CN1151236C - Catalytic conversion process of utilizing hydrogen donor component to reduce olefine content in gasoline - Google Patents
Catalytic conversion process of utilizing hydrogen donor component to reduce olefine content in gasoline Download PDFInfo
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Abstract
The present invention relates to a catalytic conversion method for reducing the olefinic content of gasoline by using a hydrogen supplying component. A hydrocarbon raw material, the hydrogen supplying component and a catalyst are mixed and reacted in a catalytic cracking reactor, oil gas and the catalyst are separated after the reaction, the oil gas is sent to a follow-up separation system, and the reacted catalyst of carbon deposition is sent to the reactor by steam stripping and regeneration for circulation use. The olefinic content of the gasoline can reduce more than 10 units by using the method, and product distribution and product properties can also be improved.
Description
The invention belongs to the catalysis conversion method of petroleum hydrocarbon, more particularly, is a kind of catalysis conversion method that utilizes hydrogen donor component to reduce olefine content in gasoline.
The sustained and rapid development of Chinese national economy has driven developing of automobile industry, has also brought problems such as vehicle emission pollution simultaneously.According to statistics, about 63% CO in the air, 50% NO
XWith 73% hydro carbons from motor vehicle emission, therefore, the discharging of automobile nuisance has become one of primary pollution source of air.In order to protect and to improve environment, reduce vehicle emission pollution, Environmental Protection in China general bureau has issued " motor spirit objectionable impurities control criterion " in June, 1999.The sulphur content of this standard-required gasoline is not more than 0.08 heavy %, and benzene content is not more than 2.5v%, and aromaticity content is not more than 40v%, and olefin(e) centent is not more than 35v%.
According to China's Petrochemical Enterprises conventional device and state of the art, also there is certain difficulty in the Fuel Petroleum that production and supply meets above-mentioned laws and regulations requirement, and especially the olefin(e) centent of gasoline is difficult to reduce to below the 35v%.Major cause is that catalytically cracked gasoline accounts for about 85% in China's motor spirit, and catalytically cracked gasoline is a kind of gasoline fraction that is rich in alkene, and its olefin(e) centent is generally 40～70v%.Make the olefin(e) centent of China's motor spirit generally greater than 40v%, be difficult to satisfy the requirement of environmental protection aspect.Therefore, reducing catalytic cracking gasoline olefine content is the key point that solves motor spirit olefin(e) centent problem.
In recent years, " reduce the olefin(e) centent of catalytically cracked gasoline " and become one of the research focus in catalytic cracking field.People have carried out extensive studies and exploration from aspects such as catalyzer, processing condition and device structures, and relevant bibliographical information is also many.
CN1323069A has disclosed a kind of method that more typically reduces content of olefin in gasoline.The reactor that this method adopted be the middle part enlarged-diameter riser reactor.Just because of the hole enlargement of reactor middle part, prolonged the duration of contact of reaction oil gas and catalyzer, for secondary reactions such as the hydrogen transference of petroleum hydrocarbon, isomerization have been created condition, thereby can obviously reduce the olefin(e) centent of gasoline.But, make its enforcement be subjected to certain limitation because the change of this method aspect equipment is bigger.
USP4871699 discloses a kind of method of improving the distribution of catalytic cracking product by means of hydrogen donor component.This method is to have amassed the reclaimable catalyst that a certain amount of coke is arranged after utilizing hydrogen donor component stripping reactions such as tetraline, anthracene dihydride, make a part of coke precursor adsorbed on the reclaimable catalyst break away from catalyst surface, and enter in the reaction oil gas with stripped vapor.Adopt this method can reduce coke yield and improve the purpose product yield.
USP4802971 has disclosed a kind of catalyst cracking method of introducing hydrocarbon fragment in riser reactor.This method is to make rich hydrogen raw material, for example, C1～C5 petroleum hydrocarbon from catalytic unit, carry out thermally splitting and/or catalytic cracking reaction in the riser tube bottom, generation contains the gaseous stream of hydrogen or hydrocarbon fragment, heavy hydrocarbon oil after processes such as viscosity breaking are handled reacts in the presence of catalyzer, hydrogen and hydrocarbon fragment from the above position of rich hydrogen material inlet injecting lift pipe.This method can improve gasoline yield and octane value thereof effectively.
USP4035285 is in the presence of molecular sieve catalyst, and the hydrocarbon fragment of small molecules carries out catalytic cracking reaction with heavy petroleum hydrocarbon, and the hydrocarbon fragment of small molecules is in order to improve the cracking performance of heavy petroleum hydrocarbon.This method not only can improve gasoline yield, can also reduce the content of impurity such as sulfur in gasoline, nitrogen etc.
USP5152883 and USP5770043 make hydrocarbon raw material at first carry out catalytic cracking reaction, reaction product isolated, and the heavy crude product more than the diesel oil distillate is delivered to hydrogenation unit carry out hydrotreatment, the above heavy ends of gasoline fraction is sent catalytic cracking unit cracking once more back in the hydrogenated oil.This method is mainly in order to produce stop bracket gasoline and low-carbon alkene.
USP5944982 adopts duo-lift tube reactor to carry out catalytic cracking reaction, and fresh feed oil reacts in a riser tube, and another root riser tube is used for turning oil behind the cracking and hydrogenation, contains some light cycle oil in the described turning oil at least.The contriver of this patent thinks, adopts turning oil behind the independent riser reactor cracking and hydrogenation can obviously improve product and distributes and product property; And adopt conventional riser reactor, the turning oil behind the hydrogenation mixed with fresh feed mix when refining, above-mentioned beneficial effect is also not obvious.
In sum, though provide some to reduce the method for catalytic cracking gasoline olefine content in the prior art, also introduce and in catalytic cracking unit, introduced hydrogen donor component, improved the method for product distribution and product property, but utilized the method for hydrogen donor component to reduce olefine content in gasoline not relate to as yet in the prior art.
Purpose of the present invention just is to provide a kind of method of utilizing hydrogen donor component to reduce catalytic cracking gasoline olefine content.
Method provided by the invention is as follows: hydrocarbon raw material, hydrogen donor component and catalyzer be thorough mixing and reaction in catalyst cracker, oil gas behind the separating reaction and catalyzer, oil gas is delivered to subsequent separation system, the catalyzer of reaction back carbon deposit is delivered to reactor cycles and is used after stripping, regeneration.
Describe method provided by the invention below in detail.
Hydrocarbon raw material used in the present invention can be selected from: the mixture of one or more in gasoline fraction, diesel oil distillate, decompressed wax oil, wax tailings, deasphalted oil, hydrocracking tail oil, vacuum residuum or the long residuum.Method provided by the invention is particularly suited for handling the gasoline fraction that is rich in alkene, for example, catalytic gasoline, coker gasoline, viscosity breaking gasoline etc., and described gasoline fraction both can be full cut, also can be the part narrow fraction, for example, 90～150 ℃ of cuts.The present invention to the olefin(e) centent in the described gasoline fraction without limits.
Hydrogen donor component of the present invention is meant that the Engler distillation boiling range is 155～400 ℃ straight run oil and/or the distillate behind the hydrogenation.Specifically, hydrogen donor component of the present invention can be selected from: the mixture of the gasoline fraction behind straight-run spirit, straight-run diesel oil, the hydrogenation, the diesel oil distillate behind the hydrogenation and above-mentioned two or more cut, gasoline fraction behind the wherein preferred hydrogenation and/or the diesel oil distillate behind the hydrogenation.
In addition, hydrogen donor component of the present invention can also be selected naphthenic hydrocarbon or the cycloalkyl aromatic hydrocarbons that contains 1～3 cycloalkyl for use, for example, and C6～C8 naphthenic hydrocarbon, tetraline, perhydronaphthalene, indane, tetrahydrochysene anthracene, octahydro anthracene etc.
In method provided by the invention, preferably hydrogen donor component is recycled.For example, when with the diesel oil distillate behind the hydrogenation (abbreviation hydrogenated diesel oil) during as hydrogen donor component, hydrogenated diesel oil, hydrocarbon raw material and catalyzer fully contact in catalyst cracker and react, oil gas behind the separating reaction and catalyzer, oil gas is sent into follow-up system and further is separated into various products such as gasoline, diesel oil, all or part of diesel product is carried out hydrotreatment (hydrofining, hydrocracking etc. all can), and the hydrogenated diesel oil that is generated promptly can be used as hydrogen donor component and recycles.
Catalyst system therefor of the present invention can be catalytic cracking field any solid acid catalyst commonly used, and it both can be a molecular sieve catalyst, also can be the amorphous silicon Al catalysts.When adopting molecular sieve catalyst, its active ingredient is selected from one or more in Y type or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, the ZSM-5 type zeolite that contains or do not contain rare earth and/or phosphorus or the supersiliceous zeolite with five-membered ring structure, β zeolite, the ferrierite.
Method provided by the invention both can be implemented on the catalytic cracking unit of routine, also can implement on improved catalytic cracking unit.Conventional catalytic cracking unit comprises: riser fluid catalytic cracking, fluidized bed catalytic cracker, Desending catalytic cracking device etc.Described improved catalytic cracking unit is meant on the basis of above-mentioned conventional equipment transforms the resulting device in back to reaction, regeneration, fractionation and/or absorption-steady component.For example, riser tube+bed device, the disclosed device of CN1237477A, application number are device related in 01102241.8 the patent application etc.
In method provided by the present invention, hydrocarbon raw material and hydrogen donor component and catalyzer thorough mixing, and under following condition, react: temperature of reaction is 450～560 ℃, preferred 460～520 ℃; Agent-oil ratio 4～100, preferred 5～20; 0.5～5 second reaction times, preferred 1～3 second; Atomizing steam amount (accounting for combined feed total feed) 0～20 heavy %, preferred 3～20 heavy %; Reaction pressure 0.1～0.5Mpa, preferred 0.1～0.3Mpa.
Method provided by the invention can be implemented separately, promptly independently finish processes such as reaction, regeneration, separation, also can with the catalytic cracking process Joint Implementation of routine, when finishing conventional catalytic cracking reaction process, gasoline fraction is carried out catalyzed conversion, reduce content of olefin in gasoline.
Below in conjunction with accompanying drawing, enumerate several concrete embodiments, further specifying the present invention, but therefore the present invention is not subjected to any restriction.
Fig. 1 is the schematic flow sheet that the present invention implements separately.
Fig. 2 is the schematic flow sheet of the catalytic cracking process Joint Implementation of the present invention and routine.
Fig. 3 is the schematic flow sheet that the present invention implements on a kind of improved catalytic cracking unit.
Embodiment one: the present invention implements separately on riser tube or fluidized bed catalytic cracker.As shown in Figure 1, enter jointly in the riser reactor 3, be in or be not in water vapor and react under existing from regenerated catalyst and the gasoline fraction after the preheating 1, the hydrogen donor component 2 of revivifier 4; Separating reaction oil gas and reacted spent agent, reaction oil gas is sent into subsequent separation system, further is separated into gasoline products and a spot of dry gas, liquefied gas, diesel oil; Spent agent is imported revivifier 4, coke burning regeneration in the presence of oxygen-containing gas behind the water vapor stripping; Catalyzer Returning reactor after the regeneration recycles.
Embodiment two: the present invention and conventional catalytic cracking process Joint Implementation.As shown in Figure 2, except being used for heavy petroleum hydrocarbon cracked riser reactor 5, need a newly-built riser reactor 6.The shared settling vessel 7 of newly-built reactor and original reactor, stripper 8, subsequent separation system and revivifier 13.The raw material of newly-built reactor 6 is a gasoline fraction, and this reactor is called gasoline reactor 6; Original reactor 5 is a raw material with the heavy petroleum hydrocarbon, and this reactor is called stock oil reactor 5.Gasoline stocks 9, hydrogen donor component 10 and catalyzer be thorough mixing and reaction in gasoline reactor 6; Conventional heavy hydrocarbon oil raw material 11 contacts with catalyzer in stock oil reactor 5, also reaction; Above-mentioned two reaction oil gas that reactor generated enter settling vessel 7 jointly and subsequent separation system is separated, and isolated raw gasline product can partly return the raw material as the gasoline reactor; Reclaimable catalyst is regenerated behind stripping.Catalyzer after the regeneration is divided into two portions, and a part is returned the stock oil reactor cycles and used, and another part returns the gasoline reactor cycles and uses.
Embodiment three: the employing application number is related reactor enforcement the present invention of Chinese patent application of 01102241.8.Application number be the related reactor of 01102241.8 Chinese patent application as shown in Figure 3, this reactor is made of riser tube 15, stripper 16, the first fluidized bed 17, second fluidized-bed 18 and settling vessel 19.The pre-medium that promotes is through pipeline 20 injecting lift pipes bottom, and 600～750 ℃ regenerator enters in the riser tube through regenerator sloped tube 21, and realizes turning to and quickening of regenerator under the effect of pre-lifting medium; Heavy raw oil sprays in the riser tube through feed nozzle 22, contacts with the high temperature regeneration agent, vaporizes rapidly and reacts; Reaction oil gas and mixture of catalysts are up along riser tube, and the grid distributor 23 through the riser tube exit enters in second fluidized-bed 18, and the catalyzer in second fluidized-bed is close and distributes mutually; Catalyzer in a part second fluidized-bed flows downward and enters in the first fluidized bed, and is close distribution mutually in the first fluidized bed; Hydrogen donor component enters in the first fluidized bed through pipeline 25, contacts with wherein catalyzer, and the oil gas that is generated upwards flows into second fluidized-bed; The gasoline fraction of pre-upgrading injects second fluidized-bed through pipeline 24, and converges from the hydrogen donor component of the first fluidized bed with from the reaction oil gas of riser tube; Hydrogen donor component also can with common second fluidized-bed that injects of the gasoline fraction of pre-upgrading, converge with reaction oil gas from riser tube; Catalyzer in above-mentioned oil gas and second fluidized-bed fully contacts and reacts; Reaction oil gas and part catalyzer upwards flow in the settling vessel, and by means of the gas solid separation facility in the settling vessel, separating reaction oil gas and catalyzer; Oil gas is sent into follow-up fractionation and absorption-stable system through pipeline 27; Reacted catalyzer flows downward, and enters in the stripper through the first fluidized bed; Reacted catalyzer removes and reaches the inner entrained reaction oil gas of catalyst pores between the granules of catalyst under the effect of stripping steam; Catalyzer behind the stripping enters the revivifier coke burning regeneration through inclined tube 26 to be generated; Catalyzer after the regeneration returns riser tube and recycles.
Compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
1, adopts method provided by the invention not only can make the olefin(e) centent of gasoline products reduce by 10 more than the unit, the content of impurity such as sulfur in gasoline, nitrogen is decreased, and do not have detrimentally affect for the octane value of gasoline.In addition, method provided by the invention also can make the cetane value of diesel product improve about 9 units, and the existent gum of diesel oil and sulphur content are reduced.
2, method provided by the invention can be improved the product distribution, and the yield of high-value product is improved.
Therefore, oil refining enterprise adopts method provided by the invention, not only can solve the content of olefin in gasoline problem, guarantee that product dispatches from the factory smoothly, can also make oil refining enterprise obtain considerable economic because of the improvement that product distributes.
3, the method for reduction content of olefin in gasoline provided by the invention is different from the existing olefins process that falls.
The present invention introduces hydrogen donor component in the catalytic conversion process of hydrocarbon ils, and under the condition that hydrogen donor component exists, hydrogen transfer reactions is strengthened, thereby has avoided the problems such as product distribution variation, dry gas and coke yield increase that usually occur in the prior art.
4, for existing catalytic cracking unit, only need set up hydrogen donor component supply line and flow control system thereof, can implement the present invention.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Used catalyzer is industrial by Lanzhou oil-refining chemical head factory catalyst plant in the test, and trade names are LV-23.This catalyzer has passed through normal pressure, 800 ℃, 100% water vapor, 15 hours burin-in process before test, the micro-activity after the catalyst aging is 62, and its main physico-chemical property sees Table 1.The physico-chemical property of testing raw materials used oil sees Table 2.The character of used hydrogen donor component sees Table 3.
Embodiment 1
Present embodiment explanation: adopt conventional catalytically cracked stock, and with perhydronaphthalene as hydrogen donor component, on the small fixed flowing bed device, implement the present invention, the olefin(e) centent of gasoline is obviously reduced, also can improve product and distribute.
This test be the catalyzer loading amount be 200 the gram the small fixed flowing bed devices on carry out.Testing raw materials used is the defeated mixing oil of 90 heavy % pipes+10 heavy % perhydronaphthalenes, and the defeated oil properties of mixing of pipe is referring to table 2.The test catalyst system therefor is LV-23, and its character is referring to table 1.Testing sequence is as follows: the mixture of above-mentioned raw materials oil with hydrogen donor component is preheated to about 200 ℃, after water vapor atomizing in the injecting reactor, contact with catalyzer in the reactor and react, reaction oil gas is collected resulting reacted gas and product liquid after three grades of condensations coolings; It forms reacted gas by gas chromatographic analysis, C
5Above component counts in the gasoline fraction; Product liquid is measured the content of gasoline, diesel oil and heavy oil by the simulation distil device; The reacted catalyzer of stripping, aerating oxygen coke burning regeneration then; Collect regenerated flue gas, and it is measured and analyzes, determine CO in the flue gas
2Content with CO; Catalytic cracking material balance by routine is calculated the material balance data of determining this test.Main operational condition and material balance are referring to table 4.
Comparative Examples 1
This Comparative Examples is the benchmark of embodiment 1, in order to implementation result of the present invention to be described.
To manage defeated mixing oil is raw material, does not adopt hydrogen donor component, repeats embodiment 1 described test, and the testing apparatus that is adopted, catalyzer and testing sequence are all identical with embodiment 1.Main operational condition and material balance are referring to table 4.
Two groups of data in the table 4 are compared as can be seen: after adopting the present invention, liquefied gas+gasoline+diesel yield improves 3.55 percentage points, and the productive rate of dry gas, heavy oil and coke obviously descends; Trimethylmethane brings up to 2.37 with the ratio of total butylene by 1.95 in the reacted gas, illustrates to adopt hydrogen transfer reactions of the present invention to be strengthened; Because the present invention is under the prerequisite that hydrogen donor component exists, and strengthens the hydrogen transfer reactions in the hydrocarbon ils catalytic conversion process, therefore method provided by the invention does not cause the raising of coke yield, and it is decreased; After adopting the present invention, the olefin(e) centent of gasoline is reduced to 21.8v% by 33.6v%, and sulphur, the nitrogen content of gasoline also decrease.
Embodiment 2
Present embodiment explanation: with gasoline fraction as stock oil, methylcyclohexane as hydrogen donor component, on the small fixed flowing bed device, implement the present invention, the olefin(e) centent of gasoline is obviously reduced.
Testing apparatus, testing sequence and the catalyzer that is adopted are all identical with embodiment 1.To manage defeated gasoline F-4 is raw material, and this gasoline fraction is the mixing oil of coker gasoline and catalytic gasoline, and blending ratio is 40: 60, and its character is referring to table 2 and table 5; As hydrogen donor component, its add-on accounts for 8 heavy % of the defeated gasoline of pipe with methylcyclohexane.Main operational condition and product distribute and see Table 5.
Comparative Examples 2
This Comparative Examples is the benchmark of embodiment 2, in order to implementation result of the present invention to be described.
Testing apparatus, testing sequence, stock oil, catalyzer and main operational condition are all identical with embodiment 2, do not add hydrogen donor component in process of the test.Main operational condition and product distribute and see Table 5.
Two groups of data in the table 5 are compared as can be seen: in the presence of hydrogen donor component, the catalytic reforming effect of the defeated gasoline of pipe is even more ideal, and liquefied gas+gasoline+diesel yield improves 2.30 percentage points, and the productive rate of coke and dry gas reduces; The character of gasoline products also further improves, and for example, olefin(e) centent is reduced to 30.7V% by 41.3V%, and sulphur content is reduced to 739mg/l by 973mg/l, and nitrogen content is by reducing to 4.9mg/l by 9.2mg/l; Trimethylmethane brings up to 3.12 with the ratio of total butylene by 1.99 in the reacted gas, employing the present invention be described after hydrogen transfer reactions strengthened.
Comparative Examples 3
This Comparative Examples is to carry out on treatment capacity is the riser catalytic cracking middle-scale device of 0.24t/d.F-1 is a raw material with the oil of the Daqing Mixing in the table 2, adopt the LV-23 catalyzer shown in the table 1, testing sequence is summarized as follows: after stock oil F-1 is preheated to 250 ℃, by being arranged in the high-efficient atomizing nozzle injecting reactor of riser reactor bottom, with from the contacting and react of revivifier through the pre-high temperature catalyst that promotes of steam, oil gas and mixture of catalysts are up along riser tube; Reaction oil gas is in settling vessel and catalyst separating, and oil gas enters subsequent separation system through transfer line, further is separated into products such as reacted gas, gasoline, diesel oil, and various products are measured and analyze; The catalyzer of reaction back carbon deposit enters the revivifier coke burning regeneration behind the water vapor stripping; Catalyzer after the regeneration returns riser reactor and recycles.Main operational condition and test-results see Table 6.
Embodiment 3
Present embodiment explanation: adopt conventional catalytically cracked stock, and with the grand celebration hydrogenated diesel oil as hydrogen donor component, on the riser catalytic cracking middle-scale device, implement the present invention, the olefin(e) centent of gasoline is obviously reduced, also can improve product and distribute.
Testing apparatus, testing sequence and the catalyzer that is adopted, stock oil are all identical with Comparative Examples 3.As hydrogen donor component, its character is referring to table 3 with grand celebration hydrogenated diesel oil D-1.Hydrogen donor component D-1 mixes in the injecting lift pipe reactor of back with Daqing Mixing oil F-1, and the injection rate of hydrogen donor component accounts for 7.6 heavy % of Daqing Mixing oil.Main operational condition and test-results see Table 6.
As can be seen from Table 6, be benchmark with Comparative Examples 3, the liquefied gas yield of embodiment 3 improves 1.07 percentage points, and diesel yield improves 3.01 percentage points, and its dry gas, coke and heavy oil productive rate all decrease; The content of olefin in gasoline of embodiment 3 has reduced by 15 units, and total sulfur and mercaptan sulfur content slightly reduce, and inductive phase and octane value slightly improve; The diesel cetane-number of embodiment 3 has improved 9 units, and its existent gum and sulphur content decrease.By above-mentioned data as can be seen, adopt the present invention not only can obviously improve product and distribute, the quality of vapour, diesel oil is increased.
Embodiment 4
Present embodiment explanation: adopt conventional catalytically cracked stock, and with straight-run spirit as hydrogen donor component, at application number is to implement the present invention on the related reactor of 01102241.8 Chinese patent application, and the olefin(e) centent of gasoline is obviously reduced, and also can improve product and distribute.
With wax oil F-2 in Jinzhou in the table 2 is raw material, adopt the LV-23 catalyzer shown in the table 1, testing sequence is summarized as follows: after stock oil F-2 is preheated to 250 ℃, in high-efficient atomizing nozzle injecting lift pipe reactor, with contacting and react from revivifier through the pre-high temperature catalyst that promotes of steam, oil gas and mixture of catalysts are up along riser tube, and the grid distributor through the riser tube exit enters second fluidized-bed; Catalyzer in a part second fluidized-bed flows downward and enters in the first fluidized bed, and is close distribution mutually in the first fluidized bed; Hydrogen donor component D-2 injects the first fluidized bed, contacts with wherein catalyzer, and the oil gas that is generated upwards flows into second fluidized-bed; The part raw gasline product of this device injects second fluidized-bed, and converges from the hydrogen donor component of the first fluidized bed with from the reaction oil gas of riser tube; Catalyzer in above-mentioned oil gas and second fluidized-bed fully contacts and reacts; Reaction oil gas and part catalyzer upwards flow in the settling vessel, and by means of the gas solid separation facility in the settling vessel, separating reaction oil gas and catalyzer; Oil gas is sent into follow-up fractionation and absorption-stable system; Reacted catalyzer flows downward, and enters in the stripper through the first fluidized bed, and reacted catalyzer removes and reaches the inner entrained reaction oil gas of catalyst pores between the granules of catalyst under the effect of stripping steam; Catalyzer behind the stripping enters the revivifier coke burning regeneration, and the catalyzer after the regeneration returns riser tube and recycles; Various products are measured and analyze.Main operational condition and test-results see Table 7.As shown in Table 7, implement the present invention and can obtain comparatively ideal product distribution and product property.
Table 1
| The catalyzer title | LV-23 |
| Chemical constitution, heavy % Al 2O 3 Na 2O RE 2O 3 | 51.2 0.32 2.0 |
| Fresh dose of physical properties specific surface, m 2/ g pore volume, ml/g tap density, g/cm 3Aging agent micro-activity | 228 0.39 0.70 62 |
Table 2
| The stock oil numbering | F-1 | F-2 | F-3 | F-4 |
| The stock oil title | Daqing Mixing oil | Jinzhou VGO | The defeated mixing oil of pipe | The defeated gasoline of pipe |
| Density (20 ℃), g/cm 3Condensation point, ℃ aniline point, ℃ carbon residue, heavy % | 0.8881 ＞50 112.9 2.7 | 0.9292 25 74.8 0.34 | 0.9048 38 92.5 2.8 | 0.7561 / / / |
| H, heavy % S, ppm N, ppm | 13.01 1300 2000 | 12.51 2400 2100 | / 5900 2000 | / 3086 96 |
| Boiling range, ℃ initial boiling point 10% 30% 50% 70% 90% 95% | 339 421 473 526 / / / | 233 328 395 430 454 495 522 | 233 295 333 429 470 539 / | 39 56 88 127 166 178 189 |
Table 3
| The hydrogen donor component numbering | D-1 | D-2 |
| The hydrogen donor component title | The grand celebration hydrogenated diesel oil | Grand celebration straight-run spirit |
| Density (20 ℃), g/cm 3Condensation point, ℃ aniline point, ℃ carbon residue, heavy % | 0.8147 -22 67.1 ＜0.001 | 0.7460 / / / |
| H, heavy % S, ppm N, ppm | / 1 / | / 127 / |
| Alkane, heavy % naphthenic hydrocarbon, heavy % aromatic hydrocarbons, heavy % | 52.7 19.0 28.3 | 57.8 32.1 10.1 |
| Alkene (fluorescent method), v% | / | / |
| Boiling range, ℃ initial boiling point 10% 30% 50% 70% 90% 95% | 151 210 227 244 267 296 340 | 50 65 111 138 173 186 201 |
| Remarks | 380 ℃ of hydro-upgrading conditions, P H26.6Mpa volume space velocity 1h -1, hydrogen-oil ratio 1242 | RON＝50.2 MON＝46.2 |
Table 4
| Test number | Comparative Examples 1 | Embodiment 1 |
| The stock oil temperature of reaction, ℃ agent-oil ratio air speed, h -1Water vapour (accounting for raw material), heavy % | F-3 500 5 8 8 | The heavy % perhydronaphthalene 500 588 of F-3+10 |
| Material balance, heavy % is in gas-liquid gasification C 5+ gasoline, diesel heavy oil coke | 2.88 20.60 49.06 11.68 6.33 9.45 | 2.52 20.70 53.02 11.17 4.75 7.83 |
| Transformation efficiency, heavy % | 81.99 | 84.07 |
| Liquefied gas+gasoline+diesel oil, heavy % | 81.34 | 84.89 |
| Cracked gas (dry gas+liquefied gas) forms, v% hydrogen hydrogen sulfide methane ethane and ethylene propane propylene normal butane iso-butane butene-1 isobutene cis-butene-2 trans-butene-2 | 7.73 0.17 11.33 4.15 6.13 10.29 22.00 4.89 22.02 2.60 2.60 2.60 3.51 | 7.94 0.05 9.05 3.73 6.33 11.55 21.33 5.62 24.19 2.46 1.98 2.46 3.31 |
| Trimethylmethane/total butylene, v/v | 1.95 | 2.37 |
| Catalytic gasoline character S, mg/l N, mg/l alkane, v% alkene, v% aromatic hydrocarbons, v% | 1430 149 37.5 33.6 28.9 | 1035 118 45.6 21.8 32.6 |
Table 5
| Test number | Comparative Examples 2 | Embodiment 2 | |
| The stock oil temperature of reaction, ℃ agent-oil ratio air speed, h -1Water vapour, heavy % (accounting for raw material) | F-4 | F-4 460 6 12 5 | F-4+8% methylcyclohexane 460 6 12 5 |
| Product distributes, heavy % dry gas liquefied gas C 5+ gasoline, diesel heavy oil coke | 0.88 11.99 81.16 2.64 0.49 2.84 | 0.67 12.15 82.98 1.96 0.31 1.93 | |
| Liquefied gas+gasoline+diesel oil, heavy % | 95.79 | 97.09 | |
| Cracked gas (dry gas+liquefied gas) forms, v% hydrogen hydrogen sulfide methane ethane and ethylene propane propylene normal butane iso-butane butene-1 isobutene cis-butene-2 trans-butene-2 | 2.58 0.06 4.65 2.01 6.31 10.42 26.73 5.71 27.62 2.84 4.46 2.77 3.83 | 2.35 0.05 2.57 1.63 6.09 15.32 24.40 5.67 31.73 2.17 2.85 2.16 3.01 | |
| Trimethylmethane/total butylene, v/v | 1.99 | 3.12 | |
| Catalytic gasoline character S, mg/l N, mg/l alkane, v% alkene, v% aromatic hydrocarbons, v% RON/MON | 3086 96 19.4 54.9 25.7 79.2/74.1 | 973 9.2 28.2 41.3 30.5 84.1/77.2 | 739 4.9 33.2 30.7 36.1 86.0/78.8 |
Table 6
| Test number | Comparative Examples 3 | Embodiment 3 |
| The outlet of stock oil hydrogen donor component riser tube, ℃ agent-oil ratio reaction times, the sec atomized water, the m% reaction pressure, Mpa regeneration temperature ℃ | F-1 / 501 5.6 2.1 7.8 0.16 680～700 | F-1 D-1 500 5.5 2.2 7.4 0.16 680～700 |
| Material balance, heavy % dry gas liquefied gas gasoline, diesel heavy oil coke amounts to | 2.60 15.85 47.11 18.32 10.99 5.13 100.00 | 2.54 16.92 47.01 21.33 7.34 4.86 100.00 |
| Gasoline property: density (20 ℃), g/cm 3Mercaptan sulfur, ppm S, ppm inductive phase, min RON MON FIA forms, v% alkane alkene aromatic hydrocarbons | 0.7281 30 115 806 90.3 78.4 26.8 59.6 13.6 | 0.7321 21 71 994 90.5 79.7 31.1 44.6 24.3 |
| Diesel oil character: density, g/cm 3Existent gum, mg/100ml S, ppm cetane value | 0.8808 113 527 23 | 0.8707 67 315 32 |
Table 7
| Test number | Embodiment 4 |
| Riser tube: reaction pressure, the outlet of MPa riser tube, ℃ agent-oil ratio reaction times, the s atomized water, heavy % | 0.16 495 5.5 1.8 8.1 |
| The first fluidized bed: hydrogen donor component hydrogen donor component injection rate, heavy % (accounting for raw material) temperature of reaction, ℃ agent-oil ratio air speed, h -1 | D-3 9.0 484 27 10 |
| Second fluidized-bed: raw gasline injection rate, heavy % (accounting for raw material) temperature of reaction, ℃ agent-oil ratio air speed, h -1 | 11.0 492 45 13 |
| Regeneration pressure, the Mpa regeneration temperature, ℃ | 0.18 692 |
| Product distributes, heavy % dry gas liquefied gas gasoline, diesel heavy oil coke | 3.41 15.09 43.62 22.47 8.86 6.55 |
| Gasoline: RON/MON alkane, V% alkene, V% aromatic hydrocarbons, V% | 92.2/81.0 31.6 30.8 37.6 |
| Diesel oil: | 25 |
Claims (9)
1, a kind of catalysis conversion method that utilizes hydrogen donor component to reduce olefine content in gasoline, it is characterized in that hydrocarbon raw material, hydrogen donor component and catalyzer mix and react in catalyst cracker, reaction conditions is as follows: temperature of reaction is 450～560 ℃, agent-oil ratio 4～100,0.5～5 second reaction times, atomizing steam amount 0～20 heavy %, reaction pressure 0.1～0.5Mpa, oil gas behind the separating reaction and catalyzer, oil gas is delivered to subsequent separation system, the catalyzer of reaction back carbon deposit is delivered to reactor cycles and is used after stripping, regeneration.
2,, it is characterized in that described hydrocarbon raw material is selected from: the mixture of one or more in gasoline fraction, diesel oil distillate, decompressed wax oil, wax tailings, deasphalted oil, hydrocracking tail oil, vacuum residuum or the long residuum according to the method for claim 1.
3, according to the method for claim 2, it is characterized in that described hydrocarbon raw material is selected from: the mixture of one or more in catalytic gasoline, coker gasoline, the viscosity breaking gasoline, it can be full cut, also can be the part narrow fraction.
4, according to the method for claim 1, it is characterized in that described hydrogen donor component can be that the Engler distillation boiling range is 155～400 ℃ straight run oil and/or the distillate behind the hydrogenation, also can be naphthenic hydrocarbon or the cycloalkyl aromatic hydrocarbons that contains 1～3 cycloalkyl.
5,, it is characterized in that described hydrogen donor component can be selected from: the mixture of the gasoline fraction behind straight-run spirit, straight-run diesel oil, the hydrogenation, the diesel oil distillate behind the hydrogenation and above-mentioned two or more cut according to the method for claim 4; Also can be selected from: C6～C8 naphthenic hydrocarbon, tetraline, perhydronaphthalene, indane, tetrahydrochysene anthracene, octahydro anthracene.
6,, it is characterized in that described hydrogen donor component is gasoline fraction behind the hydrogenation and/or the diesel oil distillate behind the hydrogenation according to the method for claim 5.
7,, it is characterized in that described activity of such catalysts component is selected from one or more in Y type or HY type zeolite, the ultrastable Y that contains or do not contain rare earth and/or phosphorus, the ZSM-5 type zeolite that contains or do not contain rare earth and/or phosphorus or the supersiliceous zeolite with five-membered ring structure, β zeolite, the ferrierite according to the method for claim 1.
8, according to the method for claim 1, it is characterized in that the reaction conditions of hydrocarbon raw material is as follows: temperature of reaction is 460～520 ℃, agent-oil ratio 5～20,1～3 second reaction times, atomizing steam amount 3～20 heavy %, reaction pressure 0.1～0.3Mpa.
9, according to the method for claim 1, it is characterized in that this method can implement separately, also can with the catalytic cracking process Joint Implementation of routine.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011184345A CN1151236C (en) | 2001-05-30 | 2001-05-30 | Catalytic conversion process of utilizing hydrogen donor component to reduce olefine content in gasoline |
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| CNB011184345A CN1151236C (en) | 2001-05-30 | 2001-05-30 | Catalytic conversion process of utilizing hydrogen donor component to reduce olefine content in gasoline |
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| CN1151236C true CN1151236C (en) | 2004-05-26 |
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| CN101642693B (en) * | 2009-08-28 | 2012-10-24 | 清华大学 | Chloroethylene-synthetized series fluidized bed reactor and method |
| CN104109557B (en) * | 2013-04-16 | 2016-03-02 | 中国石油化工股份有限公司 | The catalysis conversion method of a kind of inferior distillate oil or heavy oil product |
| CN109385306B (en) * | 2017-08-09 | 2021-05-14 | 中国石油化工股份有限公司 | Catalytic cracking process and apparatus combined with hydrotreating |
| CN114507543B (en) * | 2020-10-28 | 2023-09-05 | 中国石油化工股份有限公司 | Method for producing gasoline with ultra-low olefin content |
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