CN102453506A - Hydrocarbon oil conversion method - Google Patents
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- CN102453506A CN102453506A CN2010105189365A CN201010518936A CN102453506A CN 102453506 A CN102453506 A CN 102453506A CN 2010105189365 A CN2010105189365 A CN 2010105189365A CN 201010518936 A CN201010518936 A CN 201010518936A CN 102453506 A CN102453506 A CN 102453506A
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Abstract
The present invention provides a hydrocarbon oil conversion method. According to the method, a lift pipe reactor including an upper part reaction zone and a lower part reaction zone is adopted; a diesel raw material, a regeneration catalyst and/or a semi-regeneration catalyst are introduced to the lower part reaction zone, such that the diesel raw material and the catalyst are subjected to a contact reaction; a heavy raw material and a regeneration catalyst are introduced to the upper part reaction zone, such that the heavy raw material and the regeneration catalyst contact the material from the lower part reaction zone. With the method of the present invention, the yield of light oil products (such as gasoline, liquefied gas and diesel) is improved, and the yields of the dry gas and the coke are reduced.
Description
Technical field
The present invention relates to a kind of method of hydrocarbon oil conversion, more particularly, relating to is the high conversion method for hydrocarbon oil of productive rate of a kind of ethene and propylene.
Background technology
Catalytic cracking is one of important means of oil secondary processing, is used for producing gasoline, diesel oil, liquefied gas etc. from heavy raw oil.Catalytic cracking process adopts sieve catalyst; The steam atomizing of raw oil water also sprays in the riser reactor; High temperature catalyst (550-700 ℃) contact reacts in riser tube with from revivifier makes progress along riser tube together, leaves riser reactor subsequently.Reaction product goes separation column to carry out product separation afterwards through in settling vessel, isolating catalyzer.Along with the heaviness of catalytically cracked stock, the problem of existence is the poor qualityization of oil product, and the yield of clean cargo (like gasoline+liquefied gas+diesel oil) is lower, and the productive rate of dry gas and coke is higher.
Summary of the invention
The objective of the invention is to overcome the lower and higher shortcoming of productive rate dry gas and coke of yield of the clean cargo (like gasoline+liquefied gas+diesel oil) that existing conversion method for hydrocarbon oil exists, the yield height of a kind of clean cargo (like gasoline+liquefied gas+diesel oil) and the low conversion method for hydrocarbon oil of productive rate of dry gas and coke are provided.
The invention provides a kind of conversion method for hydrocarbon oil, wherein, this method comprises:
(1) will promote the lower reaction zone that medium, diesel raw material and regenerated catalyst and/or half regenerated catalyst are sent into riser reactor in advance; Under 600-750 ℃ temperature, carry out contact reacts, the top reaction zone that the oil gas that generates and reacted catalyzer are upwards sent into riser reactor;
(2) heavy oil feed and regenerated catalyst are sent into the top reaction zone of riser reactor, under 500-650 ℃ temperature, made said heavy oil feed, regenerated catalyst and carry out contact reacts together from the oil gas and the catalyzer of lower reaction zone;
(3) will be on top the reacted oil gas of reaction zone carry out finish with mixture of catalysts and separate, the oil gas after finish separates is sent to subsequent separation system separating reaction product, the catalyzer after the gas-oil separation obtains reclaimable catalyst behind stripping;
(4) said reclaimable catalyst is carried out coke burning regeneration; Obtain regenerated catalyst; Perhaps in the regenerating unit that contains first revivifier and second revivifier, carry out coke burning regeneration, obtain half regenerated catalyst and regenerated catalyst respectively from first revivifier and second revivifier;
(5) lower reaction zone of the regenerated catalyst that obtains and/or half regenerated catalyst being returned riser reactor recycles, and/or the top reaction zone that the regenerated catalyst that obtains returns riser reactor is recycled.
Conversion method for hydrocarbon oil provided by the invention is through in the riser reactor with top reaction zone and lower reaction zone; With diesel raw material and heavy oil feed respectively with the high temperature catalyst contact reacts; Thereby improved the yield of clean cargo (like gasoline+liquefied gas+diesel oil), and reduced the productive rate of dry gas and coke.
Description of drawings
Fig. 1 is the structural representation of the riser reactor that uses among the embodiment of the invention 1-2.
Embodiment
The invention provides a kind of conversion method for hydrocarbon oil, wherein, this method comprises:
(1) will promote the lower reaction zone that medium, diesel raw material and regeneration and/or half regenerated catalyst are sent into riser reactor in advance; Under 600-750 ℃ temperature, carry out contact reacts, the top reaction zone that the oil gas that generates and reacted catalyzer are upwards sent into riser reactor;
(2) heavy oil feed, regenerated catalyst are sent into the top reaction zone of riser reactor, under 500-650 ℃ temperature, made said heavy oil feed, regenerated catalyst and carry out contact reacts together from the oil gas and the catalyzer of lower reaction zone;
(3) will be on top the reacted oil gas of reaction zone carry out finish with mixture of catalysts and separate, the oil gas after finish separates is sent to subsequent separation system separating reaction product, the catalyzer after the gas-oil separation obtains reclaimable catalyst behind stripping;
(4) said reclaimable catalyst is carried out coke burning regeneration; Obtain regenerated catalyst; Perhaps in the regenerating unit that contains first revivifier and second revivifier, carry out coke burning regeneration, obtain half regenerated catalyst and regenerated catalyst respectively from first revivifier and second revivifier;
(5) lower reaction zone of the regenerated catalyst that obtains and/or half regenerated catalyst being returned riser reactor recycles, and/or the top reaction zone that the regenerated catalyst that obtains returns riser reactor is recycled.
Among the present invention; The definition of term " heavy oil feed " and kind are conventionally known to one of skill in the art, can be in straight-run gas oil, vacuum gas oil, hydrocracking tail oil, hydrofined oil, solvent-deasphalted oils, wax tailings, long residuum, the vacuum residuum one or more.
In addition; The definition of term " diesel raw material " and kind are conventionally known to one of skill in the art; Can be 180-380 ℃ petroleum hydrocarbon cut or the petroleum hydrocarbon cut of boiling range in 180-380 ℃ of scope for boiling range, wherein preferred boiling range be 180-330 ℃ a petroleum hydrocarbon cut.Above-described petroleum hydrocarbon cut can be a crude oil through the straight-run diesel oil (the fraction boiling range is 180-350 ℃) that time processing is produced, one or more mixture in the fraction of diesel oil (the fraction boiling range is 180-350 ℃) that secondary processing is produced; Said time processing is a crude oil atmospheric distillation, and said secondary processing comprises catalytic cracking, coking, hydrogen cracking, hydrotreatment, unifining etc.For example, can be in straight-run diesel oil, catalytic diesel oil, thermally splitting diesel oil, hydrotreatment diesel oil, hydrofining diesel oil, the hydrogen cracking diesel oil one or more.
In the present invention, under preferred situation, said diesel raw material and regenerated catalyst and/or the catalytic temperature of half regenerated catalyst can be 620-670 ℃.Among the present invention, be controlled in the above-mentioned scope through the temperature of reaction with lower reaction zone, diesel raw material is contacted with regenerated catalyst and/or half regenerated catalyst, diesel raw material is carried out cracking, thereby has increased the yield of gasoline and liquefied gas; In the reaction zone of top; Heavy oil feed contacts with the material that regenerated catalyst and lower reaction zone are come, and heavy oil feed is carried out cracking, has optimized the BO reaction environment; Reduce the yield of dry gas and coke, increased the yield of total liquid yield (gasoline+diesel oil+liquefied gas).
According to the present invention, the pressure that said diesel raw material contacts with regenerated catalyst and/or half regenerated catalyst can be 100-450 kPa, is preferably 280-320 kPa; The time of contact can be 0.1-10 second, is preferably 4-8 second.The consumption of said diesel raw material and regenerated catalyst and/or half regenerated catalyst can in very large range change, and under the preferable case, the weight ratio of said regenerated catalyst and/or half regenerated catalyst and diesel raw material can be 2-30: 1, and 5-10 more preferably: 1.
According to the present invention, under preferred situation, the catalytic temperature of said heavy oil feed and regenerated catalyst is 570-620 ℃.The pressure that said heavy oil feed contacts with regenerated catalyst can be 130-450 kPa, is preferably 150-200 kPa; The time of contact can be 0.1-10 second, is preferably 3-7 second.The consumption of said regenerated catalyst (initiate regenerated catalyst) can in very large range change, and under the preferable case, the weight ratio of said regenerated catalyst and heavy oil feed can be 2-15: 1, and 5-10 more preferably: 1.
In the present invention, in said riser reactor, lower reaction zone has no particular limits with the ratio of the volume of top reaction zone; The diameter of each reaction zone of riser reactor can be identical, also can be different, when the diameter of each reaction zone of riser reactor is identical; Then the aspect ratio of top reaction zone and top reaction zone is volume ratio, therefore, rises the flow velocity of medium through adjustment; Can control the duration of contact of reaction raw materials and catalyzer in the riser reactor; Under the preferable case, the ratio 1 of said lower reaction zone and the volume of top reaction zone: 0.2-10, more preferably 1: 6-10.
According to the present invention, said preparatory lifting medium can be a various preparatory lifting medium well known to those skilled in the art, like in water vapor, refinery dry gas, light paraffins, the light olefin one or more.The effect that promotes medium in advance is to make catalyzer quicken to rise, and forms density uniform catalyst piston flow in the riser reactor bottom.The consumption that promotes medium in advance is as well known to those skilled in the art, and preferably, the consumption that promotes medium in advance accounts for the 1-30 weight % of hydrocarbon ils total amount, preferred 2-15 weight %.
According to the present invention, the ratio between said heavy oil feed and the diesel raw material can in very large range change, and under the preferable case, the weight ratio of said heavy oil feed and diesel raw material can be 0.1-10: 1, and 0.2-5 more preferably: 1, most preferably be 2-5: 1.
Among the present invention; Said catalyzer is the cracking catalyst that contains molecular sieve, and consisting of of said cracking catalyst is conventionally known to one of skill in the art, for example; Said cracking catalyst can contain one or more molecular sieves, heat-resistant inorganic oxide, and the clay that contains of selectivity; Wherein, the content of molecular sieve, heat-resistant inorganic oxide and clay is conventionally known to one of skill in the art.
The kind of said molecular sieve is conventionally known to one of skill in the art, for example, can be mesopore and/or the large pore molecular sieve as the catalyst for cracking active ingredient.Said large pore molecular sieve as contain or not phosphorus element-containing y-type zeolite, contain or do not contain the ultrastable Y of REE; Said mesoporous molecular sieve is to contain or one or more in the supersiliceous zeolite with five-membered ring structure, β zeolite, mordenite, omega zeolite of phosphorus element-containing not; Supersiliceous zeolite with five-membered ring structure can be ZSM-5 zeolite and/or ZRP zeolite, preferably contains or not the ZSM-5 zeolite with five-membered ring structure and/or the ZRP zeolite of phosphorus element-containing.
Said heat-resistant inorganic oxide is conventionally known to one of skill in the art, as being selected from aluminum oxide, silicon oxide, amorphous silicon aluminium, zirconium white, titanium oxide, boron oxide, the alkaline earth metal oxide one or more.
Said clay is conventionally known to one of skill in the art, as being selected from kaolin, halloysite, polynite, zeyssatite, halloysite, saponite, tiredly taking off in soil, sepiolite, attapulgite, hydrotalcite, the boron-moisten soil one or more.
Following with reference to Fig. 1, describe reaction process of the present invention in detail.
Diesel raw material after the preheating gets into the bottom of lower reaction zone 1 through first atomizing nozzle 5 of riser reactor; Regenerated catalyst and/or half regenerated catalyst get into the bottom of lower reaction zone 1 through first catalyst inlet 3 of riser reactor simultaneously; Under the castering action of the preparatory lifting medium that gets into the riser reactor bottom through pipeline 7; Said regenerated catalyst and/or half regenerated catalyst and diesel raw material stream rise and contact reacts in lower reaction zone 1 along riser reactor; Afterwards, the reactant flow of lower reaction zone 1 gets into top reaction zone 2.
Heavy oil feed after the preheating is through second atomizing nozzle, the 6 entering top reaction zones 2 of riser reactor; Simultaneously regenerated catalyst is through second catalyst inlet, the 4 entering top reaction zones 2 of riser reactor, heavy oil feed and regenerated catalyst, from reactant flow mixing and contacting reaction in top reaction zone 2 of lower reaction zone 1; Afterwards; The reactant flow of top reaction zone 2 continues to rise to riser reactor outlet back and gets into settlement separator; Separating catalyst and reaction product, catalyzer obtains reclaimable catalyst through the stripper stripping, and reclaimable catalyst entering revivifier burns and obtains regenerated catalyst; Perhaps get in the regenerating unit that comprises first revivifier and second revivifier and carry out coke burning regeneration, obtain half regenerated catalyst and regenerated catalyst respectively from first revivifier and second revivifier.Regenerated catalyst and/or half regenerated catalyst recycle, and reaction product gets into the subsequent product separating device.
In aforesaid method of the present invention, in stripper, adopt water vapor to carry out stripping, its effect be with between the granules of catalyst with the particle hole in the oil gas that is full of cement out, improve the oil product productive rate.The amount that is used for steam stripped water vapor is as well known to those skilled in the art.In general, the consumption that is used for steam stripped water vapor accounts for the 0.1-0.8 weight % of catalyst recirculation amount, preferred 0.2-0.4 weight %.Term " internal circulating load " generally is meant the weight that the unit time inner catalyst transmits between reaction-regeneration system, refer in particular to interior catalyst weight through stripper of unit time here.Because catalyzer has loss after circulation after a while, therefore, need regularly or fresh makeup catalyst aperiodically, with live catalyst through in small-sized charging system or the alternate manner introducing revivifier, with the regenerated catalyst use that is mixed.
With the mode of embodiment the present invention is made detailed description further below in conjunction with accompanying drawing, but the restriction of the scope that should not think the present invention is protected.
In following examples, the consumption that is used for steam stripped water vapor accounts for about 0.4 weight % of catalyst recirculation amount, promotes medium in advance and adopts water vapor.
Present embodiment adopts medium-sized riser reactor; This riser reactor is that total height is 10 meters, and diameter is 25 centimetres a cylindrical structure, wherein; The aspect ratio of bottom, top reaction zone is 1: 7.5, and the below that this riser tube foot is a lower reaction zone is a pre lift zone.
Introduce diesel raw material and regenerated catalyst from lower reaction zone, wherein, diesel raw material is a catalytic diesel oil, and reaction zone is introduced heavy oil feed and regenerated catalyst from top, and wherein, heavy oil feed is a straight-run gas oil.The weight ratio of the inlet amount of straight-run gas oil and the inlet amount of catalytic diesel oil is 1: 2, and raw material properties is listed in table 1.
Employed catalyzer is that the trade mark of Sinopec group Shandong catalyst plant production is the catalyzer of LV-23, and its character is listed in table 2.
Concrete steps do; As shown in Figure 1, the diesel raw material after the preheating gets into lower reaction zone 1 through first atomizing nozzle 5, from the regenerated catalyst warp first catalyst inlet 3 entering lower reaction zone 1 of revivifier; Diesel raw material contacts with regenerated catalyst (CEP-1); Under the effect of the preparatory lifting medium that gets into the riser reactor bottom through pipeline 7, rise along riser reactor, get into top reaction zone 2.
Straight-run gas oil after the preheating is through second atomizing nozzle, 6 entering top reaction zones 2; From the regenerated catalyst of revivifier through second catalyst inlet, 4 entering top reaction zones 2, straight-run gas oil and regenerated catalyst (CEP-1) and from the logistics contact reacts of lower reaction zone; Reactant flow from bottom, top reaction zone rises to riser reactor outlet back entering settlement separator along riser reactor; Separating catalyst and reaction product; Catalyzer obtains reclaimable catalyst through the stripper stripping; Reclaimable catalyst entering revivifier burns and obtains regenerated catalyst, and regenerated catalyst is recycled, and reaction product gets into the subsequent product separating device.
Concrete operational condition and product distribute and list in table 3 and table 4 respectively.
Table 1
| Straight-run gas oil | Catalytic diesel oil | |
| Density (20 ℃)/gram centimeter -1 | 0.8916 | 0.8862 |
| Viscosity (100 ℃)/millimeter 2Second -1 | 6.312 | 4.3(20℃) |
| Zero pour/℃ | 47 | -18 |
| Acid number/milligram KOH gram -1 | 0.81 | 0.45 |
| Basic nitrogen/microgram gram -1 | 404 | 175 |
| Metal (nickel+vanadium)/ppm by weight | 0.6+0.8 | / |
| Carbon residue/weight % | 0.36 | / |
| Sulphur content/weight % | 0.45 | 0.38 |
| Alkene/weight % | / | / |
| Alkane/weight % | 63.6 | / |
| Aromatic hydrocarbons/weight % | 29.2 | / |
| Colloid/weight % | 7.2 | / |
| Bituminous matter/weight % | 0.0 | / |
| Over point/℃ | 288 | 192 |
| 10 volume % distillate a little/℃ | 365 | 214 |
| 30 volume % distillate a little/℃ | 416 | 240 |
| 50 volume % distillate a little/℃ | 442 | 262 |
| 70 volume % distillate a little/℃ | 466 | 295 |
| 90 volume % distillate a little/℃ | 518 | 327 |
| Do/℃ | / | 349 |
Table 2
| The catalyzer trade names | LV-23 |
| Chemical constitution, wt% | |
| Aluminum oxide | 51.4 |
| Sodium oxide | 0.22 |
| RE2O3 | 2.7 |
| Apparent density, kg/m 3 | 710 |
| Pore volume, ml/g | 0.39 |
| Specific surface area, m 2/g | 229 |
| Median size, μ m | 64 |
| Abrasion index, wt% | 1.7 |
| Size composition, wt% | |
| 0-40μm | 19.2 |
| 40-80μm | 49.3 |
| ＞80μm | 31.5 |
According to carrying out hydrocarbon oil conversion with embodiment 1 identical method, different is that reaction conditions is different.Concrete operational condition and product distribute and list in table 3 and table 4 respectively.
Comparative Examples 1
According to carrying out hydrocarbon oil conversion with embodiment 1 identical method, different is different from reaction conditions.Concrete operational condition and product distribute and list in table 3 and table 4 respectively.
Table 3
Table 4
| Product distributes, weight % | |
|
Comparative Examples 1 |
| Dry gas | 3.72 | 3.92 | 4.24 |
| Liquefied gas | 14.62 | 14.95 | 12.58 |
| C5 +Gasoline | 45.73 | 45.34 | 42.45 |
| Diesel oil | 23.23 | 23.06 | 27.24 |
| Heavy oil | 6.46 | 6.27 | 6.62 |
| Coke | 6.24 | 6.46 | 6.87 |
| Liquefied gas+C5 +Gasoline+diesel oil | 83.58 | 83.35 | 82.27 |
Can find out from table 4 result, adopt method provided by the invention, can improve the yield of lightweight oil (like gasoline+liquefied gas+diesel oil), and reduce dry gas and coke yield.
Claims (11)
1. a conversion method for hydrocarbon oil is characterized in that, this method comprises:
(1) will promote the lower reaction zone that medium, diesel raw material and regenerated catalyst and/or half regenerated catalyst are sent into riser reactor in advance; Under 600-750 ℃ temperature, carry out contact reacts, the top reaction zone that the oil gas that generates and reacted catalyzer are upwards sent into riser reactor;
(2) heavy oil feed and regenerated catalyst are sent into the top reaction zone of riser reactor, under 500-650 ℃ temperature, made said heavy oil feed, regenerated catalyst and carry out contact reacts together from the oil gas and the catalyzer of lower reaction zone;
(3) will be on top the reacted oil gas of reaction zone carry out finish with mixture of catalysts and separate, the oil gas after finish separates is sent to subsequent separation system separating reaction product, the catalyzer after the gas-oil separation obtains reclaimable catalyst behind stripping;
(4) said reclaimable catalyst is carried out coke burning regeneration; Obtain regenerated catalyst; Perhaps in the regenerating unit that contains first revivifier and second revivifier, carry out coke burning regeneration, obtain half regenerated catalyst and regenerated catalyst respectively from first revivifier and second revivifier;
(5) lower reaction zone of the regenerated catalyst that obtains and/or half regenerated catalyst being returned riser reactor recycles, and/or the top reaction zone that the regenerated catalyst that obtains returns riser reactor is recycled.
2. method according to claim 1, wherein, said diesel raw material and regenerated catalyst and/or the catalytic temperature of half regenerated catalyst are 620-670 ℃.
3. method according to claim 1 and 2, wherein, the pressure that said diesel raw material contacts with regenerated catalyst and/or half regenerated catalyst is 100-450 kPa, the time of contact is 0.1-10 second.
4. method according to claim 1, wherein, the weight ratio of said regenerated catalyst and/or half regenerated catalyst and diesel raw material is 2-30: 1.
5. method according to claim 1, wherein, the pressure that contacts of said heavy feed stock and regenerated catalyst be 130-450 kPa, the contact time be 0.1-10 second.
6. method according to claim 1, wherein, the weight ratio of said regenerated catalyst and heavy oil feed is 2-25: 1.
7. method according to claim 1, wherein, the weight ratio of said heavy oil feed and diesel raw material is 0.1-10: 1.
8. method according to claim 7, wherein, the weight ratio of heavy oil feed and diesel raw material is 0.2-5: 1.
9. method according to claim 1, wherein, said heavy oil feed is one or more in straight-run gas oil, vacuum gas oil, hydrocracking tail oil, hydrofined oil, solvent-deasphalted oils, wax tailings, long residuum and the vacuum residuum.
10. method according to claim 1, wherein, said diesel raw material is one or more in straight-run diesel oil, catalytic diesel oil, thermally splitting diesel oil, hydrotreatment diesel oil, hydrofining diesel oil, the hydrogen cracking diesel oil.
11. method according to claim 1; Wherein, Said catalyzer is the cracking catalyst that contains molecular sieve, said molecular sieve be contain or not phosphorus element-containing y-type zeolite, contain or do not contain REE ultrastable Y, contain or one or more in the supersiliceous zeolite with five-membered ring structure, β zeolite, mordenite, omega zeolite of phosphorus element-containing not.
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Application publication date: 20120516 |