CN106967458A - A kind of joint catalyst cracking method for handling residual oil and extra heavy oil - Google Patents
A kind of joint catalyst cracking method for handling residual oil and extra heavy oil Download PDFInfo
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- CN106967458A CN106967458A CN201710338271.1A CN201710338271A CN106967458A CN 106967458 A CN106967458 A CN 106967458A CN 201710338271 A CN201710338271 A CN 201710338271A CN 106967458 A CN106967458 A CN 106967458A
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- oil
- catalytic cracking
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Classifications
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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
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a kind of joint catalyst cracking method for handling residual oil or extra heavy oil raw material.Methods described comprises the following steps：Using water-fast thermocatalyst catalytic cracking mink cell focus, a stage catalytic cracking product is obtained；One stage catalytic cracking product is dry gas, liquefied gas, gasoline, diesel oil, wax oil and coke；Water-fast thermocatalyst is solid base catalyst；Two stage catalytic cracking products are obtained using one section of wax oil of acidic catalyst catalytic cracking；Two stage catalytic cracking products are dry gas, liquefied gas, gasoline, diesel oil, slurry oil and coke.The inventive method can be used for the processing of 100% residual oil or extra heavy oil raw material, and liquid yield is high, and total carbon deposition quantity of two-stage catalytic cracking is few；The base catalyst of resistance to hot water type of one stage catalytic cracking obtains the synthesis gas that H/C ratios are about 1 using gasification regeneration techniques；Two stage catalytic crackings using one section of wax oil as raw material, and raw material in residual carbon content it is low, green coke amount is few, improves two stage catalytic cracking unit capacities, and mitigate its regenerator load.
Description
Technical field
The present invention relates to a kind of joint catalyst cracking method for handling residual oil or extra heavy oil raw material, belong to oil-refining chemical technology
Field.
Background technology
With the exhaustion increasingly of world wide light petroleum resource, the trend of world's crude oil heaviness causes refinery to by again
Matter crude conversion is lightweight, the hope of high priced line grows to even greater heights.The main technique of heavy charge lighting is hydrocracked, urged
Change cracking and coking.Catalytic cracking is most important oil secondary operation means, can handle decompressed wax oil and part reduced pressure residual oil,
And light oil yield is high, but its charging is usually the mixture of decompressed wax oil and decompression residuum, and wherein decompression residuum incorporation is usual
Only 20~30%, it is impossible to directly process the non-conventional oil resource of pure resid feed or more inferior, such as oil sands bitumen；It is burnt
Change and can be used for 100% resid feed of processing, and cost of investment and operating cost are all very low, are that current most widely used residual oil adds
Work technique, but its liquid yield is low, coke output big, poor product quality, and resource value is underutilized；It is hydrocracked tool
There is the characteristics of liquid yield is high, product quality is excellent, but its investment and operating cost are also of a relatively high, and feed needs are strict, nothing
Method is used for the direct processing of residual oil.Therefore, the light of heavy charge is generally realized using the combination of two or more technique
Matter.
CN103773495B discloses a kind of hydrotreating-catalytic cracking combination process, using wax oil as raw material, warp
After hydrotreating demetalization, desulfurization nitrogen and aromatic hydrocarbons saturation, hydrogenation tail oil enters catalytic cracking unit, wherein produced light cycle oil exists
Self-loopa in catalytic cracking unit, produces heavy-cycle oil and is then recycled to hydrotreater, this method is conducive to improving gasoline production
The yield and quality of product；CN10434496C discloses the combined technical method of another wax oil hydrogenation processing and catalytic cracking,
That is, light cycle oil is produced into catalytic cracking and heavy-cycle oil is recycled back to VGO, be conducive to improving product receipts
The quality of rate and catalytic diesel oil.But the raw material of both approaches is based on wax oil, it is impossible to for residual oil or extra heavy oil raw material
Directly handle.
CN101684417B discloses a kind of hydrogenation-catalytic cracking combined technique of optimization.The hydrogenated processing of wax oil raw material
Afterwards, obtain hydrogenation wax oil and be directly entered catalytic cracking unit without fractionation, heavy-cycle oil is recycled back to hydrotreating reaction area, heat
The logistics of high score top gas phase and light cycle oil enter hydro-upgrading reaction zone, and high-quality low-sulfur gasoline, fine-quality diesel oil can be produced simultaneously
And reformer feed.This method is equally not used to the direct processing of residual oil or extra heavy oil raw material, and needs increase is a set of to add
Hydrogen processing and a set of hydro-upgrading unit, investment and operating cost are very high.
US20010052482A1 discloses the group technology of a kind of two-part catalytic cracking and hydrotreating.One-stage hydrogenation
After the hydrogenated processing of heavy-cycle oil of cracking, into two stage catalytic crackings, two-stage catalytic cracking is for different material using different
Catalyst, but coke yield is reduced to reduce a stage catalytic cracking load, sacrifice liquid product yield, and need individually to build
A set of heavy-cycle oil hydrotreater is found, cost of investment is considerably increased.
CN1262306A discloses a kind of residual hydrocracking-catalytic cracking combined technique.Residual oil and clarified oil are passed through together
After hydrotreating, hydrogenated residue enters catalytic cracking unit and carries out cracking, and heavy-cycle oil is in catalytic cracking unit interior circulation.Due to
Polycyclic aromatic hydrocarbon in heavy-cycle oil is easily caused the increase of catalytic cracking unit green coke amount, reduces heavy oil catalytically cracking equipment processing
Amount, and add regenerator load.
The content of the invention
It is an object of the invention to provide a kind of joint catalyst cracking method for handling residual oil or extra heavy oil raw material, present invention side
Method can handle decompression residuum or extra heavy oil raw material at full capacity by using a kind of new water-fast heated alkaline catalyst, and
The regeneration technology of this is water-fast heated alkaline catalyst is simple, and regeneration temperature can be higher.
The joint catalyst cracking method of processing residual oil or extra heavy oil raw material provided by the present invention, comprises the following steps：
(1) water-fast thermocatalyst Catalytic Cracking Residual Oil or extra heavy oil are used, a stage catalytic cracking product is obtained；
The one stage catalytic cracking product is dry gas, liquefied gas, gasoline, diesel oil, wax oil and coke；
The water-fast thermocatalyst is microspheric solid base catalyst；
The one stage catalytic cracking product is fractionated into after tower separation, and wax oil component enters two stage catalytic crackings.
(2) acidic catalyst one section of wax oil of catalytic cracking is used, two stage catalytic cracking products are obtained；
The two stage catalytic crackings product is dry gas, liquefied gas, gasoline, diesel oil, slurry oil and coke.
Raw material handled by the inventive method includes decompression residuum, heavy oil and/or extra heavy oil (oil sands bitumen).
In above-mentioned joint catalyst cracking method, the microspheric solid base catalyst be alkali metal loaded catalyst,
Alkaline earth metal compound-supported catalyst, hydrotalcite and/or houghite, NaOH, Ca (OH)2With spinelle etc., preferably magnesium aluminum ratio is big
Hydrotalcite in 2 (2.5 or 3)；
The carrier of the alkali metal loaded catalyst and the alkaline earth metal compound-supported catalyst is aluminum oxide, oxidation
Titanium, zirconium oxide or zeolite molecular sieve.
In above-mentioned joint catalyst cracking method, in step (1), the condition of the catalytic cracking is as follows：
Temperature can be 460~600 DEG C, preferably 520~540 DEG C；
Pressure can be 0.1~0.4Mpa, preferably 0.2Mpa；
Oil ratio can be 2~10, preferably 5~6；
The oil ratio refers to the weight ratio of catalyst and feedstock oil；
The composition of each component is following (volume content) in the one stage catalytic cracking product：
Dry gas, liquefied gas 3~6%；
Gasoline 8~12%；
Diesel oil~10%；
Wax oil 50~60%；
Coke 13~18%；
Wherein, the composition of each component is as follows in the stage catalytic cracking product obtained in embodiment of the invention
(volume content)：
1) composition of the stage catalytic cracking product compositions obtained when using Da Liya decompression residuum as raw material is as follows：
Dry gas, liquefied gas 5.8%；
Gasoline 9.6%；
Diesel oil 10.2%；
Wax oil 59.8%；
Coke 14.6%；
2) composition of the stage catalytic cracking product compositions obtained when using Peng Lai decompression residuum as raw material is as follows：
Dry gas, liquefied gas 4.6%；
Gasoline 10.9%；
Diesel oil 11.3%；
Wax oil 57.9%；
Coke 15.3%.
Wherein, the property of wax oil is as follows in the stage catalytic cracking product obtained by embodiment of the invention：
1) property of the wax oil obtained when using Da Liya decompression residuum as raw material is as follows：
Density (20 DEG C)：0.8783g/cm3；Carbon residue：0.22wt%；C：86.28wt%；H：12.78wt%；N：
0.52wt%；S：0.41wt%；Saturation point：62.52wt%；Fragrance point：30.12wt%；Colloid：7.36wt%；
2) property of the wax oil obtained when using Peng Lai decompression residuum as raw material is as follows：
Density (20 DEG C)：0.8815g/cm3；Carbon residue：0.34wt%；C：85.91wt%；H：12.95wt%；N：
0.87wt%；S：0.20wt%；Saturation point：55.43wt%；Fragrance point：36.16wt%；Colloid：8.41wt%；
The component is the Conventional catalytic cracking raw material of high-quality it can be seen from the property of above-mentioned gained wax oil.
In above-mentioned joint catalyst cracking method, in step (2), the condition of the catalytic cracking is as follows：
Temperature can be 480~530 DEG C, preferably 500~520 DEG C；
Pressure can be 0.1~0.4Mpa, preferably 0.2Mpa；
Oil ratio can be 4~8, preferably 5~6；
The composition of each component is following (volume content) in the two stage catalytic crackings product：
Dry gas, liquefied gas 10~20%；
Gasoline 35~55%；
Diesel oil 20~40%；
Slurry oil 3~20%；
Coke 2~5%；
Wherein, the composition of each component is as follows in the two stage catalytic cracking products obtained in embodiment of the invention
(volume content)：
1) composition of the two stage catalytic cracking product compositions obtained when using Da Liya decompression residuum as raw material is as follows：
Dry gas, liquefied gas 18.4%；
Gasoline 43.6%；
Diesel oil 29.7%；
Slurry oil 3.6%；
Coke 4.7%；
2) composition of the two stage catalytic cracking product compositions obtained when using Peng Lai decompression residuum as raw material is as follows：
Dry gas, liquefied gas 19.1%；
Gasoline 43.9%；
Diesel oil 28.7%；
Slurry oil 3.5%；
Coke 4.8%.
In above-mentioned joint catalyst cracking method, acidic catalyst described in step (2) can use existing conventional catalysis
Cracking catalyst, such as rare earth Y type molecular sieve, super-stable Y molecular sieves and HY molecular sieve catalysts.
In above-mentioned joint catalyst cracking method, in step (1), methods described also includes to the water-fast thermocatalyst again
Raw step；
The condition of the regeneration is as follows：
Using the mixture of vapor and air as regeneration gas, synthesis gas is obtained after the regeneration；
Temperature can be 850~1100 DEG C, preferably 880~900 DEG C；
Pressure can be 0.2~0.3MPa, preferably 0.3MPa；
The composition of the synthesis gas is following (volume content)：
H25~15%, CO 15~30%, CO25~15, N250~60%, SOx(x is 2 and 3)≤1%, NOx(x is 1
With 2)≤1%.
Present invention joint catalyst cracking method has the advantages that：Available for 100% residual oil or extra heavy oil (such as oil-sand
Pitch) raw material processing, and liquid yield is high, and total carbon deposition quantity of two-stage catalytic cracking is few；The resistance to hot water type of one stage catalytic cracking
Base catalyst can be using gasification regeneration techniques, and using vapor and air mixture as regeneration gas, it is about 1 to obtain H/C ratios
Synthesis gas；Two stage catalytic crackings using a stage catalytic cracking wax oil as raw material, and raw material in residual carbon content it is low, green coke amount is few, improve
Two stage catalytic cracking unit capacities, and mitigate its regenerator load.
Brief description of the drawings
Fig. 1 combines the flow chart of catalyst cracking method for the present invention.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise specified, are commercially obtained in following embodiments.
Embodiment 1, using magnalium than the hydrotalcite for 2.5 as a stage catalytic cracking catalyst, super-stable Y molecular sieves be two sections
Catalytic cracking catalyst, handles Da Liya decompression residuum
The fundamental property of Da Liya decompression residuum is as shown in table 1.
Table 1 reaches inner sub- decompression residuum
Carried out according to the flow shown in Fig. 1, step is as follows：
(1) decompression residuum is lifted using dry gas, a stage catalytic cracking is carried out in riser reactor I, wherein temperature is
525 DEG C, oil ratio is 5, and pressure is 0.2Mpa.Then strip the oil gas in reclaimable catalyst through stripping section, oil gas and to be generated urge
Agent is separated in settler I, obtains reclaimable catalyst and reaction oil gas I.
Reclaimable catalyst enters through inclined tube to be generated to be regenerated in regenerator I, and regeneration gas is mixing for vapor and air
(both volume ratios are 1 to compound：5.5), temperature is 880 DEG C, and pressure is 0.3MPa, and regenerated catalyst enters by regenerator sloped tube
Proceed the reaction of two stage catalytic crackings in riser reactor I.
Regenerate obtained synthesis gas composition as shown in table 2：
The 2-in-1 volume into gas of table is constituted
| Component | Content (%) |
| H2 | 11.5% |
| CO | 19.8% |
| CO2 | 14.1% |
| N2 | 53.6% |
| SOx(x is 2 and 3) | 0.4% |
| NOx(x is 1 and 2) | 0.6% |
It is as shown in table 3 that reaction oil gas I is fractionated into the isolated product distribution of tower.
The product that table 3 is obtained through base catalysis cracking is distributed
| Product | Yield (wt%) |
| Dry gas, liquefied gas | 5.8% |
| Gasoline | 9.6% |
| Diesel oil | 10.2% |
| Wax oil | 59.8% |
| Coke | 14.6% |
Liquid yield reaches 80% or so it can be seen from the data of table 3.
The property of wherein wax oil is as shown in table 4.
The property of the wax oil of table 4
| Project | The stage catalytic cracking wax oils of Da Liya VR mono- |
| Density (20 DEG C), g/cm3 | 0.8783 |
| Carbon residue, wt% | 0.22 |
| C, wt% | 86.28 |
| H, wt% | 12.78 |
| N, wt% | 0.52 |
| S, wt% | 0.41 |
| Saturation point, wt% | 62.52 |
| Fragrance point, wt% | 30.12 |
| Colloid, wt% | 7.36 |
Residual carbon content is low in wax oil it can be seen from the data of table 4, is the Conventional catalytic cracking raw material of high-quality.
(2) wax oil that step (1) is obtained proceeds catalytic cracking, and identical in basic step such as (1), difference exists
In：The acidic catalyst used is super-stable Y molecular sieves catalyst, and wherein temperature is 510 DEG C, and oil ratio is 6, and pressure is
0.2Mpa。
Reclaimable catalyst regeneration condition be：Using air as regeneration gas, temperature is 580 DEG C, and pressure is 0.3MPa, regeneration
Arranged outside flue gas.
The product distribution obtained through acid catalyst catalytic cracking is as shown in table 5.
Table 5 is distributed through acid catalyzed cracking obtained product
| Product | Yield (wt%) |
| Dry gas, liquefied gas | 18.4% |
| Gasoline | 43.6% |
| Diesel oil | 29.7% |
| Slurry oil | 3.6% |
| Coke | 4.7% |
Petrol and diesel oil yield reaches more than 73% it can be seen from the data of table 5.
Embodiment 2, using magnalium than the hydrotalcite for 3 as a stage catalytic cracking catalyst, rare-earth Y molecular sieve be two sections catalysis
Cracking catalyst, handles Peng Lai decompression residuum
The fundamental property of Peng Lai decompression residuum is as shown in table 6.
Peng Lai decompression residuum of table 6
Carried out according to the flow shown in Fig. 1, step is as follows：
(1) decompression residuum is lifted using dry gas, a stage catalytic cracking is carried out in riser reactor I, wherein temperature is
530 DEG C, oil ratio is 6, and pressure is 0.2Mpa.Then strip the oil gas in reclaimable catalyst through stripping section, oil gas and to be generated urge
Agent is separated in settler I, obtains reclaimable catalyst and reaction oil gas I.
Reclaimable catalyst enters through inclined tube to be generated to be regenerated in regenerator I, and regeneration gas is mixing for vapor and air
(both volume ratios are 1 to compound：5), temperature is 900 DEG C, and pressure is 0.3MPa, and regenerated catalyst enters by regenerator sloped tube to be carried
Proceed two stage catalytic crackings in riser reactors I.
Regenerate obtained synthesis gas composition as shown in table 7：
The volume composition of the synthesis gas of table 7
| Component | Content (%) |
| H2 | 13.5% |
| CO | 20.0% |
| CO2 | 12.5% |
| N2 | 52.8% |
| SOx(x is 2 and 3) | 0.2% |
| NOx(x is 1 and 2) | 1.0% |
It is as shown in table 8 that reaction oil gas I is fractionated into the isolated product distribution of tower.
The product that table 8 is obtained through base catalysis cracking is distributed
| Product | Yield (wt%) |
| Dry gas, liquefied gas | 4.6% |
| Gasoline | 10.9% |
| Diesel oil | 11.3% |
| Wax oil | 57.9% |
| Coke | 15.3% |
Liquid yield reaches 80% or so it can be seen from the data of table 8.
The property of wherein wax oil is as shown in table 9.
The property of the wax oil of table 9
| Project | The stage catalytic cracking wax oils of Peng Lai VR mono- |
| Density (20 DEG C), g/cm3 | 0.8815 |
| Carbon residue, wt% | 0.34 |
| C, wt% | 85.91 |
| H, wt% | 12.95 |
| N, wt% | 0.87 |
| S, wt% | 0.20 |
| Saturation point, wt% | 55.43 |
| Fragrance point, wt% | 36.16 |
| Colloid, wt% | 8.41 |
Residual carbon content is low in wax oil it can be seen from the data of table 9, is the Conventional catalytic cracking raw material of high-quality.
(2) wax oil that step (1) is obtained proceeds catalytic cracking, and identical in basic step such as (1), difference exists
In：The acidic catalyst used is HY molecular sieve catalyst, and wherein temperature is 515 DEG C, and oil ratio is 6, and pressure is 0.2Mpa.
Reclaimable catalyst regeneration condition be：Using air as regeneration gas, temperature is 580 DEG C, and pressure is 0.3MPa, regeneration
Arranged outside flue gas.
The product distribution obtained through acid catalyst catalytic cracking is as shown in table 10.
Table 10 is distributed through acid catalyzed cracking obtained product
| Product | Yield (wt%) |
| Dry gas, liquefied gas | 19.1% |
| Gasoline | 43.9% |
| Diesel oil | 28.7% |
| Slurry oil | 3.5% |
| Coke | 4.8% |
Petrol and diesel oil yield reaches more than 72% it can be seen from the data of table 10.
Claims (5)
1. a kind of joint catalyst cracking method for handling residual oil and extra heavy oil, comprises the following steps：
(1) water-fast thermocatalyst Catalytic Cracking Residual Oil or extra heavy oil are used, a stage catalytic cracking product is obtained；
The one stage catalytic cracking product is dry gas, liquefied gas, gasoline, diesel oil, wax oil and coke；
The water-fast thermocatalyst is microspheric solid base catalyst；
(2) stage catalytic cracking product is fractionated into after tower separation, and obtained wax oil component carries out two stage catalytic crackings；Using
Wax oil described in acidic catalyst catalytic cracking, obtains two stage catalytic cracking products；
The two stage catalytic crackings product is dry gas, liquefied gas, gasoline, diesel oil, slurry oil and coke.
2. joint catalyst cracking method according to claim 1, it is characterised in that：The microspheric solid base catalyst is
Alkali metal loaded catalyst, alkaline earth metal compound-supported catalyst, hydrotalcite and/or houghite, NaOH, Ca (OH)2Or point
Spar；
The carrier of the alkali metal loaded catalyst and the alkaline earth metal compound-supported catalyst is aluminum oxide, titanium oxide, oxygen
Change zirconium or zeolite molecular sieve.
3. joint catalyst cracking method according to claim 1 or 2, it is characterised in that：In step (1), the catalysis is split
The condition of change is as follows：
Temperature is 460~600 DEG C；
Pressure is 0.1~0.4Mpa；
Oil ratio is 2~10.
4. the joint catalyst cracking method according to any one of claim 1-3, it is characterised in that：It is described in step (2)
The condition of catalytic cracking is as follows：
Temperature is 480~530 DEG C；
Pressure is 0.1~0.4Mpa；
Oil ratio is 4~8.
5. the joint catalyst cracking method according to any one of claim 1-4, it is characterised in that：It is described in step (1)
The step of method also includes regenerating the water-fast thermocatalyst；
The condition of the regeneration is as follows：
Using the mixture of vapor and air as regeneration gas, synthesis gas is obtained after the regeneration；
Temperature is 850~1100 DEG C；
Pressure is 0.2~0.3MPa.
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| CN108897982A (en) * | 2018-07-17 | 2018-11-27 | 中石化（洛阳）科技有限公司 | Catalytic cracking kinetic model method for building up and device |
| WO2023109823A1 (en) * | 2021-12-13 | 2023-06-22 | 中国海洋石油集团有限公司 | Method for directly preparing chemicals from feedstock oil |
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| CN101755036A (en) * | 2007-06-08 | 2010-06-23 | 雅宝荷兰有限责任公司 | Be used to have the high diesel yield of low aromatic content and/or the catalytic cracking process of high propylene yield |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108897982A (en) * | 2018-07-17 | 2018-11-27 | 中石化（洛阳）科技有限公司 | Catalytic cracking kinetic model method for building up and device |
| WO2023109823A1 (en) * | 2021-12-13 | 2023-06-22 | 中国海洋石油集团有限公司 | Method for directly preparing chemicals from feedstock oil |
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