CN107118797A - A kind of catalyst cracking method for handling residual oil and extra heavy oil raw material - Google Patents
A kind of catalyst cracking method for handling residual oil and extra heavy oil raw material Download PDFInfo
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- CN107118797A CN107118797A CN201710339478.0A CN201710339478A CN107118797A CN 107118797 A CN107118797 A CN 107118797A CN 201710339478 A CN201710339478 A CN 201710339478A CN 107118797 A CN107118797 A CN 107118797A
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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
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of catalyst cracking method for handling residual oil and extra heavy oil raw material.The catalyst cracking method comprises the following steps：Using water-fast thermocatalyst catalytic cracking decompression residuum, heavy oil and/or extra heavy oil, catalytic cracking product is obtained；Catalytic cracking product is dry gas, liquefied gas, gasoline, diesel oil, wax oil and coke；Water-fast thermocatalyst is microspheric solid base catalyst.Catalyst cracking method of the present invention has the advantages that：Available for the processing of 100% residual oil or extra heavy oil (such as oil sands bitumen) raw material, and liquid yield is high, and wherein wax oil component saturated hydrocarbon content height, carbon residue and sulphur nitrogen content are low, can be directly used for Conventional catalytic cracking production premium and diesel oil；The used base catalyst of resistance to hot water type is using gasification regeneration techniques, using vapor and air mixture as regeneration gas, the synthesis gas that H/C ratios are about 1 is obtained, available for the production of the chemical products such as one-step method diesel oil technique or alkene, aromatic hydrocarbons, maximally utilizing for resource value is realized.
Description
Technical field
The present invention relates to a kind of catalyst cracking method for handling residual oil and extra heavy oil raw material, belong to oil-refining chemical technology neck
Domain.
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.
In China, catalytic cracking is because operation is flexible, light oil yield is high, invest and the low feature of operating cost, as most
Important oil secondary operation means, can handle decompressed wax oil and part reduced pressure residual oil.It is Conventional catalytic cracking at present many using acid
Property molecular sieve catalyst, charging is usually decompressed wax oil and decompression residuum mixture, and wherein decompression residuum amount only has 20~30%,
The non-conventional oil resource of pure resid feed or more inferior, such as oil sands bitumen can not directly be processed.
Super steady high silicon rare earth Y type zeolite catalyst, super stabilizing disclosed in CN106268932A disclosed in CN106268918A
USY molecular sieve catalyst, a kind of catalyst containing boehmite disclosed in CN105688977A, disclosed in CN101386788B
The Y zeolite catalyst of phosphorous and rare earth, when for heavy oil catalytic cracking process, its raw material is that wax oil and decompression residuum are mixed
Compound, and slag-mixing amount is not higher than 30%, from the point of view of raw material components, saturated hydrocarbon content is not less than 50%, and aromatic hydrocarbon content is not high
In 30%.Therefore, it is difficult to the direct catalytic cracking of the pure residual oil raw material for saturated hydrocarbon content only 30% or so.
There is significant limitations in process residual oils or extra heavy oil raw material in existing catalytic cracking.On the one hand, contain in residual oil
The macromolecular compound of the easily green coke such as a large amount of colloid, asphalitines, reduces the treating capacity of catalytic cracking unit, and add regeneration
Device load；On the other hand, heavy metal (such as nickel, vanadium) content in residual oil is high, and easily deposition on a catalyst, causes catalyst
Irreversible inactivation, so as to increase catalyst consumption amount, greatly improves operating cost.Residual hydrocracking and it is catalytic cracking combined plus
Work method can be used for the cleaning of residual oil advanced treating to reprocess, and improves yield of light oil and reduces coke output.
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.
CN105199779A discloses a kind of residual hydrocracking and catalytic cracking combined processing method, residual hydrocracking
Obtained liquid phase stream enters catalytic cracking unit, gained catalytic cracking diesel oil hydrogenation after diesel oil is steamed together with wax oil
Posterior circle is refined to catalytic cracking unit.This method can realize the raising of light oil yield, but need additionally to increase a set of residual oil
Hydrotreating and diesel hydro-refining unit, cost of investment is high and flow is complicated.
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 catalyst cracking method for handling residual oil or extra heavy oil raw material, the inventive method is led to
Cross using a kind of new water-fast heated alkaline catalyst, decompression residuum or extra heavy oil raw material can be handled completely, and this is water-fast
The regeneration technology of heated alkaline catalyst is simple, and regeneration temperature can be higher.
The catalyst cracking method of processing residual oil and extra heavy oil provided by the present invention, comprises the following steps：
Water-fast thermocatalyst catalytic cracking decompression residuum, heavy oil and/or extra heavy oil (oil-sand are used in riser reactor
Pitch), obtain catalytic cracking product；
The 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 catalytic cracking product is fractionated into after tower separation, and wax oil component can be used for Conventional catalytic cracking production premium
And diesel oil.
In above-mentioned catalyst cracking method, methods described also comprises the following steps：
Gasification regeneration is carried out to decaying catalyst by regeneration gas of the mixture of vapor and air in a regenerator, obtained
Gaseous product after to regeneration；
The decaying catalyst refers to carrying out the water-fast thermocatalyst after the catalytic cracking；
The condition of the gasification regeneration is as follows：
The volume ratio of vapor and air is more than 1：2, less than 1：1；
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 gaseous product is following (volume content) after the regeneration：
H25~15%, CO 15~30%, CO25~15, N250~60%, SOx(x is 2 and 3)≤1%, NOy(y is 1
With 2)≤1%.
Gaseous product is isolated to the synthesis gas that H/C ratios are about 1 after the regeneration, available for one-step method diesel oil technique
Or the production of the chemical products such as alkene, aromatic hydrocarbons.
In above-mentioned catalyst cracking method, the microspheric solid base catalyst is alkali metal loaded catalyst, alkaline earth
Metal load type catalyst, hydrotalcite and/or houghite, NaOH, Ca (OH)2With spinelle etc., preferably magnesium aluminum ratio is more than 2
The hydrotalcite of (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 catalyst cracking method, 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 catalytic cracking product：
Dry gas, liquefied gas 3~6%；
Gasoline 8~12%；
Diesel oil~10%；
Wax oil 50~60%；
Coke 13~18%；
Wherein, the following (volume of the composition of each component in the catalytic cracking product obtained in embodiment of the invention
Content)：
1) composition of the catalytic cracking product each component 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 catalytic cracking product each component 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 the catalytic cracking wax oil obtained in embodiment of the invention is as follows：
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.
Residual oil or extra heavy oil catalyst cracking method of the present invention has the advantages that：Available for 100% residual oil or overweight
The processing of oily (such as oil sands bitumen) raw material, and liquid yield height, wherein wax oil component saturated hydrocarbon content height, carbon residue and sulphur nitrogen content
It is low, it can be directly used for Conventional catalytic cracking production premium and diesel oil；The used base catalyst of resistance to hot water type uses gas
Change regeneration techniques, using vapor and air mixture as regeneration gas, the synthesis gas that H/C ratios are about 1 is obtained, available for one-step method
The production of the chemical products such as diesel oil technique processed or alkene, aromatic hydrocarbons, realizes maximally utilizing for resource value.
Brief description of the drawings
Fig. 1 is the flow chart of catalyst cracking method of 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, with magnalium than for 2.5 hydrotalcite catalyst handle 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：
Decompression residuum is lifted using dry gas, catalytic cracking is carried out in riser reactor, wherein temperature is 525 DEG C, agent
Oil is than being 5, and pressure is 0.2Mpa.Then the oil gas in reclaimable catalyst is stripped through stripping section, oil gas and reclaimable catalyst are heavy
Separated in drop device, obtain reclaimable catalyst and reaction oil gas.
Reclaimable catalyst enters through inclined tube to be generated to be regenerated in regenerator, and regeneration gas is the mixing of vapor and air
(both volume ratios are 1 to thing：5.5), temperature is 880 DEG C, and pressure is 0.3MPa, and regenerated catalyst enters by regenerator sloped tube to be carried
Proceed catalytic cracking in riser reactors.
Gaseous product composition after regeneration is as shown in table 2：
The volume composition of gaseous product after table 2 regenerates
| Component | Content (%) |
| H2 | 11.5% |
| CO | 19.8% |
| CO2 | 14.1% |
| N2 | 53.6% |
| SOx | 0.4% |
| NOx | 0.6% |
It is as shown in table 3 that reaction oil gas 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, and wherein wax oil component accounts for 60%.
The property of wherein wax oil is as shown in table 4.
The property of the wax oil of table 4
| Project | Da Liya VR catalytic cracking wax oils |
| 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.Embodiment
2nd, Peng Lai decompression residuum is handled than the hydrotalcite catalyst for 3 with magnalium
The fundamental property of Peng Lai decompression residuum is as shown in table 5.
Peng Lai decompression residuum of table 5
Carried out according to the flow shown in Fig. 1, step is as follows：
Decompression residuum is lifted using dry gas, catalytic cracking is carried out in riser reactor, wherein temperature is 530 DEG C, agent
Oil is than being 6, and pressure is 0.2Mpa.Then the oil gas in reclaimable catalyst is stripped through stripping section, oil gas and reclaimable catalyst are heavy
Separated in drop device, obtain reclaimable catalyst and reaction oil gas.
Reclaimable catalyst enters through inclined tube to be generated to be regenerated in regenerator, and regeneration gas is the mixing of vapor and air
(both volume ratios are 1 to thing：5), temperature is 900 DEG C, and pressure is 0.3MPa, and regenerated catalyst enters lifting by regenerator sloped tube
Proceed catalytic cracking in pipe reactor.
The composition of gaseous product is as shown in table 6 after regeneration：
The volume composition of gaseous product after table 6 regenerates
| Component | Content (%) |
| H2 | 13.5% |
| CO | 20.0% |
| CO2 | 12.5% |
| N2 | 52.8% |
| SOx | 0.2% |
| NOx | 1.0% |
It is as shown in table 7 that reaction oil gas is fractionated into the isolated product distribution of tower.
The product that table 7 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 7, and wherein wax oil component accounts for 60%.
The property of wherein wax oil is as shown in table 8.
The property of the wax oil of table 8
Residual carbon content is low in wax oil it can be seen from the data of table 8, is the Conventional catalytic cracking raw material of high-quality.
Embodiment 3, the wax oil obtained with embodiment 2 proceed it is Conventional catalytic cracking, using HY molecular sieve catalysts, instead
It is 515 DEG C to answer temperature, 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 9.
Table 9 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 9.
Embodiment 4, using embodiment 2 regenerate after gaseous product as raw material, hydrogen and carbon monoxide volume are obtained after separation
Than the synthesis gas for 0.7, a certain amount of hydrogen is supplemented, makes H2/ CO=2, is fixed a F- T synthesis, using cobalt as raw material
Base aluminium oxide catalyst, wherein cobalt content (in terms of oxide) 25wt%, process conditions are：240 DEG C of temperature, pressure 2.0Mpa,
Unstripped gas gas hourly space velocity 500h-1.Result of the test is as shown in table 10.
The one-step method from syngas diesel oil result of the test of table 10
The Fischer-Tropsch synthetic that this method is obtained it can be seen from the data of table 10 has good C5 +Yield, and without solid
Body wax is present, and aviation Determination of Diesel Oil is up to more than 65% in liquid-phase product.
Claims (5)
1. a kind of catalyst cracking method for handling residual oil and extra heavy oil, comprises the following steps：
Using water-fast thermocatalyst catalytic cracking decompression residuum, heavy oil and/or extra heavy oil, catalytic cracking product is obtained；
The 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. catalyst cracking method according to claim 1, it is characterised in that：Methods described also comprises the following steps：
Gasification regeneration is carried out to decaying catalyst by regeneration gas of the mixture of vapor and air in a regenerator, obtained again
Gaseous product after life；
The decaying catalyst refers to carrying out the water-fast thermocatalyst after the catalytic cracking；
The condition of the gasification regeneration is as follows：
The volume ratio of vapor and air is more than 1：2, less than 1：1；
Temperature can be 850~1100 DEG C；
Pressure can be 0.2~0.3MPa.
3. catalyst cracking method according to claim 2, it is characterised in that：The composition of gaseous product is such as after the regeneration
Under, volume content：
H25~15%, CO 15~30%, CO25~15, N250~60%, SOx(x is 2 and 3)≤1%, NOy(y is 1 and 2)
≤ 1%；
Gaseous product is isolated to synthesis gas after the regeneration.
4. renovation process according to claim 3, it is characterised in that：Product syngas after the regeneration can be used for one-step method
Diesel oil technique processed or alkene, the production of aromatic hydrocarbons chemical products.
5. the catalyst cracking method according to any one of claim 1-4, it is characterised in that：The condition of the catalytic cracking
It is as follows：
Temperature is 460~600 DEG C；
Pressure is 0.1~0.3Mpa；
Oil ratio is 2~10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114292665A (en) * | 2021-12-13 | 2022-04-08 | 中国海洋石油集团有限公司 | Heavy oil modification method and heavy oil modification system |
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- 2017-05-15 CN CN201710339478.0A patent/CN107118797A/en active Pending
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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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| CN114292665A (en) * | 2021-12-13 | 2022-04-08 | 中国海洋石油集团有限公司 | Heavy oil modification method and heavy oil modification system |
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