CN101979470B - Method for removing free oxygen from inferior hydrogenated feedstock oil - Google Patents
Method for removing free oxygen from inferior hydrogenated feedstock oil Download PDFInfo
- Publication number
- CN101979470B CN101979470B CN 201010546935 CN201010546935A CN101979470B CN 101979470 B CN101979470 B CN 101979470B CN 201010546935 CN201010546935 CN 201010546935 CN 201010546935 A CN201010546935 A CN 201010546935A CN 101979470 B CN101979470 B CN 101979470B
- Authority
- CN
- China
- Prior art keywords
- oil
- inferior
- gas
- hydrogenation
- degassing tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for removing free oxygen from inferior hydrogenated feedstock oil. The method comprises the following steps of: heating the inferior hydrogenated feedstock oil, delivering to a degassing tower, continuously introducing gas from a lower part of the degassing tower and performing gas stripping, recycling light oil by condensing steam on the top of the tower, reflowing the light oil to the degassing tower, and allowing the gas to enter a venting system, wherein the inferior hydrogenated feedstock oil in the degassing tower serves as a hydrogenation device feedstock. The method of the invention is simple and easy, the cost is low, the running period of the hydrogenation device is obviously extended, and the method is suitable for the full-fraction inferior hydrogenated feedstock oil hydrogenation process, particularly suitable for the inferior hydrogenated feedstock oil hydrogenation process with high-concentration free oxygen.
Description
Technical field
The present invention relates to the deep processing of hydrogenating materials oil inferior, particularly relate to a kind of method of removing free oxygen from inferior hydrogenation raw oil.
Background technology
Along with the fast development of economy, China increases day by day to the demand of the energy.At present, China's oil import interdependency surpasses 50%, considerably beyond the safe-guard line of internationally recognized petroleum import interdependency 30%.Therefore, be based on China's Energy Situation, give full play to abundant cheap inferior feedstock oil resources advantage, be converted into clean fuel oil by hydro-upgrading, replenish domestic petroleum and gas resources not enough, for ensureing the national energy strategic security, have reality and long-range strategic importance.
But inferior feedstock oil is prone to coking phenomenon in the hydro-upgrading process, the long period smooth running of serious threat device.Coking refers under the katalysis of higher temperatures or metal, causes forming of hydro carbons free radical by oxygen, sulphur, nitrogen, forms polymkeric substance with alkene, this polymkeric substance at high temperature dehydrogenative condensation, be cyclized into condensed-nuclei aromatics and finally form coke.
In hydrogenating materials oil hydrogenation process inferior, the existence of free oxygen has obvious promoter action to coking.Free oxygen can make the aromatic thiol oxidation in hydrogenating materials oil inferior produce sulfonic acid, and sulfonic acid and pyrroles condensation reaction occur produce sediment; In addition, alkene and the oxygen formation oxidation products that can react, oxidation products forms sediment with the active heteroatomic compound polymerization reaction take place of sulfur-bearing, nitrogen, oxygen again.And sediment is the precursor of coking, and they are easily in the further condensation coking of equipment high temperature position.If hydrogenating materials oil free oxygen content inferior is higher, be easy to cause its bad stability, and easily form coking at high temperature equipment such as raw materials furnace and heating, interchanger and hydrogenator tops, cause the device unplanned shutdown.Therefore, suppress hydrogenating materials oil inferior coking and realize that the key of hydrogenation unit long-period stable operation is the free oxygen content that reduces in hydrogenating materials oil inferior, generally should be lower than 5 μ L/L.
At present, delaying hydrogenating materials oil inferior is the method that adopts the pre-hydrogenation of catalyzer at the conventional treatment method of beds coking, namely at first easily carries out main hydrogenation after the organic compound of coking removing the heteroato mic organic compounds such as part sulphur, nitrogen, oxygen, saturated diolefine, vinylbenzene etc. under the effect of the temperature of 150～300 ℃ and catalyzer again.But due to temperature required higher, hydrogenating materials oil inferior might coking in the high temperature heat-exchange equipments such as interchanger, process furnace before entering pre-hydrogenator, also coking may appear when entering pre-hydrogenator top bed, when particularly the free oxygen concentration in oil was higher, this coking situation just more likely occured.
Therefore, for preventing the coking and blocking problem in pre-hydrogenation process, generally before the pre-hydrogenation of hydrogenating materials oil inferior, it is carried out pre-treatment.Remove heavy constituent in coal tar as the pretreatment technology of the employings such as CN200610028263, CN200610018476, CN200400123146.4 distillations.The method not only can be taken off the coking precursorses such as colloid, bituminous matter, also can remove free oxygen.But can't be applicable to the coal tar hydrogenation modification technique of full cut, waste valuable tar resource.And because distillation temperature is too high, 300～360 ℃ of left and right, not only energy consumption is larger usually, and easily makes coal tar coking in Distallation systm, affects the normal operation of water distilling apparatus, and then affects the operation of whole coal tar hydrogenating unit.
In addition, also have the pretreatment processs such as electric desalting, extraction sedimentation for the coking that delays hydrogenating materials oil hydrogenation process inferior, but can't remove free oxygen in hydrogenating materials oil inferior.
Summary of the invention
The purpose of this invention is to provide a kind ofly be applicable to full cut hydrogenating materials oil inferior hydrogenation technique, simple, energy consumption is low, without the method for free oxygen in removing of coking hydrogenating materials oil inferior.
Content of the present invention is achieved through the following technical solutions: a kind of method of removing free oxygen from inferior hydrogenation raw oil, it is characterized in that: will be transported in degassing tower after hydrogenating materials oil inferior heating, pass into gas from the degassing tower bottom again and carry out air lift, overhead vapours reclaims a small amount of light oil by condensation and is back to degassing tower, and gas enters blowdown system; Hydrogenating materials oil inferior in degassing tower after air lift is as the hydrogenation unit charging.
Described hydrogenating materials oil inferior is one or more in coal tar, crude benzol, coker gasoline, biomass thermal cracking oil, tire wet goods hydrogenating materials oil inferior.Coal tar, crude benzol are the liquid product of by-product in the dry distillation of coal, gasification, can be used as clean fuel oil and the sale of high quality chemical product by hydrogenation; Coker gasoline is the Partial Liquid Phase product that the black petroleum products coking obtains; Biomass thermal cracking oil, tire wet goods are the organic oil product of liquid phase that thermo-cracking obtains.Above-mentioned hydrogenating materials oil inferior has produced a large amount of unsaturated olefins in thermal cracking processes, if dissolved a certain amount of free oxygen in accumulating and the course of processing, the character of hydrogenating materials oil product inferior is sharply worsened, and subsequent treatment process is made troubles.
The Heating temperature scope of described hydrogenating materials oil inferior is 40 ~ 150 ℃.Higher temperature is conducive to the free oxygen volatilization, but too high temperature can be accelerated the free radical generation, causes coking reaction aggravation.
Described degassing tower is gas stripping column, at tower bottom, gas service pipes is installed, and guarantees to pass into gas uniform and distributes.
Described gas is the industrial gasses that do not contain free oxygen, as: hydrogen, nitrogen, carbonic acid gas, hydrogenation unit tail gas etc., because can also reacting with more active free radical in hydrogenating materials oil inferior, hydrogen further reduces the probability that the coking reaction occurs, preferred hydrogen and hydrogenation unit tail gas simultaneously.This gas passes into as carrier gas, blow and drive the free oxygen that is dissolved in hydrogenating materials oil inferior out of, effectively suppress the coking reaction that hydrogenating materials oil inferior causes due to oxyradical in heat transfer process, thereby delayed the coking trend of hydrogenating materials oil hydrogenation process inferior.
The described flow that passes into degassing tower gas is: carrier gas/hydrogenating materials oil inferior (volume ratio) is 10～150:1.
It is relatively poor that the inventive method is equally applicable to character, can be used as shale oil and the coal-based liquefaction oil of hydrogenating materials oil inferior.
Compare with existing other processing method, the present invention has the following advantages:
(1) automatization is controlled, and is simple to operation.
(2) only need to increase a gas stripping column before the pre-hydrogenation of hydrogenating materials oil inferior and get final product, less investment, technical process is simple, energy consumption is low.
(3) deoxidation effect is good, and to delaying the coking successful of hydrogenation process, the hydrogenation unit cycle of operation obviously extends.
(4) be applicable to the hydrogenating materials oil hydrogenation technique inferior of full cut.
(5) be applicable to the high hydrogenating materials oil inferior of free oxygen content and carry out hydro-upgrading.
The inventive method can improve the working time of a whole set of hydrogenating materials oil hydrogenation unit inferior greatly, and is specially adapted to the high hydrogenating materials oil inferior of free oxygen concentration.
Embodiment
The present invention will be further described below by embodiment:
Embodiment 1
Coal tar is heated to 120 ℃, with being pumped in degassing tower, then the hydrogen that passes into from the degassing tower bottom, the volume flow ratio of hydrogen and coal tar is 150:1, and overhead gas reclaims light oil by condensation, and gas enters blowdown system, and light oil is back to degassing tower; The coal tar that flow out the tower bottom namely can be used as the hydrogenation unit charging, and hydrogenation process has pre-hydrogenation and main hydrogenation two-stage process.Effect after the coal tar hydrogenating feeding gas shifts to an earlier date sees Table 1.
Effect after table 1 coal tar hydrogenating feeding gas shifts to an earlier date
| The coal tar hydrogenating charging | Install runtime, h |
| Air lift not | 352 |
| After air lift | 2260 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 1.
Embodiment 2
Coker gasoline is heated to 40 ℃, with being pumped in degassing tower, then the nitrogen that passes into from the degassing tower bottom, the volume flow ratio of nitrogen and coker gasoline is 10:1, and overhead gas reclaims light oil by condensation, and gas enters blowdown system, and light oil is back to degassing tower; The coker gasoline that flow out the tower bottom namely can be used as the hydrogenation unit charging, and hydrogenation process has pre-hydrogenation and main hydrogenation two-stage process.Effect after the Hydrogenation of Coker Gasoline feeding gas shifts to an earlier date sees Table 2.
Effect after table 2 Hydrogenation of Coker Gasoline feeding gas shifts to an earlier date
| The Hydrogenation of Coker Gasoline charging | Install runtime, h |
| Air lift not | 178 |
| After air lift | 1856 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 2.
Embodiment 3
Crude benzol is heated to 70 ℃, with being pumped in degassing tower, then passes into crude benzole hydrogenation refining plant tail gas from the degassing tower bottom, the volume flow ratio of its volumetric flow rate and crude benzol is 50:1, overhead gas reclaims light oil by condensation, and gas enters blowdown system, and light oil is back to degassing tower; The crude benzol that flow out the tower bottom namely can be used as the hydrogenation unit charging, and hydrogenation process has pre-hydrogenation and main hydrogenation two-stage process.Effect after the crude benzole hydrogenation feeding gas shifts to an earlier date sees Table 3.
Effect after table 3 crude benzole hydrogenation feeding gas shifts to an earlier date
| The crude benzole hydrogenation charging | Install runtime, h |
| Air lift not | 168 |
| After air lift | 2250 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 3.
Embodiment 4
Biomass thermal cracking oil is heated to 150 ℃, with being pumped in degassing tower, pass into carbon dioxide from the degassing tower bottom again, the volume flow ratio of its volumetric flow rate and biomass thermal cracking oil is 100:1, overhead gas reclaims light oil by condensation, gas enters blowdown system, and light oil is back to degassing tower; The biological heat cracked oil that flow out the tower bottom namely can be used as the hydrogenation unit charging, and hydrogenation process has pre-hydrogenation and main hydrogenation two-stage process.Effect before and after biological heat cracked oil air lift sees Table 4.
Effect after table 4 biological heat cracked oil hydrogenation feeding gas shifts to an earlier date
| The biological heat cracked oil | Install runtime, h |
| Air lift not | 210 |
| After air lift | 1725 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 4.
Embodiment 5
Tire oil is heated to 150 ℃, with being pumped in degassing tower, then passes into carbon dioxide from the degassing tower bottom, the volume flow ratio of its volumetric flow rate and tire oil is 150:1, overhead gas reclaims light oil by condensation, and gas enters blowdown system, and light oil is back to degassing tower; The tire oil that flow out the tower bottom namely can be used as the hydrogenation unit charging, and hydrogenation process has pre-hydrogenation and main hydrogenation two-stage process.Effect before and after the tire oil air lift sees Table 5.
Effect after table 5 tire oil hydrogenation feeding gas shifts to an earlier date
| Tire oil | Install runtime, h |
| Air lift not | 368 |
| After air lift | 2046 |
After coal tar hydrogenating charging air lift, device extends runtime greatly as can be seen from Table 5.
Claims (4)
1. the method for a removing free oxygen from inferior hydrogenation raw oil, it is characterized in that: will be transported in degassing tower after hydrogenating materials oil inferior heating, pass into gas from the degassing tower bottom again and carry out air lift, overhead vapours reclaims a small amount of light oil by condensation and is back to degassing tower, gas enters blowdown system, wherein passing into gas is hydrogen and hydrogenation unit tail gas, and the flow that passes into gas is: carrier gas/hydrogenating materials oil volume inferior ratio=10 ~ 150:1; Hydrogenating materials oil inferior in degassing tower is as the hydrogenation unit charging.
2. method according to claim 1, it is characterized in that: described hydrogenating materials oil inferior is one or more in coal tar, crude benzol, coker gasoline, biomass thermal cracking oil, tire oil.
3. method according to claim 1 is characterized in that: the temperature range of described hydrogenating materials oil inferior heating is 40 ~ 150 ℃.
4. method according to claim 1, it is characterized in that: described degassing tower is gas stripping column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010546935 CN101979470B (en) | 2010-11-17 | 2010-11-17 | Method for removing free oxygen from inferior hydrogenated feedstock oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010546935 CN101979470B (en) | 2010-11-17 | 2010-11-17 | Method for removing free oxygen from inferior hydrogenated feedstock oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101979470A CN101979470A (en) | 2011-02-23 |
| CN101979470B true CN101979470B (en) | 2013-05-15 |
Family
ID=43600015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010546935 Active CN101979470B (en) | 2010-11-17 | 2010-11-17 | Method for removing free oxygen from inferior hydrogenated feedstock oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101979470B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3977972A (en) * | 1975-04-02 | 1976-08-31 | Exxon Research And Engineering Company | Method and apparatus for reclaiming contaminated liquid |
| US4261838A (en) * | 1978-11-01 | 1981-04-14 | Lee Halleron | By-pass oil filtration system for internal combustion engines |
| CN1876767A (en) * | 2006-06-28 | 2006-12-13 | 沈和平 | Coal tar hydrocracking method |
| CN1880411A (en) * | 2006-03-04 | 2006-12-20 | 荆门市金吉化工有限公司 | Process for preparing fuel oil by using coal tar |
-
2010
- 2010-11-17 CN CN 201010546935 patent/CN101979470B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3977972A (en) * | 1975-04-02 | 1976-08-31 | Exxon Research And Engineering Company | Method and apparatus for reclaiming contaminated liquid |
| US4261838A (en) * | 1978-11-01 | 1981-04-14 | Lee Halleron | By-pass oil filtration system for internal combustion engines |
| CN1880411A (en) * | 2006-03-04 | 2006-12-20 | 荆门市金吉化工有限公司 | Process for preparing fuel oil by using coal tar |
| CN1876767A (en) * | 2006-06-28 | 2006-12-13 | 沈和平 | Coal tar hydrocracking method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101979470A (en) | 2011-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102153449B (en) | Continuous refining separation device and method for coal gasification crude phenol | |
| CN102899087B (en) | Deep processing method for medium and low temperature coal tar | |
| Zhang et al. | Improving hydrocarbon yield by two-step pyrolysis of pinewood in a fluidized-bed reactor | |
| CN106916044A (en) | A kind of method for refining carbonization crude benzole | |
| EP2995672B1 (en) | Method for modifying biomass pyrolysis oil | |
| CN103695036A (en) | Medium and low temperature coal tar processing method | |
| CN101724420A (en) | Production method of needle coke raw material | |
| CN102786986A (en) | Refining technology of microalgae pyrolysis oil | |
| CN105037103B (en) | A kind of method of the efficient depolymerization of lignin | |
| CN102021010A (en) | Processing method of middle and low temperature coal tar | |
| CN101608127B (en) | Method for producing diesel oil and heavy fuel oil from coal tar | |
| CN107365241A (en) | A kind of crude benzole hydrogenation process for refining | |
| CN102888235B (en) | Device and method for performing pyrolysis on solid fuel and performing reductive coupling on iron ore | |
| CN101250433A (en) | Coal tar hydrogenation technique | |
| CN103205275A (en) | Method for preparing phenol compound and clean fuel oil from coal tar | |
| CN101974345A (en) | Method for processing low-temperature pyrolyzed coal tar | |
| CN101979470B (en) | Method for removing free oxygen from inferior hydrogenated feedstock oil | |
| CN101507929A (en) | Catalyst for coal tar hydrogenation modification and its preparation method and use | |
| CN100523136C (en) | Method for decreasing petroleum acid value | |
| CN113897208B (en) | Method for circularly pyrolyzing tar | |
| CN1255367C (en) | Preparing method for phenol series substances | |
| CN106147853B (en) | A kind of method of coal tar raw material weighted BMO spaces | |
| CN204151301U (en) | Take aromatic hydrocarbons as the multistage deep processing device of coalite tar of guiding | |
| CN201952379U (en) | Continuous refining and separating device of gasified crude phenol | |
| CN204111354U (en) | A kind of sour water steam stripping at reduced pressure device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190131 Address after: 243000 Ma'anshan Economic and Technological Development Zone, Anhui Province, No. 398 Yanghu Road, No. 14 Fuma Zhisheng Ninth Floor Patentee after: Molifu Environmental Protection Technology Co., Ltd. Address before: 414012 Changling, Yunxi District, Yueyang City, Hunan Province Patentee before: Hunan Changling Petrochemical Technology Development Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210511 Address after: 244000 No.1 warehouse of Fengze home in Yi'an Economic Development Zone, Yi'an District, Tongling City, Anhui Province Patentee after: Anhui molifu renewable resources Co.,Ltd. Address before: 243000 Ma'anshan Economic and Technological Development Zone, Anhui Province, No. 398 Yanghu Road, No. 14 Fuma Zhisheng Ninth Floor Patentee before: Molifu Environmental Protection Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |