chain lengths is less than 5 respectively.
Chinese patent CN1664068A is open enters coke drum with by coal tar after process furnace is heated to 500-520 DEG C, carries out pyrogenic reaction, through oil fuel, liquefied gas and coke that coking obtains under the pressure of 0.22-0.26Mpa.Adopt full cut delay coking process.
Chinese patent CN101429456A invention provides the combined technical method of a kind of delay coking of coal tar and hydrogenation.This invention adopts the method for delayed coking and hydrogenation to coal tar, and carry out delayed coking, hydrogenation and rear refining, hydrogenation comprises hydrotreatment, hydrofining and hydrocracking.The key of this invention utilizes delayed coking and hydrogenation combination technique technology, and the processing condition of adjustment delayed coking and hydrogenation technique, realize the final purpose of coal tar upgrading.
But the technology adopted disclosed in above-mentioned patent does not make full use of coal tar characteristic, carries out differential process.
Summary of the invention
The object of the invention is to the deficiency overcoming above-mentioned prior art, provide a kind of and technology is utilized to coal tar processing optimization.
Compared with vacuum residuum, middle coalite tar complicated components, distribution are wide, and ratio of carbon-hydrogen is high, is rich in oxygen, and light constituent is high, component physical properties and the chemical reactivity such as cracking, condensation difference large.
The object of the invention makes full use of coal tar characteristic, carries out differential process, optimizes coal tar processing.Coal tar processing of the present invention, comprises coal tar substep cracking, light constituent and is separated in advance and faces hydrogen coking.
The cracking of coal tar provided by the invention substep, face hydrogen coking process and comprise the steps:
1. first coal tar is delivered to process furnace convection zone and be heated to 200 ~ 350 DEG C, enter cracking reactor and carry out preliminary scission reaction, reactor operating pressure is: 0.05 ~ 0.5MPa;
2. the easy cracking group that 1. step obtains divide cracking produce comparatively in light constituent and coal tar light constituent enter separation column from reactor head;
3. the heavy constituent furnace charge that 1. step obtains is pumped into process furnace radiation section and is heated to 350 ~ 480 DEG C further, and 0.1 ~ 0.5MPa enters coke drum and carries out pyrogenic reaction, recycle ratio: 0.1 ~ 0.6, generates oil gas and coke;
4. inject hydrogen (recycle hydrogen that hydrogenation unit comes) at radiation section entrance, hydrogen injecting tolerance is 0.1 ~ 0.5% (m) of inlet amount;
5. the oil gas reacting generation enters separation column and is separated, and obtains gasoline, diesel oil, wax oil component send downstream hydrogenation device, and rich gas can be used for hydrogen manufacturing or as furnace fuel.
As the technical scheme optimized further, in described cracking reactor, preliminary scission reaction is temperature prioritised is 280 ~ 350 DEG C, and reaction pressure is preferably 0.1 ~ 0.3MPa; In order to reach better separating effect, cracking reactor middle and lower part arranges tower tray; Described furnace outlet is temperature prioritised is 440 ~ 470 DEG C, and coke drum pyrogenic reaction pressure is preferably 0.1 ~ 0.3MPa, and recycle ratio is preferably 0.2 ~ 0.4, and hydrogen injecting tolerance is preferably 0.1 ~ 0.3% (m) of inlet amount;
Core of the present invention is the cracking of employing substep, light constituent is first separated and faces hydrogen coking.Make full use of coal tar characteristic and carry out differential process, the part easily advanced row low temperature pyrolyzer reaction of cracking component, control temperature simultaneously, does not allow easy condensation component generation condensation reaction wherein generate coke.Cracking group easy in coal tar is divided cracking produce comparatively in light constituent and coal tar light constituent enter separation column from reactor head, under avoiding this part cut high temperature on the one hand, deep pyrolytic produces rich gas, reduces gas phase yield, increases liquid and receives; Effectively reduce process furnace load on the other hand, energy efficient.
Inject hydrogen (recycle hydrogen that hydrogenation unit comes) at radiation section entrance, first improve heating furnace tube flow velocity, prevent tube coking, secondly reduce oil gas dividing potential drop, light constituent is easily gasificated into oil gas, and the 3rd reduces coal tar dehydrogenation carburizing reagent, reduce coke yield, improve liquid and receive.In addition, because coal tar is rich in oxygen, in cracking, condensation reaction, generate water, hydrogen valuable in coal tar is reduced further.Under hydro condition, part oxygen enrichment and hydrogen reaction, can effectively reduce hydrogen loss in coal tar.Compared with water filling (water vapour), hydrogen heat content is low, and the thermal load that heating, cooling need is less, energy-conservation.Comparatively prior art not only has rational technology, liquid receipts are high, energy consumption is low; And auxiliary material hydrogen of the present invention is the recycle hydrogen from hydrogenation unit, cheap, does not need special process, reduces cost.
Adopt the present invention to increase liquid receipts principle as follows: to inject hydrogen at radiation section, reduce coal tar dehydrogenation carburizing reagent, reduce coke yield, improve liquid receipts; In coal tar, light constituent is separated from cracking reactor, and after avoiding this part cut to enter process furnace, coke drum, at high temperature cracking produces rich gas, reduces gas phase yield, increases liquid and receives.
Adopt energy-saving principle of the present invention as follows: in coal tar, light constituent is separated from cracking reactor, furnace charge amount reduces, and effectively reduces process furnace load; Process furnace changes note hydrogen, and compared with water filling (water vapour), hydrogen heat content is low, and the thermal load that heating, cooling need is less, energy efficient.
Accompanying drawing explanation
Fig. 1 is coalite tar substep cracking in the present invention, faces the schema of hydrogen coking process.
In figure, code name illustrates: 1-coal tar/product interchanger; 2-cracking reactor; 3-furnace charge pump; 4-process furnace; 5-coke drum; 6-circulating oil pump; 7-separation column; 8-fractionation overhead condenser; 9-separation column top knockout drum
Embodiment
Fig. 1 is coalite tar substep cracking in the present invention, faces the schema of hydrogen coking process.Coal tar enters process furnace 4 convection zone after coal tar-product interchanger 1 heat exchange, through flue gas heating to 200 ~ 350 DEG C, enter under 0.05 ~ 0.5MPa in cracking reactor 2 and carry out preliminary scission reaction, easy cracking group divide cracking produce comparatively in light constituent and coal tar light constituent enter separation column 7 from reactor head; In reactor 2, heavy constituent is sent into process furnace 4 radiation section through furnace charge pump 3 and is heated to 350 ~ 500 DEG C further, enters coke drum 5 and carry out pyrogenic reaction under 0.1 ~ 0.5MPa, generates oil gas and coke; Hydrogen (the high recycle hydrogen of assigning to of hydrogenation unit) is injected at radiation section entrance.The oil gas that reaction produces enters separation column 7 and is separated, and obtains diesel oil, wax oil component, and separation column ejects the oil gas come and obtains gasoline and rich gas through overcooling, separation.
Table 1 stock oil character
| Character | Unit | Stock oil |
| Proportion d 20 4 | Kg／m 3 | 1034 |
| Sulfur-bearing | m％ | 0.16 |
| Carbon residue | m％ | 5.0 |
| Ash content | m％ | 0.038 |
| Bituminous matter | m％ | 0.6 |
| Colloid | m％ | 73 |
| Stable hydrocarbon | m％ | 9 |
| Aromatic hydrocarbon | m％ | 17.4 |
Table 2 operational condition table
| Sequence number | Operational condition | Embodiment 1 | Remarks |
| 1 | Scission reaction actuator temperature, DEG C | 340 | |
| 2 | Furnace outlet temperature, DEG C | 470 | |
| 3 | Coke column bottom temperature, DEG C | 463 | |
| 4 | Top of coke tower pressure, Mpa | 0.17 | |
| 5 | Top of coke tower temperature, DEG C | 420 | |
| 6 | Recycle ratio | 0.4 | |
| 7 | Note amounts of hydrogen, % | 0.25 |
Table 2 material balance table
Claims (6)
1. coal tar substep cracking, face a hydrogen coking process, make full use of coal tar characteristic, carry out differential process, optimize coal tar processing.Coal tar processing of the present invention, comprises coal tar substep cracking, light constituent and is separated in advance and faces hydrogen coking.It is characterized in that comprising the steps:
1. first coal tar is delivered to process furnace convection zone and be heated to 200 ~ 350 DEG C, enter cracking reactor;
2. in the coal tar that 1. obtains of step, comparatively light constituent enters separation column from cracking reactor top;
3. in the coal tar that 1. obtains of step, heavy constituent furnace charge is pumped into process furnace and is heated to 350 ~ 480 DEG C further, and 0.1 ~ 0.5MPa enters coke drum and carries out pyrogenic reaction, recycle ratio: 0.1 ~ 0.6, generates oil gas and coke;
4. inject hydrogen (recycle hydrogen) at process furnace radiation section entrance, hydrogen injecting tolerance is 0.1 ~ 0.5% (m) of inlet amount;
5. the oil gas that the reaction that 3., 4. obtains of step produces enters separation column and is separated, and obtains diesel oil, wax oil component send hydrogenation unit to produce oil fuel;
6. the tower top oil gas that 5. step obtains enters fractionation tower top catch pot carry out oil, gas, water separation through separation column head space cooler, water cooler cooling, and gasoline is extracted out by petrol-feed pump and sent hydrogenation unit to produce oil fuel;
7. generate oil at the bottom of the tower that 5. obtains of step after recycle pump boosting, to turn back to stock oil feeding line mix with coal tar, enter cracking reactor.
2. coal tar according to claim 1 substep cracking, face hydrogen coking process, it is characterized in that coal tar delivers to the heating of process furnace convection zone, enter cracking reactor, first carry out preliminary cracking; It is 280 ~ 350 DEG C that cracking reactor temperature of reaction is preferably, and it is 0.1 ~ 0.3MPa that reaction pressure is preferably.
3. coal tar according to claim 1 substep cracking, face hydrogen coking process, it is characterized in that first separating and cracking produces comparatively light constituent, then coking in light constituent and coal tar.
4. coal tar according to claim 1 substep cracking, face hydrogen coking process, it is characterized in that injecting hydrogen (recycle hydrogen that hydrogenation unit comes) at radiation section entrance, hydrogen injecting tolerance is preferably 0.1 ~ 0.3% (m) of inlet amount.
5. coal tar according to claim 1 and 2 substep cracking, face hydrogen coking process, it is characterized in that furnace outlet is temperature prioritised for being 440 ~ 470 DEG C, it is 0.1 ~ 0.3MPa that top of coke tower pressure is preferably, and recycle ratio is preferably 0.2 ~ 0.5.
6. coal tar according to claim 1 substep cracking, face hydrogen coking process, it is characterized in that generating oil at the bottom of tower returns cracking reactor, is mixed into process furnace with coal tar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310452684.4A CN104449843A (en) | 2013-09-17 | 2013-09-17 | Step-by-step cracking and hydrogen-present coking process for coal tar |
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| CN201310452684.4A CN104449843A (en) | 2013-09-17 | 2013-09-17 | Step-by-step cracking and hydrogen-present coking process for coal tar |
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| CN104449843A true CN104449843A (en) | 2015-03-25 |
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| CN201310452684.4A Pending CN104449843A (en) | 2013-09-17 | 2013-09-17 | Step-by-step cracking and hydrogen-present coking process for coal tar |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541247A (en) * | 2017-10-04 | 2018-01-05 | 山东胜星化工有限公司 | A kind of sump oil continues uninterrupted freshening device |
| CN113897208A (en) * | 2021-10-09 | 2022-01-07 | 重庆三峡学院 | Method for circularly pyrolyzing tar |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394250A (en) * | 1982-01-21 | 1983-07-19 | Chevron Research Company | Delayed coking process |
| US4443325A (en) * | 1982-12-23 | 1984-04-17 | Mobil Oil Corporation | Conversion of residua to premium products via thermal treatment and coking |
| CN101597518A (en) * | 2009-06-25 | 2009-12-09 | 中国石油化工集团公司 | A kind of improved delay coking process |
| 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 |
-
2013
- 2013-09-17 CN CN201310452684.4A patent/CN104449843A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394250A (en) * | 1982-01-21 | 1983-07-19 | Chevron Research Company | Delayed coking process |
| US4443325A (en) * | 1982-12-23 | 1984-04-17 | Mobil Oil Corporation | Conversion of residua to premium products via thermal treatment and coking |
| CN101597518A (en) * | 2009-06-25 | 2009-12-09 | 中国石油化工集团公司 | A kind of improved delay coking process |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541247A (en) * | 2017-10-04 | 2018-01-05 | 山东胜星化工有限公司 | A kind of sump oil continues uninterrupted freshening device |
| CN113897208A (en) * | 2021-10-09 | 2022-01-07 | 重庆三峡学院 | Method for circularly pyrolyzing tar |
| CN113897208B (en) * | 2021-10-09 | 2023-01-10 | 重庆三峡学院 | Method for circularly pyrolyzing tar |
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Address after: Hangzhou road in Baohe District of Hefei city in Anhui province 230091 and Tibet road junction of the northeast corner of the Binhu Times Square building C3 No. 1301 Applicant after: ANHUI SHIHUA ENGINEERING & TECHNOLOGY CO., LTD. Address before: 246002 No. 8, No. 1, oil production road, Anqing, Anhui Applicant before: ANHUI SHIHUA ENGINEERING & TECHNOLOGY CO., LTD. |
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Application publication date: 20150325 |