CN1122099C - Reforming process for combined low-pressure bed - Google Patents
Reforming process for combined low-pressure bed Download PDFInfo
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- CN1122099C CN1122099C CN 99119281 CN99119281A CN1122099C CN 1122099 C CN1122099 C CN 1122099C CN 99119281 CN99119281 CN 99119281 CN 99119281 A CN99119281 A CN 99119281A CN 1122099 C CN1122099 C CN 1122099C
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Abstract
The present invention relates to a low-pressure combined bed reforming technology. Raw oil is in contact with platinum-rhenium catalysts in a semi regeneration and reformation reacting section which is formed by the series connection of two fixed bed reactors in a low pressure, and reacted effluents completely enter a continuous regeneration reacting section which is formed by series connection of two moving bed reactors and a regenerator to be further contacted with the platinum-rhenium catalysts. After cooled and steamed in a flash way, products are divided into hydrogen rich gases and reformation generated oil. After regenerated in the regenerator, the catalysts in a moving bed return into the moving bed reactors to be recycled, and the catalysts and reaction material flows are formed into the backward flow in the moving bed reactors. Compared with the prior art, the technology has the advantages that the yield of arene and hydrogen is improved and the octane number of the reformation generated oil is improved. Besides, when the octane number of the reformation generated oil is the same or the yield of the arene is the same, the yield of the reformation generated oil and the hydrogen is improved.
Description
The invention belongs to a kind of catalytic reforming process, more particularly, is under low pressure by two fixed-bed reactor and two reforming process for combined low-pressure bed that moving-burden bed reactor constitutes.
Catalytic reforming process is to be raw material with low octane value gasoline or petroleum naphtha, in the presence of catalyzer, make it be converted into the stop bracket gasoline component, this component or process extracting can be produced highly purified petrochemical materials-benzene, toluene and dimethylbenzene light aromaticss such as (hereinafter to be referred as BTX), the while by-product is the hydrogen of cheapness in a large number, can make the hydrogen source of hydrogenation technique process.The reaction that raw material takes place in the presence of catalyzer comprises: the dehydrocyclization reaction of straight-chain paraffin isomerization reaction, hexa-atomic cycloalkanes dehydrogenation reaction, five-ring alkane isomery dehydrogenation reaction, alkane, hydrocracking reaction and green coke reaction, the coke laydown of generation is on the surface of catalyzer.The catalyzer that adopts in the catalytic reforming is the dual-function catalyst with metal function and acid function, wherein constitutes hydrogenation-dehydrogenation activity center by the metal constituent element; Constitute acid sites by hydroxyl on the alumina catalyst support and the halogen (being generally chlorine) that adds.
Existing thermo-negative reaction also has thermopositive reaction in the catforming process, based on thermo-negative reaction.For this reason, the reforming process flow process adopts reactors in series, is provided with process furnace between reactor, is used for streams is heated to temperature required.At present mainly contain three kinds at the reforming process of industrial widespread use: semi-regenerative reforming, cyclic reforming, continuous regenerative reforming.Semi-regenerative reforming and cyclic reforming technology all adopt fixed-bed reactor, and continuous regenerative reforming process using moving-burden bed reactor.
The characteristics of semi-regenerative reforming technology are: on-stream activity of such catalysts slowly descends, for keeping certain reformed oil octane value or aromatics yield just need constantly improve temperature of reaction, arrived last stage reaction, the raising of temperature of reaction causes the reformed oil yield to descend, and hydrogen purity and productive rate reduce; For guaranteeing certain production equipment running period, need higher reaction pressure and hydrogen oil molecule than (hereinafter to be referred as hydrogen-oil ratio).At present, the reaction conditions of typical in the world half generative reforming technology is: 480～540 ℃ of temperature of reaction, reaction pressure are 1.5～2.5 MPas, and weight space velocity is 1～3 hour
-1, hydrogen-oil ratio is 5～8.
Cyclic reforming technology is to be equipped with an independent catalyst regeneration system in half generative reforming technology, can regenerate successively catalyzer in each reactor, each reactor can switch away from reactive system at any time, regenerates separately, and will not stop work by full device.
In the cyclic regeneration reforming process, the reactive system back is ad hoc a catalyst regenerator, and under the CONTINUOUS REFORMER normal operating condition, catalyzer flows between reactor and revivifier, the reclaimable catalyst of final reaction is delivered in the revivifier and is regenerated, and the catalyzer after the regeneration is back to reactor.Promptly be in high reactivity, highly selective state all the time at reacting middle catalyst, hydrogen-oil ratio and reaction pressure reduce greatly than half regenerative technology.
Enter the nineties, the refinery is faced with many new problem and requirements: 1, along with the enforcement of stricter environmental protection standard, the unleaded operating severity that will force refinery to improve reformer of gasoline is to produce more stop bracket gasoline component; 2,, also constantly increasing as the reformer treatment capacity of BTX main source along with the increase of market to stop bracket gasoline and light aromatics demand; 3, the refinery hydrogenation technique impels the further expansion of reformation scale to the increase of hydrogen demand.Therefore, be maximum performance activity of such catalysts and selectivity, improve the efficient (being the yield of reformed oil, aromatic hydrocarbons and hydrogen) of catforming process, need constantly to reduce reaction pressure and hydrogen-oil ratio.
The existing old device in many refineries can not satisfy above-mentioned requirements.For existing semi-regenerative reforming process, improve treatment capacity, improve temperature of reaction and reduce reaction pressure, can increase product yield, but the stability to catalyzer causes great infringement, the speed of catalyzer coking increases, and causes the catalyst regeneration frequency to increase, so the runtime of full scale plant and total treatment capacity will reduce.
Two-stage reforming technology, promptly first conversion zone adopts fixed-bed reactor semi-regenerative reforming technology, is moving than under the low severity; Second conversion zone adopts moving-burden bed reactor cyclic regeneration reforming process, is reacting than under the high severity.Original fixed bed semi regenerative reformer is transformed, effectively utilized existing installation, reduced investment cost, reached the desired octane value of product, improved the treatment capacity of existing apparatus simultaneously.
CN1223293A discloses a kind of low-pressure combined bed two-stage catalytic reforming process, stock oil is contacted with platinum-rhenium catalyst in the half generative reforming reactor that is made of two fixed bed first reactors, second reactors in series, reacted effluent all enters mainly in the cyclic regeneration conversion zone that is made of two moving-bed the 3rd reactors, the 4th reactor and revivifier series connection and further contacts with platinum-tin catalyst, and product is divided into hydrogen-rich gas and reformed oil after cooling, flash distillation; The reclaimable catalyst that comes out from the 4th reactor enters revivifier and carries out cyclic regeneration, the regenerated catalyst that comes out from revivifier enters the 3rd reactor head, dependence gravity moves down, the catalyzer that comes out from the 3rd reactor bottom enters the 4th reactor head, dependence gravity moves down, the reclaimable catalyst that comes out from the 4th reactor bottom enters revivifier to carry out being back to the 3rd reactor cycles after the cyclic regeneration and uses, and the flow direction of catalyzer is identical with the flow direction of reactant flow in moving-bed.
The objective of the invention is to provide on the basis of existing technology a kind of reforming process for combined low-pressure bed.
Technology provided by the invention is: stock oil is contacted with catalyzer in half regeneration reaction section that is made of two fixed-bed reactor series connection, reacted effluent all enters mainly in the cyclic regeneration conversion zone that is made of two moving-burden bed reactors series connection and the further contact reacts of catalyzer, cooling, separating obtained product, be back to moving-burden bed reactor after regenerating in revivifier from the reclaimable catalyst of moving-burden bed reactor and recycle, catalyzer and reactant flow form countercurrent flow at moving-burden bed reactor.
Technology provided by the invention is so concrete enforcement:
This technology is divided into two sections: half regeneration reaction section and cyclic regeneration conversion zone.Half regeneration reaction section is made of two fixed bed first reactors, second reactors in series, and a process furnace is all arranged before each fixed-bed reactor; The cyclic regeneration conversion zone is made of two moving-bed the 3rd reactors, the 4th reactor and a revivifier series connection, and a process furnace is all arranged before each moving-burden bed reactor.
Reactive moieties: stock oil enters first reactor successively, second reactor contacts with platinum-rhenium catalyst and reacts, and the effluent that comes out from second reactor all enters the 3rd reactor, the 4th reactor successively and contacts with platinum-tin catalyst and proceed reaction; The product that comes out from the 4th reactor is divided into gas-liquid two-phase after cooling, flash distillation: recycle after a hydrogen-rich gas part is boosted, another part removes downstream unit, and liquid phase stream is delivered to the downstream fractionating system, removes the product jar as reformed oil after stable;
The cyclic regeneration part: the reclaimable catalyst that comes out from the 3rd reactor enters revivifier and carries out cyclic regeneration, the regenerated catalyst that comes out from revivifier is introduced into the 4th reactor head, dependence gravity moves down, the catalyzer that comes out from the 4th reactor bottom enters the 3rd reactor head, dependence gravity moves down, the reclaimable catalyst that comes out from the 3rd reactor bottom enters revivifier to carry out being back to the 4th reactor cycles after the cyclic regeneration and uses, and catalyzer and reactant flow form countercurrent flow in moving-burden bed reactor.Its objective is that the high reactivity platinum-tin catalyst that makes after the regeneration contacts with oil gas from the 3rd reactor at the 4th reactor earlier, the dehydrating alkanes cyclization that carries out the most difficult generation generates aromatic hydrocarbons, and will enter the 3rd reactor through the lower platinum-tin catalyst of activity that the 4th reactor contains a certain amount of carbon deposit, the oil gas that flows out with second reactor contacts, carry out more incident alkane aromatization reaction, even the difficulty or ease of activity of such catalysts and the cyclisation of reactant dehydrating alkanes are complementary, in the hope of improving the aromizing selectivity, reach and improve the product octane value, the purpose of aromatics yield and hydrogen yield, or when identical or aromatics yield is identical, improve the reformed oil yield at the octane value of reformed oil, hydrogen yield; Or the reduction temperature of reaction, save energy consumption.
Stock oil used in the present invention is one or more the mixture that is selected among coking naphtha behind virgin naphtha, the hydrogenation, visbreaking petroleum naphtha, the hydrocracking heavy naphtha; Before stock oil enters combined low-pressure bed technological reaction, all need make with extra care in the raw materials pretreatment system, to remove impurities in raw materials, the especially sulphur in the raw material, nitrogen, arsenic and heavy metal.
Processing condition are: reaction pressure 0.4～0.9 MPa, and hydrogen-oil ratio 3.0～4.5, weight hourly space velocity is 1～4 hour
-1, temperature of reaction is 460～540 ℃.
Catalyzer in two fixed bed first reactors, second reactor be have high reactivity, the difunctional platinum-rhenium catalyst of highly selective and good stability, the method preparation that preferred platinum-rhenium catalyst provides according to CN1147536A, (with the butt aluminum oxide is benchmark to its composition, heavy %) is: platinum 0.10～1.00, rhenium 0.10～3.00, titanium 0.01～0.15, chlorine 0.50～3.00, carrier are gama-alumina.The Intake Quantity of platinum-rhenium catalyst accounts for 20～35 heavy % of catalyzer general reserve in the reaction system.
Catalyzer in two moving-bed the 3rd reactors, the 4th reactor is the difunctional platinum-tin catalyst of high reactivity, highly selective, the method preparation that preferred platinum-tin catalyst provides according to CN1150169A, (with the butt aluminum oxide is benchmark to its composition, heavy %) is: platinum 0.10～1.00, tin 0.10～1.00, titanium 0.01～0.20, chlorine 0.50～2.50, carrier are gama-alumina.The Intake Quantity of catalyzer accounts for 65～80 heavy % of general reserve in the reaction system.
Two fixed bed first reactors, second reactor and two moving-bed the 3rd reactors, the 4th reactors both can be radial reactors, also can be axial flow reactors.
Below in conjunction with accompanying drawing technology provided by the present invention is given further instruction.
Accompanying drawing illustrates the flow process of low-pressure combined bed two-stage catalyzer adverse current reforming process, and the shape and size of equipment and pipeline are not subjected to the restriction of accompanying drawing, but determines as the case may be.
Half regeneration reaction section of this technological process is made of process furnace 2,6 and fixed- bed reactor 4,8 series connection, in the fixed- bed reactor 4,8 difunctional platinum-rhenium catalyst is housed; The cyclic regeneration conversion zone is by process furnace 10,14, and moving- burden bed reactor 12,17 and continuous catalyst regenerating device 20 constitute, and in the moving- burden bed reactor 12,17 difunctional platinum-tin catalyst are housed.
Stock oil after refining through pipeline 1 with enter process furnace 2 after circulating hydrogen from pipeline 30 mixes, be heated to desired reaction temperature at this, enter fixed-bed reactor 4 through pipeline 3.The reaction product of coming out from reactor 4 enters process furnace 6 through pipeline 5 and is heated to desired reaction temperature, enters fixed-bed reactor 8 through pipeline 7 and reacts.So far, finished half regeneration reaction section reforming reaction in the combined low-pressure bed catalytic reforming process.
Effluent from half regeneration reaction section all enters cyclic regeneration conversion zone cyclic regeneration reforming reaction section, and the effluent of fixed-bed reactor 8 enters process furnace 10 through pipeline 9, enters moving-burden bed reactor 12 by pipeline 11 after being heated to required temperature of reaction.The effluent that comes out from reactor 12 enters process furnace 14 from pipeline 13, is heated to desired reaction temperature and enters moving-burden bed reactor 17 through pipeline 15.So far, reforming reaction finishes.
Deliver to cold exchange device 22 from the outflow product of reactor 17 through pipeline 18, cooled product enters separator 24 through pipeline 23.In separator 24, logistics is divided into gas-liquid two-phase through flash distillation: the top is a hydrogen-rich gas, wherein a part after pipeline 28 enters recycle compressor 29 compression, through pipeline 30 with go half regeneration reaction section after refining stock oil from pipeline 1 mixes; Another part hydrogen-rich gas as hydrogen product after pipeline 26 enters supercharger 27, dehydrogenation gas purification system or directly remove downstream unit, the logistics of separator bottom liquid phases is delivered to the downstream fractionating system through pipeline 25, removes the product jar or goes to aromatic hydrocarbons extracting unit as reformed oil after stable.
Be provided with a revivifier 20 in moving- burden bed reactor 12,17 back, used platinum-tin catalyst in the cyclic regeneration conversion zone moving-bed is carried out cyclic regeneration.After the reaction beginning, the carbon deposit reclaimable catalyst that moving-burden bed reactor 12 bottoms emit enters regeneration in the revivifier 20 by catalyzer lift line 19, catalyzer after the regeneration is delivered in the reactor 17 through pipeline 21, original catalyzer is by catalyzer lift line 16 dereaction devices 12 in the reactor 17, catalyzer is cyclic regeneration so continuously, makes the catalyzer in the reactor 12,17 remain high reactivity and highly selective.
The invention has the advantages that: compared with prior art, improved the octane value of aromatics yield, hydrogen yield and reformed oil.When identical or aromatics yield is identical at the octane value of reformed oil, improves reformed oil yield, hydrogen yield, or reduce temperature of reaction, save energy consumption.
Accompanying drawing is the schematic flow sheet of low-pressure combined bed two-stage catalyzer adverse current reforming process.
Each numbering is described as follows in the accompanying drawing: 1,3,5,7,9,11,13,15,18,21,23,25,26,28,30 be pipeline, 2,6,10,14 be process furnace, 4,8 be fixed-bed reactor, 12,17 be moving-burden bed reactor, 16,19 are the catalyzer lift line, and 20 is revivifier, 22 is cold exchange device, 24 is separator, and 27 is supercharger, and 29 is recycle compressor.Heavy line in the accompanying drawing is represented the reactant flow pipeline, and fine line is represented the hydrogen-rich gas pipeline, and dotted line is represented catalyst line.
The following examples will give further instruction to technology provided by the invention, but not thereby limiting the invention.
Embodiment adopts combined low-pressure bed catalyzer adverse current reforming process, is back to moving-burden bed reactor after the reclaimable catalyst in the moving-bed is regenerated and recycles in revivifier, and this catalyzer and reactant flow form countercurrent flow in moving-burden bed reactor; Comparative Examples adopts combined low-pressure bed catalyzer following current reforming process, its technical process is as described in the CN1223293A, be back to moving-bed after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, its flow direction is identical with the flow direction of reactant flow in moving-burden bed reactor.Test is carried out on the adiabatic reformation pilot plant of four pipes, and two fixed-bed reactor in front use platinum-rhenium catalyst, and its trade names are CB-7, are produced by China PetroChemical Corporation's Chang Ling refinery head factory catalyst plant; Next two moving-burden bed reactors use platinum-tin catalyst, and its trade names are 3961, are produced by Fushun No.3 Petroleum Factory of China National Petroleum Corporation (CNPC) catalyst plant.Reforming raw oil is a petroleum naphtha, and wherein A is the narrow fraction petroleum naphtha, and B is a hydrocracking heavy naphtha, and its main character sees Table 1; The reaction conditions and the test-results of embodiment, Comparative Examples see Table 2～table 5, and the octane value in the table is the not clean research octane number (RON) of leading, i.e. RONC.
Comparative Examples 1
In combined low-pressure bed following current reforming process, stock oil A after the hydrofining enters half regeneration reaction section that is made of two fixed-bed reactor series connection, the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection, be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, its flow direction is identical with the flow direction of reactant flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.7 MPa, weight hourly space velocity 1.98 hours
-1, hydrogen/oil mol ratio 3.3, temperature of reaction WAIT (being Weighted Average Inlet Temperature weighted mean temperature in, down together) is 504.2 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 2.
Embodiment 1
In combined low-pressure bed catalyzer adverse current reforming process, stock oil A after the hydrofining enters half regeneration reaction section that is made of two fixed-bed reactor series connection, and the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection.Be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, this catalyzer and reactant flow form countercurrent flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.7 MPa, weight hourly space velocity 1.98 hours
-1, hydrogen/oil mol ratio 3.4, temperature of reaction WAIT are 504.6 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 2.
Data in the table 2 show, under identical reaction conditions, combined low-pressure bed following current reforming process aromatics yield and hydrogen yield that combined low-pressure bed catalyzer adverse current reforming process is conventional are high 2.18 percentage points and 0.27 percentage point respectively, although the reformed oil yield reduces by 0.29 percentage point, improved 1 unit but generate oily octane value, the octane value productive rate has improved 0.6 percentage point.Illustrate that the aromizing selectivity obviously improves, so net effect is obvious.
Comparative Examples 2
In combined low-pressure bed following current reforming process, stock oil A after the hydrofining enters half regeneration reaction section that is made of two fixed-bed reactor series connection, the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection, be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, its flow direction is identical with the flow direction of reactant flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.7 MPa, weight hourly space velocity 1.99 hours
-1, hydrogen/oil mol ratio 3.3, temperature of reaction WAIT are 507.7 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 3.
In combined low-pressure bed catalyzer adverse current reforming process, stock oil A after the hydrofining enters half regeneration reaction section that is made of two fixed-bed reactor series connection, and the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection.Be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, this catalyzer and reactant flow form countercurrent flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.7 MPa, weight hourly space velocity 1.98 hours
-1, hydrogen/oil mol ratio 3.4, temperature of reaction WAIT are 501.3 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 3.
Data in the table 3 show, under identical reaction conditions, combined low-pressure bed catalyzer adverse current reforming process is high 0.54 percentage point than conventional combined low-pressure bed following current reforming process reformed oil yield, the octane value productive rate has improved 0.53 percentage point, aromatics yield and hydrogen yield also slightly improve, and reactor inlet temperature then will hang down 6.4 ℃.
Comparative Examples 3
In combined low-pressure bed following current reforming process, stock oil B enters half regeneration reaction section that is made of two fixed-bed reactor series connection, the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection, be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, its flow direction is identical with the flow direction of reactant flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.8 MPa, weight hourly space velocity 2.5 hours
-1, hydrogen/oil mol ratio 4.4, temperature of reaction WAIT are 503.2 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 4.
In combined low-pressure bed catalyzer adverse current reforming process, stock oil B enters half regeneration reaction section that is made of two fixed-bed reactor series connection, and the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection.Be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, this catalyzer and reactant flow form countercurrent flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.8 MPa, weight hourly space velocity 2.5 hours
-1, hydrogen/oil mol ratio 4.4, temperature of reaction WAIT are 502.7 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 4.
Data in the table 4 show, under identical reaction conditions, be at 95.8 o'clock with the reformed oil octane value, combined low-pressure bed catalyzer following current reforming process reformed oil yield and hydrogen yield that combined low-pressure bed catalyzer adverse current reforming process is conventional are high 1.29 percentage points and 0.12 percentage point respectively, and aromatics yield also slightly improves.
Comparative Examples 4
In combined low-pressure bed following current reforming process, stock oil B enters half regeneration reaction section that is made of two fixed-bed reactor series connection, the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection, be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, its flow direction is identical with the flow direction of reactant flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.5 MPa, weight hourly space velocity 1.5 hours
-1, hydrogen/oil mol ratio 3.7, temperature of reaction WAIT are 496.5 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 5.
In combined low-pressure bed adverse current reforming process, stock oil B enters half regeneration reaction section that is made of two fixed-bed reactor series connection, and the effluent that comes out from half regeneration reaction section all enters the cyclic regeneration conversion zone that is made of two moving-burden bed reactor series connection.Be back to moving-burden bed reactor after reclaimable catalyst in the moving-bed is regenerated and recycle in revivifier, this catalyzer and reactant flow form countercurrent flow in moving-burden bed reactor.Reaction conditions is: reaction pressure 0.5 MPa, weight hourly space velocity 1.5 hours
-1, hydrogen/oil mol ratio 3.7, temperature of reaction WAIT are 495.6 ℃, the filling ratio of catalyzer is 32/68 in fixed bed and the moving-bed.Test-results sees Table 5.
Data in the table 5 show, under identical reaction conditions, be at 98.0 o'clock with the reformed oil octane value, combined low-pressure bed following current reforming process reformed oil yield and hydrogen yield that combined low-pressure bed catalyzer adverse current reforming process is conventional are high 1.19 percentage points and 0.35 percentage point respectively, aromatics yield also slightly improves, and the octane value productive rate has improved 1.17 percentage points.
Table 1
| Stock oil | A | B |
| Density (20 ℃), gram per centimeter 3Boiling range (ASTM-D86); 10% 30% 50% 70% 90% end point of distillation group compositions of ℃ initial boiling point, heavy % alkane cycloalkane aromatic hydrocarbons | 0.7241 80 90 98 107 118 134 150 56.44 40.39 3.17 | 0.7314 80 93 106 116 132 159 194 56.33 37.80 5.87 |
Table 2
| Numbering | Embodiment 1 | Comparative Examples 1 |
| Stock oil reaction conditions reaction pressure, the MPa weight hourly space velocity, hour -1Hydrogen/oil mol ratio temperature of reaction WAIT, ℃ test-results generates oily yield, heavy % aromatics yield, heavy % hydrogen yield, heavy % generates oily octane value (RONC) octane value productive rate, % | A 0.7 1.98 3.4 504.6 87.5 60.53 3.57 97.4 85.23 | A 0.7 1.98 3.3 504.2 87.79 58.35 3.30 96.4 84.63 |
Table 3
| | Embodiment | 2 | Comparative Examples 2 |
| Stock oil reaction conditions reaction pressure, the MPa weight hourly space velocity, hour -1Hydrogen/oil mol ratio temperature of reaction WAIT, ℃ test-results generates oily yield, heavy % aromatics yield, heavy % hydrogen yield, heavy % generates oily octane value (RONC) octane value productive rate, % | A 0.7 1.98 3.4 501.3 88.03 59.62 3.45 96.7 85.13 | A 0.7 1.99 3.3 507.7 87.49 59.50 3.41 96.7 84.60 |
Table 4
| | Embodiment | 3 | Comparative Examples 3 |
| Stock oil reaction conditions reaction pressure, the MPa weight hourly space velocity, hour -1Hydrogen/oil mol ratio temperature of reaction WAIT, ℃ test-results generates oily yield, heavy % aromatics yield, heavy % hydrogen yield, heavy % generates oily octane value (RONC) octane value productive rate, % | B 0.8 2.5 4.4 502.7 89.66 56.60 2.88 95.8 85.89 | B 0.8 2.5 4.4 503.2 88.37 56.08 2.76 95.8 84.66 |
Table 5
| | Embodiment | 4 | Comparative Examples 4 |
| Stock oil reaction conditions reaction pressure, the MPa weight hourly space velocity, hour -1Hydrogen/oil mol ratio temperature of reaction WAIT, ℃ test-results generates oily yield, heavy % aromatics yield, heavy % hydrogen yield, heavy % generates oily octane value (RONC) octane value productive rate, % | B 0.5 1.5 3.7 495.6 87.45 61.21 3.71 98.0 85.70 | B 0.5 1.5 3.7 496.5 86.26 60.43 3.36 98.0 84.53 |
Claims (5)
1, a kind of reforming process for combined low-pressure bed, it is characterized in that under low pressure making stock oil to enter two fixed bed first reactors, second reactors successively contacts with catalyzer, catalyzer in the fixed-bed reactor is platinum-rhenium catalyst, the Intake Quantity of platinum-rhenium catalyst accounts for catalyzer in the reaction system, 20～35 heavy % of general reserve, reaction pressure is 0.4～0.9 MPa, and hydrogen oil molecule ratio is 3.0～4.5, and weight hourly space velocity is 1～4 hour
-1Temperature of reaction is 460～540 ℃, reacted effluent all enters in two moving-bed the 3rd reactors, the 4th reactor and the further contact reacts of catalyzer successively, catalyzer in the moving-burden bed reactor is a platinum-tin catalyst, the Intake Quantity of platinum-tin catalyst accounts for 65～80 heavy % of reaction system general reserve, reaction pressure is 0.4～0.9 MPa, and hydrogen oil molecule ratio is 3.0～4.5, and weight hourly space velocity is 1～4 hour
-1, temperature of reaction is 460～540 ℃, cooling, separating obtained product; After regenerating, the reclaimable catalyst that the 3rd reactor bottom is emitted returns the 4th reactor head earlier in revivifier, be promoted to the 3rd reactor head from the 4th reactor bottom again, form the movable bed catalyst circulation loop, make catalyzer and reactant flow be countercurrent flow at moving-burden bed reactor.
2,, it is characterized in that described stock oil is coking naphtha, visbreaking petroleum naphtha, hydrocracking heavy naphtha or its mixture behind virgin naphtha, the hydrogenation according to the technology of claim 1.
3,, it is characterized in that before described each fixed-bed reactor a placed in-line with it process furnace being arranged all according to the technology of claim 1.
4,, it is characterized in that before described each moving-burden bed reactor a placed in-line with it process furnace being arranged all according to the technology of claim 1.
5, according to the technology of claim 1, it is characterized in that the described product that comes out from last moving-burden bed reactor is divided into gas-liquid two-phase after cooling, flash distillation: recycle after a hydrogen-rich gas part is boosted, another part removes downstream unit, liquid phase stream is delivered to the downstream fractionating system, removes the product jar or goes to aromatic hydrocarbons extracting unit as reformed oil after stable.
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| CN1286292A (en) | 2001-03-07 |
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