CN1119388C - Thermocracking process for heavy oil - Google Patents
Thermocracking process for heavy oil Download PDFInfo
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- CN1119388C CN1119388C CN 98117809 CN98117809A CN1119388C CN 1119388 C CN1119388 C CN 1119388C CN 98117809 CN98117809 CN 98117809 CN 98117809 A CN98117809 A CN 98117809A CN 1119388 C CN1119388 C CN 1119388C
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Abstract
The present invention relates to a thermal cracking process for heavy oil, which combines a delayed coking process and a moderate thermal cracking process, namely that coking oil gas generated by delayed coking in one-way or cyclic procedure is fractionated so as to obtain coking wax oil, the obtain coking wax oil enters a reactor for moderate thermal cracking reaction, and generate oil gas and the coking oil gas are fractionated together. Gas, gasoline and diesel oil are mixed and sent to a downstream device for being processed, and unconverted oil returns to the coking device as circulation oil. The diesel oil yield of the process is increased by 5 to 15% than single delayed coking, and a cetane value of the diesel oil can reach about 50.
Description
The invention belongs to a kind of under the situation that does not have hydrogen the thermal non-catalytic cracking technology of hydrocarbon ils, more particularly, be a kind of delayed coking and the process integration that relaxes thermally splitting.
Delayed coking is a kind of degree of depth thermocracking process that residual oil is converted into gas, gasoline, diesel oil, wax oil and coke.Conventional delay coking process flow process is: stock oil enters separation column after the process furnace preheating, the coking oil gas heat exchange next with coke drum, entering the process furnace radiation section again is heated to coking temperature and enters the coke drum coking, coking oil gas distillates from the coke cat head and enters separation column, fractionate out gas, gasoline, diesel oil, wax oil, coking heavy oil mixes the radiation section that enters process furnace at the bottom of the tower as turning oil with stock oil, coke is flocked in the coke drum.
Relaxing thermally splitting is the lower thermocracking process of a kind of depth of conversion.This technology is raw material with the heavy distillate of straight run, coking and catalytic cracking generally, is raw material with straight-run heavy fraction oil mainly wherein, generates thermally splitting gas, gasoline, diesel oil and residual oil by thermal cracking reactor.
In order to improve yield of light oil, it is that the diesel oil distillate of 168～454 ℃, 232～399 ℃ or 266～343 ℃ is extracted out from coking fractional distillation column and entered the radiation section of coking heater as turning oil that CN85103235A proposes boiling spread, to reduce recycle ratio, reach the purpose of volume increase liquid product, this method be with gasoline or diesel oil distillate at the coker internal recycle, and the diesel oil that increases is few.
USP4,534,854th, the coking heavy oil fraction is carried out separated from solvent, the heavy that fractionates out partly enters coking, and lightweight is partly advanced catalytic cracking and is obtained lightweight oil.This method is that delay coking process and separated from solvent process are combined.
USP5,645,712nd, between coking heater and coke drum or in the coke drum, add thinner, before adding, thinner need be heated to about 400 ℃, its effect is the temperature that improves liquid phase stream in the coke drum, reach the purpose that improves liquid product yield, but diesel yield increases hardly.
The objective of the invention is to provide on the basis of existing technology a kind of delayed coking and the combination thermal cracking technology that relaxes thermally splitting.
Technology provided by the invention comprises the delayed coking of single-pass operation and the delayed coking and the two kinds of technical schemes of process integration that relax thermally splitting of the process integration that relaxes thermally splitting, cyclical operation.
The delayed coking of single-pass operation with the processing step that relaxes the thermally splitting associating is:
(A). heavy oil feedstock is heated to coking temperature by the process furnace radiation section again and advances the coke drum coking through the preheating of process furnace convection zone, and coke is flocked in the coke drum, and coking oil gas enters the separation column fractionation and obtains gas, gasoline, diesel oil and wax oil;
(B). the wax oil that step (A) obtains enters reactor and relaxes heat cracking reaction after entering another process furnace preheating, generates the thermally splitting oil gas and the unconverted oil that contain gas, gasoline, diesel oil;
(C). the thermally splitting oil gas that step (B) obtains enters the separation column in the step (A), obtains gas, gasoline, diesel oil and wax oil with the coking oil gas fractionation.
The used heavy oil feedstock of the present invention is to be selected from long residuum, vacuum residuum, visbreaking residue, catalytically cracked oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil to extract one or more mixture in the oil out.
Can also add straight-run gas oil, deasphalted oil or its mixture in the wax oil of step (B); The condition of process furnace is in the step (B): the furnace outlet temperature is 370～510 ℃, and water injection rate accounts for 0～30 heavy % of wax oil; The condition of reactor is in the step (B): pressure 0～1.0 MPa (absolute pressure), 10～180 minutes residence time.
The delayed coking of cyclical operation with the processing step that relaxes the thermally splitting associating is:
(A). heavy oil feedstock enters separation column bottom and turning oil and is mixed into the process furnace radiation section and is heated to coking temperature and advances the coke drum coking, and coke is flocked in the coke drum, and coking oil gas enters the separation column fractionation and obtains gas, gasoline, diesel oil and wax oil;
(B). after the wax oil that step (A) obtains enters another process furnace preheating, enter reactor and carry out heat cracking reaction, generate the thermally splitting oil gas and the unconverted oil that contain gas, gasoline, diesel oil;
(C). the thermally splitting oil gas that step (B) obtains enters the separation column in the step (A), obtains gas, gasoline, diesel oil and wax oil with the coking oil gas fractionation.
The used heavy oil feedstock of the present invention is to be selected from long residuum, vacuum residuum, visbreaking residue, catalytically cracked oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil to extract one or more mixture in the oil out.
The weight ratio (hereinafter to be referred as recycle ratio) of turning oil and heavy oil feedstock is 0～1.0: 1 in the step (A); Can also add straight-run gas oil, deasphalted oil or its mixture in the wax oil of step (B).
The condition of process furnace is in the step (B): the furnace outlet temperature is 370～510 ℃, and water injection rate accounts for 0～30 heavy % of wax oil; The condition of reactor is in the step (B): pressure 0～1.0 MPa (absolute pressure), 10～180 minutes residence time.
Below in conjunction with accompanying drawing two kinds of technical schemes that the invention provides process integration provided by the present invention are given further instruction respectively.
Joint process when accompanying drawing 1 is the delayed coking single-pass operation.
After stock oil enters the convection zone preheating of process furnace 1 through pipeline 8, the radiation section that enters process furnace 1 is heated to coking temperature, enter coke drum 2 or 3 coking through pipeline 9, coke is flocked in the coke drum, coking oil gas enters separation column 4 from the coke drum cat head through pipeline 10, fractionation obtains gas, gasoline, diesel oil and wax oil, wax oil is after pipeline 11 enters process furnace 5 and is preheated to 360 ℃～490 ℃, enter reactor 6 through pipeline 12, the material that generates enters separation column 7 through pipeline 13, the thermally splitting oil gas that generates enters separation column 4 through pipeline 15, fractionate out device with coking oil gas, wherein blend gasoline and diesel oil enter hydrogenation unit, and unconverted oil enters the radiation section of process furnace 1 as turning oil through pipeline 14.
Joint process when accompanying drawing 2 is the delayed coking cyclical operation.
After stock oil enters the convection zone preheating of process furnace 1 through pipeline 8, enter the bottom preheating of separation column 4 through pipeline 16 after, the radiation section that enters process furnace 1 through pipeline 17 is heated to coking temperature, enter coke drum 2 or 3 coking through pipeline 9, coke is flocked in the coke drum, coking oil gas enters separation column 4 from the coke drum cat head through pipeline 10, fractionation obtains gas, gasoline, diesel oil and wax oil, wax oil is after pipeline 11 enters process furnace 5 and is preheated to 360 ℃～490 ℃, enter reactor 6 through pipeline 12, the material that generates enters separation column 7 through pipeline 13, the thermally splitting oil gas that generates enters separation column 4 through pipeline 15, fractionate out device with coking oil gas, wherein blend gasoline and diesel oil enter hydrogenation unit, and unconverted oil enters the radiation section of process furnace 1 as turning oil through pipeline 14.
The difference of accompanying drawing 1 and accompanying drawing 2 is that the coking raw material oil of accompanying drawing 1 enters the radiation section of process furnace 1 after process furnace 1 convection zone preheating; And the coking raw material of accompanying drawing 2 oil is first after process furnace 1 convection zone preheating, and entering separation column 4 mixes with turning oil, enters the radiation section of process furnace 1 again.
The invention has the advantages that:
1, because wax tailings sulphur, nitrogen content height that delayed coking generates, and a spot of bituminous matter is arranged, raw material as catalytic cracking and hydrocracking, yield of light oil is reduced, the device severity increases, process cost increases, and the investment height of hydrogenation unit, and the delayed coking of adopting the present invention to propose can address this problem with mitigation thermally splitting combination process.
2, the present invention is in delayed coking unit and mitigation thermally splitting combination process, and the diesel yield that is produced increases by 5～15 percentage points than independent delayed coking.
3, be better than catalytic cracking diesel oil from the diesel quality that thermal cracking process produced, can reach about 50 as cetane value.
4, the fractionation process and the delayed coking of gas, gasoline and the diesel oil of mitigation thermally splitting are shared, can reduce investment outlay.
5, relaxing unconverted oil that thermally splitting generates returns the radiation section of process furnace and helps to suppress the furnace tubing coking.
Accompanying drawing 1 is one way delayed coking and the process flow diagram that relaxes the thermally splitting associating.
Accompanying drawing 2 is circulation delay coking and the process flow diagram that relaxes the thermally splitting associating.
Each numbering is described as follows in the accompanying drawing:
1,5 be process furnace, 2,3 are coke drum, and 4,7 are separation column, and 6 is reactor, and 8～17 are pipeline.
The following examples will give further instruction to process integration provided by the invention, but not thereby limiting the invention.
The used heavy oil feedstock of this example is a vacuum residuum, and its character sees Table 1, and test is to be that 10 kilograms/hour medium-sized coker and 5 kilograms/hour relax on the thermal crackers and carry out in processing power, and the raw material that relaxes thermally splitting is a wax tailings, and its character sees Table 1.Coking operation is single-pass operation, and material balance and product property see Table 2.
Single-pass operation is adopted in delayed coking, and test conditions is: Outlet Temperature in Delayed Coking Furnace is 500 ℃, and the coke tower top pressure is 0.17 MPa, and water injection rate is 1.5 heavy % of heavy oil feedstock.The condition that relaxes thermally splitting is: thermally splitting furnace outlet temperature is 443 ℃, and water injection rate is 20 heavy % of wax oil; Reactor pressure is 0.3 MPa, and the residence time is 40 minutes.
As can be seen from Table 2, compare with independent delayed coking one way, the diesel oil of process integration increases by 13.0 percentage points, diesel-fuel cetane number about 50.
The used heavy oil feedstock of this example is identical with embodiment 1 with testing apparatus, and different is that cyclical operation is adopted in delayed coking, and the feedstock property that relaxes thermally splitting sees Table 1, and material balance and product property see Table 3.
The operational condition of delayed coking unit is: Outlet Temperature in Delayed Coking Furnace is 500 ℃, and the coke tower top pressure is 0.17 MPa, and recycle ratio is 0.4, and water injection rate is 1.5 heavy % of heavy oil feedstock.The operational condition that relaxes thermal cracker is: the furnace outlet temperature is 444 ℃, and water injection rate is that 20 heavy % reactor pressures of wax oil are 0.3 MPa, and reactor residence time is 40 minutes.
As can be seen from Table 3, compare with independent delayed coking cyclical operation, the diesel oil of process integration increases by 8.58 percentage points, diesel-fuel cetane number about 50.
Used heavy oil feedstock, testing apparatus and the coking operation mode of this example is identical with embodiment 1, and the raw material that relaxes thermally splitting is wax tailings and straight-run gas oil by weight 1: 1 mixed gatch, and material balance and product property see Table 4.
Delayed coking unit adopts single-pass operation, and test conditions is identical with embodiment 1.The test conditions that relaxes thermal cracker is also identical with embodiment 1.
As can be seen from Table 4, compare with independent delayed coking one way, the diesel oil of process integration increases by 13.62 percentage points, diesel-fuel cetane number about 50.
Table 1
Table 2
| Material balance; Heavy % casing head gasoling diesel gas oil unconverted oil coke product character gasoline density (20 ℃), gram per centimeter3The bromine valency, the gBr/100g sulphur content, heavy % boiling range, ℃ diesel oil density (20 ℃), gram per centimeter 3Condensation point, ℃ bromine valency, gBr/100g cetane value sulphur content, heavy % boiling range, ℃ wax oil/unconverted oil density (20 ℃), gram per centimeter 3Viscosity, milli m2/S carbon residue, heavy % sulphur content, heavy % boiling range, ℃ coke fugitive constituent, heavy % sulphur content, heavy % | The one way delayed coking is to decompression residuum 6.96 14.00 29.11 30.71-19.22 0.7484 43.6 0.81 67～185 0.8494-9 16.6 51.0 0.84 191～343 wax oil 0.9129 13.57 1.91 0.97 333～550 8.7 1.7 | Relax thermal cracking to thermal cracking raw material 2.62 5.64 42.34-49.40 0 0.7514 38.6 0.61 65～182 0.8506-8 16.4 49.0 0.78 195～345 unconverted oil 0.9151 11.82 1.00 0.87 351～538-- | Process integration is to decompression residuum 7.76 15.73 42.11 15.18-19.22 0.7496 41.7 0.73 65～184 0.8499-9 16.6 50.0 0.82 192～345 wax oil 0.9129 13.57 1.91 0.97 333～550 8.7 1.7 |
Table 3
| Material balance; Heavy % casing head gasoling diesel gas oil unconverted oil coke product character gasoline density (20 ℃), gram per centimeter3The bromine valency, the gBr/100g sulphur content, heavy % boiling range, ℃ diesel oil density (20 ℃), gram per centimeter 3Condensation point, ℃ bromine valency, gBr/1 00g cetane value sulphur content, heavy % boiling range, ℃ wax oil/unconverted oil density (20 ℃), gram per centimeter 3Viscosity, milli m2/S carbon residue, heavy % sulphur content, heavy % boiling range, ℃ coke fugitive constituent, heavy % sulphur content, heavy % | The circulation delay coking is to decompression residuum 8.30 16.10 32.00 20.70-22.90 0.7458 45.1 0.67 66～189 0.8488-11 18.7 50.0 0.77 194～346 wax oil 0.9032 12.55 0.53 0.82 333～470 9.1 1.6 | Relax thermal cracking to thermal cracking raw material 2.34 5.88 41.45-50.33 0 0.7483 40.2 0.59 62～181 0.8587-7 15.4 48.0 0.76 194～341 unconverted oil 0.9192 10.96 0.63 0.80 353～476-- | Process integration is to decompression residuum 8.78 17.32 40.58 10.42-22.90 0.7468 43.6 0.64 62～188 0.8528-9 17.3 49.0 0.77 194～345 wax oil 0.9032 12.55 0.53 0.82 333～470 9.1 1.6 |
Table 4
| Material balance; Heavy % casing head gasoling diesel gas oil unconverted oil coke product character gasoline density (20 ℃), gram per centimeter3The bromine valency, the gBr/100g sulphur content, heavy % boiling range, ℃ diesel oil density (20 ℃), gram per centimeter 3Condensation point, ℃ bromine valency, gBr/100g cetane value sulphur content, heavy % boiling range, ℃ wax oil/unconverted oil density (20 ℃), gram per centimeter 3Viscosity, milli m2/S carbon residue, heavy % sulphur content, heavy % boiling range, ℃ coke fugitive constituent, heavy % sulphur content, heavy % | The one way delayed coking is to decompression residuum 6.96 14.00 29.11 30.71-19.22 0.7484 43.6 0.81 67～185 0.8494-9 16.6 51.0 0.84 191～343 wax oil 0.9129 13.57 1.91 0.97 333～550 8.7 1.7 | Relax thermal cracking to thermal cracking raw material 2.71 6.85 44.34-46.10 0 0.7402 38.1 0.58 60～180 0.8434-12 13.1 52.0 0.77 189～344 unconverted oil 0.9003 9.55 0.22 0.78 341～544-- | Process integration is to decompression residuum 7.79 16.10 42.73 14.16-19.22 0.7451 41.3 0.76 61～184 0.8471-11 16.2 51.0 0.80 190～343 wax oil 0.9129 13.57 1.91 0.97 333～550 8.7 1.7 |
Claims (6)
1, a kind of thermocracking process of heavy oil is characterized in that processing step is:
(A). heavy oil feedstock is heated to coking temperature by the process furnace radiation section again and advances the coke drum coking through the preheating of process furnace convection zone, and coking oil gas enters the separation column fractionation;
(B). the wax oil that step (A) obtains enters another process furnace, this furnace outlet temperature is 370～510 ℃, and water injection rate accounts for 0～30 heavy % of wax oil, and the wax oil after the preheating enters reactor and relaxes heat cracking reaction, reactor pressure is 0～1.0 MPa, 10～180 minutes residence time;
(C). the thermally splitting oil gas that step (B) generates enters the separation column in the step (A), with the coking oil gas fractionation.
2,, it is characterized in that the described heavy oil feedstock of step (A) is to be selected from long residuum, vacuum residuum, visbreaking residue, catalytically cracked oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil to extract one or more mixture in the oil out according to the described technology of claim 1.
3,, it is characterized in that to add straight-run gas oil, deasphalted oil or its mixture in the wax oil described in the step (B) according to the described technology of claim 1.
4, a kind of thermocracking process of heavy oil is characterized in that processing step is:
(A). heavy oil feedstock enters the separation column bottom to be mixed with turning oil, the weight ratio of turning oil and heavy oil feedstock is 0～1.0: 1, the mixture of heavy oil feedstock and turning oil enters the process furnace radiation section and is heated to coking temperature and advances the coke drum coking, and coking oil gas enters separation column;
(B). the wax oil that step (A) obtains enters another process furnace, this furnace outlet temperature is 370～510 ℃, and water injection rate accounts for 0～30 heavy % of wax oil, and the wax oil after the preheating enters reactor and relaxes heat cracking reaction, reactor pressure is 0～1.0 MPa, 10～180 minutes residence time;
(C). the thermally splitting oil gas that step (B) generates enters the separation column in the step (A), with the coking oil gas fractionation.
5,, it is characterized in that the described heavy oil feedstock of step (A) is to be selected from long residuum, vacuum residuum, visbreaking residue, catalytically cracked oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil to extract one or more mixture in the oil out according to the described technology of claim 4.
6,, it is characterized in that to add straight-run gas oil, deasphalted oil or its mixture in the wax oil described in the step (B) according to the described technology of claim 4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 98117809 CN1119388C (en) | 1998-08-27 | 1998-08-27 | Thermocracking process for heavy oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98117809 CN1119388C (en) | 1998-08-27 | 1998-08-27 | Thermocracking process for heavy oil |
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| CN1246512A CN1246512A (en) | 2000-03-08 |
| CN1119388C true CN1119388C (en) | 2003-08-27 |
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| CN 98117809 Expired - Fee Related CN1119388C (en) | 1998-08-27 | 1998-08-27 | Thermocracking process for heavy oil |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US7311746B2 (en) * | 2004-05-21 | 2007-12-25 | Exxonmobil Chemical Patents Inc. | Vapor/liquid separation apparatus for use in cracking hydrocarbon feedstock containing resid |
| CN101724419B (en) * | 2008-10-28 | 2013-05-01 | 中国石油化工股份有限公司 | Method for producing needle coke by utilizing delay coking of coal tar |
| CN101724421B (en) * | 2008-10-29 | 2013-05-01 | 中国石油化工股份有限公司 | Production method of needle coke |
| CN104312639B (en) * | 2014-10-17 | 2015-12-02 | 上海千茂化工科技有限公司 | A kind of polyether class clean diesel oxygenatedchemicals and preparation method thereof |
| CN107384473A (en) * | 2017-09-13 | 2017-11-24 | 南通意特化工有限公司 | A kind of thermocracking process of heavy oil |
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