CN102732310B - Device and method for hydrogenation reaction of naphtha - Google Patents
Device and method for hydrogenation reaction of naphtha Download PDFInfo
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- CN102732310B CN102732310B CN201110095296.6A CN201110095296A CN102732310B CN 102732310 B CN102732310 B CN 102732310B CN 201110095296 A CN201110095296 A CN 201110095296A CN 102732310 B CN102732310 B CN 102732310B
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Abstract
The invention discloses a device and a method for a hydrogenation reaction of naphtha. The device for a hydrogenation reaction of naphtha comprises a feeding system, a heating furnace, a fixed bed hydrogenation reactor and a hydrogenation reaction product separation system and also comprises a decoking tank, wherein the feeding system is communicated with an inlet of the heating surface by a pipe; an outlet of the heating surface is communicated with an inlet of the decoking tank by a pipe; an outlet of the decoking tank is communicated with an inlet of the fixed bed hydrogenation reactor by a pipe; and an outlet of the fixed bed hydrogenation reactor is communicated with the hydrogenation reaction product separation system by a pipe. Through the method provided by the invention, the device for a hydrogenation reaction of naphtha realizes hydrofining of a naphtha feedstock under appropriate conditions. Compared with the prior art, the device and the method can effectively and economically prolong a naphtha hydrogenation device running period.
Description
Technical field
The present invention relates to a kind of petroleum naphtha hydrogenation reaction unit and process for selective hydrogenation, specifically a kind of petroleum naphtha hydrogenation reaction unit hydrogenation reaction device and process for selective hydrogenation of running period of extending.
Background technology
Petroleum naphtha (being gasoline fraction) is important gasoline stocks and industrial chemicals, mainly for the production of the Fuel Petroleum of the various trades mark, catalytic reforming is produced aromatic hydrocarbons (or stop bracket gasoline blend component) raw material, steam cracking or catalytic pyrolysis are produced the industrial chemicals such as ethene, propylene, butylene, and for the production of the raw material of hydrogen etc.Petroleum naphtha generally derives from the virgin naphtha that petroleum distillation obtains, and the petroleum naphtha that secondary processing obtains, as coking naphtha, catalytic cracking petroleum naphtha, cracking naphtha etc.The various uses of various sources petroleum naphtha all needs the sulphur in raw material, nitrogen, rare hydrocarbon, metal impurities deep removal, and hydrogen addition technology is the optimum technology that removes various impurity in feed naphtha at present.Produce stop bracket gasoline as catalytic cracking naphtha selective hydrogenation, coking naphtha hydrogenation is produced steam crack material or hydrogen feedstock, and the pre-hydrogenation of virgin naphtha is produced catalytic reforming raw material etc.
In the various hydrogen addition technologies of petroleum naphtha, what generally use is fixed bed hydrogenation technology, be that fixed bed hydrogenation beds is set in hydrogenator, under hydrofining condition, feed naphtha and hydrogen enter reactor from top, carry out hydrofining by hydrogenation catalyst bed and remove the various impurity in raw material, the reaction product after refining is discharged reactor from reactor bottom, carries out obtaining hydrotreated naphtha product after follow-up separation.
In petroleum naphtha hydrogenation technology, the principal element of restriction hydrogenation unit long period steady running is the pressure drop rising speed of fixed bed hydrogenation reactor, in general, in the time that the pressure drop of hydrogenator reaches 0.3MPa, must shutdown process.
For example, concerning coking naphtha Hydrofining Technology, owing to containing the impurity such as diolefine, tiny coke powder in raw material, often affect the operational stability of device.Daqing petrochemical company 300kt/a Hydrogenation of Coker Gasoline device went into operation after half a year, occurred that continuously twice system pressure difference is too high, caused being forced to stop work (the rising analysis of causes of coking gasoline hydrogenation refining system pressure difference and countermeasure, " refining and chemical industry ", the 19th volume: 20).Also there is the reactor catalyst bed pressure drop too fast problem that rises when coker gasoline processing in Guangzhou Branch 300kt/a hydrogenation unit.This device once, within the time of a year and a half, caused stopping work defect elimination 5 times (analysis of causes and countermeasure that hydrofining reaction system pressure drop raises, " China and foreign countries' energy ", 2007, the 12 volumes) because reactive system bed pressure drop raises.Anqing branch office general 3～5 days needs of two I Hydrogenation of Coker Gasoline devices of oil refining clean strainer No. one time, hydrogenator will be stopped work in 1 year and be skimmed for 2～3 times, has a strong impact on normal operation (Coke Inhibitor for Coker Gasoline Hydrofining Unit, " petrochemical technology " of device, 2006,13(4): 5).All there is in various degree Similar Problems in domestic and international device of the same type, the increase of pressure difference between bed, make the inner member such as support bar and back up pad of catalyzer in bearing catalyst weight, the pressure outside necessary commitment, brings hidden trouble to the safety operation of device again.Therefore, it is the conspicuous contradiction that affects coking naphtha hydrogenation unit long-term operation that bed pressure drop rises too fast always, in the urgent need to working out effective means, solves coking problem.
Also often there is the similar problem of above-mentioned coking naphtha hydrogenation unit in catalytic cracking Naphtha hydrofining unit, virgin naphtha hydrogenation unit etc., be the hydrogenation unit running short period to occur the problem that reactor pressure falling-rising is high, can only the stop work partially catalyzed agent on purge reactor beds top, goes into operation after removable parts live catalyst again.
Naphtha hydrofining unit running is put into practice and is shown, the rising of hydrogenator pressure drop all comes from the bed coking of catalyzer top.Coking factor is very complicated, is converted into and is deposited on beds top after settling and causes mainly due to the polymerization of the unsaturated hydro carbons such as the diolefine in raw material and mechanical impurity that upstream device is brought into or impurity precursor.Diolefine in raw material is being easy to occur polymerization, particularly contain other impurity as oxygen, water, iron etc. in raw material time, is easier to polymerization coking.In the sample of coking, the content of general iron is also higher, may be to have formed naphthenic acid with organic hydrocarbon after stock oil dissolved oxygen, the iron of naphthenic acid corrosion device generates iron naphthenate, stably be dissolved in stock oil, iron naphthenate is easy to occur hydrogenolysis after mixed hydrogen, and react generation Iron sulfuret with hydrogen sulfide and be deposited on reactor top bed, the coking reaction that promotes coking parent, has accelerated the obstruction of beds.In addition, in some raw material, containing a small amount of tiny coke powder and tiny microorganism may be also one of reason of some feed naphthas coking in hydrogenator.Varied due to petroleum naphtha source, in the production of some feed naphtha, storage, transport, introduce and cannot filter the impurity of removing by raw material, these impurity are oil-soluble sometimes, are the particulate suspending sometimes, cannot effectively remove by a kind of or simple several method.And the feed naphtha of hydrogenation unit source is fixing, often change, therefore, also certain device can not be fixed as to certain raw material of processing and use the fixing impurity method of falling.
The method that existing solution petroleum naphtha hydrogenation reactor step-down raises has following several:
1, carry out the management work of raw material, adopt the modes such as nitrogen protection, avoid raw material to contact with air, at utmost reduced the chance of unsaturated hydro carbons formation colloid in raw material.This is a kind of passive raw material guard method, if the raw material mechanical impurity of upstream input is more, diene content is very high, or carries a lot of coke powders secretly, and the party's rule is helpless.
2, mix artificial coal oil or diesel oil distillate, diluted the unsaturated hydro carbons such as the diolefine in raw material, reduced the severity of hydrogenation unit, make device operation more stable.But the method has been sacrificed the amount of finish of hydrogenation device for treatment feed naphtha, has in fact reduced the air speed to feed naphtha, also to increase follow-up tripping device burden (existing tripping device can not meet the demands), economy is poor.
3, between the entrance and exit of pretreatment reaction device, by-pass is set, when normal production, reaction mass enters process furnace after by pretreatment reaction device, in the time that pretreatment reaction device beds Pressure Drop raises, reaction mass enters process furnace through by-pass, until pretreatment reaction device, partly or entirely more after catalyst changeout, reaction mass switches to pretreatment reaction device again and enters process furnace.Although the method can not operation downtime of assurance device, in the not pretreated situation of raw material, can cause larger impact to main reactor temperature rise, make the more difficult control of operation.The replacing of pretreatment catalyst simultaneously also can cause financial loss.Pretreatment reaction device is the impurity adopting in protective material bed deposition raw material, holds impurity limited in one's ability, needs often to change the protective material in pretreatment reaction device.
CN1109495A discloses a kind of Rifining method for catalylic cracking gasoline by adding hydrogen, and described is by the pre-sulfide catalyst series connection of two different activities and variable grain diameter.Adopt the mode of different catalysts grating to there is certain effect for alleviating the coking of hydrogenation catalyst bed, but effect is not outstanding.US4,113,603 reports use the hydrofinishing process of two sections to process diolefine and the sulfide in pyrolysis gasoline, first paragraph uses the catalyzer of nickeliferous-tungsten to remove mercaptan, second segment uses precious metals palladium catalyst to remove diolefine, this technique is comparatively complicated, can not effectively play a role with the coking of other factor for etidine hydrocarbon.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of petroleum naphtha hydrogenation reaction unit and petroleum naphtha hydrogenation reaction method, can effectively ensure the stable operation of petroleum naphtha hydrogenation reaction unit, extend the running period of Naphtha hydrofining unit.
Petroleum naphtha hydrogenation reaction unit of the present invention comprises feed system, process furnace, decoking tank, fixed bed hydrogenation reactor and hydrogenation reaction product separation system, feed system is communicated with process furnace entrance by pipeline, furnace outlet is communicated with decoking tank entrance by pipeline, the outlet of decoking tank is communicated with fixed bed hydrogenation reactor entrance by pipeline, and fixed bed hydrogenation reactor outlet is communicated with hydrogenation reaction product separation system by pipeline; Decoking tank is set, between furnace outlet and fixed bed hydrogenation reactor entrance, direct connecting pipeline is set, on this direct connecting pipeline, shutoff valve is set, on decoking tank source line and decoking tank outlet line, shutoff valve is set.In the time that decoking tank need to be cleared up, on decoking tank source line and decoking tank outlet line, shutoff valve being set closes, decoking tank is cut out to reactive system and clear up, reaction mass enters hydrogenator by direct connecting pipeline being set between furnace outlet and fixed bed hydrogenation reactor entrance.
In apparatus of the present invention, sump is preferably set in fixed bed hydrogenation reactor upper cover, in the time that decoking tank is cleared up, decoking tank excises out reactive system, reaction mass directly enters fixed bed hydrogenation reactor by pipeline, now sump completes the effect that removes solid impurity of material, after decoking tank cleans out, again comes into operation.Sump can use the structure of this area routine, the sump that inside reactor as disclosed in CN200410050765.2, CN200410050800.0, CN200510069872.4, CN200520017581.6 etc. uses etc.
In apparatus of the present invention, decoking tank is vertical structure, and decoking tank is made up of body skin and the inner separation assembly arranging, and body skin arranges material inlet and material outlet, and material inlet is preferably arranged on decoking tank top.Separation assembly is tube structure, and the internal layer of separation assembly cylindrical shell and skin are screen cloth, fill incrustation agent between inner screen and outer screen.The inner barrel passage of separation assembly is communicated with body skin material outlet.Separation assembly at least arranges one, and when multiple separation assembly is set, separation assembly inner barrel passage is all communicated with body skin material outlet, as separation assembly inner barrel passage manifold trunk can be set, after collecting, is communicated with body skin material outlet.In the middle of separation assembly screen cloth, the incrustation agent of filling is particle diameter 1.1～3mm, the preferably filler of 1.2 ~ 1.5mm, the material of filler can be aluminum oxide, silicon oxide, pottery etc., also can make spent hydroprocessing catalyst or useless hydrogenation catalyst etc., and the thickness of filler is generally 10～200mm.Decoking tank bottom arranges lets out ash mouthful, and decoking tank body skin bottom arranges ash blowing mouth, and the position of ash blowing mouth is higher than letting out ash mouthful.
Petroleum naphtha hydrogenation reaction method of the present invention, uses the above-mentioned petroleum naphtha hydrogenation reaction unit of the present invention, specifically comprises the steps:
(1) mixture of feed naphtha and hydrogen is delivered to and in process furnace, is heated to the required temperature of hydrogenation reaction through feed system;
(2) feed naphtha after heating and the mixture of hydrogen enter decoking tank;
(3) enter fixed bed hydrogenation reactor through feed naphtha and the hydrogen of decoking tank decoking, feed naphtha and hydrogen pass through the Hydrobon catalyst bed of fixed bed hydrogenation reactor under hydrofining condition, petroleum naphtha after hydrofining and hydrogen are discharged reactor and are entered separation system and separates and obtain hydrotreated naphtha, separate the hydrogen recycle use obtaining.
In the inventive method, feed naphtha can be virgin naphtha, coking naphtha, catalytic cracking petroleum naphtha, cracking naphtha etc., can be also the mixture of two or more petroleum naphtha.It is 180～350 DEG C that the refining condition of petroleum naphtha hydrogenation is generally reactor inlet temperature, and reaction pressure is 0.5～12MPa, and when the liquid of feed naphtha, volume space velocity is 0.5～20h
-1, hydrogen to oil volume ratio is 50:1～1500:1(standard state), concrete reaction conditions can specifically be determined according to the specification of quality of product after the character of feed naphtha and hydrogenation.Hydrobon catalyst is generally taking aluminum oxide as carrier, taking one or more in W, Mo, Ni and Co as hydrogenation activity component, can also contain suitable auxiliary agent, and active ingredient is generally sulphided state in use, to improve the catalytic activity of catalyzer.
When the inventive method work, feed naphtha through process furnace heating has at high temperature gasified as gas phase, petroleum naphtha and the hydrogen mixture of gasification enter decoking tank from the material inlet of decoking tank, vapor phase stream is through the barrel of separation assembly cylindrical shell, incrustation agent has suitable porosity, gas enters the inner core runner of separation assembly through incrustation agent, flow out decoking tank through decoking tank material outlet, then enter fixed bed hydrogenation reactor and carry out hydrogenation reaction, material after hydrogenation reaction enters separation system, obtain petroleum naphtha and gas phase after hydrogenation, gas phase is mainly hydrogen and can recycles.Solid impurity in gaseous phase materials is trapped, and is deposited in the space of decoking tank body skin and separation assembly cylindrical shell formation.Along with the accumulation of solid impurity, until solid impurity floods separation assembly, so far decoking tank loses decoking effect, from system, excise this decoking tank, open and let out ash mouth and ash blowing mouth, to ash blowing mouth injecting compressed air or nitrogen, the coke powder in decoking tank tank to be removed, the decoking tank after excretion coke powder can recover to use.Also can between the entrance and exit of decoking tank, pressure recorder be set, judge whether to clear up decoking tank according to the pressure drop rising situation of decoking tank.
Show through research, in Naphtha hydrofining unit, although the reason that causes hydrogenator pressure drop to raise is fast that in hydrogenator, beds coking and fouling causes, but these dirty thing overwhelming majority are not to form after hydrogenation catalyst carries out hydrogenation reaction, but feed naphtha and hydrogen are heated to after high temperature at process furnace, along with feed naphtha transfers gas phase to from liquid phase, coking precursor is assembled and is transformed gradually owing to gasifying, finally become burnt shape solid matter, these burnt shape solid matters enter in hydrogenator under gaseous stream conveying effect, be deposited in beds, and then blocking catalyst bed causes hydrogenator pressure drop rising.Show by great many of experiments, petroleum naphtha and hydrogen are heated to the coking material forming in high-temperature gasification process, with heating before be diverse material, cannot address this problem by the filtration of raw material.Meanwhile, these coking materials are easy to deposition, in suitable deposition equipment, can effectively separate.Adopt decoking tank of the present invention, the gaseous stream of entrained solids impurity enters after decoking tank, because circulation area expands, gas flow rate reduces, solid impurity deposits because inertia effect drops down onto decoking pot bottom fast, and can not brought in the deposition agent of decoking tank separation assembly by gas phase major part, because now gas phase flow velocity is slower, gas phase separates with the fluidised form of solid impurity, therefore, separation assembly can not lose efficacy by fast blocking, only can constantly rise and bury separation assembly and partial failure with settling, and the work-ing life of this decoking tank is very long.The present invention, by the mechanism of the above-mentioned petroleum naphtha hydrogenation process of research coking, arranges the incrustation tank that structure is suitable, and petroleum naphtha hydrogenation technical process reasonable in design, can effectively solve hydrogenator short problem running period in petroleum naphtha hydrogenation technology.
Petroleum naphtha hydrogenation reaction unit of the present invention only needs to increase a decoking tank, that decoking tank has is simple in structure, it is little to take up an area, no-rotary part, space utilization fully, the feature such as large, the less investment of solid impurity deposition, the investment to hydrogenation reaction device and process cost increase seldom.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of apparatus of the present invention decoking tank set-up mode in whole device;
Wherein: 101-process furnace, 102-furnace outlet and the direct connecting pipeline of fixed bed hydrogenation reactor entrance, 103-decoking tank, 104-fixed bed hydrogenation reactor, 105-decoking tank differential manometer, the inner sump of 106-fixed bed hydrogenation reactor.
Fig. 2 is the concrete decoking jar structure of the one schematic diagram that the present invention uses;
Wherein: 1-material inlet, 2-inlet diffuser, 3-upper cover, 4-separation assembly, 5-outer cylinder body, 6-ash blowing mouth, 7-exit collector, 8-material outlet, 9-skirt, 10-lets out ash mouthful, 11-lower cover, the drop-down support component of 12-, the upper stay bolt assembly of 13-.
Embodiment
Further illustrate the technology contents of the inventive method and decoking tank below in conjunction with accompanying drawing, and further illustrate the technique effect of the inventive method by embodiment.
Decoking tank is as shown in Figure 2 set between the process furnace of petroleum naphtha hydrogenation processing method of the present invention in existing petroleum naphtha hydrogenation technique and hydrogenator, and other content does not need to change substantially.As shown in Figure 1, the reaction mass heating through process furnace 101 enters decoking tank 103 decokings, then enters fixed bed hydrogenation reactor 104, carries out entering separation system after hydrogenation reaction.In the time that decoking tank 103 is cleared up, reaction mass enters reactor through furnace outlet and the direct connecting pipeline 102 of fixed bed hydrogenation reactor entrance, solid impurity wherein can remove by the inner sump 106 of fixed bed hydrogenation reactor, can not stop up hydrogenation catalyst bed, after the cleaning of decoking tank, switch into reactive system and reuse again.
As shown in Figure 2, a kind of concrete structure of the decoking tank using in the inventive method is as follows: decoking tank forms body skin by upper cover 3, outer cylinder body 5 and lower cover 11, upper cover 3 tops arrange material inlet 1, material inlet 1 bottom inlet porting scatterer 2, lower cover 11 bottoms arrange exit collector 7, and exit collector 7 communicates with material outlet 8.The existing decoking tank outer cylinder body 5 of separation assembly 4 is coaxially arranged in decoking tank, and separation assembly 4 is fixed in decoking tank by drop-down support component 12 and upper stay bolt assembly 13, and separation assembly 4 is that the agent of the inner filling of two-layer screen cloth incrustation forms.Decoking tank lower cover bottom arranges lets out ash mouth 10, and decoking tank outer cylinder body 5 bottoms arrange ash blowing mouth 6.Whole decoking tank is fixed on working face by skirt 9.
Further illustrate the effect of the inventive method and device below by embodiment.The decoking jar structure that embodiment uses is: the high and diameter ratio of aspect ratio 5(), separation assembly cylindrical shell thickness is 50mm, the alumina globule that interior filling particle diameter is 1.5mm, separation assembly cylinder internal diameter is identical with hydrogenator source line diameter, and between separation assembly and decoking tank body skin, annular space distance is 1 meter.Separation assembly rain cap and separation assembly are not established gap.
Embodiment 1 and comparative example 1
Coking naphtha hydrofining technology.Coking naphtha mixes through process furnace and is heated to 230 DEG C with hydrogen, enters hydrogenator after entering decoking tank decoking.Hydrogenation catalyst FH-40A is the business Hydrobon catalyst of Sinopec Fushun Petrochemical Research Institute development and production.Feedstock property is in table 1, operational condition and the results are shown in Table 2.The difference of comparative example is not for arranging decoking tank.
Table 1 stock oil character.
| Raw material | Coking naphtha |
| Boiling range scope, DEG C | 36～192 |
| Sulphur, μ g/g | 4960 |
| Nitrogen, μ g/g | 126 |
| Bromine valency, gBr/ (100mL) | 48 |
Table 2 operational condition and product property.
| ? | Embodiment 1 | Comparative example 1 |
| Reaction hydrogen pressure, MPa | 4.0 | 4.0 |
| Hydrogen to oil volume ratio | 800:1 | 800:1 |
| Volume space velocity, h -1 | 2.0 | 2.0 |
| Reactor inlet temperature, DEG C | 230 | 230 |
| Hydrogenation catalyst | FH-40A | FH-40A |
| Reactor pressure decrease, MPa(30 days) | 0.10 | 0.12 |
| Reactor pressure decrease, MPa(60 days) | 0.10 | 0.20 |
| Reactor pressure decrease, MPa(90 days) | 0.10 | 0.28 |
| Reactor pressure decrease, MPa(100 days) | 0.10 | Stop work |
Can find out from above-mentioned contrast, the inventive method can solve the pressure drop rising problem of coking naphtha hydrogenation unit, can effectively extend the running period of hydrogenation unit.
Embodiment 2 and comparative example 2
Catalytic cracking heavy naphtha selective hydrogenation desulfurization process.Catalytic cracking petroleum naphtha adopts commodity AFS-12 catalyzer (University of Petroleum's production), at pressure 0.5MPa, 35 DEG C～45 DEG C of temperature, volume space velocity 2.0h
-1, carry out deodorization under gas-oil ratio (air/gasoline) 4:1 condition.Deodorization product is through fractionation, and cut point is 70 DEG C and obtains catalytic cracking heavy naphtha, and catalytic cracking heavy naphtha mixes through process furnace and is heated to 250 DEG C with hydrogen, enters hydrogenator after entering decoking tank decoking.Hydrogenation catalyst FGH-11 is the business catalyst for selectively hydrodesulfurizing of Sinopec Fushun Petrochemical Research Institute development and production.Feedstock property is in table 3, operational condition and the results are shown in Table 4.The difference of comparative example is not for arranging decoking tank.
Table 3 catalytic cracking heavy naphtha main character.
| Raw material | The last running of catalytic cracking petroleum naphtha |
| Sulphur content, μ g/g | 900 |
| Olefin(e) centent, v% | 22 |
| Research octane number (RON), RON | 91.0 |
| Boiling range, DEG C (initial boiling point～final boiling point) | 58～179 |
Table 4 operational condition and result.
| ? | Embodiment 2 | Comparative example 2 |
| Reaction hydrogen pressure, MPa | 1.6 | 1.6 |
| Hydrogen to oil volume ratio | 300:1 | 300:1 |
| Volume space velocity, h -1 | 2.0 | 2.0 |
| Reactor inlet temperature, DEG C | 250 | 250 |
| Hydrogenation catalyst | FGH-11 | FGH-11 |
| Reactor pressure decrease, MPa(5 days) | 0.09 | 0.15 |
| Reactor pressure decrease, MPa(10 days) | 0.09 | 0.20 |
| Reactor pressure decrease, MPa(20 days) | 0.09 | Stop work |
| Reactor pressure decrease, MPa(50 days) | 0.09 | ? |
Embodiment 3 and comparative example 3
Virgin naphtha is hydrogenated in advance catalytic reforming and supplies raw materials.Virgin naphtha mixes through process furnace and is heated to 300 DEG C with hydrogen, enters hydrogenator after entering decoking tank decoking.Hydrogenation catalyst FH-40C is the business Hydrobon catalyst of Sinopec Fushun Petrochemical Research Institute development and production.Feedstock property is in table 5, operational condition and the results are shown in Table 6.The difference of comparative example is not for arranging decoking tank.
Table 5 virgin naphtha main character.
| Raw material | Virgin naphtha |
| Source | Mix virgin naphtha |
| Density (20 DEG C), g/cm 3 | 0.7348 |
| Sulphur content, μ g/g | 800 |
| Nitrogen content, μ g/g | 2.8 |
Table 6 operational condition and result.
| Processing condition | Embodiment 3 | Comparative example 3 |
| Reaction pressure, MPa | 1.6 | 1.6 |
| Temperature of reaction, DEG C | 300 | 300 |
| Volume space velocity, h -1 | 6.0 | 6.0 |
| Hydrogen-oil ratio, Nm 3/m 3 | 100 | 100 |
| Oil property | Treated oil | Treated oil |
| Sulphur content, μ g/g | <0.5 | <0.5 |
| Nitrogen content, μ g/g | <0.5 | <0.5 |
| Hydrogenation catalyst | FH-40C | FH-40C |
| Reactor pressure decrease, MPa(30 days) | 0.11 | 0.15 |
| Reactor pressure decrease, MPa(60 days) | 0.11 | 0.20 |
| Reactor pressure decrease, MPa(100 days) | 0.11 | 0.26 |
| Reactor pressure decrease, MPa(120 days) | 0.11 | Stop work |
Can find out by embodiment, by using the decoking tank of suitable structure, the pressure drop of petroleum naphtha hydrogenation reactor is not risen substantially, can estimate, within catalyzer work-ing life, can not stop work because of problem of pressure drop.
Claims (9)
1. a petroleum naphtha hydrogenation reaction unit, comprise feed system, process furnace, fixed bed hydrogenation reactor and hydrogenation reaction product separation system, it is characterized in that: also comprise decoking tank, feed system is communicated with process furnace entrance by pipeline, furnace outlet is communicated with decoking tank entrance by pipeline, the outlet of decoking tank is communicated with fixed bed hydrogenation reactor entrance by pipeline, and fixed bed hydrogenation reactor outlet is communicated with hydrogenation reaction product separation system by pipeline, decoking tank is set, between furnace outlet and fixed bed hydrogenation reactor entrance, direct connecting pipeline is set, on this direct connecting pipeline, shutoff valve is set, on decoking tank source line and decoking tank outlet line, shutoff valve is set, decoking tank is vertical structure, decoking tank is made up of body skin and the inner separation assembly arranging, body skin arranges material inlet and material outlet, separation assembly is tube structure, the internal layer of separation assembly cylindrical shell and skin are screen cloth, between inner screen and outer screen, fill incrustation agent, the inner barrel passage of separation assembly is communicated with body skin material outlet.
2. according to device claimed in claim 1, it is characterized in that: in fixed bed hydrogenation reactor upper cover, sump is set.
3. according to device claimed in claim 1, decoking tank it is characterized in that: in the time that need to be cleared up, on decoking tank source line and decoking tank outlet line, shutoff valve being set closes, decoking tank is cut out to reactive system and clear up, reaction mass enters hydrogenator by direct connecting pipeline being set between furnace outlet and fixed bed hydrogenation reactor entrance.
4. according to device claimed in claim 1, it is characterized in that: material inlet is arranged on decoking tank top.
5. according to device claimed in claim 1, it is characterized in that: separation assembly at least arranges one, in the middle of separation assembly screen cloth, the incrustation agent of filling is the filler of particle diameter 1.1～3mm, the material of filler is aluminum oxide, silicon oxide, pottery, filler or make spent hydroprocessing catalyst or useless hydrogenation catalyst, the thickness of filler is 10～200mm.
6. according to device claimed in claim 5, it is characterized in that: in the middle of separation assembly screen cloth, the incrustation agent of filling is the filler of particle diameter 1.2～1.5mm.
7. according to device claimed in claim 1, it is characterized in that: decoking tank bottom arranges lets out ash mouthful, and decoking tank body skin bottom arranges ash blowing mouth, and the position of ash blowing mouth is higher than letting out ash mouthful.
8. a petroleum naphtha hydrogenation reaction method, is characterized in that: right to use requires the petroleum naphtha hydrogenation reaction unit described in 1 to 7 arbitrary claim, comprises the steps:
(1) mixture of feed naphtha and hydrogen is delivered to and in process furnace, is heated to the required temperature of hydrogenation reaction through feed system;
(2) feed naphtha after heating and the mixture of hydrogen enter decoking tank;
(3) enter fixed bed hydrogenation reactor through feed naphtha and the hydrogen of decoking tank decoking, feed naphtha and hydrogen pass through the Hydrobon catalyst bed of fixed bed hydrogenation reactor under hydrofining condition, petroleum naphtha after hydrofining and hydrogen are discharged reactor and are entered separation system and separates and obtain hydrotreated naphtha, separate the hydrogen recycle use obtaining.
9. in accordance with the method for claim 8, it is characterized in that: feed naphtha is virgin naphtha, coking naphtha, catalytic cracking petroleum naphtha, cracking naphtha, or the mixture of two or more petroleum naphtha; The refining reaction conditions of petroleum naphtha hydrogenation is: reactor inlet temperature is 180～350 DEG C, and reaction pressure is 0.5～12MPa, and when the liquid of feed naphtha, volume space velocity is 0.5～20h
-1, hydrogen to oil volume ratio is 50:1～1500:1.
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| CN101376828A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Hydrofinishing method for coker gasoline |
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