CN103289742B - Starting method for semi-regenerative catalytic reforming device using sulphureous crude gasoline as raw material - Google Patents
Starting method for semi-regenerative catalytic reforming device using sulphureous crude gasoline as raw material Download PDFInfo
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Abstract
The invention relates to a starting method for a semi-regenerative catalytic reforming device using sulphureous crude gasoline as a raw material. The starting method comprises the following steps of: (1) introducing straight-run naphtha into a hydrogen production reactor of a reforming pre-hydrogenation reaction system, and hydrogenizing the straight-run naphtha in a pre-hydrogenation reactor by using crude hydrogen generated by a hydrogen production reaction so as to obtain refined naphtha; and (2) filling a reforming catalyst in an oxidation state into a reactor of a reforming reaction system, circularly heating by using sulphureous hydrogen generated by the hydrogen production reaction, treating the catalyst by using the crude hydrogen at 100-250 DEG C, heating to 450-550 DEG C, treating continuously, then introducing the refined naphtha into a reforming reactor to perform catalytic reforming reaction, adjusting to normal production pressure and temperature, removing the hydrogen production reactor, introducing hydrogen generated by the reforming reactor into the pre-hydrogenation reaction system, refining a naphtha raw material, and putting the refined naphtha into the reforming reaction system to serve as a reforming reaction raw material. According to the starting method, the hydrogen generated by the straight-run naphtha which is used as the raw material is directly used for preparing refined oil for starting as well as starting a reforming device; and the starting method is simple and convenient to operate, low in cost, high in efficiency and good in effect.
Description
Technical field
The present invention is a kind of start-up method of catalytic reforming unit, specifically, is a kind of no hydrogen source, without the start-up method of the semi-regenerating catalytic reforming device of refining petroleum naphtha.
Background technology
Catalytic reforming is the oil refining process of a kind of product octane value or the lower convert naphtha of aromaticity content being become stop bracket gasoline or high aromaticity content, the cheap hydrogen of production high-quality simultaneously.
Reforming catalyst is chief active constituent element with precious metal, and metal content is low, responsive to the poisonous substance such as sulphur, nitrogen.General requirement catalytic reforming feedstock, namely in reformation treated oil, sulphur and nitrogen content are less than 0.5 μ g/g.For meeting the requirement of catalytic reforming feedstock to foreign matter content, reformer is equipped with pre-hydrogenation unit simultaneously, removes sulphur in raw material, nitrogen and metallic impurity in advance, obtain treated oil by hydrogenation reaction.In the prior art, reforming under-stream needs to carry out in a hydrogen atmosphere, simultaneously the strict content controlling hydrogen sulfide in hydrogen.Hydrogen for reforming under-stream generally has following source: (1) electrolysis hydrogen, (2) reformer institute hydrogen producing, and (3) catalytic unit dry gas etc. are separated (PSA) concentrate hydrogen through pressure-variable adsorption.These hydrogen are all without sulphur or low sulfur content hydrogen (sulphur content is less than 0.5 μ l/l).In the prior art, need after reforming catalyst reduction, under specific temperature conditions, add vulcanizing agent and carry out prevulcanized.
Some grassroots refinery does not have treated oil and hydrogen.Going into operation of this kind of reformer arranges a small-sized hydrogen-manufacturing reactor, and with sulfur-bearing raw gasline for raw material, production treated oil and hydrogen go into operation for reformer.
CN91100635.4 and improvement opportunity thereof (" refining of petroleum and chemical industry " the 29th volume 5 phases of ground) disclose raw gasline treated oil, the reforming under-stream method of treated oil hydrogen.The method sets up a reactor at pre-hydrotreating reaction unit, load the aluminium oxide catalyst of high platinum content, hydrogen-manufacturing reactor entrance 370 ~ 430 DEG C is warming up under nitrogen circulation condition, enter raw gasline, product obtains hydrogen through gas-liquid separation, because in raw material, sulphur content is higher, in obtained hydrogen, hydrogen sulfide content is also higher, and these sulfur-bearing hydrogen is removed hydrogen sulfide through the retort that sweetening agent is housed and is used further to reformer and goes into operation by this method.The producing process of treated oil is, first obtain sulfur-bearing raw hydrogen as stated above, with raw hydrogen by after nitrogen replacement in system, carry out hydrogen recycle, pre-hydrogenator is accessed reactive system, pre-hydrotreating reaction after product is isolated to treated oil.The more difficult enforcement in industrial practice of this method hydrogen making.This is because the hydrogen sulfide in hydrogen mainly relies on the adsorbing and removing of sweetening agent in digester, but the loading capacity of sweetening agent is limited, and is that in the obtained hydrogen of raw material, hydrogen sulfide content is very high with raw gasline, generally more than 100 μ l/l.Rely on adsorption desulfurize purified hydrogen, sweetening agent displacement is frequent, cannot realize operation, also be difficult to load economically.This technology is not almost applied on full scale plant.
In order to solve hydrogen desulphurization problem, inventor has carried out technological improvement (" refining of petroleum and chemical industry " the 29th volume ground 5 phases), be about to obtained hydrogen not as hydrogen for reforming under-stream, but first treated oil processed, pre-hydrotreating reaction is stopped after storing up sufficient treated oil, with the treated oil stored as raw material, prepare by hydrogen-manufacturing reactor the high-purity hydrogen (hydrogen sulfide content is lower than 0.5 μ l/l) that sulphur content meets reforming under-stream requirement.Although the technology after this improvement can produce qualified hydrogen, still there is the defect of flow process complexity, complex operation, production cycle length in this method.Due to hydrogen production reaction not independently flow and temperature controlling system, but use flow control and the temperature controlling system of pre-hydrotreating reaction, device hydrogen making and produce treated oil operation scheme between switch complicated, loaded down with trivial details, difficult.
For the defect that above-mentioned technology exists, CN02109678.3 proposes following improvement project: pre-hydrotreating reaction unit sets up a reactor, loads high platinum content aluminium oxide catalyst, loads oxidation state Hydrobon catalyst in pre-hydrogenator.Under nitrogen circulation condition, be warming up to hydrogen-manufacturing reactor temperature in is 370 ~ 430 DEG C, enter raw gasline, product obtains containing the raw hydrogen compared with high hydrogen sulfide through gas-liquid separation, sulfur-bearing raw hydrogen circulates, progressively improve pre-hydrotreating reaction actuator temperature, utilize hydrogen sulfide in hydrogen as vulcanizing agent by catalyst for pre-hydrogenation sulfuration, make it to be converted into active condition.Catalyst for pre-hydrogenation sulfidation is again the process removing hydrogen sulfide in recycle hydrogen simultaneously, the obtained hydrogen of hydrogen production reaction is purified, meets the requirement of reforming under-stream.Catalyst for pre-hydrogenation sulfuration back end hydrogenation activity improves, and may be used for again preparing treated oil.The defect of this technology is apparent: require that catalyst for pre-hydrogenation is non-sulphided state (oxidation state), be live catalyst or regenerated catalyst.Because the catalyst for pre-hydrogenation life-span is usually far above reforming catalyst, reforming catalyst is made to change agent or regeneration period and catalyst for pre-hydrogenation asynchronous, when often occurring that reforming catalyst goes into operation, catalyst for pre-hydrogenation neither changes agent, situation about not regenerating again, this patent is not suitable for going into operation of this kind of device.On the other hand, the sulfur content needed for catalyst for pre-hydrogenation sulfuration is usually far above the sulfur content that raw gasline can provide, and general needs add a large amount of sulfocompounds specially.This technology cannot ensure the sulfuration of catalyst for pre-hydrogenation, thus can not ensure normally going into operation and using of catalyst for pre-hydrogenation.
CN02109679.1 has carried out following improvement on the basis of CN91100635.4: cancel digester, substitutes with alkaline cleaners such as hollow-spraying-tower, packing tower or tray-type columns.Because device for producing hydrogen is the accessory device that a frequency of usage is very low, a cycle just uses once, and be usually separated by 2 ~ 3 years, the input of alkali cleaning equipment increases considerably production cost equally.In addition, alkali washing method is adopted also to relate to a series of the difficult problem of environmental protections such as liquid waste disposal.This technology does not obtain industrial application.
Summary of the invention
The object of this invention is to provide a kind of with the start-up method of the sulfur-bearing raw gasline half-regeneration reformer that is raw material, this method need not be carried out reformer and goes into operation by external hydrogen, but the hydrogen directly using virgin naphtha to produce for raw material carries out reformer go into operation for the preparation of the treated oil gone into operation, easy and simple to handle, cost is low, efficiency is high.
Sulfur-bearing raw gasline provided by the invention carries out the method that semi-regenerating catalytic reforming device goes into operation, and comprising:
(1) virgin naphtha from refinery's atmospheric and vacuum distillation unit is passed into the hydrogen-manufacturing reactor of reformed pre-hydrogenated reactive system, in pre-hydrogenator, pre-hydrogenation is carried out to described virgin naphtha with the raw hydrogen that hydrogen production reaction produces, the refining petroleum naphtha obtained after pre-hydrotreating reaction is collected in refining Naphtha tank
(2) in the reactor of reforming reaction system, load the reforming catalyst of oxidation state, reforming reaction system is fully replaced with nitrogen, introduce the raw hydrogen that hydrogen production reaction produces, boost to 0.2 ~ 1.2MPa, circulation, reaction bed temperature is risen to 100 ~ 250 DEG C to process catalyzer with raw hydrogen, be warming up to 450 ~ 550 DEG C again and continue process, then adjusting reaction bed temperature is 380 ~ 420 DEG C, the refining petroleum naphtha passing into (1) step obtained in reforming reactor starts catalytic reforming reaction, after the pressure of reactive system to be reformed reaches the normal pressure produced, stop hydrogen-manufacturing reactor operation, hydrogen reforming reaction produced introduces pre-hydrotreating reaction system, feed naphtha is refined, again treated oil is sent into reforming reaction system and carry out normal reforming reaction operation as reforming reaction raw material.
The inventive method increases a hydrogen-manufacturing reactor in pre-hydrotreating reaction system, with the virgin naphtha from refinery's atmospheric and vacuum distillation unit, namely sulfur-bearing raw gasline is raw material, first carry out hydrogen production reaction, obtaining the raw hydrogen of sulfur-bearing, then refine sulfur-bearing raw gasline with described hydrogen, is then reformer feed with treated oil, sulfur-bearing hydrogen is that reformation reactive system goes into operation medium, completes the start-up process of reforming reaction system.The present invention compared with prior art, eliminates the treating processes of sulfur-bearing hydrogen, and utilizes the sulphur in hydrogen manufacturing hydrogen to reduce and prevulcanized to reforming catalyst, simplifies flow process, saves investment.
Accompanying drawing explanation
Fig. 1 is the inventive method schematic flow sheet.
In Fig. 1, sign flag implication is as follows:
1, pre-hydrogenation system fresh feed pump, 2, in advance hydrogenation system generate oil/product exchanger,
3, process furnace, 41 ~ 48, pipeline switch valve, 5, hydrogen-manufacturing reactor, 6, pre-hydrogenator,
7, atmospheric condenser, 8, water condenser, 9, gas-liquid separator, 10, compressor,
11, dehydration by evaporation tower, 12, treated oil storage tank, 13, reforming reaction system feeding pump,
14, reformed oil/product exchanger, 15, reforming reaction system first to fourth reactor,
16, reforming reaction system heating stove, 18, in advance hydrogenation system recycle hydrogen pipeline.
Embodiment
The inventive method sets up a hydrogen-manufacturing reactor in reformer pre-hydrotreating reaction system, can contact with pre-hydrogenator, single platinum catalyst that in hydrogen-manufacturing reactor, filling platinum content is higher or used containing platinum-reforming catalyst, direct utilization is from virgin naphtha (the sulfur-bearing raw gasline of refinery, sulphur content is less than 1000 μ g/g) carry out hydrogen production reaction, with the hydrogen that hydrogen production reaction produces, namely raw hydrogen carries out pre-hydrogenation removing sulphur wherein and other impurity to virgin naphtha, be reforming under-stream medium again with raw hydrogen, oxidation state reforming catalyst is reduced and sulfuration, in raw hydrogen in low-sulfur content situation, also can be injected with machine sulfide to reduce and prevulcanized to oxidized catalyst.The sulfur-bearing hydrogen that the present invention directly utilizes raw gasline hydrogen manufacturing to produce carries out reforming under-stream, compared with the prior art, the inventive method simplifies Hydrogen making technological process, eliminate sulfur-bearing hydrogen digester, simplify and produce reforming reaction system and to go into operation the step of hydrogen used, and utilize sulfur-bearing hydrogen directly to reduce and prevulcanized to reforming catalyst, simplify the operation steps of reforming catalyst prevulcanized.
Raw gasline described in the inventive method refers to the virgin naphtha from refinery's atmospheric and vacuum distillation unit, and its boiling range is 80 ~ 180 DEG C, wherein containing the sulphur of 100 ~ 1000 μ g/g, also has other micro-detrimental impurity, as arsenic, lead etc.
In aforesaid method, (1) step is the operation of pre-hydrotreating reaction system, and reformed pre-hydrogenated reactive system of the present invention comprises hydrogen-manufacturing reactor and pre-hydrogenator, and described hydrogen-manufacturing reactor is connected in the upstream of pre-hydrogenator.The operation of pre-hydrotreating reaction system mainly prepares hydrogen, and carries out pre-hydrogenation with obtained hydrogen to raw gasline and produce reformer and to go into operation required refining petroleum naphtha.Described raw hydrogen is take virgin naphtha as the sulfur-bearing hydrogen that raw material carries out hydrogen production reaction generation.
Pre-hydrotreating reaction system described in the inventive method mainly comprises hydrogen-manufacturing reactor, pre-hydrogenator, gas-liquid separator, dehydration by evaporation tower and treated oil storage tank, and passes into the equipment such as pipeline, product liquid condenser, gas compressor of each reactor.
Reforming reaction system of the present invention comprises reforming reactor, reformate separating device and circulating hydrogen pipeline etc.
The temperature of hydrogen production reaction described in the present invention (1) step is 300 ~ 500 DEG C, preferably 350 ~ 450 DEG C, and pressure is 0.02 ~ 3.0MPa, preferably 0.08 ~ 1.5MPa.The temperature of virgin naphtha pre-hydrotreating reaction is 200 ~ 400 DEG C, preferably 250 ~ 360 DEG C, and pressure is 0.02 ~ 3.0MPa, preferably 0.08 ~ 1.5MPa.
The preferred method preparing raw hydrogen and refining petroleum naphtha by pre-hydrotreating reaction system is: described virgin naphtha is passed into hydrogen-manufacturing reactor, preferably uses nitrogen purging pre-hydrotreating reaction system before.Cut out pre-hydrogenator, even if pre-hydrogenator departs from pre-hydrotreating reaction system, described virgin naphtha is passed into hydrogen-manufacturing reactor, with the intrasystem gas of hydrogen exchange pre-hydrotreating reaction that hydrogen-manufacturing reactor produces, and make hydrogen at pre-hydrotreating reaction system internal recycle, when density of hydrogen reaches 70 more than volume %, pre-hydrogenator is contacted into hydrogen-manufacturing reactor downstream, a described virgin naphtha part is passed into hydrogen-manufacturing reactor, all the other pass into pre-hydrogenator as cold burden adjustment pre-hydrotreating reaction actuator temperature, it is made to reach the temperature of pre-hydrotreating reaction requirement, with the raw hydrogen that hydrogen production reaction produces, hydrofining is carried out to virgin naphtha.
The catalyst for preparing hydrogen of filling preferably includes alumina supporter and take alumina supporter as the following active ingredient of the content of benchmark in hydrogen-manufacturing reactor described in the inventive method (1) step: the group VIII metal of 0.1 ~ 2.0 quality %, preferably 0.15 ~ 0.3 quality %, the halogen of 0.1 ~ 5.0 quality %, preferably 0.1 ~ 3.0 quality %, more preferably 0.5 ~ 2.0 quality %, the preferred platinum of described group VIII metal, the preferred chlorine of described halogen.The preferred active metal component of above-mentioned catalyst for preparing hydrogen is single platinum catalyst of platinum, also can be the still activated dual metal reforming catalyst used.
The inventive method (2) step is directly reduce and prevulcanized to oxidation state semi regeneration reforming catalyst with the raw hydrogen that pre-hydrotreating reaction system is obtained, and carries out reforming reaction and go into operation.
(2) 2 ~ 8 hours are preferably with raw hydrogen in the time of 100 ~ 250 DEG C of process catalyzer in step, this section of process is mainly absorption sulphur, preferably 2 ~ 6 hours treatment times of 450 ~ 550 DEG C, this section was treated to and uses sulfur-bearing raw hydrogen directly to reduce and prevulcanized to oxidized catalyst.If sulphur content is not less than 100 μ L/L in raw hydrogen, without the need to injecting organic compounds containing sulfur in raw hydrogen, if sulphur content is less than 100 μ L/L in raw hydrogen, need to inject organic compounds containing sulfur in raw hydrogen, make sulphur content in reforming catalyst be 0.01 ~ 0.2 quality % (taking carrier as benchmark).
(2) the oxidation state reforming catalyst described in step preferably includes alumina supporter and take alumina supporter as the following active ingredient of the content of benchmark: the halogen of the group VIII metal of 0.1 ~ 2.0 quality %, the VIIB race metal of 0.1 ~ 2.0 quality % and 0.1 ~ 3.0 quality %, preferably 0.1 ~ 2.0 quality %.
Described oxidation state reforming catalyst also can comprise lanthanide series metal and the yttrium of 0.1 ~ 3.0 quality % further, preferred ytterbium, samarium, neodymium or yttrium.
The preferred platinum of group VIII metal in above-mentioned oxidation state reforming catalyst, the preferred rhenium of VIIB race metal, the preferred chlorine of halogen.
(2) in step oxidized catalyst through reduction and prevulcanized after, by the pressure adjusting of reforming reaction system to the normal pressure produced, stop the operation of hydrogen-manufacturing reactor, hydrogen is produced in reformation and introduces pre-hydrotreating reaction system, adjust reaction bed temperature again to normal temperature of producing, the treatment capacity of normally producing by reforming reaction device is introduced hydrofining petroleum naphtha and is carried out normal reforming reaction operation, terminates to go into operation operation.The reaction pressure that described reforming reaction system is normally produced is 0.5 ~ 3.5MPa, preferably 0.8 ~ 2.0MPa, and temperature of reaction is 450 ~ 550 DEG C.
After hydrogen introducing pre-hydrotreating reaction system is produced in reformation, any feed naphtha can be used to carry out reforming reaction, and described feed naphtha is the coking naphtha after virgin naphtha, hydrocracked naphtha or hydrogenation, preferred virgin naphtha.
Below in conjunction with accompanying drawing, the present invention is described.
In Fig. 1, pre-hydrotreating reaction system mainly comprises pre-hydrogenator 6, gas-liquid separator 9, dehydration by evaporation tower 11 and hydrogen-manufacturing reactor 5, and hydrogen-manufacturing reactor 5 can be connected with pre-hydrogenator 6, also can with its disengaging, filling catalyst made from platonic in hydrogen-manufacturing reactor 5.Blanked-off pipe wiretap valve 46, open pipeline switch valve 41,42,43,44,45, be 0.2 ~ 1.0MPa to pre-hydrotreating reaction system introducing nitrogen to pressure and circulate, then blanked-off pipe wiretap valve 42,43,45, pre-hydrogenator 6 and hydrogen-manufacturing reactor 5 are departed from.By the virgin naphtha from refinery's atmospheric and vacuum distillation unit, namely sulfur-bearing raw gasline pumps into pre-hydrotreating reaction system by pre-hydrogenation system fresh feed pump 1, oil/product exchanger 2 heat exchange is generated through pre-hydrogenation system, enter the temperature that process furnace 3 is heated to needed for hydrogen production reaction, preferably 360 ~ 460 DEG C, enter hydrogen-manufacturing reactor 5, hydrogen production reaction product is discharged bottom hydrogen-manufacturing reactor, through pipeline 19 again through interchanger 2 and raw gasline heat exchange, cool through air-cooler 7 and water condenser 8, enter gas-liquid separator 9, the gas that hydrogen production reaction produces, namely the raw hydrogen of sulfur-bearing is discharged by top, at pre-hydrotreating reaction system internal recycle after being compressed by compressor 10, product liquid is discharged by bottom, enter dehydration by evaporation tower 11, the product liquid obtained after dehydration is discharged by bottom and is entered treated oil storage tank 12.
Pre-hydrotreating reaction system pressure is increased to pre-hydrotreating reaction pressure 0.8 ~ 2.0MPa by the raw hydrogen utilizing hydrogen-manufacturing reactor to produce, valve-off 44, open pipeline switch valve 43, 45, pre-hydrogenator 6 is contacted to the downstream of hydrogen-manufacturing reactor 6, open valve 47, by pipeline 17, a part of virgin naphtha is sent into pre-hydrogenator 6, and be 260 ~ 360 DEG C by inlet amount control pre-hydrogenator 6 temperature in of virgin naphtha, by the raw hydrogen in hydrogen production reaction product, pre-hydrogenation is carried out to the virgin naphtha entering pre-hydrogenator, remove sulphur wherein and other impurity, pre-hydrotreating reaction product is discharged by bottom pre-hydrogenator, through pipeline 20 and pipeline 19, air-cooler 7 and watercooler 8 cool, enter gas-liquid separator 9 and carry out gas-liquid separation, gaseous product is after recycle compressor 10, a part uses at system internal recycle as recycle hydrogen, rest part introduces reforming reaction system for catalyst reduction with go into operation through switch-valve 46 and pipeline 21, the product liquid obtained after dehydration, namely treated oil storage tank 12 sent into by refining petroleum naphtha, to go into operation charging as reformer.
Reforming reaction system mainly comprises reforming reactor 15 and reforming reaction system heating stove 16, and follow-up reformate tripping device (not shown in figure 1).The method of carrying out reforming under-stream with above-mentioned raw hydrogen and pre-hydrofined oil is: in described reforming reactor 15, load oxidation state reforming catalyst, after qualified for reforming reaction system nitrogen replacement (in system, oxygen content is less than 0.5 volume %), introduce the sulfur-bearing raw hydrogen from hydrogen production reaction system, be pressurized to 0.2 ~ 1.8MPa and make raw hydrogen at reforming reaction system internal recycle.Reforming catalyst bed temperature is first risen to 100 ~ 250 DEG C, with raw hydrogen, is carried out to catalyzer process for some time, be preferably 2 ~ 8 hours, then be warming up to the process of 450 ~ 550 DEG C, preferably 2 ~ 6 hours time.Then adjusting reaction bed temperature is 380 ~ 420 DEG C, refining petroleum naphtha in treated oil storage tank 12 is sent into the feeding line of reforming reaction system by catalytic reforming feedstock pump 13, after reformed oil/product exchanger 14 heat exchange, enter reforming reactor 15, then, reforming reactor temperature in is raised, when in reactive system to be reformed, the pressure of hydrogen reaches pressure when reformer is normally produced, open valve 42, blanked-off pipe wiretap valve 41, 43, 44, hydrogen-manufacturing reactor is made to depart from pre-hydrotreating reaction system, stop the operation of hydrogen-manufacturing reactor, and the hydrogen produced in reforming reaction system is passed into pre-hydrogenation compressor 10 entrance (not indicating pipeline in figure), close the switch-valve 46 that raw hydrogen enters reforming reaction system simultaneously.Feed naphtha (can be the coking naphtha after virgin naphtha, hydrocracked naphtha or hydrogenation) is passed into pre-hydrogenator 6, produces hydrogen with reformation and hydrofining is carried out to feed naphtha, remove the impurity such as sulphur wherein.Then the refining petroleum naphtha obtained with pre-hydrogenation, for reformation reaction raw materials, carries out normal reforming reaction operation, completes the start-up process of whole semi regeneration reforming reaction device.
The inventive method is applicable to semi regeneration reforming reaction device, when not having hydrogen source, uses virgin naphtha directly to be gone into operation by hydrogen production reaction.
Further describe the present invention below by example, but the present invention is not limited to this.
Example 1
The virgin naphtha (raw gasline) using refinery's atmospheric and vacuum distillation unit output is raw material, and described virgin naphtha boiling range is 83 ~ 165 DEG C, and sulphur content is 950 μ g/g, and its character is in table 1.
Each reactor charge catalyzer is as follows:
Hydrogen-manufacturing reactor filling 500kg CB-3B height platinum content pellet catalyst (production of China Petrochemical Industry's catalyzer Chang Ling branch office), its active metal component is platinum, and content is 0.5 quality %, and carrier is aluminum oxide.
Pre-hydrogenator filling 20000kg RS-1000 catalyzer (production of China Petrochemical Industry's catalyzer Chang Ling branch office).
Four reforming reactors load 30000kg oxidation state bimetallic catalyst (production of China Petrochemical Industry's catalyzer Chang Ling branch office) altogether, wherein (Pt content is 0.25 quality % to the first reactor charge 3000kg PRT-C catalyzer, Re content is 0.26 quality %, yttrium content 0.3 quality %, carrier is aluminum oxide), second reactor charge 4500kg PRT-C catalyzer, 3rd reactor charge 7500kg PRT-D catalyzer (Pt content 0.22 quality %, Re content 0.46 quality %, yttrium content 0.4 quality %, carrier is aluminum oxide), 4th reactor charge 15000kg PRT-D catalyzer.
Reforming under-stream is carried out by the flow process virgin naphtha of Fig. 1.
(1) raw hydrogen and refining petroleum naphtha is prepared
Blanked-off pipe wiretap valve 46,47, opens pipeline switch valve 41 ~ 45.The oxygen in nitrogen replacement system is introduced to pre-hydrotreating reaction system, 0.5 volume % is less than to system oxygen level, 0.8MPa is pressurized to nitrogen, and make at system internal recycle, raise temperature of reactor, when pre-hydrogenator and hydrogen-manufacturing reactor temperature in reach 300 DEG C, blanked-off pipe wiretap valve 42,43,45, makes pre-hydrogenator 6 detachment system.Continue to be warming up to hydrogen-manufacturing reactor 5 temperature in and reach 420 DEG C, with 3 tons of/hour oil inlet quantities, raw gasline is introduced hydrogen-manufacturing reactor, carry out hydrogen production reaction.Utilize the hydrogen that hydrogen-manufacturing reactor produces, i.e. nitrogen in raw hydrogen exchange system, when the density of hydrogen in raw hydrogen in system reaches 70 volume %, close gas drop-out line 22, outer winding displacement valve 48 and voltage-controlled valve, make the pressure of gas-liquid separator 9 rise to 1.5MPa, the voltage-controlled valve that comes into operation maintains system pressure.Shut-off valve 44, open pipeline switch valve 43, 45, make pre-hydrogenator connecting system again, be positioned at hydrogen-manufacturing reactor downstream, open valve 47, virgin naphtha is passed into pre-hydrogenator by pipeline 17, controlling pre-hydrogenator temperature in is 310 DEG C, with raw hydrogen, pre-hydrofining is carried out to virgin naphtha, pre-hydrotreating reaction product is through heat exchange, enter gas-liquid separator 9 after cooling and carry out gas-liquid separation, gained product liquid enters treated oil storage tank 12 and to go into operation treated oil used as reformer after dehydration by evaporation tower 11 dewaters, institute's aerogenesis body part introduces reforming reaction system through pipeline 21.Hydrogen manufacturing and pre-hydrogenator operational condition, refining petroleum naphtha foreign matter content and raw hydrogen character are in table 1.
(2) reforming under-stream is carried out with raw hydrogen and refining petroleum naphtha
Reforming reaction system nitrogen replacement to oxygen level is less than 0.5 volume %, introduce the raw hydrogen displacement nitrogen that pre-hydrotreating reaction system is obtained, then reforming reaction system pressure is charged to 0.8MPa, set up gas circulation, reforming reactor is warming up to its temperature in and reaches 250 DEG C, make reaction bed temperature maintain 1 hour at 250 DEG C, then reforming reactor is warming up to its temperature in and reaches 480 DEG C, stop heating up, make reaction bed temperature maintain 2 hours at 480 DEG C.Be cooled to 400 DEG C, with the normal resurfacing operation inlet amount of 30 tons of/hour, the treated oil in treated oil storage tank 12 introduced reforming reactor.When in system, the pressure of hydrogen reaches 1.0MPa, blanked-off pipe wiretap valve 41,43,44, open valve 42, hydrogen-manufacturing reactor 5 is made to depart from pre-hydrotreating reaction system, the hydrogen that reforming reaction system is produced is passed into pre-hydrogenation compressor 10 entrance (not indicating pipeline in figure), close the switch-valve 46 that raw hydrogen enters reforming reaction system simultaneously.Virgin naphtha is introduced pre-hydrogenator 6, reforming reactor 15 is warming up to normal production temperature 480 DEG C, proceed to normal reforming reaction operation of producing, complete whole start-up process.
After going into operation, the stable gasoline yield that reforming reaction obtains is 88.9 quality %, RON octane value is 96.6, and in product liquid, aromaticity content is 65.2 quality %.
Comparative example 1
Produce the hydrogen of treated oil and not sulfur-bearing by the method for ZL91100635, reforming under-stream method goes into operation routinely.
Raw materials used and each reactor charge catalyzer is all identical with example 1, and raw material is refinery's atmospheric and vacuum distillation unit virgin naphtha out (raw gasline), and boiling range is 83 ~ 165 DEG C, and sulphur content is 950 μ g/g.
By the method for example 1, virgin naphtha is passed into pre-hydrotreating reaction system and produce raw hydrogen and treated oil, unlike, produced raw hydrogen is passed into digester desulfurization to wherein sulphur content and be less than 0.5 μ L/L, then be introduced into reforming reaction system for going into operation.Hydrogen manufacturing and pre-hydrogenator operational condition, refining petroleum naphtha foreign matter content and institute's hydrogen producing character are in table 1.
Going into operation of reforming reaction system is carried out by the method for example 1, unlike the purified hydrogen that hydrogen used is after desulfurization, and reactor inlet temperature is risen to 480 DEG C of reductase 12s hour after setting up hydrogen recycle, then before oil-feed, reactor inlet temperature is down to 420 DEG C, in hydrogen, injects Methyl disulfide by 0.15% of reforming catalyst quality carry out reforming catalyst prevulcanized.After completing whole start-up process, the stable gasoline yield that reforming reaction obtains is 88.0 quality %, RON octane value is 96.1, and in product liquid, aromaticity content is 65.1 quality %.
Example 2
The virgin naphtha (raw gasline) using refinery's atmospheric and vacuum distillation unit output is raw material, and described virgin naphtha boiling range is 80 ~ 160 DEG C, and sulphur content is 959 μ g/g, and its character is in table 2.
Each reactor charge catalyzer is as follows:
Hydrogen-manufacturing reactor filling 500kg CB-3B height platinum content pellet catalyst (production of China Petrochemical Industry's catalyzer Chang Ling branch office), its active metal component is only platinum, and carrier is aluminum oxide.
Pre-hydrogenator filling 20000kg RS-1000 catalyzer (production of China Petrochemical Industry's catalyzer Chang Ling branch office).
Four reforming reactors load 30000kg oxidation state bimetallic catalyst (production of China Petrochemical Industry's catalyzer Chang Ling branch office) altogether, wherein (Pt content is 0.25 quality % to the first reactor charge 3000kg CB-60 catalyzer, Re content is 0.26 quality %, carrier is aluminum oxide), second reactor charge 4500kg CB-60 catalyzer, 3rd reactor charge 7500kg CB-70 catalyzer (Pt content 0.22 quality %, Re content 0.46 quality %, carrier is aluminum oxide), the 4th reactor charge 15000kg CB-70 catalyzer.
Carry out reforming under-stream by the flow process virgin naphtha of Fig. 1, the operation of pre-hydrotreating reaction system and reforming reaction system is all with example 1, and hydrogen manufacturing and pre-hydrogenator operational condition, refining petroleum naphtha foreign matter content and institute's hydrogen producing character are in table 2.After reforming reaction system goes into operation and enters normal running, gained stable gasoline yield is 88.2 quality %, RON octane value is 96.3, and in product liquid, aromaticity content is 64.9 quality %.
Comparative example 2
Produce the hydrogen of treated oil and not sulfur-bearing by the method for ZL91100635, reforming under-stream method goes into operation routinely.
Raw materials used and each reactor charge catalyzer is all identical with example 2, and raw material is refinery's atmospheric and vacuum distillation unit virgin naphtha out (raw gasline), and boiling range is 80 ~ 160 DEG C, and sulphur content is 959 μ g/g.
By the method for example 1, virgin naphtha is passed into pre-hydrotreating reaction system and produce raw hydrogen and treated oil, unlike, produced raw hydrogen is passed into digester desulfurization to wherein sulphur content and be less than 0.5 μ L/L, then be introduced into reforming reactor and go into operation for reforming reaction.Hydrogen manufacturing and pre-hydrogenator operational condition, refining petroleum naphtha foreign matter content and institute's hydrogen producing character are in table 2.
Going into operation of reforming reaction system is carried out by the method for example 1, unlike the purified hydrogen that hydrogen used is after desulfurization, and reactor inlet temperature is risen to 480 DEG C of reductase 12s hour after setting up hydrogen recycle, then before oil-feed, reactor inlet temperature is down to 420 DEG C, in hydrogen, injects Methyl disulfide by 0.15% of reforming catalyst quality carry out presulfiding of catalyst.After completing whole start-up process, the stable gasoline yield that reforming reaction obtains is 87.1 quality %, RON octane value is 95.5, and in product liquid, aromaticity content is 63.9 quality %.
From the result of above-mentioned example and comparative example, the method that the hydrogen of the more conventional use of the inventive method not sulfur-bearing carries out reforming under-stream has better effect.
Table 1
Table 2
Claims (13)
1. be a start-up method for the semi-regenerating catalytic reforming device of raw material with sulfur-bearing raw gasline, comprise:
(1) virgin naphtha from refinery's atmospheric and vacuum distillation unit is passed into the hydrogen-manufacturing reactor of reformed pre-hydrogenated reactive system, in pre-hydrogenator, pre-hydrogenation is carried out to described virgin naphtha with the raw hydrogen that hydrogen production reaction produces, the refining petroleum naphtha obtained after pre-hydrotreating reaction is collected in refining Naphtha tank
(2) in the reactor of reforming reaction system, load the reforming catalyst of oxidation state, reforming reaction system is fully replaced with nitrogen, introduce the raw hydrogen that hydrogen production reaction produces, boost to 0.2 ~ 1.2MPa, circulation, reaction bed temperature is risen to 100 ~ 250 DEG C to process catalyzer with raw hydrogen, be warming up to 450 ~ 550 DEG C again and continue process, then adjusting reaction bed temperature is 380 ~ 420 DEG C, the refining petroleum naphtha passing into (1) step obtained in reforming reactor starts catalytic reforming reaction, after the pressure of reactive system to be reformed reaches the normal pressure produced, stop hydrogen-manufacturing reactor operation, hydrogen reforming reaction produced introduces pre-hydrotreating reaction system, feed naphtha is refined, again treated oil is sent into reforming reaction system and carry out normal reforming reaction operation as reforming reaction raw material,
(2) the oxidation state reforming catalyst described in step comprises alumina supporter and take alumina supporter as the following active ingredient of the content of benchmark: the halogen of the group VIII metal of 0.1 ~ 2.0 quality %, the VIIB race metal of 0.1 ~ 2.0 quality % and 0.1 ~ 3.0 quality %.
2. in accordance with the method for claim 1, it is characterized in that the boiling range of the described virgin naphtha from refinery's atmospheric and vacuum distillation unit is 80 ~ 180 DEG C, wherein containing the sulphur of 100 ~ 1000 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that the reformed pre-hydrogenated reactive system described in (1) step comprises hydrogen-manufacturing reactor and pre-hydrogenator, described hydrogen-manufacturing reactor is connected in the upstream of pre-hydrogenator.
4. in accordance with the method for claim 1, it is characterized in that the temperature of hydrogen production reaction in (1) step is 350 ~ 450 DEG C, the temperature of reaction that virgin naphtha carries out pre-hydrogenation is 250 ~ 360 DEG C.
5. according to the method described in claim 1 or 3, it is characterized in that (1) step cuts out pre-hydrogenator, described virgin naphtha is passed into hydrogen-manufacturing reactor, the intrasystem gas of raw hydrogen displacement pre-hydrotreating reaction produced with hydrogen-manufacturing reactor, and make circulation, when density of hydrogen reaches 70 more than volume %, pre-hydrogenator is sealed in the downstream of hydrogen-manufacturing reactor, a described virgin naphtha part is passed into hydrogen-manufacturing reactor, and all the other pass into the entrance of pre-hydrogenator to regulate the temperature of reaction of pre-hydrogenation.
6. in accordance with the method for claim 1, it is characterized in that the catalyst for preparing hydrogen of filling in (1) step hydrogen-manufacturing reactor comprises alumina supporter and take alumina supporter as the following active ingredient of the content of benchmark: the group VIII metal of 0.1 ~ 2.0 quality %, the halogen of 0.1 ~ 5.0 quality %.
7. in accordance with the method for claim 6, it is characterized in that described group VIII metal is platinum, described halogen is chlorine.
8. in accordance with the method for claim 1, it is characterized in that in (2) step with raw hydrogen 100 ~ 250 DEG C process catalyzer time be 2.0 ~ 8.0 hours, 450 ~ 550 DEG C process catalyzer time be 2 ~ 6 hours.
9. in accordance with the method for claim 1, it is characterized in that, in (2) step raw hydrogen used, if sulphur content is less than 100 μ l/l, needing to inject sulfocompound wherein.
10. in accordance with the method for claim 1, it is characterized in that described oxidation state reforming catalyst also comprises lanthanide series metal and the yttrium of 0.1 ~ 3.0 quality %.
11. according to the method described in claim 1 or 10, it is characterized in that described group VIII metal is platinum, VIIB race metal is rhenium, halogen is chlorine.
12. in accordance with the method for claim 1, it is characterized in that the reaction pressure that described in (2) step, reforming reaction system is normally produced is 0.5 ~ 3.5MPa, temperature of reaction is 450 ~ 550 DEG C.
13. in accordance with the method for claim 1, and the feed naphtha that it is characterized in that described in (2) step is the coking naphtha after virgin naphtha, hydrocracked naphtha or hydrogenation.
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| CN108611119A (en) * | 2016-12-12 | 2018-10-02 | 河北新启元能源技术开发股份有限公司 | Naphtha catalytic reforming unit and its catalytic reforming process |
| FR3120076A1 (en) * | 2021-02-22 | 2022-08-26 | IFP Energies Nouvelles | Process for the production of aromatic compounds and/or gasolines from a naphtha-type hydrocarbon feedstock |
| CN113025375B (en) * | 2021-03-18 | 2023-05-02 | 中国神华煤制油化工有限公司 | Method for starting up catalytic reforming of naphtha by direct coal liquefaction |
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| CA748409A (en) * | 1966-12-13 | Douglas Baldwin, Jr. | Sulfide treatment of reforming catalyst | |
| CN1458239A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Under-stream method of catalytic reforming device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA748409A (en) * | 1966-12-13 | Douglas Baldwin, Jr. | Sulfide treatment of reforming catalyst | |
| CN1458239A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Under-stream method of catalytic reforming device |
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