CN1814704A - Method for deeply removing petroleum acids from acid-contained raw oil - Google Patents
Method for deeply removing petroleum acids from acid-contained raw oil Download PDFInfo
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- CN1814704A CN1814704A CNA2005100049644A CN200510004964A CN1814704A CN 1814704 A CN1814704 A CN 1814704A CN A2005100049644 A CNA2005100049644 A CN A2005100049644A CN 200510004964 A CN200510004964 A CN 200510004964A CN 1814704 A CN1814704 A CN 1814704A
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- China
- Prior art keywords
- acid
- oil
- containing raw
- raw oil
- coke
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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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment
Abstract
This invention relates to a method for eliminating petroleum acid in the crude oil with acid in depth, which heats the crude oil with acid in a heating furnace to 480-510 deg.C then sends it in a coke tower and the crude oil remains for 30-120 minutes in it, the pressure of the tower top is at 0.10-0.30MPa, the oil gas from the tower enters into a fractionation tower to be distillated to coke gas, gas oil, diesel oil, wax oil and circulation oil fraction, which can utilizes a delay coke device to process crude oil with acid.
Description
Technical field
The invention belongs to a kind of under the situation that does not have hydrogen the thermal non-catalytic cracking method of hydrocarbon ils, more particularly, be a kind of delayed coking method of acid-containing raw oil.
Background technology
Often contain bulk petroleum acid in some crude oil, these petroleum acids can corrode refining equipment in Crude Oil Processing, make the oil refining apparatus frequent break-down maintenance of having to, even have an accident.
Crude oil PetroChina Company Limited. acid content represents with acid number that usually the oil product acid number is the milligram number of the used KOH of the petroleum acid in the every gram oil sample of neutralization, it is generally acknowledged that acid value for crude oil is low sour crude oil below 0.5mgKOH/g, can not bring heavy corrosion to refining equipment.
In order from crude oil or its cut, to remove petroleum acid, proposition such as US3806437, US4199440, with the method for NaOH or KOH solution-treated crude oil and cut thereof, the shortcoming of these class methods is: be easy to generate emulsification in treating processes, alkali lye can't be separated with oil product.
For fear of producing emulsification in treating processes, US4634419 proposes, and adopts ammonia-ethanolic soln extracting to separate petroleum acid in the oil product, still since the alkalescence of ammonia a little less than, thereby can't obtain the low crude oil of acid number with this kind method.
Owing to be easy to generate emulsification with the caustic alkali processing, and ammonia-ethanolic soln extracting can't obtain the low crude oil of acid number, therefore US5985137, US6022494 propose to remove petroleum acid in the crude oil with CaO, crude oil and milk of lime are handled down at 150 ℃-350 ℃, flash separation moisture and some lightweight oil then, mink cell focus after the dehydration then with whizzer or cyclonic separator to remove petroleum coal acid calcium wherein, its shortcoming is: make petroleum coal acid calcium separate relatively difficulty fully from mink cell focus.
US5914031, US5897769 propose, and the method for employing shortening removes the petroleum acid in the crude oil, this kind method and technology maturation, but hydrogenation unit construction investment and process cost are all higher.
US5891325, US6086751 propose, with heat-treating methods to remove the petroleum acid in the crude oil.After the crude flashing dehydration, petroleum acid is decomposed, therefore this method is difficult to obtain the low crude oil of acid number because treatment temp is lower.
In sum, still there is not method a kind of less expensive, the acid of energy deep removal acid-containing raw oil PetroChina Company Limited. in the above-mentioned prior art.
Summary of the invention
The objective of the invention is to propose a kind of can deep removal the acid of acid-containing raw oil PetroChina Company Limited., and the acid-containing raw oil working method of less expensive.
Method provided by the invention comprises the following steps:
Acid-containing raw oil directly is heated to 480 ℃-510 ℃ through process furnace, send in the coke drum then, make acid-containing raw oil in coke drum, stop 30min-120min, the coke tower top pressure maintains 0.10-0.30MPa, eject the coking oil gas that comes from coke drum and enter separation column and carry out fractionation, be fractionated into cooking gas, gasoline, diesel oil, wax oil and cycle oil fraction.
Method provided by the invention can be utilized raw materials such as delayed coking unit processing acid-containing raw oil, and this method simple economy can the acid of deep removal acid-containing raw oil PetroChina Company Limited..
Description of drawings
Accompanying drawing is the method synoptic diagram of deep removal acid-containing raw oil provided by the invention PetroChina Company Limited. acid.
Embodiment
The contriver finds after deliberation, and acid-containing raw oil is heated to more than 480 ℃, can make petroleum acid wherein be decomposed into CO fully
2And H
2O, so the present invention adopts the pyrogenic technology of coarse delay to process acid-containing raw oil.
Method provided by the invention is so concrete enforcement:
Acid-containing raw oil directly is heated to 480 ℃-510 ℃ through process furnace, send in the coke drum then, make acid-containing raw oil in coke drum, stop 30min-120min, the coke tower top pressure maintains 0.10-0.30MPa, petroleum acid is wherein decomposed fully, and make objectionable impurities in the acid-containing raw oil, for example colloid and bituminous matter pyrocondensation become coke.Eject the coking oil gas that comes from coke drum and enter separation column and carry out fractionation, be fractionated into cooking gas, gasoline, diesel oil, wax oil and cycle oil fraction.
Charging of the present invention can be the full cut of acid-containing raw oil, also can be the long residuum of acid-containing raw oil, can also be, the mixture of the long residuum of also full cut and acid-containing raw oil, the full cut of preferred acid-containing raw oil enters the processing unit (plant) in downstream without decomposition with the lighting end of avoiding acid-containing raw oil.
The difference of method of the present invention and conventional delayed coking is: acid-containing raw oil directly is heated to 480 ℃-510 ℃ through process furnace, to decompose all petroleum acids in the acid-containing raw oil, and unlike conventional delayed coking, raw material is introduced into separation column and coking oil gas heat exchange, and then enters process furnace.After avoiding crude oil and coking oil gas heat exchange, some low-density oils acid evaporation and sneaking in the coking distillate and the various processing unitss in corrosion coking fractional distillation column and downstream.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is the delayed coking synoptic diagram of high acid value hydrocarbon ils provided by the invention.
The concise and to the point flow process of this method is as follows:
Acid-containing raw oil is successively after pipeline 1, pump 2, pipeline 3 enter process furnace 4 and be heated to 480 ℃-510 ℃, enter coke drum 6 or 7 through pipeline 5, for the petroleum acid in the acid-containing raw oil can be decomposed fully, and make objectionable impurities in the acid-containing raw oil, for example colloid and bituminous matter pyrocondensation become coke, acid-containing raw oil should stop 30min-120min in coke drum, coke drum pressure maintains in the scope of 0.10-0.30MPa, so that reaction product can enter separation column smoothly.Reaction oil gas flows out from coke drum 7 tops, and coke is flocked in coke drum 6 or 7, treats that an operational cycle finishes the back and switches coke drum, cooling and decoking; Coking oil gas enters separation column 9 through pipeline 8 and carries out fractionation, fractionate out cooking gas, gasoline, diesel oil, wax oil and turning oil, wherein through pipeline 16,17,18 and 19 caterpillars, turning oil loops back coke drum 6 or 7 through pipeline 14 respectively for gas, gasoline, diesel oil and wax oil.
Method provided by the invention can be utilized raw materials such as delayed coking unit processing acid-containing raw oil, and this method simple economy can the acid of deep removal acid-containing raw oil PetroChina Company Limited..
The following examples will give further instruction to present method, but therefore not limit present method.Used its character of acid-containing raw oil of the present invention sees Table 1.
Table 1 acid-containing raw oil character
| Density (20 ℃), g/cm 3 | 0.9404 |
| Kinematic viscosity, mm 2/s | |
| 100℃ | 84.35 |
| 80℃ | 218.0 |
| Carbon residue, m% | 7.39 |
| Acid number, mgKOH/g | 12.09 |
The acid-containing raw oil of table 1 after process furnace is heated to 480 ℃, is entered coke drum, and coke drum pressure is 0.2MPa, and acid-containing raw oil residence time in coke drum is 30min, and from coke cat head material sampling analysis, its acid number only is 0.3mgKOH/g.
The acid-containing raw oil of table 1 after process furnace is heated to 500 ℃, is entered coke drum, and coke drum pressure is 0.2MPa, and acid-containing raw oil residence time in coke drum is 120min, and its acid number of coke cat head material sampling analysis only is 0.15mgKOH/g.
Comparative Examples 1
The acid-containing raw oil of table 1 after process furnace is heated to 430 ℃, is entered coke drum, and coke drum pressure is 0.2MPa, and acid-containing raw oil residence time in coke drum is 30min, and its acid number of coke cat head material sampling analysis is 1.5mgKOH/g.
From above embodiment and Comparative Examples as can be known, the acid-containing raw oil of table 1 only is heated to more than 480 ℃, can obtain the low crude oil of acid number.
Claims (2)
1, the method for a kind of deep removal acid-containing raw oil PetroChina Company Limited. acid, it is characterized in that this method comprises the following steps: acid-containing raw oil directly is heated to 480 ℃-510 ℃ through process furnace, send in the coke drum then, make acid-containing raw oil in coke drum, stop 30min-120min, the coke tower top pressure maintains 0.10-0.30MPa, eject the coking oil gas that comes from coke drum and enter separation column and carry out fractionation, be fractionated into cooking gas, gasoline, diesel oil, wax oil and cycle oil fraction.
2,, it is characterized in that described acid-containing raw oil is that full cut is or/and its long residuum according to the method for claim 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100049644A CN1814704A (en) | 2005-01-31 | 2005-01-31 | Method for deeply removing petroleum acids from acid-contained raw oil |
| PCT/CN2006/000147 WO2006079287A1 (en) | 2005-01-31 | 2006-01-25 | A method for removing petroleum acid from acid-containing hydrocarbon oil |
| MYPI20060374A MY169511A (en) | 2005-01-31 | 2006-01-26 | A process for removing petroleum acids in hydrocarbon oils containing acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100049644A CN1814704A (en) | 2005-01-31 | 2005-01-31 | Method for deeply removing petroleum acids from acid-contained raw oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1814704A true CN1814704A (en) | 2006-08-09 |
Family
ID=36740048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005100049644A Pending CN1814704A (en) | 2005-01-31 | 2005-01-31 | Method for deeply removing petroleum acids from acid-contained raw oil |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1814704A (en) |
| MY (1) | MY169511A (en) |
| WO (1) | WO2006079287A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280211B (en) * | 2007-04-04 | 2012-01-25 | 中国石油化工股份有限公司 | Thermal cracking method of acid-containing hydrocarbon oil |
| CN101280213B (en) * | 2007-04-04 | 2012-06-27 | 中国石油化工股份有限公司 | Coking method for processing highly acid crude oil |
| CN102732285A (en) * | 2011-04-12 | 2012-10-17 | 中国石油化工股份有限公司 | Method for alleviating coking of coke tower top oil gas pipeline |
| CN101724429B (en) * | 2008-10-28 | 2012-11-21 | 中国石油化工股份有限公司 | Delayed coking method for processing high-acid crude oil |
| CN115449397A (en) * | 2021-06-08 | 2022-12-09 | 中国石油天然气股份有限公司 | Visbreaking device and visbreaking method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1953353A (en) * | 1930-08-19 | 1934-04-03 | Associated Oil Company | Process of treating hydrocarbon oils |
| GB428526A (en) * | 1933-08-11 | 1935-05-13 | Scottish Gas Utilities Corp Lt | Improvements in or relating to the production of oils of low boiling point and low viscosity fuel oil by the heat treatment of tars and oils |
| EP0809683B1 (en) * | 1995-02-17 | 2001-11-14 | ExxonMobil Research and Engineering Company | Thermal decomposition of naphthenic acids |
| US6086751A (en) * | 1997-08-29 | 2000-07-11 | Exxon Research And Engineering Co | Thermal process for reducing total acid number of crude oil |
| CN1212373C (en) * | 2002-06-27 | 2005-07-27 | 中国石油化工股份有限公司 | Method for reducing acid value of petroleum |
-
2005
- 2005-01-31 CN CNA2005100049644A patent/CN1814704A/en active Pending
-
2006
- 2006-01-25 WO PCT/CN2006/000147 patent/WO2006079287A1/en not_active Application Discontinuation
- 2006-01-26 MY MYPI20060374A patent/MY169511A/en unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280211B (en) * | 2007-04-04 | 2012-01-25 | 中国石油化工股份有限公司 | Thermal cracking method of acid-containing hydrocarbon oil |
| CN101280213B (en) * | 2007-04-04 | 2012-06-27 | 中国石油化工股份有限公司 | Coking method for processing highly acid crude oil |
| CN101724429B (en) * | 2008-10-28 | 2012-11-21 | 中国石油化工股份有限公司 | Delayed coking method for processing high-acid crude oil |
| CN102732285A (en) * | 2011-04-12 | 2012-10-17 | 中国石油化工股份有限公司 | Method for alleviating coking of coke tower top oil gas pipeline |
| CN102732285B (en) * | 2011-04-12 | 2014-11-19 | 中国石油化工股份有限公司 | Method for alleviating coking of coke tower top oil gas pipeline |
| CN115449397A (en) * | 2021-06-08 | 2022-12-09 | 中国石油天然气股份有限公司 | Visbreaking device and visbreaking method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006079287A1 (en) | 2006-08-03 |
| MY169511A (en) | 2019-04-17 |
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