CN102732310A - Device and method for hydrogenation reaction of naphtha - Google Patents
Device and method for hydrogenation reaction of naphtha Download PDFInfo
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- CN102732310A CN102732310A CN2011100952966A CN201110095296A CN102732310A CN 102732310 A CN102732310 A CN 102732310A CN 2011100952966 A CN2011100952966 A CN 2011100952966A CN 201110095296 A CN201110095296 A CN 201110095296A CN 102732310 A CN102732310 A CN 102732310A
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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 prolonging.
Background technology
Petroleum naphtha (being gasoline fraction) is important gasoline stocks and industrial chemicals; Be mainly used in the Fuel Petroleum of producing the various trades mark; CR is produced aromatic hydrocarbons (or stop bracket gasoline blend component) raw material; Steam cracking or catalytic pyrolysis are produced industrial chemicals such as ethene, propylene, butylene, and the raw material etc. that is used to produce hydrogen.Petroleum naphtha generally derives from the virgin naphtha that petroleum distillation obtains, and the petroleum naphtha that secondary processing obtains is like coking naphtha, catalytic cracking petroleum naphtha, cracking naphtha etc.The various uses of various sources petroleum naphtha all need be with the sulphur in the raw material, nitrogen, rare hydrocarbon, metal impurities deep removal, and hydrogen addition technology is the optimum technology that removes various impurity in the feed naphtha at present.Produce stop bracket gasoline like catalytic cracking naphtha selective hydrogenation, the coking naphtha hydrogenation is produced steam crack material or hydrogen feedstock, and the preparatory hydrogenation of virgin naphtha is produced catalytic reforming raw material etc.
In the various hydrogen addition technologies of petroleum naphtha; What generally use is the fixed bed hydrogenation technology, the fixed bed hydrogenation beds promptly is set, in the hydrogenator under the unifining condition; Feed naphtha and hydrogen get into reactor drum from top; Carry out unifining through the hydrogenation catalyst bed and remove the various impurity in the raw material, the reaction product after making with extra care is discharged reactor drum from reactor bottom, carries out obtaining the hydrotreated naphtha product after the follow-up separation.
In the petroleum naphtha hydrogenation technology, the principal element of restriction hydrogenation unit LP steady running is the pressure drop rising rapid speed of fixed bed hydrogenation reactor, in general, when the pressure drop of hydrogenator reaches 0.3MPa, must stop work and handle.
For example concerning coking naphtha unifining technology,, often influence the operational stability of device owing to contain diolefine, tiny impurity such as coke powder in the raw material.Daqing petrochemical company 300kt/a coker gasoline hydrogenation unit is after the half a year that goes into operation, and it is too high to occur two subsystem pressure reduction continuously, causes compelled shut-down the (the pressure reduction rising analysis of causes of coking gasoline hydrogenation refining system and countermeasure, " oil refining and chemical industry ", the 19th volume: 20).The too fast problem of reactor catalyst bed pressure drop rising also appears in Guangzhou Branch 300kt/a hydrogenation unit when handling coker gasoline.This device once in the time of a year and a half, lacked (the analysis of causes and countermeasure that the hydrofining reaction system pressure drop raises, " China and foreign countries' energy ", 2007, the 12 volumes) 5 times because the reactive system bed pressure drop raises to cause stopping work disappearing.General 3～5 days needs of two I coker gasoline hydrogenation units of Anqing branch office oil refining clean a strainer; Hydrogenator will be stopped work in 1 year and cast aside for 2～3 times, has a strong impact on normal operation (coker gasoline hydrogenation scorch retarder, " petrochemical technology " of device; 2006,13 (4): 5).All there is similar problem in various degree in domestic and international device of the same type; The increase of pressure difference between bed; Make the inner members such as support bar and back up pad of catalyzer when bearing catalyst weight, again must the outer pressure of commitment, bring serious hidden danger for the safety operation of device.Therefore, it is the conspicuous contradiction that influences coking naphtha hydrogenation unit long-term operation that bed pressure drop rises too fast always, presses for and works out effective means, solves coking problem.
Above-mentioned coking naphtha hydrogenation unit similar problem also often appears in catalytic cracking petroleum naphtha hydrogenation device, virgin naphtha hydrogenation unit etc.; Be the hydrogenation unit running short period the high problem of reactor pressure falling-rising promptly to occur; Can only the stop work part catalyzer on purge reactor beds top goes into operation after the removable parts live catalyst again.
Petroleum naphtha hydrogenation device running practice shows that the rising of hydrogenator pressure drop all comes from the bed coking of catalyzer top.The coking factor is very complicated, is converted into mainly due to the polymerization of the unsaturated hydro carbons such as diolefine in the raw material and mechanical impurity that upstream device is brought into or impurity precursor to be deposited on beds top behind the settling and to cause.Diolefine in the raw material is being easy to take place polymerization, when particularly in raw material, containing other impurity such as oxygen, water, iron etc., is easier to polymerization coking.In the sample of coking, the content of general iron is also higher, possibly be to have formed naphthenic acid with organic hydrocarbon behind the raw oil dissolved oxygen; The iron of naphthenic acid corrosion device generates iron naphthenate; Stably be dissolved in the raw oil, iron naphthenate is easy to take place hydrogenolysis after mixing hydrogen, and is deposited on reactor drum top bed with hydrogen sulfide reaction generation Iron sulfuret; Promote the green coke reaction of coking parent, quickened the obstruction of beds.In addition, containing a spot of tiny coke powder and tiny mikrobe in some raw material also possibly be one of reason of some feed naphthas coking in hydrogenator.Because the petroleum naphtha source is varied; Introduced in the production of some feed naphtha, storage, the transportation and can't filter the impurity of removing through raw material; These impurity are oil-soluble sometimes, are the particulate that suspends sometimes, can't effectively remove through a kind of or simple several method.And the feed naphtha source of a hydrogenation unit is unfixing, often changes, and therefore, yet can not certain device is fixed as certain raw material of processing and use fixed to fall the impurity method.
The method that existing solution petroleum naphtha hydrogenation reactor drum step-down raises has following several kinds:
1, carries out the management work of raw material, adopt modes such as nitrogen protection, avoid raw material to contact, at utmost reduced unsaturated hydro carbons formation gelationus chance in the raw material with air.This is a kind of passive raw material guard method, if the raw material mechanical impurity of upper reaches input is more, diene content is very high, or carries a lot of coke powders secretly, and this method is then powerless.
2, mix artificial coal oil or diesel oil distillate, diluted the unsaturated hydro carbons such as diolefine in the raw material, reduced the severity of hydrogenation unit, make the device operation more stable.But this 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 will increase follow-up tripping device burden (existing tripping device can not meet the demands), and economy is relatively poor.
3, between the entrance and exit of pretreatment reaction device, by-pass is set; Reaction mass gets into process furnace after through the pretreatment reaction device during ordinary production; When the falling-rising of pretreatment reaction device catalyst bed stressor layer is high; Reaction mass gets into process furnace through by-pass, treats the pretreatment reaction device partly or entirely more behind the catalyst changeout, and reaction mass switches to the pretreatment reaction device again and gets into process furnace.Though this method can assurance device operation downtime not, raw material without pretreated situation under, can cause bigger impact to the main reactor temperature rise, make the difficult control of operation.The replacing of pretreatment catalyst simultaneously also can cause financial loss.The pretreatment reaction device is to adopt protective material bed deposition impurities in raw materials, and it is limited in one's ability to hold impurity, needs often to change the protective material in the pretreatment reaction device.
CN1109495A discloses a kind of Rifining method for catalylic cracking gasoline by adding hydrogen, and described is that the pre-sulfide catalyst of two different activities and variable grain diameter is connected.Adopt the mode of different catalysts grating to have certain effect, but effect is not outstanding for alleviating the coking of hydrogenation catalyst bed.US4; 113; 603 reports use two sections hydrofinishing process to handle diolefine and sulfide in the pyrolysis gasoline, and the catalyzer of first section nickeliferous-tungsten of use is removed mercaptan, and second section is used precious metals palladium catalyst to remove diolefine; This technology is comparatively complicated, and the coking with other factor can not play a role effectively for the etidine hydrocarbon.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of petroleum naphtha hydrogenation reaction unit and petroleum naphtha hydrogenation reaction method, can effectively guarantee the stable operation of petroleum naphtha hydrogenation reaction unit, prolongs the running period of petroleum naphtha hydrogenation device.
Petroleum naphtha hydrogenation reaction unit of the present invention comprises feed system, process furnace, decoking jar, fixed bed hydrogenation reactor and hydrogenation reaction product separation system; Feed system is communicated with the process furnace inlet through pipeline; Furnace outlet is communicated with decoking jar inlet through pipeline; The outlet of decoking jar is communicated with the fixed bed hydrogenation reactor inlet through pipeline, and the fixed bed hydrogenation reactor outlet is communicated with the hydrogenation reaction product separation system through pipeline; The decoking jar is set, between furnace outlet and the fixed bed hydrogenation reactor inlet direct connecting pipeline is set, on this direct connecting pipeline shutoff valve is set, on decoking jar source line and the decoking jar outlet line shutoff valve is set.When the decoking jar need be cleared up; On decoking jar source line and the decoking jar outlet line shutoff valve being set closes; The decoking jar is cut out reactive system clear up, reaction mass gets into hydrogenator through between furnace outlet and the fixed bed hydrogenation reactor inlet direct connecting pipeline being set.
In apparatus of the present invention; Sump preferably is set in the fixed bed hydrogenation reactor upper cover, and when the decoking jar was cleared up, the decoking jar excised out reactive system; Reaction mass directly gets into fixed bed hydrogenation reactor through pipeline; This moment, sump was accomplished the effect that removes solid impurity of material, after the decoking jar cleans out, came into operation again.Sump can use the conventional structure in this area, the sump that uses like disclosed inside reactor such as CN200410050765.2, CN200410050800.0, CN200510069872.4, CN200520017581.6 etc.
In apparatus of the present invention, the decoking jar is a vertical structure, and the decoking jar is made up of the separation assembly of body skin and set inside, and body skin is provided with material inlet and material outlet, and material inlet preferably is arranged on the decoking tank top.Separation assembly is a tube structure, and the internal layer of separation assembly cylindrical shell is a screen cloth with skin, fills the incrustation agent between inner screen and the outer screen.The barrel passage of separation assembly is communicated with the body skin material outlet.Separation assembly is provided with one at least, and when a plurality of separation assembly was set, separation assembly barrel passage all was communicated with the body skin material outlet, as separation assembly barrel passage manifold trunk can be set, compile the back and is communicated with the body skin material outlet.The incrustation agent of filling is particle diameter 1.1～3mm in the middle of the separation assembly screen cloth; The filler of preferred 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 jar bottom is provided with lets out the ash mouth, and decoking jar body skin bottom is provided with blows grey mouthful, and the position of blowing the ash mouth is higher than lets out the ash mouth.
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 through feed system and is heated to the required temperature of hydrogenation reaction in the process furnace;
(2) mixture of feed naphtha after the heating and hydrogen gets into the decoking jar;
(3) feed naphtha and the hydrogen through decoking jar decoking gets into fixed bed hydrogenation reactor; Feed naphtha and hydrogen pass through the Hydrobon catalyst bed of fixed bed hydrogenation reactor under the unifining condition; Petroleum naphtha after the unifining and hydrogen are discharged reactor drum and are got into separation system and separate and obtain hydrotreated naphtha, separate the hydrogen recycle that obtains and use.
In the inventive method, feed naphtha can be virgin naphtha, coking naphtha, catalytic cracking petroleum naphtha, cracking naphtha etc., also can be the mixture of two or more petroleum naphtha.It is 180～350 ℃ that petroleum naphtha hydrogenation purified condition is generally reactor inlet temperature, and reaction pressure is 0.5～12MPa, and volume space velocity is 0.5～20h during the liquid of feed naphtha
-1, hydrogen to oil volume ratio is 50:1～1500:1 (standard state), concrete reaction conditions can specifically be confirmed according to the specification of quality of product behind the character of feed naphtha and the hydrogenation.Hydrobon catalyst generally is carrier with the aluminum oxide, is the hydrogenation activity component with among W, Mo, Ni and the Co one or more, can also contain suitable auxiliary agent, and active ingredient is generally sulphided state in use, to improve the catalytic activity of catalyzer.
During the inventive method work, the feed naphtha of process process furnace heating has at high temperature gasified and has been gas phase, and the petroleum naphtha of gasification and hydrogen mixture get into the decoking jar from the material inlet of decoking jar; Vapor phase stream is through the barrel of separation assembly cylindrical shell; The incrustation agent has suitable porosity, and gas passes the inner core runner that the incrustation agent gets into separation assembly, flows out the decoking jar through decoking jar material outlet; Get into fixed bed hydrogenation reactor then and carry out hydrogenation reaction; Material after the hydrogenation reaction gets into separation system, obtains petroleum naphtha and gas phase behind the hydrogenation, and gas phase is mainly hydrogen and can recycles.Solid impurity in the gaseous phase materials is trapped, and is deposited in the space of decoking jar body skin and separation assembly cylindrical shell formation.Accumulation along with solid impurity; Flood separation assembly until solid impurity, so far the decoking jar loses the decoking effect, this decoking jar of excision from system; Open and let out the ash mouth and blow the ash mouth; To blowing ash mouthful injecting compressed air or nitrogen, the coke powder in the decoking jar jar to be removed, the decoking jar behind the drainage coke powder can recover to use.Also can between the entrance and exit of decoking jar, pressure recorder be set, judge whether needs cleaning decoking jar according to the pressure drop rising situation of decoking jar.
Show through research; In the petroleum naphtha hydrogenation device; Though the reason that causes the hydrogenator pressure drop to raise fast is that the beds coking and fouling causes in the hydrogenator, these dirty thing overwhelming majority are not to carry out forming after the hydrogenation reaction through hydrogenation catalyst, but feed naphtha and hydrogen are after process furnace is heated to high temperature; Along with feed naphtha transfers gas phase to from liquid phase; The coking precursor assemble to transform owing to can't gasify gradually, finally becomes burnt shape solid matter, and these burnt shape solid matters are under gaseous stream conveying effect in the entering hydrogenator; Be deposited in the beds, and then the blocking catalyst bed causes hydrogenator pressure drop rising.Show that through a large amount of experiments petroleum naphtha and hydrogen are heated to the coking material that forms in the high-temperature gasification process, with the heating before be diverse material, can't address this problem through the filtration of raw material.Simultaneously, these coking materials are easy to deposition, in suitable deposition equipment, can effectively separate.Adopt decoking jar of the present invention, after the gaseous stream of entrained solids impurity gets into the decoking jar, because circulation area enlarges; Gas flow rate reduces, and solid impurity deposits owing to inertia effect drops down onto the decoking pot bottom fast, and can not brought in the deposition agent of decoking jar separation assembly by the gas phase major part; Because this moment, the gas phase flow velocity was slower; Gas phase is separated with the fluidised form of solid impurity, and therefore, separation assembly can not stop up inefficacy fast; Only can constantly rise with settling and bury separation assembly and partial failure, the work-ing life of this decoking jar is very long.The present invention is provided with the suitable incrustation jar of structure through the mechanism of the above-mentioned petroleum naphtha hydrogenation process of research coking, and petroleum naphtha hydrogenation technical process reasonable in design can effectively solve hydrogenator short problem running period in the petroleum naphtha hydrogenation technology.
Petroleum naphtha hydrogenation reaction unit of the present invention only need increase a decoking jar; That the decoking jar has is simple in structure, it is little to take up an area of, no-rotary part, space utilization fully, characteristics such as big, the less investment of solid impurity deposition, to the investment of hydrogenation reaction device and process cost increase seldom.
Description of drawings
Fig. 1 is the schematic flow sheet of apparatus of the present invention decoking jar set-up mode in whole device;
Wherein: 101-process furnace, 102-furnace outlet and the fixed bed hydrogenation reactor direct connecting pipeline that enters the mouth, 103-decoking jar, 104-fixed bed hydrogenation reactor, 105-decoking jar differential manometer, the inner sump of 106-fixed bed hydrogenation reactor.
Fig. 2 is a kind of concrete decoking jar structure synoptic diagram that the present invention uses;
Wherein: 1-material inlet, 2-inlet diffuser, 3-upper cover, 4-separation assembly, 5-outer cylinder body, 6-blow the ash mouth, and 7-exit collector, 8-material outlet, 9-skirt, 10-are let out ash mouth, 11-lower cover, the drop-down support component of 12-, the last stay bolt assembly of 13-.
Embodiment
Further specify the technology contents of the inventive method and decoking jar below in conjunction with accompanying drawing, and further specify the technique effect of the inventive method through embodiment.
Between process furnace and the hydrogenator of petroleum naphtha hydrogenation process method of the present invention in existing petroleum naphtha hydrogenation technology decoking jar as shown in Figure 2 is set, other content need not change basically.As shown in Figure 1, reaction mass entering decoking jar 103 decokings through process furnace 101 heating get into fixed bed hydrogenation reactor 104 then, carry out getting into separation system after the hydrogenation reaction.When decoking jar 103 is cleared up; Reaction mass is through furnace outlet and the fixed bed hydrogenation reactor direct connecting pipeline 102 entering reactor drums that enter the mouth; Solid impurity wherein can remove through the inner sump 106 of fixed bed hydrogenation reactor; Can not stop up the hydrogenation catalyst bed, switch again after the cleaning of decoking jar and advance the reactive system repeated use.
As shown in Figure 2; A kind of concrete structure of the decoking jar that uses in the inventive method is following: the decoking jar constitutes body skin by upper cover 3, outer cylinder body 5 and lower cover 11; Upper cover 3 tops are provided with material inlet 1; Material inlet 1 bottom inlet porting scatterer 2, lower cover 11 bottoms are provided with exit collector 7, and exit collector 7 communicates with material outlet 8.Separation assembly 4 existing decoking jar outer cylinder body 5 coaxial being arranged in the decoking jar, separation assembly 4 is fixed in the decoking jar with last stay bolt assembly 13 through drop-down support component 12, and separation assembly 4 is that the agent of the inner filling of two-layer screen cloth incrustation constitutes.Ash mouth 10 is let out in the setting of decoking jar lower cover bottom, and decoking jar outer cylinder body 5 bottoms are provided with blows ash mouth 6.Whole decoking jar is fixed on the workplace through skirt 9.
Further specify the effect of the inventive method and device below through embodiment.The decoking jar structure that embodiment uses is: aspect ratio 5 (height and diameter ratio); Separation assembly cylindrical shell thickness is 50mm; Interior filling particle diameter is the alumina globule of 1.5mm; The separation assembly cylinder internal diameter is identical with hydrogenator source line diameter, and the annular space distance is 1 meter between separation assembly and the decoking jar body skin.Separation assembly rain cap and separation assembly are not established the gap.
Embodiment 1 and comparative example 1
The coking naphtha hydrogen refining process.Coking naphtha mixes with hydrogen through process furnace and is heated to 230 ℃, gets into hydrogenator after getting into decoking jar decoking.Hydrogenation catalyst FH-40A is the commercial Hydrobon catalyst of Sinopec Fushun Petrochemical Research Institute development and production.Feedstock property is seen table 1, and operational condition and result see table 2.The difference of comparative example is not for being provided with the decoking jar.
Table 1 raw oil character.
| Raw material | Coking naphtha |
| The boiling range scope, ℃ | 36～192 |
| Sulphur, μ g/g | 4960 |
| Nitrogen, μ g/g | 126 |
| The bromine valency, gBr/ (100mL) | 48 |
Table 2 operational condition and product property.
| ? | Embodiment 1 | Comparative example 1 |
| The 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, ℃ | 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 that from above-mentioned contrast the inventive method can solve the pressure drop rising problem of coking naphtha hydrogenation unit, can effectively prolong the running period of hydrogenation unit.
Embodiment 2 and comparative example 2
Catalytic cracking heavy naphtha selective hydrogenation desulfurization process.The catalytic cracking petroleum naphtha adopts commodity AFS-12 catalyzer (University of Petroleum's production), at pressure 0.5MPa, 35 ℃～45 ℃ of temperature, volume space velocity 2.0h
-1, carry out deodorization under gas and oil volume ratio (air/gasoline) the 4:1 condition.The deodorization product is through fractionation, and cut point is 70 ℃ and obtains catalytic cracking heavy naphtha, and catalytic cracking heavy naphtha mixes with hydrogen through process furnace and is heated to 250 ℃, gets into hydrogenator after getting into decoking jar decoking.Hydrogenation catalyst FGH-11 is the commercial catalyst for selectively hydrodesulfurizing of Sinopec Fushun Petrochemical Research Institute development and production.Feedstock property is seen table 3, and operational condition and result see table 4.The difference of comparative example is not for being provided with the decoking jar.
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 |
| RON, RON | 91.0 |
| Boiling range, ℃ (over point～final boiling point) | 58～179 |
Table 4 operational condition and result.
| ? | Embodiment 2 | Comparative example 2 |
| The 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, ℃ | 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 to CR in advance and supplies raw materials.Virgin naphtha mixes with hydrogen through process furnace and is heated to 300 ℃, gets into hydrogenator after getting into decoking jar decoking.Hydrogenation catalyst FH-40C is the commercial Hydrobon catalyst of Sinopec Fushun Petrochemical Research Institute development and production.Feedstock property is seen table 5, and operational condition and result see table 6.The difference of comparative example is not for being provided with the decoking jar.
Table 5 virgin naphtha main character.
| Raw material | Virgin naphtha |
| The source | Mix virgin naphtha |
| Density (20 ℃), 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, ℃ | 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 that through embodiment through using the decoking jar of suitable structure, the pressure drop of petroleum naphtha hydrogenation reactor drum is not risen basically, can estimate, can not stop work because of problem of pressure drop in work-ing life at catalyzer.
Claims (10)
1. 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 the decoking jar, feed system is communicated with the process furnace inlet through pipeline, and furnace outlet is communicated with decoking jar inlet through pipeline; The outlet of decoking jar is communicated with the fixed bed hydrogenation reactor inlet through pipeline, and the fixed bed hydrogenation reactor outlet is communicated with the hydrogenation reaction product separation system through pipeline; The decoking jar is set, between furnace outlet and the fixed bed hydrogenation reactor inlet direct connecting pipeline is set, on this direct connecting pipeline shutoff valve is set, on decoking jar source line and the decoking jar outlet line shutoff valve is set.
2. according to the described device of claim 1, it is characterized in that: in the fixed bed hydrogenation reactor upper cover sump is set.
3. according to the described device of claim 1; The decoking jar it is characterized in that: when need be cleared up; On decoking jar source line and the decoking jar outlet line shutoff valve being set closes; The decoking jar is cut out reactive system clear up, reaction mass gets into hydrogenator through between furnace outlet and the fixed bed hydrogenation reactor inlet direct connecting pipeline being set.
4. according to the described device of claim 1, it is characterized in that: the decoking jar is a vertical structure, and the decoking jar is made up of the separation assembly of body skin and set inside, and body skin is provided with material inlet and material outlet.
5. according to the described device of claim 4, it is characterized in that: material inlet is arranged on the decoking tank top.
6. according to the described device of claim 4; It is characterized in that: separation assembly is a tube structure; The internal layer of separation assembly cylindrical shell is a screen cloth with skin, fills the incrustation agent between inner screen and the outer screen, and the barrel passage of separation assembly is communicated with the body skin material outlet.
7. according to the described device of claim 4; It is characterized in that: separation assembly is provided with one at least; The incrustation agent of filling is the filler of particle diameter 1.1～3mm in the middle of the separation assembly screen cloth; The material of filler is aluminum oxide, silicon oxide, pottery, and filler perhaps makes spent hydroprocessing catalyst or useless hydrogenation catalyst etc., and the thickness of filler is 10～200mm.
8. according to claim 1 or 4 described devices, it is characterized in that: decoking jar bottom is provided with lets out the ash mouth, and decoking jar body skin bottom is provided with blows grey mouthful, and the position of blowing the ash mouth is higher than lets out the ash mouth.
9. a petroleum naphtha hydrogenation reaction method is characterized in that: use claim 1 in the described petroleum naphtha hydrogenation reaction unit of 9 arbitrary claims, comprise the steps:
(1) mixture of feed naphtha and hydrogen is delivered to through feed system and is heated to the required temperature of hydrogenation reaction in the process furnace;
(2) mixture of feed naphtha after the heating and hydrogen gets into the decoking jar;
(3) feed naphtha and the hydrogen through decoking jar decoking gets into fixed bed hydrogenation reactor; Feed naphtha and hydrogen pass through the Hydrobon catalyst bed of fixed bed hydrogenation reactor under the unifining condition; Petroleum naphtha after the unifining and hydrogen are discharged reactor drum and are got into separation system and separate and obtain hydrotreated naphtha, separate the hydrogen recycle that obtains and use.
10. according to the described method of claim 9, 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; Petroleum naphtha hydrogenation purified reaction conditions is: reactor inlet temperature is 180～350 ℃, and reaction pressure is 0.5～12MPa, and volume space velocity is 0.5～20h during the liquid of feed naphtha
-1, hydrogen to oil volume ratio is 50:1～1500:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373226A (en) * | 2019-03-27 | 2019-10-25 | 宁波中金石化有限公司 | It is a kind of to refine the device and method that C6-C10 hydrocarbon component coking is prevented in naphtha preparation process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2011
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373226A (en) * | 2019-03-27 | 2019-10-25 | 宁波中金石化有限公司 | It is a kind of to refine the device and method that C6-C10 hydrocarbon component coking is prevented in naphtha preparation process |
| CN110373226B (en) * | 2019-03-27 | 2021-06-11 | 宁波中金石化有限公司 | Device and method for preventing C6-C10 hydrocarbon components from coking in refined naphtha preparation process |
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