CN100366709C - Combined process for processing heavy oil - Google Patents
Combined process for processing heavy oil Download PDFInfo
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- CN100366709C CN100366709C CNB2006100176536A CN200610017653A CN100366709C CN 100366709 C CN100366709 C CN 100366709C CN B2006100176536 A CNB2006100176536 A CN B2006100176536A CN 200610017653 A CN200610017653 A CN 200610017653A CN 100366709 C CN100366709 C CN 100366709C
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Abstract
The present invention discloses a combined process for processing heavy oil, which has the processing steps (1) all or a part of heavy oil is independently or mixed with catalytic cracking clarified oil, and then the heavy oil enters a solvent deasphalting device; after solvent deasphalting processing, one type of deasphalted oil and one type of deoiled asphalt can be obtained; (2) the deoiled asphalt from the step (1) is independently or mixed with the other part of heavy oil and enters into a coking device for coking processing, and the obtained coking heavy oil returns to the solvent deasphalting device or enters a heavy oil hydrotreater; or a part of the coking heavy oil returns to the solvent deasphalting device, and the other part enters the heavy oil hydrotreater, a catalytic cracker or a hydrocracking device. (3) the deasphalted oil from the step (1) is independently or mixed with decompression wax oil, atmospheric residue oil, vacuum residue oil, catalytic cracking cycle oil and one type or more than one type of heavy oil in the coking heavy oil from the step (2), the deasphalted oil secondly enters the heavy oil hydrotreater for hydrotreatment so as to obtain naphtha, aviation kerosene, diesel oil fraction and hydrogenation heavy oil via distillation after the hydrotreatment. The method of the present invention can improve the feeding performance of the heavy oil hydrotreater, moderate operating conditions of the heavy oil hydrotreater, prolong operation cycles of the heavy oil hydrotreater and provide high-quality raw oil for downstream catalytic cracking devices, etc.
Description
Technical field
The invention belongs to the petroleum refining technology field, relate to that a kind of usefulness is taken off charcoal and hydrogenation technique organically combines the technology of handling heavy oil.
Background technology
Fast development along with global economy, demand to lightweight, clean fuel oil also increases fast, and former oil quality along with the continuous increase of Oil extraction amount worse and worse, show mainly that density is big, viscosity is high, heavy metal content is high, sulphur content is high, nitrogen content is high, colloid and asphalt content height, this has brought big difficulty for processing of crude oil.
Heavy oil upgrading has two class complete processings, and a class is a hydrogenation technique, mainly comprises hydrotreatment, hydrofining etc.; Another kind of for taking off charcoal technology, mainly comprise solvent deasphalting, coking, heavy oil fluid catalytic cracking etc.Heavy oil improves hydrogen-carbon ratio by this two classes Technology, and heavy hydrocarbon is converted into lower boiling compound.
At present, the processing of heavy oil is to take off charcoal technology, it is subjected to the influence of heavy oil character bigger, especially the influence that is subjected to sulphur content, nitrogen content, heavy metal content and aromatic hydrocarbons, colloid and asphalt content in the heavy oil is more obvious, the yield that mainly shows liquid product is low, character is poor, needs further processing treatment.
In recent years, along with the pay attention to day by day of people to environmental protection, heavy oil hydrogenation process is favored.Hydrogenation technique can remedy the deficiency of taking off charcoal technology, and heavy oil has higher liquid product yield after handling by hydrogenation technique, and the foreign matter content of product is low, and character is good; But big because of the density of heavy oil, viscosity is high, heavy metal content is high, colloid and asphalt content are high, make that the operational condition of hydrogenation unit is very harsh, working pressure height, temperature of reaction height, air speed is low, on-stream time is short, the process cost height, and the one-time investment of device is also big, thereby has limited the fast development of heavy oil hydrogenation process.
For inferior heavy oil effectively being converted into the oil fuel of cleaning, the refining of petroleum investigator has researched and developed hydrogenation technique and has taken off the COMBINED PROCESS that charcoal technology combines.
A kind of method has been described among the CN 1117071A, this method is with the advanced deasphalting unit of residual oil raw material, obtain deasphalted oil and pitch fractions, in the presence of hydrogen, deasphalted oil obtains the deasphalted oil of upgrading by the catalyst for demetalation bed, and the deasphalted oil behind the upgrading mixes with one or more flash distillation distillates, its mixing oil carries out hydroeracking unit again, to produce one or more distillate cuts.For obtaining higher yield of light oil, the pitch of being produced by this method is difficult to utilize; And solvent deasphalting technology is physical process, can only separate high boiling point components such as the bituminous matter in the residual oil, colloid, macromole condensed-nuclei aromatics, can not make these high boiling components that contain in the residual oil be chemically converted to lower boiling ideal composition.
A kind of method has been described among the USP 4235703, the vacuum residuum that this method has proposed with high-sulfur, high metal content is stock oil, after hydrogenating desulfurization, hydrodemetallation (HDM), mix with other conventional raw materials of producing needle coke, carry out coking under the operational condition of producing needle coke, wherein coker gas oil returns the process furnace of coker with recycle ratio (accounting for coking raw material) 0.5～1.5.Although the needle coke CTE that this method is produced is very low, its sulphur content is very high; The raw material that requires simultaneously to be processed is the naphthenic base crude of characterization factor≤11.4, as Saudi Arabia's heavy crude.
For the higher residual oil of viscosity, directly hydrogenating desulfurization, hydrodemetallation (HDM) can influence the hydrogenation reaction effect, patent EP 0462823A1 has proposed from atmospheric gas oil (AGO), vacuum gas oil (VGO), catalytic cracking light cycle oil (LCO) or heavy cycle oil (HCO) to select a kind ofly to dilute vacuum residuum as thinner for this reason, but sulphur in the effective elimination residual oil and/or metal.The thinner that this method is used mostly is to be worth higher light ends oil, some can be directly as the blend component of product or product, and VGO is the main raw material of hydroeracking unit and catalytic cracking unit.
A kind of method has been described among the CN 1309164A, this method is that residual oil and coker gas oil, hydrogen are mixed together, entering hydrotreater in the presence of catalyzer reacts, reaction product is separated, wherein the residual oil behind the hydrogenation carries out pyrogenic reaction separately or with other conventional raw material of producing needle coke, separate the coking product, wherein coker gas oil is circulated to hydrotreatment.This method energy greatly preparing hihg-quality needle coke, the quality of product, but because the foreign matter content height such as heavy metal, colloid and bituminous matter of residual oil make shorten the process cost height work-ing life of catalyzer.
CN 1162518C has described a kind of heavy, combined technologic process for manufacturing petroleum residue, this method is with residual hydrogenation, catalytic cracking, technologies such as coking make up, make residue fixed-bed hydrogenation device for treatment raw material flexible, the treatment capacity and/or the corresponding severity that reduces the device operation of stock oil have also been increased, the processing power of catalytic cracking unit and the total liquid yield of device have also been improved simultaneously, reduced the productive rate of coke and reacted gas, but residual oil contains higher heavy metal and impurity such as bituminous matter and colloid, make that the catalyst deactivations such as demetalization of residue fixed-bed hydrogenation unit are very fast, the on-stream time of device is short, the process cost height.
CN 1123625C has described a kind of combined technologic process for manufacturing petroleum residue, and this method makes up technologies such as residual hydrogenation, catalytic cracking, solvent deasphalting.Residual oil is handled on the fixed bed hydrogenation device earlier, it generates, and oil often carries out, underpressure distillation, the part of long residuum is gone underpressure distillation, and vacuum residuum enters solvent deasphalting unit processing, and deasphalted oil, decompressed wax oil and remaining long residuum enter catalytic cracking unit and handle.This method is at first handled residual oil, has the same technical problem of patent CN 1162518C.
A kind of method has been described among the CN 1169920C, this method is hydrogenation technique and takes off charcoal technology and carry out combination, resid feed at first relaxes thermally splitting, and then carry out solvent deasphalting with catalytically cracked oil, deasphalted oil is carried out hydrotreatment under the condition that hydrogenation catalyst and hydrogen exist.This method has not only reduced the severity of residual hydrogenation equipment, has prolonged the work-ing life of hydrogenation catalyst, and the yield height of liquid product, and quality is good, utilizes but de-oiled asphalt is difficult.
In sum, heavy oil directly adopts hydroprocessing technique, good product quality, and liquid is received high, but operational condition is very harsh, and the work-ing life of catalyzer is shorter, has influenced the long-term operation of device; Take off charcoal technology and hydrogenation technique and combine,, follow gilsonite to be difficult to new problems such as utilization though reduced the severity of heavy-oil hydrogenation device operation.
Summary of the invention
Purpose of the present invention is exactly at prior art heavy-oil hydrogenation treatment unit operational condition harshness, and follow gilsonite to be difficult to problems such as utilization, and a kind of novel process of taking off charcoal and hydrogenation combination of handling heavy oil of exploitation makes the high heavy oil of metal content height, colloid and asphalt content height, carbon residue height and sulphur content and nitrogen content by solvent deasphalting technology and coking process combination treatment.Deasphalted oil after the processing and wax tailings are as the charging of heavy-oil hydrogenation treatment unit, thereby improve the character of heavy-oil hydrogenation treatment unit charging, relax the operational condition of heavy-oil hydrogenation treatment unit, prolong the operational cycle of heavy-oil hydrogenation treatment unit, for the devices such as catalytic cracking in downstream provide fine stock oil.
This combination process comprises the steps:
(1) all or part of heavy oil is separately or with after fluid catalytic cracking decant oil mixes, enter solvent deasphalting unit, wherein the weight ratio of solvent and solvent deasphalting unit stock oil is 1.5: 1～10: 1, service temperature is 55 ℃～300 ℃, working pressure is 0.104Mpa～6.0Mpa, after solvent deasphalting is handled, obtain a kind of deasphalted oil and a kind of de-oiled asphalt;
(2) from the de-oiled asphalt of step (1) separately or and another part heavy oil enter coker after mixing and carry out coking and handle, obtain coker gasoline, coker gas oil and coking heavy oil, its operational condition is: pressure 0.104Mpa～1.0Mpa, preferred 0.104Mpa～0.25Mpa; 450 ℃～550 ℃ of temperature, preferred 490～510 ℃; Resulting coking heavy oil turns back to solvent deasphalting unit or enters the heavy-oil hydrogenation treatment unit, or a part of coking heavy oil turns back to solvent deasphalting unit, and another part enters heavy-oil hydrogenation treatment unit, catalytic cracking unit or hydroeracking unit;
(3) heavy-oil hydrogenation is handled: from the deasphalted oil of step (1) separately or and decompressed wax oil, long residuum, vacuum residuum, catalytic cracking recycle oil and mix from one or more the mink cell focus in the coking heavy oil of step (2) after, enter the heavy-oil hydrogenation treatment unit, under the situation that has hydrogen to exist, carry out hydrotreatment, hydrotreatment is after distillation obtains petroleum naphtha, aviation kerosene, diesel oil distillate and hydrogenation heavy oil, its operational condition is: the hydrogen dividing potential drop is 6.5Mpa～30Mpa, preferred 9.0Mpa～18Mpa; Service temperature is 340 ℃～480 ℃, preferred 360 ℃～420 ℃; Volume space velocity is 0.1h
-1～4.0h
-1Preferred 0.2h
-1～2.5h
-1The volume ratio of hydrogen and heavy-oil hydrogenation treatment unit feed oil is 500～4000, preferred 800～2500.
Among the present invention, the described heavy oil of step (1) is boiling range greater than one or more mixing oil in 350 ℃ the heavy oil, as one or more mixing oil in crude oil, long residuum and the vacuum residuum.The Technology that above-mentioned solvent deasphalting process using those of ordinary skills know.The employed solvent of solvent deasphalting unit normally contains low-carbon alkanes (as C
3～C
8) material, the alkane compounds of knowing as those of ordinary skills such as propane, butane, pentane, hexane, heptane and octane, or the mixture of two kinds and two or more alkane, or light naphtha fraction etc., the solvent that recommendation is used is the mixture or the light naphtha fraction of butane, pentane, butane and pentane.Solvent in the solvent deasphalting unit can carry out one section or two sections solvent deasphaltings processing to the charging of device under subcritical or postcritical condition.The extraction tower of solvent deasphalting unit can be tray column, rotating disc contactor or packing tower.
The described coking process of step of the present invention (2) is delay coking process well known to those skilled in the art of the present technique, fluidized coking process or flexicoking technology.When adopting delay coking process to add man-hour, should adopt distillate circulation, the regular circulation of flexible turning oil and both combinations according to the character of charging, recycle ratio is generally 0.05～1.00, and preferred 0.2～0.6.The coking dry gas that the rich tail gas of coking plant that is obtained by coking process obtains after absorbing can be used as the raw material of hydrogen manufacturing and the C that obtains
3And C
4Can be used as liquefied gas after the deodorization, the hydro-refining unit that coker gasoline and coker gas oil dehydrogenation dividing potential drop are lower is handled or other refining plant is handled.The coking heavy oil that is obtained by step (2) is divided into light wax tailings and heavy wax tailings, and heavy wax tailings can mix the part charging of back as step (1) solvent deasphalting unit separately or with light wax tailings; Or light wax tailings separately or and heavy wax tailings mix the back as step (3) heavy-oil hydrogenation treatment unit mix material or as the material of mixing of catalytic cracking unit; Or light wax tailings is as the material of mixing of hydroeracking unit.The preferably heavy wax tailings of the present invention is as the material of mixing of step (1) solvent deasphalting unit charging, and light wax tailings goes the processing of heavy-oil hydrogenation treatment unit or as the material of mixing of catalytic cracking unit or hydroeracking unit charging.When the described coking process of step (2) was delay coking process, the refinery coke of production should go to do the raw material of oxidation hydrogen manufacturing or the use that acts as a fuel according to its character, when acting as a fuel, if the higher charging that can be used as the CFB boiler of sulphur content of refinery coke, with the protection environment.
The charging of the described heavy-oil hydrogenation treatment unit of step (3) is the deasphalted oil from step (1), or and decompressed wax oil, long residuum, vacuum residuum, catalytic cracking recycle oil and from the mixing oil of one or more mink cell focus in the coking heavy oil of step (2), when the foreign matter content of long residuum, vacuum residuum is higher, for prolonging the on-stream time of heavy-oil hydrogenation treatment unit, can not mix long residuum or vacuum residuum in the charging of step (3).Mix catalytic cracking recycle oil in the charging of heavy-oil hydrogenation treatment unit and can play diluting effect, can obviously reduce the viscosity of device charging, also can reduce the foreign matter content of device charging, improve the naphtha yield and the virtue of device and dive, simultaneously the on-stream time of device is obviously prolonged.
The described heavy Oil Hydrotreating Processes of step (3) (long residuum hydrogen addition technology, vacuum residuum hydrogen addition technology and decompressed wax oil hydrogen addition technology etc.) is meant hydrogenation technique technology well known to those skilled in the art of the present technique, the fixed bed hydrogenation treatment technology, floating bed hydrogenation treatment technology, the boiling bed hydrogenation treatment technology that comprise heavy oil, and expanded bed hydrotreatment technology etc.At present, using comparatively sophisticated heavy Oil Hydrotreating Processes on full scale plant is the fixed bed hydrogenation treatment technology.When adopting this technology, having a kind of hydrogenation catalyst at least is the hydrogenation catalyst that fixed-bed reactor use.This hydrogenation catalyst be meant have heavy oil hydrogenation demetal, a kind of catalyzer of function such as removal of ccr by hydrotreating, hydrogenating desulfurization, hydrodenitrification and hydrocracking or the combination of multiple catalyzer.Catalyzer is a carrier with the resistant to elevated temperatures inorganic oxide of porous generally, such as silicon-dioxide, aluminum oxide and silicon-aluminum mixture etc.; Oxide compound with group vib and/or group VIII metal is an active ingredient, such as the oxide compound of W, Mo, Ni and Co; And optionally add some other auxiliary element, such as F, B, P etc.This class catalyzer has CEN, the FZC series Hydrodemetalation catalyst of Fushun Petrochemical Research Institute's development, and ZTN, the ZTS series hydrogenation catalyst of first fertilizer plant of Qilu Petrochemical company production etc.In the bed technology that heavy-oil hydrogenation is handled is used, often with the supporting use of multiple catalyzer, wherein the kind of hydrogenation catalyst has Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst and hydrocracking catalyst etc., these several catalyzer are mixed packing in order, makes stock oil demetalization successively, desulfurization, denitrogenation and cracking under the effect of hydrogen; But the heavy Oil Hydrotreating Processes of only using one or both catalyzer is also arranged, as only using hydrodemetallation (HDM) and Hydrobon catalyst.Therefore, should select rational heavy Oil Hydrotreating Processes according to the operational path of raw material oil properties and hydrogenated oil reprocessing.In processing condition of the present invention were selected, the heavy-oil hydrogenation treatment process condition should require to select appropriate volume air speed and hydrogen dividing potential drop according to the transformation efficiency of handling raw material oil properties, requirement and to giving birth to olefiant refining depth.Hydrogen-oil ratio described in the step of the present invention (3) refers to hydrogen and the volume ratio that enters the feed oil of this device in the heavy-oil hydrogenation treatment unit.
Described its hydrogenated oil of heavy-oil hydrogenation treatment unit of step (3) obtains petroleum naphtha or/and aviation kerosene, diesel oil and hydrogenation heavy oil after distillation.The foreign matter content of hydrogenation heavy oil is lower, is the high quality raw material oil of following process device such as catalytic cracking unit and hydroeracking unit.
The present invention is applicable to the processing treatment of heavy oil, is particularly useful for the high heavy oil upgrading of metal content height, colloid and asphalt content height, carbon residue height, sulphur content height and nitrogen content and handles.
The present invention compared with prior art, its advantage is:
1) in the inventive method, heavy oil is handled by this combination process, the feed properties of present weight, residue fixed-bed hydrotreater is obviously improved, heavy metal content reduction, colloid and asphalt content reduce, carbon residue reduces, viscosity reduces etc., the operational condition of weight, residual hydrocracking device is relaxed, prolong more than one times the work-ing life of catalyzer, thereby the on-stream time of device is prolonged, and process cost reduces; Raw material heavy simultaneously, the processing of residual hydrocracking device is more flexible, has reduced the scale of investment of newly-built heavy, residue fixed-bed hydrotreater or has improved the processing power of original heavy, residue fixed-bed hydrotreater.
2) among the present invention, when the charging of fluid catalytic cracking decant oil being mixed in the heavy oil as solvent deasphalting unit, also can reduce the viscosity of solvent deasphalting unit charging, improve its character, improve the yield of deasphalted oil; Simultaneously fluid catalytic cracking decant oil is rich in heavy arene, and this aromatic hydrocarbons enters in the de-oiled asphalt after by extracting, has improved the aromaticity content of de-oiled asphalt, thereby has improved the critical decomposition temperature of de-oiled asphalt.
When 3) coking heavy oil of the present invention (heavy wax tailings separately or and the mixing oil of light wax tailings) is as the part charging of solvent deasphalting unit, also can reduce the viscosity of solvent deasphalting unit charging, improve the character of device charging; The heavy oil of coking is simultaneously handled by solvent deasphalting unit and is made it obtain making with extra care, and mixes material preferably for the heavy oil hydrotreater provides character.
4) de-oiled asphalt is as the charging of delayed coking unit, the drawback of having avoided gilsonite to be difficult to utilize.
5) when catalytic cracking recycle oil is expected as mixing of heavy-oil hydrogenation treatment unit in the step of the present invention (3), can reduce heavy-oil hydrogenation treatment unit charging oil viscosity, improve the charging oil properties, prolong the on-stream time of heavy-oil hydrogenation treatment unit; Simultaneously, catalytic cracking recycle oil is rich in heavy arene, under the effect of higher reaction temperatures, higher hydrogen partial pressure and catalyzer, and the saturated open loop of part aromatic ring, thus improved the yield of petroleum naphtha.
6) heavy oil adopts combination process processing of the present invention, and the one-time investment of device obviously reduces, the yield height of lightweight oil, and quality is good.
7) the hydrogenation heavy oil of being produced by the heavy-oil hydrogenation treatment unit, its foreign matter content is low, is the high quality raw material oil of devices such as downstream processing unit (plant) such as catalytic cracking.
Embodiment
Following specific examples will be further specified the method for combination process of the present invention, but does not therefore limit method of the present invention.
M% all in the embodiment of the invention all refer to the quality percentage composition.
Embodiment 1
Process husky weight oil.
Husky light vacuum residuum is divided into two parts, wherein accounts for the charging of the portion of husky light vacuum residuum gross weight 48 weight % as solvent deasphalting unit; Account for another part of husky light vacuum residuum gross weight 52 weight % and the de-oiled asphalt of solvent deasphalting unit production and mix the charging of back as delayed coking unit; The charging of heavy-oil hydrogenation treatment unit is: the mixing oil of decompressed wax oil, deasphalted oil and coking heavy oil.Solvent deasphalting test, delayed coking test and heavy-oil hydrogenation Processing Test are all carried out on medium-sized tester.
Adopt this operational path can avoid husky light normal slag directly as the charging of heavy-oil hydrogenation treatment unit, thereby reduce the operating severity of heavy-oil hydrogenation treatment unit, prolong the cycle of operation of heavy-oil hydrogenation treatment unit, and provide fine stock oil for the processing unit (plant) in downstream.
Husky light normal slag obtains decompressed wax oil and vacuum residuum after underpressure distillation, the main character of husky light normal slag, decompressed wax oil and vacuum residuum sees Table 1.
The main character of the husky light long residuum of table 1, decompressed wax oil and vacuum residuum
| Project name | Long residuum | Decompressed wax oil | Vacuum residuum |
| Account for the amount of normal slag, m% density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% metal content, μ g/g Ni V Fe | 100 958.1 9.96 3.174 0.2035 17.69 42.35 6.61 | 53.05 908.3 0.23 2.186 0.0795 0.58 0.86 0.49 | 46.80 1016.5 21.3 4.251 0.336 37.39 90.57 14.32 |
The solvent that the solvent deasphalting test is used mixes the small part butane based on pentane, and its ratio is 85: 15, and the temperature of test is 185 ℃, and pressure is 2.5Mpa, and agent weight of oil ratio is 6: 1.The diasphaltene oil properties sees Table 2.
The main character of table 2 deasphalted oil
| Project name | Deasphalted oil |
| The deasphalted oil yield, m% density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% Ni+V, μ g/g | 81.20 989.6 13.60 3.815 0.235 32.78 |
Control furnace outlet temperature is 492 ℃, the pressure of coke drum cat head is 0.21Mpa, and water injection rate is that the mixing oil that 2.0m% and circulation (recycle ratio 0.41) mode that adopts distillate circulation and regular circulation to combine are mixed de-oiled asphalt naturally to the light vacuum residuum of sand has carried out the delayed coking test.The character of test raw material and product distribute and see Table 3.
The heavy-oil hydrogenation Processing Test is carried out on heavy oil fixed bed hydrogenation medium-sized tester.Hydrodemetalation catalyst (RF-220), Hydrobon catalyst (RF-1000) that the residue fixed-bed hydrogenation catalyst that uses in the test is produced for Dutch Aksu chemical company; also loaded the protective material of a spot of hydrogenation catalyst before the above-mentioned two kinds of catalyzer of filling, this protective material is the RG-1 type hydrogenation protecting agent that Chang Ling branch office of China Petrochemical Corp. produces.The filling ratio of wherein hydrogenation protecting agent, Hydrodemetalation catalyst and Hydrobon catalyst is 8: 44: 48.The feed composition of heavy-oil hydrogenation treatment unit and the main character of charging see Table 4, and the operational condition of heavy-oil hydrogenation treatment unit, product distribute and hydrogenation heavy oil character sees Table 5.In order to compare (testing apparatus and catalyzer are the same) with the light normal direct hydroprocessing technique of slag of sand, feedstock property, operational condition, the product of also having listed its heavy-oil hydrogenation treatment unit in table 4 and table 5 distributes and the main character of hydrogenation heavy oil etc.
The feed properties of table 3 delayed coking unit and product distribute
| Project name | The parallel feeding of delayed coking unit |
| The feed composition of coker, m% be wherein: vacuum residuum, and de-oiled asphalt, | 85.47 14.53 |
| Coker feed character: density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% metal content, μ g/g Ni V Fe | 1035.5 25.87 4.523 0.402 54.91 134.00 20.63 |
| Product distributes: m% natural gas liquid cut diesel oil distillate wax tailings coke | 9.41 7.97 21.95 23.31 36.87 |
The feed composition and the main character of table 4 heavy-oil hydrogenation treatment unit
| Project name | The parallel feeding of hydrogenation unit | The husky light normal direct charging of slag |
| Heavy-oil hydrogenation treatment capacity, weight part be wherein: long residuum, m% decompressed wax oil, m% deasphalted oil, m% wax tailings, m% | 78 - 68.06 23.44 8.50 | 100 100.00 - - - |
| The feed properties of heavy-oil hydrogenation treatment unit: density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% metal content, μ g/g Ni V Fe | 927.9 3.38 2.578 0.132 2.74 5.96 1.45 | 958.1 9.96 3.174 0.2035 17.69 42.35 6.61 |
As seen from Table 1, the heavy metal Ni+V content of husky light normal slag is 60.04 μ g/g, and carbon residue is 9.96m%, and after underpressure distillation, the character of decompressed wax oil is obviously improved, and metal content and carbon residue are very low, and the most of impurity in the long residuum is concentrated in the vacuum residuum.The Ni+V content of vacuum residuum is 127.96 μ g/g, and carbon residue is 21.3m%.
The main character analysis of the operational condition of table 5 heavy-oil hydrogenation, product distribution and hydrogenation heavy oil
| Project name | The parallel feeding of hydrogenation unit | The husky light normal direct charging of slag |
| Operational condition: temperature of reaction, ℃ hydrogen dividing potential drop, Mpa volume space velocity, h -1Chemistry hydrogen consumption, m% | 385 12.0 0.386 1.19 | 385 14.0 0.215 1.55 |
| Product distributes: m% petroleum naphtha diesel oil hydrogenation heavy oil | 6.75 15.93 74.52 | 1.87 9.06 85.93 |
| Hydrogenation heavy oil property analysis: density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% metal content, μ g/g Ni V Fe | 902.7 1.06 0.213 0.0535 1.07 1.34 1.05 | 923.4 4.89 0.384 0.0986 7.1 9.4 3.9 |
Vacuum residuum diasphaltene oil properties behind solvent deasphalting is obviously improved.As seen from Table 2, when the yield of deasphalted oil was 81.20m%, Ni+V content was 32.78 μ g/g, and demetallization per is about 74m%, and carbon residue is 13.60m%, and taking off carbon yield is about 36m%.
After vacuum residuum was mixed the small part de-oiled asphalt, although the product distribution variation of delay coking process, the yield of coke and gas increased, and liquid is received corresponding reduction, sees Table 3, has solved the difficult problem that de-oiled asphalt is difficult to dispatch from the factory.After the delayed coking process processing of vacuum residuum and de-oiled asphalt, the character of coking gasoline and diesel that obtains and coking heavy oil is obviously improved, be fine system ethylene raw after the coking gasoline and diesel hydrofining, or coker gas oil after hydrofining a high-quality blend component of producing diesel oil; The metal content and the carbon residue of wax tailings obviously reduce, and as the material of mixing of heavy-oil hydrogenation treatment unit, can improve the feed properties of heavy-oil hydrogenation treatment unit.High-sulfur Jiaozhuo is the fuel of CFB boiler, has solved high-sulfur Jiao difficult problem of dispatching from the factory, and has also protected environment, provides part electric power and part steam for factory simultaneously.
After husky light long residuum was processed by present technique, the feed properties of heavy-oil hydrogenation treatment unit was obviously improved, and sees Table 4.The charging density of heavy-oil hydrogenation treatment unit is by the 958.1kg/m of long residuum
3Be reduced to 927.9kg/m
3, carbon residue is reduced to 3.38m% by 9.96m%, and the content of heavy metal Ni+V is reduced to 8.7 μ g/g by 60.4 μ g/g, thereby the operational condition of heavy-oil hydrogenation treatment unit is obviously relaxed, and the hydrogen dividing potential drop reduces 2.0Mpa, and air speed improves about 80v%, the character of hydrogenation heavy oil is also obviously improved, and sees Table 5.
Mix the part long residuum in the mixing oil of heavy-oil hydrogenation treatment unit employing the art of this patent processing decompressed wax oil, deasphalted oil, coking heavy oil or this mixing oil, the operational condition of hydrotreater relaxes, processing power obviously improves, and on-stream time obviously prolongs.
Embodiment 2
Process husky weight oil.
Long residuum is divided into two parts, and its portion that accounts for long residuum gross weight 92.5 weight % obtains decompressed wax oil and vacuum residuum after underpressure distillation, and another part that accounts for long residuum gross weight 7.5 weight % enters the heavy-oil hydrogenation treatment unit.The vacuum residuum that obtains after the underpressure distillation also is divided into two parts, the portion that wherein accounts for vacuum residuum gross weight 50.0 weight % is mixed catalytically cracked oil and is weighed the charging of wax tailings as solvent deasphalting unit, this charging obtains deasphalted oil after the mixed solvent diasphaltene, the yield of deasphalted oil is 84.6m%, and character sees Table 6.Another part that accounts for vacuum residuum gross weight 50.0 weight % enters the heavy-oil hydrogenation treatment unit.The employed solvent situation of solvent deasphalting process is identical with embodiment 1.De-oiled asphalt and remaining vacuum residuum mix the charging of back as delayed coking unit, and coking raw material character, product yield and character see Table 7.The stock oil of heavy-oil hydrogenation treatment unit is the mixing oil of long residuum, decompressed wax oil, deasphalted oil, light wax tailings and catalytic cracking recycle oil, and its weight ratio is 8.43: 55.13: 26.56: 3.48: 6.40.The operational condition of this mixing oil properties and heavy-oil hydrogenation treatment unit, product distribute, product property sees Table 8, and the catalyzer of employing is the same with embodiment 1, and the comparative example is with embodiment 1.Hydrogenation heavy oil is as the raw material of catalytic cracking unit.
The charging of table 6 deasphalting unit and the property analysis of deasphalted oil
| Project name | The charging of solvent deasphalting unit | Deasphalted oil |
| The deasphalted oil yield, m% density (20 ℃), kg/m 3Carbon residue, m% viscosity (100 ℃), mm 2/ s sulphur content, m% nitrogen content, m% metal content, μ g/g | 1011.7 18.92 1156 3.723 0.294 110.81 | 84.60 984.6 12.60 531.6 2.928 0.205 29.53 |
Table 7 delayed coking unit feed properties, operational condition and product distribute
| Project name | Parallel feeding |
| Coker feed character: density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% Ni+V, μ g/g | 1036.8 25.47 4.763 0.402 190.0 |
| Operational condition: furnace outlet temperature, ℃ coke drum tower top pressure, Mpa master's water yield; The m% recycle ratio; (routine+distillate) | 496 0.19 2.0 0.38 |
| Product distributes: m% natural gas liquid cut diesel oil distillate wax tailings coke | 9.20 8.11 22.01 23.62 36.57 |
Feed composition, character and the operational condition of table 8 heavy-oil hydrogenation treatment unit and product distribute
| Project name | Parallel feeding | Atmospheric resid feed |
| Heavy-oil hydrogenation treatment unit amount of finish, weight part | 89 | 100 |
| The feed properties of heavy-oil hydrogenation treatment unit: density (20 ℃), kg/m 3Carbon residue, m% viscosity (100 ℃), mm 2/ s sulphur content, m% nitrogen content, m% bituminous matter, m% Ni+V, μ g/g | 933.6 3.93 18.57 2.378 0.128 0.243 12.75 | 958.1 9.96 38.96 3.174 0.2035 2.9 60.04 |
| Operational condition: temperature of reaction, ℃ hydrogen dividing potential drop, Mpa volume space velocity, h -1Chemistry hydrogen consumption, m% | 380 12.5 0.382 1.21 | 385 14.0 0.215 1.55 |
| Product distributes: m% petroleum naphtha diesel oil hydrogenation heavy oil | 5.72 13.81 77.78 | 1.87 9.06 85.93 |
| Hydrogenation heavy oil property analysis: density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% group composition, m% stable hydrocarbon aromatic hydrocarbons colloid+bituminous matter Ni+V, μ g/g | 908.9 2.12 0.273 0.0605 63.97 31.73 4.37 3.48 | 923.4 4.89 0.384 0.0986 57.29 32.85 9.86 16.5 |
Embodiment 3
The normal slag of Iran that the technical program working properties is relatively poor.Its processing technology route is that the normal slag of Iran is directly as the charging of solvent deasphalting unit; De-oiled asphalt is as the charging of delayed coking unit; Deasphalted oil and wax tailings mix the charging of back as the heavy-oil hydrogenation treatment unit, and this mixing oil substitutes the normal slag of former Iran and directly advances the heavy-oil hydrogenation treatment unit.Hydrogenation heavy oil is as the raw material of catalytic cracking unit.Solvent deasphalting test, delayed coking test and heavy-oil hydrogenation Processing Test are all carried out on medium-sized tester.
With the stock oil of the normal slag of Iran as the solvent deasphalting testing apparatus, the solvent of use mixes the small part butane based on pentane, and its weight ratio is 85: 15, and the temperature of test is 175 ℃, and pressure is 3.0Mpa, and agent weight of oil ratio is 5.5: 1.The main character of normal slag of Iran and deasphalted oil sees Table 9.
The main character analysis of normal slag of table 9 Iran and solvent-deasphalted oils
| Project name | Long residuum | Deasphalted oil |
| The deasphalted oil yield, m% main character analytic density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% Ni+V, μ g/g | 974.6 10.23 2.935 0.369 208.59 | 70.63 949.8 3.78 2.296 0.257 47.99 |
As seen from Table 9, the normal slag of Iran is behind solvent deasphalting, and the diasphaltene oil properties is obviously improved, and carbon residue is reduced to 3.78m% by the 10.23m% of stock oil, and taking off carbon yield is 63.05m%; The content of heavy metal Ni+V is reduced to 47.99 μ g/g by 208.59 μ g/g, and the removing heavy-metal rate is 76.99m%.
De-oiled asphalt is that 494 ℃, the pressure of coke drum cat head are that 0.20Mpa, water injection rate are to have carried out the delayed coking test under 2.0m% and circulation (recycle ratio 0.40) mode that adopts distillate circulation and regular circulation to combine in the furnace outlet temperature.The character of test raw material and product distribute and see Table 10.
As seen from Table 10, it is poor that the product of the delayed coking of de-oiled asphalt test distributes, and the yield of coke and gas is higher, and liquid is received corresponding reduction, but this has solved the difficult problem that de-oiled asphalt is difficult to dispatch from the factory.After the delayed coking process processing of de-oiled asphalt, the character of coking gasoline and diesel that obtains and coking heavy oil is obviously improved, and is fine system ethylene raw after the coking gasoline and diesel hydrofining, or coker gas oil is the high-quality blend component of producing diesel oil after hydrofining; The metal content and the carbon residue of wax tailings obviously reduce, and as the material of mixing of heavy-oil hydrogenation treatment unit, can improve the feed properties of heavy-oil hydrogenation treatment unit.High-sulfur Jiao is the same with embodiment 1, as the fuel of CFB boiler, has solved high-sulfur Jiao difficult problem of dispatching from the factory, and has also protected environment, provides part electric power and part steam for factory simultaneously.
The product of the main character of table 10 de-oiled asphalt and delayed coking test distributes
| Project name | De-oiled asphalt |
| Coker feed character: density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% Ni+V, μ g/g | 1046.2 25.93 4.529 0.643 590 |
| Product distributes: m% natural gas liquid cut diesel oil distillate wax tailings coke | 10.23 7.91 20.83 22.85 37.65 |
The heavy-oil hydrogenation Processing Test is carried out on heavy oil fixed bed hydrogenation medium-sized tester equally.Hydrodemetalation catalyst (RF-220), Hydrobon catalyst (RF-1000) that the residue fixed-bed hydrogenation catalyst that uses in the test is still produced for Dutch Aksu chemical company; also loaded the protective material of a spot of hydrogenation catalyst before the above-mentioned two kinds of catalyzer of filling, this protective material still is the RG-1 type hydrogenation protecting agent that Chang Ling branch office of China Petrochemical Corp. produces.The filling ratio of wherein hydrogenation protecting agent, Hydrodemetalation catalyst and Hydrobon catalyst is 8: 44: 48.The feed composition of heavy-oil hydrogenation treatment unit and the main character of charging see Table 11, and the operational condition of heavy-oil hydrogenation treatment unit, product distribute and the heavy oil character of hydrogenation heavy oil sees Table 12.For ease of Iran's original processing technology of normal slag is compared, the feedstock property, operational condition, product of also having listed its heavy-oil hydrogenation treatment unit in table 11 and table 12 distributes and the main character of hydrogenation heavy oil etc.
The feed composition of table 11 heavy-oil hydrogenation treatment unit and main character analysis
| Project name | Parallel feeding | The normal direct charging of slag of Iran |
| Heavy-oil hydrogenation treatment unit amount of finish, weight part be wherein: long residuum, m% deasphalted oil, m% wax tailings, m% | 77.24 - 91.44 8.56 | 100 100.00 - - |
| The feed properties of heavy-oil hydrogenation treatment unit: density (20 ℃), kg/m 3Carbon residue, m% viscosity (100 ℃), mm 2/ s sulphur content, m% nitrogen content, m% Ni+V, μ g/g | 948.3 3.49 25.13 2.379 0.269 44.05 | 974.6 10.23 97.63 2.935 0.369 208.6 |
The normal slag of Iran by the art of this patent processing after, the charging of heavy-oil hydrogenation treatment unit changes the mixing oil of deasphalted oil and coking heavy oil into by the normal slag of Iran, the feed properties of heavy-oil hydrogenation treatment unit has obtained obvious improvement, sees Table 11.The charging density of heavy-oil hydrogenation treatment unit is by the 974.6kg/m of long residuum
3Be reduced to 948.3kg/m
3, carbon residue is reduced to 3.49m% by 10.23m%, and the content of heavy metal Ni+V is reduced to 44.05 μ g/g by 208.59 μ g/g, thereby the operational condition of heavy-oil hydrogenation treatment unit is obviously relaxed, and air speed improves nearly 1 times, and the character of hydrogenation heavy oil is also obviously improved.As can be seen from Table 12, the density of hydrogenation heavy oil, carbon residue and heavy metal content obviously reduce, especially the content of heavy metal Ni+V is reduced to 11.34 μ g/g by 54.17 μ g/g of the direct hydrogenation heavy oil of the normal slag of Iran, reaches the requirement of heavy oil catalytically cracking equipment to Ni+V content substantially.
The main character analysis of the operational condition of table 12 heavy-oil hydrogenation, product distribution and hydrogenation heavy oil
| Project name | Parallel feeding | The normal direct charging of slag of Iran |
| Operational condition: temperature of reaction, ℃ hydrogen dividing potential drop, Mpa volume space velocity, h -1Chemistry hydrogen consumption, m% | 382 14.0 0.351 1.27 | 382 14.0 0.182 1.79 |
| Product distributes: m% petroleum naphtha diesel oil hydrogenation heavy oil | 4.23 11.09 80.94 | 1.93 8.65 87.12 |
| Hydrogenation heavy oil property analysis: density (20 ℃), kg/m 3Carbon residue, m% sulphur content, m% nitrogen content, m% metal content, μ g/g Ni V Fe | 913.2 1.89 0.218 0.127 3.35 7.99 0.38 | 929.4 4.89 0.355 0.176 18.92 35.25 1.17 |
Claims (4)
1. a combined technique for processing heavy oil is characterized in that comprising the steps,
(1) all or part of heavy oil is separately or with after fluid catalytic cracking decant oil mixes, enter solvent deasphalting unit, wherein the weight ratio of solvent and solvent deasphalting unit feed oil is 1.5: 1～10: 1, service temperature is 55 ℃～300 ℃, working pressure is 0.104Mpa～6.0Mpa, after solvent deasphalting unit is handled, obtain a kind of deasphalted oil and a kind of de-oiled asphalt;
(2) from the de-oiled asphalt of step (1) separately or and another part heavy oil enter coker after mixing and carry out coking and handle, obtain coker gasoline, coker gas oil and coking heavy oil, wherein operational condition is: pressure 0.104Mpa～1.0Mpa, 450 ℃～550 ℃ of temperature, resulting coking heavy oil turns back to solvent deasphalting unit or enters the heavy-oil hydrogenation treatment unit, or a part of coking heavy oil turns back to solvent deasphalting unit, and another part enters heavy-oil hydrogenation treatment unit, catalytic cracking unit or hydroeracking unit;
(3) heavy-oil hydrogenation is handled; From the deasphalted oil of step (1) separately or and decompressed wax oil, long residuum, vacuum residuum, catalytic cracking recycle oil and mix from one or more the mink cell focus in the coking heavy oil of step (2) after, enter the heavy-oil hydrogenation treatment unit, under the situation that has hydrogen to exist, carry out hydrotreatment, hydrotreatment is after distillation obtains petroleum naphtha, aviation kerosene, diesel oil distillate and hydrogenation heavy oil, its operational condition is: hydrogen dividing potential drop 6.5Mpa～30Mpa, 340 ℃～480 ℃ of service temperatures, volume space velocity 0.1h
-1～4.0h
-1, the volume ratio 500～4000 of hydrogen and heavy-oil hydrogenation treatment unit feed oil.
2. technology according to claim 1 is characterized in that: the described coking operation condition of step (2) is: pressure 0.104～0.25Mpa, 490～510 ℃ of temperature.
3. technology according to claim 1 is characterized in that: the described hydrotreatment operational condition of step (3) is: hydrogen dividing potential drop 9.0～18Mpa, 360～420 ℃ of service temperatures, volume space velocity 0.2～2.5h
-1, hydrogen to oil volume ratio 800～2500.
4. technology according to claim 1 is characterized in that: the described heavy oil of step (1) is boiling range greater than one or more mixing oil in 350 ℃ the heavy oil.
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| CN107033952B (en) * | 2016-02-03 | 2020-04-03 | 中国海洋石油集团有限公司 | Heavy oil processing method |
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