CN1462792A - Method for eatalyzing and transfering petroleum hydrocarbon compounds by using reactor with dual reacting regions - Google Patents
Method for eatalyzing and transfering petroleum hydrocarbon compounds by using reactor with dual reacting regions Download PDFInfo
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Abstract
A process using the reactor with dual reaction regions for catalytic conversion of petroleum hydrocarbon includes reaction between raw material of gasoline, prelifted medium and catalyst in fluidized-bed reactor to generate the mixture of oil gas and catalyst, flowing upward into lifting-tube reaction region, reaction between raw hydrocarbon oil and said mixture to generate the mixture of oil gas and catalyst, separating oil gas from catalyst with carbon deposit in settling unit, further separating the oil gas, and regenerating catalyst.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of method for catalytic conversion of petroleum hydrocarbon that adopts the double-reaction area reactor.
Background technology
Fluid catalytic cracking develops into the history in 60 years today, is the main means of countries in the world oil refining always.It is the effective means that gas oil and residual oil is converted into lightweight oil.。Catalytic cracking unit is the main technique of China petroleum refining industry secondary processing, is used to produce liquefied gas, catalytic gasoline and diesel oil.In China's motor spirit, about 80% (molar fraction) is from catalytic gasoline.Proposed the new standard (GB17930-1999) of China's motor spirit recently, wherein aromaticity content is not more than 40% (molar fraction); Olefin(e) centent is not more than 35% (molar fraction); Benzene is not more than 2.5% (molar fraction); Sulphur is not more than 800ppm (molar fraction), and the quality of catalytic gasoline directly influences the quality of motor spirit.The content of alkene is 40%-60% (molar fraction) in the catalytic gasoline, and therefore must reduce olefin content in gasoline significantly just can obtain qualified motor spirit.Need to develop a kind of method that reduces olefin(e) centent in the catalytic gasoline significantly for this reason.
Disclose the method for a kind of voluminous liquefied gas and gasoline among the CN1085885A, reaction conditions is as follows: temperature of reaction 480-550 ℃, pressure 130-350 kPa, weight hourly space velocity 1-150 hour
-1, agent-oil ratio is that the weight ratio of 4-15, steam and raw material hydrocarbon is 0.05-0.12: 1, yield of liquefied gas reaches the heavy % of 30 heavy %-40 in the reaction product, but contains higher alkene in the gasoline.
CN1065900C discloses a kind of Aromatizatian catalytic method for transformation of gasoline fraction, temperature of reaction 500-650 ℃, pressure 150-400 kPa, weight hourly space velocity 1-6 hour
-1, agent-oil ratio is that the weight ratio of 5-15, steam and raw material hydrocarbon is 0.05-0.5: though 1 this method can be produced a large amount of aromatic hydrocarbons, need to use special-purpose catalyzer.
A kind of catalysis conversion method that improves low-quality gasoline fraction octane value is disclosed among the CN1160746A,
Low-quality gasoline injects from the riser tube bottom, in 600 ℃-730 ℃ of temperature of reaction, weight hourly space velocity 1-180 hour
-1, agent-oil ratio 6-180 condition under the gasoline upgrading reaction takes place, mainly be to obtain high-octane gasoline.This method is raw materials used to be low-quality gasoline such as straight-run spirit, coker gasoline, and the yield of liquefied gas and diesel oil is respectively heavy % of 24 heavy %-39 and the heavy % of 0.5 heavy %-2.3 in the reaction product.But olefin content in gasoline is too high.
The catalysis conversion method of disclosed a kind of high-yield diesel oil and liquefied gas among the CN1279270A, be reflected in the four reaction areas and carry out, gasoline stocks injects the gasoline reaction zone, the heavy % part of 20 heavy %-100 of conventional cracking stock separately or be mixed with slurry oil and/or heavy cycle oil injects the mink cell focus cracking zone together, the heavy % part of 20 heavy %-100 of conventional cracking stock separately or be mixed with slurry oil and/or heavy cycle oil injects the light-oil cracking section together, reaction terminating agent injects the reaction terminating section stops reaction.The residence time of gasoline reaction zone is too short, is unfavorable for the carrying out of aromatization.
USP3,784,463 disclosed methods are to adopt two or more riser reactors, one of them riser tube injects low-quality gasoline, and catalytic conversion reaction takes place, and improves the yield of gasoline octane rating and liquefied gas, need to increase more than one riser tube, equipment is changed bigger.
USP5,846,403 disclose a kind of catalysis raw gasline method of cracking production maximum yield light olefin again, and this method is to carry out in a riser reactor that contains two reaction zones, and reactor lower part is a upstream reaction zone, and top is the downstream reaction district.The raw material of upstream reaction zone is light catalytic naphtha (boiling point is below 140 ℃), and reaction conditions is: 620 ℃-775 ℃ of finish contact temperature, and the oil gas residence time is lower than 1.5 seconds, and agent-oil ratio 75-150, water vapour account for the heavy % of 2 heavy %-50 of petroleum naphtha; The raw material in downstream reaction district is conventional catalytically cracked material (boiling point is 220 ℃-575 ℃), and reaction conditions is: 600 ℃-750 ℃ of temperature, the oil gas residence time is lower than 20 seconds.This method is compared with conventional catalytic cracking, and yield of liquefied gas improves 0.97-1.21 percentage point, and the top reaction zone residence time is too short, is unfavorable for the carrying out of aromatization.
The method of another kind of raising yield of liquefied gas is to add promotor in catalytic cracking catalyst, and as USP4, disclosed method is that the HZSM-5 zeolite that will account for the heavy % of catalyzer 0.01 heavy %-1 directly adds in the catalytic cracking reaction device in 309,280.Do not have gasoline as a kind of independent charging, for the gasoline cracking provides suitable reaction conditions.
USP3,758, disclosing in 403 with ZSM-5 zeolite and large pore zeolite (as Y type, X type) is that (ratio of the two is 1: 10-3: catalyzer 1) can improve the yield and the gasoline octane rating of liquefied gas to active ingredient significantly, and wherein the yield of propylene and butylene increases about 10 heavy %.Other also have CN1004878B, USP4,980,053 and CN1043520A in disclosed mixture with ZSM-5 zeolite and y-type zeolite be the catalyzer of active ingredient, improve the yield of liquefied gas significantly.These class methods mainly are the yields that increases liquefied gas by the mode that changes catalyzer, but olefin(e) centent is too high in the gasoline.
In sum, the method that above-mentioned document provided, its purpose and result are in order to increase the yield of liquefied gas, or improve the yield of gasoline or diesel oil simultaneously, can not reduce the content of alkene in the catalytic gasoline simultaneously significantly, and the some of them method also needs special-purpose catalyzer and equipment, and some needs that also existing catalytic cracking unit is carried out bigger change and is just implemented.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method for catalytic conversion of petroleum hydrocarbon that adopts the double-reaction area reactor, to improve gasoline quality, increasing production of liquid gas and diesel oil.
Method provided by the invention may further comprise the steps:
(a) gasoline stocks and the pre-medium that promotes are injected by the fluidized bed reaction zone bottom, contacts, react with regenerated catalyst in it, and reaction oil gas that is generated and mixture of catalysts make progress mobile, enter riser reaction zone;
(b) hydrocarbon oil crude material injecting lift tube reaction district contacts, reacts with mixture of catalysts with reaction oil gas from step (a), and the reaction oil gas of generation and mixture of catalysts enter in the settling vessel through riser reaction zone;
(c) catalyzer of separating reaction oil gas and reaction back carbon deposit in settling vessel, reaction oil gas is sent into subsequent separation system, and the catalyzer of reaction back carbon deposit is sent into stripper and is carried out stripping;
(d) catalyzer behind the stripping is sent into the revivifier coke burning regeneration, and the catalyzer Returning reactor after the regeneration recycles.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
1, the present invention can be gasoline stocks and creates suitable reaction conditions, makes it have enough residence time that aromizing takes place, takes off alkyl, reaction such as coincide.Gasoline stocks turns to low-molecular-weight hydro carbons and other secondary reaction takes place in the fluidized bed reaction zone implosion, reduces sulphur content and olefin(e) centent in the gasoline simultaneously, improves the octane value of gasoline.
2, adopt already used catalyzer on the device, adding minor amounts of promoters just can increase LPG simultaneously significantly.
3, the sulphur of gasoline stocks mainly is distributed in the heavy constituent, after gasoline stocks enters fluidized bed reaction zone, and under high temperature, high hydrogen transfer activity catalyzer, sulfocompound cracking, hydrogen transference, thus reduce sulphur content in the gasoline significantly.
4, in method provided by the invention, the gasoline stocks of injection can all or part of replacement promote steam in advance, reduces the energy consumption of device, reduces the device sewage emissions, helps environmental protection, can reduce the hydrothermal deactivation of catalyzer simultaneously;
5, increasing considerably of aromatic hydrocarbon can remedy that alkene reduces the loss of the octane value that is brought in the gasoline during gasoline was formed, thereby made gasoline octane rating can maintain higher level or increase.
6, the increasing considerably of aromatic hydrocarbon content in the gasoline can also provide more aromatic hydrocarbon potential content for reformation.Aromatic hydrocarbons is mainly C in the gasoline
6--C
8So, be mainly BTX.
7, can increase substantially diesel and gasoline ratio, satisfy the requirement in market.
8, contact with high temperature catalyst at the fluidized bed reaction zone gasoline stocks, the micro-coke of generation can make the metal passivation that is deposited on the catalyzer, thereby reduces the negative impact that the metal pair product distributes.The coke of trace has covered the most of strong acid center on matrix and the zeolite, the coke forming property when helping suppressing the fresh feed cracking.
9, the present invention can be used for all FCCU, comprise conventional FCC, RFCC, DCC, MGG, ARGG, MGD etc., utilize existing catalytic cracking unit, the transformation that its reactive moieties is carried out a little gets final product, and is about to the riser tube bottom section and is transformed into a dense bed reactor.Less investment, the transformation cycle is short, and gain quick return, favourable promoting the use of.The design and construction that also can be used for new device.
Description of drawings
Fig. 1 is the schematic flow sheet of method provided by the present invention.
Embodiment
The present invention has carried out following improvement to the riser fluid catalytic cracking of routine: the pre-lifting zone in riser tube bottom is designed to the fluidized bed reaction zone of close phase, and this reaction zone top is connected with riser reaction zone, and the two coaxial setting, fixedly connected.In method provided by the invention, the density of fluidized bed reaction zone inner catalyst is 100-500 kilogram/rice
3, preferred 150-400 kilogram/rice
3
The catalyzer that the present invention is suitable for is conventional catalytic cracking catalyst, i.e. solid acid catalyst, and it can be 100% amorphous silicon aluminium, but preferably comprises molecular sieve active ingredient and porous and resistant to elevated temperatures matrix, for example silicon-dioxide (SiO
2), aluminium sesquioxide (Al
2O
3), clay and composition thereof etc.The total content of molecular sieve is generally the heavy % of 10 heavy %-40 in the catalyzer, and remaining is matrix and caking agent.The common y-type zeolite of molecular sieve active ingredient comprises the super steady Y of REY, REHY, Different Silicon aluminum ratio, high silicon Y.Also can contain rare earth in the molecular sieve, the content of rare earth can be the heavy % of 0.1 heavy %-10.Active ingredient preferably contain ZRP, ZSM-5 series zeolite or have in the supersiliceous zeolite of five-membered ring structure, β zeolite, the phosphorus aluminium zeolite a kind of, two or three with the mixing of Y type component.In a word, the present invention adapts to any catalytic cracking catalyst.
In addition, various assistant for calalytic cracking also are applicable to the present invention.Auxiliary agent can add to separately in the device, also can add this adjuvant component in the Preparation of catalysts process.Auxiliary agent can be improve aromatization of gas optionally composition (as shape-selective molecular sieve, ZRP, ZSM-5 and some other have the molecular sieve of analog structure, ZSM-11, ZSM-12, ZSM-21, TEA mordenite), and this molecular sieve of process ion-exchanged, ion-exchange can be H, Cr, ZR, MN, CE, LA etc.Molecular sieve component is carried on and contains Al
2O
3, Al
2O
3-SiO
2, high soil carrier on, as independent auxiliary agent, or sneak in the Primary Catalysts when the general catalytic cracking catalyst of preparation with the component form, make the catalyzer that contains auxiliary agent.The more detailed description of ZRP is referring to CN1058382A; The more detailed description of ZSM-5 is referring to USP3702886; The more detailed description of ZSM-11 is referring to USP3709979; The more detailed description of ZSM-12 is referring to USP3832449; The more detailed description of ZSM-23 is referring to USP4076842, and U.S. Patent application 130442 is seen in the more detailed description of TEA.
Gasoline stocks of the present invention is selected from: the mixture of one or more behind straight-run spirit, coker gasoline, catalytic gasoline, the hydrogenation in gasoline, the viscosity breaking gasoline, wherein, catalytic gasoline both can be the catalytic cracking raw gasline, also can be the catalytic cracking stable gasoline.The boiling range scope of described gasoline stocks can be C
5 +～221 ℃ also can be part narrow fraction wherein, is 90 ℃～140 ℃ or 110 ℃～210 ℃ as boiling spread.The preferred C of gasoline stocks of the present invention
5 +～180 ℃ catalytically cracked gasoline cut.This catalytically cracked gasoline cut both can be that this device is produced, also can be from other device, but be the best with the catalytic gasoline of this device.Pre-lifting medium is dry gas and/or steam.
Hydrocarbon oil crude material of the present invention can be any conventional catalytically cracked material.Hydrocarbon oil crude material is selected from: the mixture of one or more in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum or the long residuum.
The reaction conditions of dense phase fluidized bed reaction zone is as follows: temperature of reaction is 500 ℃-700 ℃, is preferably 550 ℃-680 ℃; Reaction pressure is normal pressure-300,000 fearness, is preferably 100-230 kPa; Weight hourly space velocity is 0.5-6.0 hour
-1, be preferably 1-4 hour
-1The weight ratio of catalyzer and gasoline stocks is 10-150, is preferably 20-80; The weight ratio of gasoline stocks and hydrocarbon oil crude material is 0.05-0.50: 1; Be preferably 0.1-0.3: 1; Regenerated catalyst temperature is 600 ℃-750 ℃, is preferably 660 ℃-700 ℃.
The reaction conditions of riser reaction zone is conventional catalytic cracking reaction condition.The riser tube temperature out is 460 ℃-550 ℃, and the reaction times is 2-10 second, and agent-oil ratio is 3-12, and the weight ratio of water vapor and raw material is 0.02-0.30, and reaction pressure is 130-450kPa.Preferable range is as follows: the riser tube temperature out is 480 ℃-530 ℃, and the reaction times is 2.5-8.0 second, and agent-oil ratio is 4-10, and the weight ratio of water vapor and raw material is 0.05-0.20, and reaction pressure is 200-400kPa.
In method provided by the invention, gasoline stocks both can enter from bottom, close phase reaction district, also can enter from being distributed in this reaction zone nozzle all around.The mode that the present invention enters Mi Xiangfanyingqu to gasoline stocks is disperseed at Mi Xiangfanyingqu as far as possible equably as long as can guarantee gasoline stocks without limits.
Below in conjunction with accompanying drawing method provided by the invention is given further instruction, but therefore the present invention is not subjected to any restriction.The shape and size of equipment and pipeline are not limited by accompanying drawing, and should determine as the case may be.
As shown in Figure 1, promote steam 20 and gasoline stocks 21 in advance and enter from the bottom of close phase reaction district A, contact with regenerated catalyst, the oil gas of generation and reacted catalyzer upwards enter riser reaction zone B; Chargings such as hydrocarbon oil crude material, recycle stock, slurry oil enter the B district through pipeline 2 and nozzle 3 after mixing with certain proportion separately or between them, contact with catalyzer with reaction oil gas from the A reaction zone, oil gas that generates and reacted catalyzer upwards enter the thick cyclonic separator 5 in the settling vessel 8, realize the initial gross separation of catalyzer and oil gas.Oil gas continues to enter secondary cyclone 6, and the oil gas that goes out cyclonic separator 6 continues to enter collection chamber 31, and the fine powder catalyst of being carried secretly in the thick cyclonic separator oil gas is through behind the secondary cyclone 6, and fine powder catalyst returns settling vessel by dipleg.The catalyst stream of inactivation is to stripping stage 11 in the settling vessel, through the chevron shaped baffle plate 12 in the stripping stage with contact from the steam in the steam distribution pipe 23 13.Strip the oil gas in the reclaimable catalyst, oil gas enters collection chamber 31 through behind the cyclonic separator 7.Spent agent behind the stripping enters revivifier 16 through inclined tube 15, and main air 18 enters revivifier, and the coke on the burning-off reclaimable catalyst makes the catalyst regeneration of inactivation, and the regenerated catalyzer flows in the dense bed reactor A through inclined tube 17, recycles.Flue gas 19 enters the cigarette machine.Oil gas in the collection chamber 31 enters follow-up separation system 10, with production sharing thousand gas 25, liquefied gas 26, gasoline 27, diesel oil 28, turning oil 29 and slurry oil 30 through main oil gas piping 9.Part in the gasoline 27 is as the bottom of feed cycle to close phase reaction district A.
The following examples will give further instruction to method provided by the invention, but therefore the present invention is not subjected to any restriction.
Embodiment 1
The present embodiment explanation: adopt method provided by the invention, the use conventional catalyst carries out gasoline cracking, aromizing, desulfurization, falls the situation of alkene in the small fixed flowing bed reactor.The catalytic gasoline feedstock property is referring to the raw material A in the table 1.
Testing sequence is identical with the operation steps of the fixed fluidized bed device of conventional catalytic cracking.With the catalytic gasoline is raw material, uses MLC-500 catalyzer (trade names, Qilu Petrochemical company catalyst plant industrial production) to investigate the influence of temperature variation to aromatic hydrocarbons in the product gasoline.The character of catalyzer sees Table 3.Agent-oil ratio is 30, air speed is 4Hr
-1, temperature is respectively 500 ℃, 550 ℃, 600 ℃, 650 ℃.Testing data is listed in table 4.By data in the table 4 as can be known, aromaticity content increases substantially in the product gasoline, brings up to 97.19 heavy % by 62.77 heavy %, and olefin(e) centent drops to 0.24 heavy % by 5.71 heavy %.Sulphur content drops to below the 26ppm, and octane value increases.
Embodiment 2
Present embodiment explanation: adopt method provided by the invention, use dissimilar catalyzer in the small fixed flowing bed reactor, to carry out gasoline cracking, aromizing, desulfurization, fall the situation of alkene.Testing sequence is identical with the operation steps of the fixed fluidized bed device of conventional catalytic cracking.Feedstock property sees Table the B in 1.With the catalytic gasoline is raw material, uses conventional MLC-500+ to contain the catalyzer of shape-selective molecular sieve auxiliary agent, auxiliary agent catalyzer, RAG-6, the CRP-1 that the conventional LV-23+ of use contains shape-selective molecular sieve.The character of catalyzer sees Table 2, table 3.Testing data is listed in table 5.As shown in Table 5, aromaticity content increases substantially in the product gasoline, reaches more than the 77.68 heavy %; Olefin(e) centent drops to below the 6.67 heavy %; Sulphur content drops to below the 120ppm, and octane value increases.
Embodiment 3
Present embodiment explanation: adopt method provided by the invention, use the MLC-500+ auxiliary agent in the small fixed flowing bed reactor, to carry out gasoline cracking, aromizing, desulfurization under the different operating condition, fall the situation of alkene.
Testing sequence is identical with the operation steps of the fixed fluidized bed device of conventional catalytic cracking.The character of catalyzer sees Table 2; Feedstock property sees Table the A in 1.Test-results is listed in table 6.By the data in the table 6 as can be known, aromaticity content increases substantially in the product gasoline, and olefin(e) centent descends, and sulphur content descends, and octane value increases.
Embodiment 4
Present embodiment explanation: adopt method provided by the invention can improve product and distribute, improve product quality.
On catalytic cracking middle-scale device as shown in Figure 1, test.Main testing sequence is as follows: promote steam and gasoline stocks A (its character is as shown in table 1) in advance and enter from the bottom of dense phase fluidized bed reaction zone, contact, react with regenerated catalyst (MLC-500+ auxiliary agent), the oil gas of generation and reacted catalyzer upwards enter riser reaction zone; Hydrocarbon oil crude material C (its character is as shown in table 7) enters riser reaction zone through pipeline 2 and nozzle 3, contact, react with catalyzer with the reaction oil gas from fluidized bed reaction zone, the oil gas of generation and reacted catalyzer enter in the settling vessel 8 through riser reaction zone; Separating reaction oil gas and reacted catalyzer, reaction oil gas is sent into subsequent separation system, further is separated into various products; And reacted catalyzer is sent into the revivifier coke burning regeneration behind stripping; Catalyzer after the regeneration returns fluidized bed reaction zone and recycles.Main operational condition and test-results see Table 8.
Comparative Examples
This Comparative Examples adopts the disclosed method of CN1279270A to test, and raw materials used oil is with identical with embodiment 4, and catalyzer is MLC-500, and main operational condition and test-results see Table 8.
As can be seen from Table 8, compare with the disclosed method of CN1279270A, method provided by the present invention is compared with Comparative Examples, and sulfur in gasoline content drops to 480ppm by 760ppm; Olefin(e) centent drops to 29 heavy % by 33.17 heavy %; Aromaticity content is raised to 37.4 heavy % by 27.83 heavy %; RON and MON are raised to 94.2 and 81.4 by 93.2 and 80.5 respectively.Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
| The fresh feed numbering | ????A | ????B |
| Density (20 ℃), g/cm 3 | ????0.7431 | ????0.7279 |
| RON | ????91.1 | ????91.4 |
| MON | ????78.9 | ????79.3 |
| Boiling range, ℃ IP 10% 30% 50% 70% 90% EP | ????49 ????65 ????84 ????109 ????140 ????177 ????198 | ????45 ????60 ????79 ????101 ????138 ????168 ????201 |
| C, heavy % | ????86.81 | ????86.72 |
| H, heavy % | ????13.03 | ????13.25 |
| S，ppm | ????202 | ????1988 |
| N，ppm | ????31 | ????142 |
| Group composition, heavy % alkane naphthenic hydrocarbon alkene aromatic hydrocarbons | ????29.64 ????8.25 ????37.79 ????24.32 | ????26.84 ????7.46 ????46.95 ????18.75 |
| The catalyzer title | ????CRP-1 | ????RAG-6 |
| Chemical constitution, heavy % Al 2O 3??Na 2O | ????54.2 ????0.03 | ????45.8 ????0.24 |
| The physical properties specific surface, m 2/ g pore volume, cm 3/ g tap density, g/cm 3Abrasion index, the wt%/hr burning decrement, the wt% size composition, wt% 0～20, micron 20～40, micron 40～80, micron＞80, micron | ????160 ????0.26 ????0.86 ????2 ????12.0 ????5.8 ????20.2 ????60.8 ????13.2 | ????257 ????0.31 ????0.70 ????3.1 ????12.3 ????4.9 ????20.4 ????64.4 ????10.3 |
| Catalyzer | ????MLC-500 | ????LV-23 |
| Chemical constitution, heavy % | ||
| ????Al 2O 3 | ????44.7 | ????51.7 |
| ????Fe 2O 3 | ????0.38 | ????0.40 |
| Physical properties | ||
| Specific surface area, m2/g | ????203 | ????220 |
| Pore volume, cm 3/g | ????2.14 | ????2.39 |
| Apparent density, g/cm 3 | ????0.7921 | ????0.7654 |
| Size composition, % | ||
| 0～40 micron | ????8.5 | ????22.4 |
| 0～80 micron | ????66.3 | ????-- |
| 0～110 micron | ????87.2 | ????81.9 |
| 0～150 micron | ????95.9 | ????-- |
| Catalyzer | ?????????????????????????MLC-500 | |||
| Raw material | Catalytic gasoline A | |||
| Air speed Hr -1 | ?????????????????????????4 | |||
| Agent-oil ratio | ?????????????????????????30 | |||
| Temperature of reaction, ℃ | ????500 | ????550 | ????600 | ????650 |
| Product yield, heavy % | ||||
| Dry gas | ????4.98 | ????10.14 | ????17.08 | ????30.06 |
| Liquefied gas | ????30.37 | ????33.18 | ????31.23 | ????25.71 |
| Gasoline | ????52.27 | ????40.02 | ????31.82 | ????21.50 |
| Diesel oil | ????3.52 | ????3.26 | ????2.31 | ????2.16 |
| Heavy oil | ????0.71 | ????0.60 | ????0.70 | ????0.77 |
| Coke | ????8.15 | ????12.80 | ????16.86 | ????19.80 |
| Gasoline family forms | ||||
| Isoparaffin | ????25.84 | ????17.23 | ????5.83 | ????2.16 |
| Alkene | ????5.71 | ????4.72 | ????1.00 | ????0.24 |
| Naphthenic hydrocarbon | ????5.68 | ????3.67 | ????0.87 | ????0.41 |
| Aromatic hydrocarbons | ????62.77 | ????74.38 | ????92.30 | ????97.19 |
| RON | ????91.4 | ????91.9 | ????92.3 | ????92.9 |
| MON | ????79.2 | ????79.8 | ????80.4 | ????80.8 |
| Sulphur content, ppm | ????26 | ????20 | ????15 | ????11 |
| Catalyzer | The MLC-500+ auxiliary agent | The LV-23+ auxiliary agent | ?RAG-6 | ?CRP-1 |
| Raw material | Catalytic gasoline B | |||
| Air speed Hr -1 | ??????????????????????????4 | |||
| Agent-oil ratio | ??????????????????????????10 | |||
| Temperature of reaction ℃ | ??????????????????????????600 | |||
| Product yield, weigh % dry gas liquefied gas gasoline coke gasoline family and form heavy % alkene aromatic hydrocarbons | ?21.0 ?14.4 ?71.3 ?4.4 ?3.88 ?83.3 | ?20.1 ?13.4 ?72.3 ?4.1 ?4.16 ?81.5 | ?18.36 ?12.6 ?74.4 ?3.68 ?5.78 ?77.68 | ?19.37 ?12.58 ?75.0 ?3.39 ?6.67 ?80.25 |
| Octane value | ||||
| RON | ?93.0 | ?92.7 | ?91.9 | ?91.6 |
| MON | ?81.9 | ?81.2 | ?80.8 | ?79.9 |
| Sulphur content, ppm | ?89 | ?96 | ?104 | ?120 |
| Catalyzer | The MLC-500+ auxiliary agent | |||
| Raw material | Catalytic gasoline A | |||
| Air speed, Hr -1 | ??1.5 | ??4 | ??6 | ??8 |
| Agent-oil ratio | ??4 | ??8 | ??12 | ??16 |
| Temperature of reaction, ℃ | ??500 | ??550 | ??600 | ??650 |
| Product yield, weigh % dry gas liquefied gas gasoline coke gasoline family and form heavy % alkene aromatic hydrocarbons | ??12.5 ??10.4 ??80.3 ??3.23 ??6.89 ??76.8 | ??14.8 ??125 ??78.3 ??4.31 ??4.16 ??78.3 | ??17.87 ??15.1 ??76.01 ??5.07 ??5.78 ??79.52 | ??19.56 ??17.94 ??73.78 ??4.92 ??6.67 ??82.7. |
| Octane value | ||||
| ??RON | ??92.9 | ??91.3. | ??92.1 | ??92.7 |
| ??MON | ??81.8 | ??79.4 | ??80.3 | ??80.5 |
| Sulphur content, ppm | ??38 | ??25 | ??29 | ??19 |
| The stock oil title | ????C |
| Density (20 ℃), g/cm 3Condensation point, ℃ carbon residue, heavy % | ????0.9053 ????45 ????2.3 |
| C, heavy % | ????86.27 |
| H, heavy % S, heavy % N, heavy % | ????12.60 ????1.12 ????0.23 |
| Boiling range, ℃ IP 5% 10% 30% 50% 70% EP | ????268 ????370 ????400 ????453 ????480 ????521 ????-- |
| Test number | Comparative Examples | Embodiment |
| Pre-steam/the gasoline stocks that promotes | ????0.05 | ????0.05 |
| Gasoline stocks/fresh feed | ????0.20 | ????0.20 |
| Gasoline stocks reaction conditions: temperature of reaction, ℃ reaction pressure (gauge pressure), the Kpa agent-oil ratio residence time, h -1 | ????660 ????150 ????77 ????0.3 | ????660 ????150 ????77 ????3.2 |
| Hydrocarbon oil crude material reaction conditions: riser tube outlet, ℃ agent-oil ratio reaction times, sec regeneration temperature ℃ | ????500 ????6 ????2.1 ????670 | ????500 ????6 ????2.1 ????670 |
| Material balance, heavy % dry gas liquefied gas gasoline, diesel slurry oil coke | ????3.56 ????16.34 ????37.96 ????26.51 ????9.25 ????6.38 | ????3.68 ????17.59 ????36.50 ????26.90 ????9.30. ????6.03 |
| Gasoline property: density (20 ℃), g/cm 3S, ppm inductive phase, min RON MON hydrocarbon system forms, v% alkane alkene aromatic hydrocarbons | ????0.7614 ????760 ????632 ????93.2 ????80.5 ????39 ????33.17 ????27.83 | ????0.7701 ????480 ????659 ????94.2 ????81.4 ????33.6 ????29.0 ????37.4 |
Claims (10)
1, a kind of method for catalytic conversion of petroleum hydrocarbon that adopts the double-reaction area reactor is characterized in that this method may further comprise the steps:
(a) gasoline stocks and the pre-medium that promotes are injected by the fluidized bed reaction zone bottom, contacts, react with regenerated catalyst in it, and reaction oil gas that is generated and mixture of catalysts make progress mobile, enter riser reaction zone;
(b) hydrocarbon oil crude material injecting lift tube reaction district contacts, reacts with mixture of catalysts with reaction oil gas from step (a), and the reaction oil gas of generation and mixture of catalysts enter in the settling vessel through riser reaction zone;
(c) catalyzer of separating reaction oil gas and reaction back carbon deposit in settling vessel, reaction oil gas is sent into subsequent separation system, and the catalyzer of reaction back carbon deposit is sent into stripper and is carried out stripping;
(d) catalyzer behind the stripping is sent into the revivifier coke burning regeneration, and the catalyzer Returning reactor after the regeneration recycles.
2,, it is characterized in that described fluidized bed reaction zone is positioned at the bottom of riser reaction zone, with the coaxial setting of riser reaction zone and be connected according to the method for claim 1.
3, according to the method for claim 1 or 2, the density that it is characterized in that described fluidized bed reaction zone inner catalyst is 100-500 kilogram/rice
3
4, according to the method for claim 3, the density that it is characterized in that described fluidized bed reaction zone inner catalyst is 150-400 kilogram/rice
3
5,, it is characterized in that described gasoline stocks is selected from: the mixture of one or more behind straight-run spirit, coker gasoline, catalytic gasoline, the hydrogenation in gasoline, the viscosity breaking gasoline according to the method for claim 1.
6, according to the method for claim 1 or 5, the boiling range scope that it is characterized in that described gasoline stocks can be C
5 +～221 ℃ also can be part narrow fraction wherein.
7,, it is characterized in that described gasoline stocks is a catalytic gasoline according to the method for claim 6.
8,, it is characterized in that described hydrocarbon oil crude material is selected from: the mixture of one or more in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum or the long residuum according to the method for claim 1.
9,, it is characterized in that described gasoline stocks is temperature of reaction 500-700 ℃ at the reaction conditions of fluidized bed reaction zone, reaction pressure normal pressure-300 kPa, weight hourly space velocity 0.5-6.0 hour according to the method for claim 1
-1, the weight ratio of gasoline stocks and hydrocarbon oil crude material is 0.05-0.50: 1.
10, according to the method for claim 9, it is characterized in that described gasoline stocks is temperature of reaction 550-680 ℃ at the reaction conditions of fluidized bed reaction zone, reaction pressure 100-230 kPa, weight hourly space velocity 1-4 hour
-1, the weight ratio of gasoline stocks and hydrocarbon oil crude material is 0.1-0.3: 1.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101164686B (en) * | 2006-10-20 | 2010-05-12 | 中国石油化工股份有限公司 | Multi-bed combination type reactor |
| CN101164687B (en) * | 2006-10-20 | 2010-05-12 | 中国石油化工股份有限公司 | Multi-reaction-area combination type reactor |
| CN101987964A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Catalytic conversion method of hydrocarbon oil |
| CN102102026A (en) * | 2009-12-17 | 2011-06-22 | 中国石油大学(北京) | Method and device for heavy oil tandem regional catalytic cracking |
| CN102234532A (en) * | 2010-05-06 | 2011-11-09 | 中国石油天然气股份有限公司 | Method and device for serial connection, partition and grading catalytic cracking of heavy oil |
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| CN114426895A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for removing sulfide in liquefied gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101164686B (en) * | 2006-10-20 | 2010-05-12 | 中国石油化工股份有限公司 | Multi-bed combination type reactor |
| CN101164687B (en) * | 2006-10-20 | 2010-05-12 | 中国石油化工股份有限公司 | Multi-reaction-area combination type reactor |
| CN102264870A (en) * | 2008-12-23 | 2011-11-30 | 英特卡设备有限公司 | Material withdrawal apparatus and methods of regulating material inventory in one or more units |
| CN102264870B (en) * | 2008-12-23 | 2014-01-08 | 英特卡设备有限公司 | Material withdrawal apparatus and methods of regulating material inventory in one or more units |
| CN101987964A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Catalytic conversion method of hydrocarbon oil |
| CN101987964B (en) * | 2009-07-30 | 2013-12-25 | 中国石油化工股份有限公司 | Catalytic conversion method of hydrocarbon oil |
| CN102102026A (en) * | 2009-12-17 | 2011-06-22 | 中国石油大学(北京) | Method and device for heavy oil tandem regional catalytic cracking |
| CN102102027B (en) * | 2009-12-17 | 2014-04-02 | 中国石油大学(北京) | Heavy oil serial graded and zoned catalytic conversion method and device |
| CN102234532A (en) * | 2010-05-06 | 2011-11-09 | 中国石油天然气股份有限公司 | Method and device for serial connection, partition and grading catalytic cracking of heavy oil |
| CN102234532B (en) * | 2010-05-06 | 2014-08-06 | 中国石油天然气股份有限公司 | Method and device for serial connection, partition and grading catalytic cracking of heavy oil |
| US10117816B2 (en) | 2011-04-01 | 2018-11-06 | L'oreal | Cosmetic process for treating human body odor using a 4-(3-ethoxy-4-hydroxyphenyl)alkyl ketone or 2-ethoxy-4-hydroxyalkylphenol compound |
| CN114426895A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Method for removing sulfide in liquefied gas |
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