CN1082080C - Delayed coking technology for producing more diesel oil - Google Patents
Delayed coking technology for producing more diesel oil Download PDFInfo
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- CN1082080C CN1082080C CN96109779A CN96109779A CN1082080C CN 1082080 C CN1082080 C CN 1082080C CN 96109779 A CN96109779 A CN 96109779A CN 96109779 A CN96109779 A CN 96109779A CN 1082080 C CN1082080 C CN 1082080C
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Abstract
The present invention relates to a delayed coking technique for producing more diesel oil, which is characterized in that a delayed coking technique and a lubricating oil solvent refining technique are combined, namely that coking oil gas is divided into coking wax oil with the temperature of 350 to 420 DEG C and coking heavy oil with the temperature of larger than 420 DEG C by a fractionating tower, wherein the coking wax oil is used as the circulation oil of a coking device, the coking heavy oil is extracted by the extracting liquid of a lubricating oil solvent refining extraction tower, and residuum after extraction is recycled by a solvent as a raw material of catalytic cracking or hydrogen cracking. The present invention can increase the yield of diesel oil by about 10%, and coke yield is reduced by about 1.5%.
Description
The invention belongs to refining of petroleum technology, more particularly, the present invention is a kind of delayed coking and lubricating oil solvent process integration.
Delayed coking is a kind of heat processing technique that residual oil is converted into gas, light, middle matter distillate and coke through drastic cracking.Conventional delay coking process: 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 and wax oil, coking heavy oil recycles, and coke is flocked in the coke drum.The recycle ratio of this technology is bigger, be generally 0.4: 1, so the light oil products yield is low, and the coking yield height, and also systemic circulation is than the processing power that also reduces device.
In order to improve delayed coking unit light oil products yield, reduce coking yield, people carry out number of research projects.For example the CN85103235A patent application proposes, and with coking heavy oil carrying device, 168～454 ℃, 232～399 ℃ or 266～343 ℃ of diesel oil distillate circulations to reduce recycle ratio, reach the purpose that increases liquid product yield, reduces coke yield.This method main drawback is to have increased the circulation of diesel product in device that can dispatch from the factory, has in fact reduced the treatment capacity of device.The technology that U.S. Pat 4534854 is introduced be coking heavy oil that coking fractional distillation column is told through solvent extraction or solvent deasphalting, tell high carbon residue and low carbon residue product, high carbon residue product circulation coking, the low all or part of catalytically cracked material of doing of carbon residue product.The weak point of this technology is to need a newly-built cover solvent extraction or a solvent deasphalting unit, thereby has increased facility investment and process cost.
The objective of the invention is to overcome the shortcoming of prior art, propose a kind of improved coking process, be about to delayed coking and lubricating oil solvent and form process integration,, reduce the purpose of coke yield to reach high-yield diesel oil and liquid product.
The objective of the invention is to realize by following proposal: 350～420 ℃ the wax tailings that coking fractional distillation column is told is made the turning oil of coker,＞420 ℃ coking heavy oil utilizes the Extract extraction of lubricating oil solvent, the raffinate after the extraction after solvent recuperation as catalytic cracking or hydrocracking raw material.
Operating process of the present invention is followed successively by:
(1) coking raw material 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 obtains 350～420 ℃ wax tailings through the separation column fractionation, and＞420 ℃ coking heavy oil;
(2) lube stock and solvent counter-current extraction in the lubricating oil solvent extraction tower, cat head gets the lubricating oil raffinate, gets the lubricating oil Extract at the bottom of the tower;
(3) 350～420 ℃ of wax tailings that (1) step is obtained are with after coking raw material through the preheating of process furnace convection zone mixes, advance the process furnace radiation section, be heated to coking temperature and advance the coke drum coking, the weight ratio of wax tailings and coking raw material, promptly recycle ratio is 0.1～0.3: 1;
(4) (1) step is obtained＞lubricating oil Extract that 420 ℃ of wax tailings and (2) step obtain extracts in coking heavy oil extractor, squeeze into the anti-solvent that comprises water during extraction in extractor or in the lubricated Extract, its operational condition: 30～100 ℃ of extraction temperature, pressure 0～0.5MPa (absolute pressure), lubricating oil Extract and coking heavy oil weight ratio (calling agent-oil ratio in the following text) are 0.1～5.0: 1, preferably 0.3～3.0: 1, water and lubricating oil Extract weight ratio (call in the following text aqua than) are 0.01～0.25: 1;
(5) coking heavy oil raffinate and the Extract that the extraction of (4) step is obtained carries out solvent recuperation respectively, the raffinate oil that obtains is made catalytic cracking or hydrocracking raw material, extract oil out as pitch blend component or production needle-shape coke raw material, solvent is used for lube oil finishing, recycles.
Described coking raw material comprises long residuum, vacuum residuum, visbreaking residue, fluid catalytic cracking decant oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil extraction oil and two or more the mixing oil thereof of any crude oil.
Described lubricating oil Extract is meant when lube stock carries out solvent extraction in extraction tower the liquid of discharging at the bottom of the tower, wherein contain undesirable components and solvents such as aromatic hydrocarbons, colloid and bituminous matter in the lube stock, generally include the Extract that after the mixture extracting of phenol, furfural, N-Methyl pyrrolidone solvent or its water, obtains by any crude oil atmosphere 3rd side cut, normal four lines, vacuum 1st side cut～subtract four lines or lube stock light, heavy deasphalted oil.
Described anti-solvent comprises water and low-carbon alcohol, its main effect is that two of control coking heavy oil raffinate and Extract is separated, because coking heavy oil medium pitch matter content height, divide the difficulty of comparing, add an amount of anti-solvent and make two to be separated and to be easier to, and can regulate the yield and the quality of coking heavy oil raffinate oil.
Described coking heavy oil extractor comprises normally used packing tower, rotating disc contactor, sieve-tray tower, grid tray tower or mixer-settler.
Below in conjunction with accompanying drawing characteristics of the present invention are described:
Accompanying drawing is technical process of the present invention.
As shown in drawings, coking raw material I is after heating furnace 1 convection section preheating, enter heating furnace 1 radiant section and be heated to coking temperature, advance again coke drum 2,3 coking, coking oil gas enters fractionating column 4 by the coke drum overhead line, and fractionation obtains gas II, gasoline III, diesel oil IV, wax oil V and heavy oil VI. 350～420 ℃ wax tailings V with mix through the coking raw material after the preheating of heating furnace convection section, enter together heating furnace 1 radiant section and be heated to 495～505 ℃ of coking temperatures, enter again the coke drum coking.＞420 ℃ coking heavy oil VI extracts out from Fractionator Bottom, with the lubricating oil Extract VII extracting in coking heavy oil extractor 5 from Lubricating oil refining device, and in lubricating oil Extract VII, squeeze into a certain proportion of water simultaneously, the extractor top gets coking heavy oil raffinate VIII, get coking heavy oil raffinate oil through solvent recovery, as the raw material of catalytic cracking or hydrocracking, solvent recycles as the lube oil finishing solvent; The extractor bottom gets coking heavy oil Extract IX, gets coking heavy oil and extract oil out after reclaiming, and makes the raw material of pitch blend component or production acicular petroleum coke, and solvent recycles as the lube oil finishing solvent.
The solvent recovery of described coking heavy oil raffinate and Extract can share a cover solvent recovery unit (not marking in the figure) with lube oil finishing.
Advantage of the present invention:
1. in conventional coking process, recycle stock is coking heavy oil, the coking yield height. The present invention adopted 350～420 ℃ light wax oil circulation, and recycle ratio dropped to 0.3～0.1: 1 from 0.4: 1, thereby made diesel yield improve 1～12.5%, and coking yield reduces by 1～2%, and had improved the disposal ability of coking plant.
2. the present invention is actually a kind of delayed coking and lubricating oil solvent process integration, system extracts the coking heavy oil of asphaltenes with the lubricating oil Extract, wherein colloid, asphalitine and basic nitrogen compound are extracted out, as the raw material of pitch blend component or production acicular petroleum coke; Raffinate oil after dealkalize nitrogen and the asphalitine is as the raw material of catalytic cracking or hydrocracking.
3. in the used-oil Extract extraction coking heavy oil process of the present invention, in lubricating oil Extract or extraction tower, squeeze into a certain proportion of anti-solvent, separating of coking heavy oil raffinate and Extract two-phase be can effectively control, coking heavy oil raffinate oil yield and quality regulated well.
4. adopt lubricating oil Extract extraction coking heavy oil technology of the present invention, coking heavy oil raffinate oil yield height is compared with the neat solvent extracting, and under the prerequisite that reaches equal alkali nitrogen and gum asphaltic content, the raffinate oil yield is high more than 20%.
5. the raffinate that obtains of coking heavy oil extraction and the solvent recovery of Extract share a cover solvent recovery unit with lubricating oil solvent, thus the saving equipment investment, and cut down the consumption of energy.
Further describe characteristics of the present invention below in conjunction with example.
Example 1
This example adopts LIAOHE CRUDE vacuum residuum, carries out coking test of the present invention on the medium-sized coker of treatment capacity 10kg/h.Recycle stock is 350～420 ℃ of wax tailings, and recycle ratio was respectively 0.11: 1,0.18: 1 and 0.28: 1, test conditions and the results are shown in Table 1.
Example 2
This example is to adopt above-mentioned raw materials, and delayed coking flow test recycle stock is a coking heavy oil routinely on sampling device, and recycle ratio is 0.4: 1.Test conditions and result are as shown in table 1.
Example 1 and example 2 contrasts can be drawn:
Adopt technology of the present invention, 350～420 ℃ of light wax oils circulate, recycle ratio was reduced to from 0.4: 1 0.11: 1,0.18: 1 and 0.28: 1, diesel yield can improve 1.15%, 8.14% and 12.42% respectively, and coke yield reduces by 1.91%, 1.53% and 0.17% total liquid and receives raising 4.59%, 3.05% and 1.24%.
Example 3
This example with in the example 1＞420 ℃ of coking heavy oil and LIAOHE CRUDE subtract three-way lubricating oil furfural Extract and the extraction of phenol Extract, extraction conditions and result are as shown in table 2.Data show: the coking heavy oil that adopts lubricating oil Extract extraction asphaltenes, can significantly reduce the colloid and the asphalt content of coking heavy oil, basic nitrogen compound content also reduces significantly, raffinate oil can be used as catalytic cracking or hydrocracking raw material, extracts the raw material that oil is used for the pitch blend component or produces acicular petroleum coke out.Data it can also be seen that from table, and along with the add-on increase of water, coking heavy oil raffinate oil yield improves, the relative variation of quality.
Example 4
This example is to adopt in fresh furfural and the phenol solvent extraction example 3＞420 ℃ of coking heavy oil, extraction conditions and the results are shown in table 2.
Comparison example 3 and example 4 be as can be seen:
Coking heavy oil with lubricating oil Extract extraction asphaltenes is compared with the neat solvent extracting, and under the prerequisite that reaches equal gum asphalt and basic nitrogen compound content, coking heavy oil raffinate oil yield is high more than 20%.
Example 5
Adopt phenol Extract extraction＞420 ℃ coking heavy oil same with example 3, difference is not add water, and discovery can not be divided into raffinate and Extract two-phase.During with＞420 ℃ of coking heavy oil of furfural Extract extraction, though raffinate and Extract two-phase can layerings, the raffinate oil yield has only 78.0%.
Table 1
| Title | Example 1 | Example 2 | ||
| The technology title | The present invention | The present invention | The present invention | Conventional delayed coking |
| Recycle stock | 350～420 ℃ of wax tailings | 350～420 ℃ of wax tailings | 350～420 ℃ of wax tailings | Coking heavy oil |
| Operating condition: recycle ratio (weight) furnace outlet temperature; ℃ top of coke tower pressure; The MPa water filling, heavy % material balance (heavy %): gas+loss gasoline, diesel wax oil coke amounts to liquid and receives | 0.11 500 0.17 1.50 7.47 13.36 33.36 22.38 24.10 100.00 69.10 | 0.18 500 0.17 1.50 7.96 14.18 40.35 13.03 24.48 100.00 67.56 | 0.28 500 0.17 1.50 8.41 15.02 44.63 6.10 25.84 100.00 65.75 | 0.40 500 0.17 1.50 9.48 15.39 32.21 16.91 26.01 100.00 64.51 |
Table 2
| Title | The coking heavy oil feedstock | Example 3 | Example 4 | |||
| The technology title | - | The present invention | The present invention | The present invention | The neat solvent extracting | The neat solvent extracting |
| Spe medium | - | The furfural Extract | The phenol Extract | The phenol Extract | Furfural | Phenol |
| Extraction conditions and yield: agent-oil ratio (weight) aqua is than (weight) tower top temperature, ℃ column bottom temperature, ℃ raffinate oil yield, heavy % raw material and raffinate oil character: density (20 ℃), g/cm 3Kinematic viscosity (100 ℃), mm 2/ s alkali nitrogen, μ g/g dealkalize nitrogen rate, heavy % sulphur, heavy % nitrogen, heavy % carbon residue, heavy % forms (heavy %): stable hydrocarbon aromatic hydrocarbons gum asphalt gum asphalt decreasing ratio, heavy % | - - - - - 0.9589 19.36 3364 - 0.34 0.88 7.6 41.38 27.20 31.42 - | 2.0∶1 0.04∶1 70 50 91.5 0.9184 11.14 1683 50.0 0.24 0.32 2.5 56.19 24.51 19.30 38.6 | 2.0∶1 0.14∶1 70 50 93.4 0.9270 12.99 1556 53.8 0.25 0.38 3.3 55.00 25.93 19.07 39.3 | 2.0∶1 0.22∶1 70 50 99.5 0.9376 14.85 1993 40.8 0.28 0.45 4.1 50.47 26.59 22.94 27.0 | 2.0∶1 0.04∶1 70 50 66.0 0.9077 12.58 1715 49.0 0.24 0.33 2.7 56.64 25.59 17.77 43.4 | 2.0∶1 0.14∶1 70 50 67.5 0.9123 11.81 1454 56.8 0.24 0.34 3.4 51.95 25.44 22.61 28.0 |
Claims (4)
1. the delay coking process of a high-yield diesel oil is characterized in that operation steps is followed successively by:
(1) coking raw material 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 obtains 350～420 ℃ wax tailings and＞420 ℃ coking heavy oil through the separation column fractionation;
(2) lube stock and solvent counter-current extraction in the lubricating oil solvent extraction tower, cat head gets the lubricating oil raffinate, gets the lubricating oil Extract at the bottom of the tower;
(3) 350～420 ℃ of wax tailings that (1) step is obtained mix laggard process furnace radiation section with coking raw material through the preheating of process furnace convection zone, are heated to coking temperature and advance the coke drum coking, and the weight ratio of wax tailings and coking raw material is 0.1～0.3: 1;
(4) (1) step is obtained＞lubricating oil Extract that 420 ℃ of coking heavy oil obtained with (2) step extracts in coking heavy oil extractor, squeeze into anti-aqueous solvent, low-carbon alcohol during extraction in extractor or in the lubricating oil Extract, its operational condition: 30～100 ℃ of extraction temperature, pressure 0～0.5MPa (absolute pressure), lubricating oil Extract and coking heavy oil weight ratio are 0.1～5.0: 1, and the weight ratio of anti-aqueous solvent, low-carbon alcohol and lubricating oil Extract is 0.01～0.25: 1;
(5) coking heavy oil raffinate and the Extract that the extraction of (4) step is obtained carries out solvent recuperation respectively, the raffinate oil that obtains is made catalytic cracking or hydrocracking raw material, extract oil out as pitch blend component or production needle-shape coke raw material, solvent is used for lube oil finishing, recycles.
2. according to the described technology of claim 1, it is characterized in that the described coking raw material of step (1) comprises long residuum, vacuum residuum, visbreaking residue, fluid catalytic cracking decant oil, hydrocracking tail oil, ethylene bottom oil, lubricating oil extraction oil and two or more the mixing oil thereof of any crude oil.
3. according to the described technology of claim 1, it is characterized in that the described lubricating oil Extract of step (2) comprises the Extract that obtains after the mixture extracting of lube stock through comprising phenol, furfural, N-Methyl pyrrolidone solvent or its water by any crude oil atmosphere 3rd side cut, normal four lines, vacuum 1st side cut～subtract four lines or light, heavy deasphalted oil.
4. according to the described technology of claim 1, it is characterized in that described lubricating oil Extract of step (4) and coking heavy oil weight ratio are 0.3～3.0: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109779A CN1082080C (en) | 1996-09-19 | 1996-09-19 | Delayed coking technology for producing more diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109779A CN1082080C (en) | 1996-09-19 | 1996-09-19 | Delayed coking technology for producing more diesel oil |
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| Publication Number | Publication Date |
|---|---|
| CN1176287A CN1176287A (en) | 1998-03-18 |
| CN1082080C true CN1082080C (en) | 2002-04-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109779A Expired - Lifetime CN1082080C (en) | 1996-09-19 | 1996-09-19 | Delayed coking technology for producing more diesel oil |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0803545A2 (en) * | 2008-07-31 | 2010-06-15 | Petroleo Brasileiro Sa | bio-oil production process by biomass co-processing in delayed coking unit |
| CN102041091B (en) * | 2009-10-16 | 2013-08-28 | 中国石油化工股份有限公司 | Method for processing ethylene tar |
| CN102041013B (en) * | 2009-10-16 | 2013-07-24 | 中国石油化工股份有限公司 | Method for producing needle coke raw material by using delayed coking process |
| CN102373080A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Coking delaying method |
| JP6100775B2 (en) | 2011-07-29 | 2017-03-22 | サウジ アラビアン オイル カンパニー | Solvent-assisted delayed coking process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4534954A (en) * | 1982-08-17 | 1985-08-13 | Virginia Chemicals Inc. | Sodium hydrosulfite slurries |
| CN1107174A (en) * | 1994-11-15 | 1995-08-23 | 荆门石油化工研究院 | Reusing method for extracted solution of lubricating oil solvent |
-
1996
- 1996-09-19 CN CN96109779A patent/CN1082080C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4534954A (en) * | 1982-08-17 | 1985-08-13 | Virginia Chemicals Inc. | Sodium hydrosulfite slurries |
| CN1107174A (en) * | 1994-11-15 | 1995-08-23 | 荆门石油化工研究院 | Reusing method for extracted solution of lubricating oil solvent |
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| Publication number | Publication date |
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| CN1176287A (en) | 1998-03-18 |
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