CN103074102A - Continuous liquid phase hydrotreatment method for hydrocarbon oil - Google Patents
Continuous liquid phase hydrotreatment method for hydrocarbon oil Download PDFInfo
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Abstract
The invention provides a continuous liquid phase hydrotreatment method for hydrocarbon oil. According to the invention, a plurality of catalyst bed layers are arranged in a reactor, and mixers are arranged among the bed layers and can mix material flows in the reactor with hydrogen; multiple mixers in the reactor are not used at the same time, and instead, hydrogen is introduced into different mixers for mixing according to the properties of raw oil to be processed and product requirements. Compared with a conventional two-phase hydrogenation process, the process provided by the invention has stronger adaptability to raw oil, can guarantee a hydrogenation reaction in the whole reactor to have a high reaction rate and high catalyst stability and allows mixing frequency of hydrocarbon oil and hydrogen to be minimized, thereby reducing processing cost.
Description
Technical field
The invention belongs to the treatment process of hydrocarbon ils in the situation that hydrogen exists, more particularly, is a kind of method for hydrotreating hydrocarbon oil of no hydrogen circulation.
Background technology
Along with the increasingly stringent of world wide environmental requirement, people are also more and more harsher to the requirement of petroleum product-quality.European Union member countries came into effect Euro V emissions from 2009, and the developed countries such as the U.S., Japan have also promulgated vapour separately, diesel product index.China has also come into effect the state III standard that is equivalent to Europe III emission standard from 2010, in Beijing, Shanghai come into effect local vapour, the diesel product index that is equivalent to Europe IV emission standard.
The vapour of Europe IV, Euro V emissions is satisfied at present production, the hydrotreatment technology that diesel oil adopts mostly is the trickle bed hydrogenator, and namely the gas phase in the reactor is external phase, and liquid phase is existed by the form of gas-phase space encirclement with drop or liquid film.Studies show that in trickle-bed reactor, hydrogen is the control step of whole hydrogenation reaction from gas phase diffusion and the speed that is dissolved into the oil.One of reason that higher hydrogen-oil ratio is adopted in traditional trickle bed reaction is exactly to strengthen gas-liquid mass transfer, accelerates the dissolving of hydrogen, thereby improves the speed of reaction of hydrogenating desulfurization, denitrification reaction.In addition, hydrogenation reaction is a strong exothermal reaction, in order to keep reaction bed temperature, need to utilize a large amount of excessive hydrogens to take away the heat that reaction produces by beds.Therefore, the original volume of hydrogen and stock oil larger (the standard state hydrogen to oil volume ratio is generally 4～8 times of chemical hydrogen consumption amount) in traditional trickle bed hydrogenation technique reactant.These excessive hydrogen that do not participate in chemical reaction need to constantly recycle, and this just causes the investment cost of hydro-refining unit and running cost to increase substantially.
In order to solve the problem of a large amount of circulations of hydrogen, each patent merchant begins to consider to utilize hydrocarbon ils to be the hydrogenation process hydrogen supply as molten hydrogen medium.US4857168 discloses the method for hydrogen cracking of heavy distillate.The method adopts thinner and hydrogen to come to cracking process supply hydrogen.The interpolation of thinner is the formation of limit coke on catalyzer, and can be basically or eliminate the formation of coke fully.But thinner needs constantly regeneration, and regeneration need to be carried out within another contains the reactor of catalyzer.
US6123835 discloses the two-phase hydrogenation treatment process.This technique is fully mixed stock oil, thinner and hydrogen so that stock oil and thinner all with mix, and hydrogen fully is dissolved in the mixing solutions of stock oil and thinner.Then carry out gas-liquid separation, make liquid phase part enter reactor, hydrogenation reaction occurs.The hydrocarbon ils of reactor outlet is divided into two portions, and part is mixed with stock oil as thinner, and part enters follow-up unit, and both ratio is called recycle ratio, and the recycle ratio of this technique is 1: 1～2.5: 1.The method need not hydrogen recycle, has avoided the use of circulating hydrogen compressor.But because the dissolve hydrogen capacity of stock oil and thinner is limited, have difficulties for processing the larger stock oil of chemical hydrogen consumption.
US6428686, US6881326, US7291257 and US7569136 replenish the content of US6123835, and these patents point out and can extract out from reactor middle part with hydrocarbon ils, and the hydrocarbon ils Returning reactor are continued reaction after hydrogen fully mixes; Perhaps increase Liqiud-gas mixing device at inside reactor, hydrocarbon ils allows hydrocarbon ils enter the beds continuation again and reacts with after hydrogen fully mixes in this device.This design is so that stock oil and thinner can repeatedly fully mix with hydrogen, and hydrocarbon ils can dissolve more hydrogen, and this technique can be processed the larger stock oil of chemical hydrogen consumption, has widened the range of application of this technique.But do not have the clear and definite position that hydrocarbon ils mixes with hydrogen of pointing out in these patents, hybrid position is selected incorrect may cause mixing number of times too much, quality product descends or catalyst deactivation.
US2009/0321310A1 discloses does not have the three-phase of gas circulating compressor hydroprocessing process.The method adopts the operation of two reactors in series, and stock oil separates the hydrogen-rich gas that obtains with the high pressure separating tank of an anti-part hydrocarbon ils that exports and two anti-afterbodys and mixes, and mixed hydrocarbon ils enters an anti-hydrogenation reaction of carrying out.One anti-outlet hydrocarbon ils partly circulates and mixes with stock oil, and it is two anti-that another part hydrocarbon ils and new hydrogen together enter, and two is the trickle-bed reactor that gas-liquid-solid three-phase coexists instead, and the hydrocarbon ils deep hydrogenation obtains product in this reactor.The method is compared with traditional trickle bed technique and be need not circulating hydrogen compressor, has saved investment; Compare with pure two-phase hydrogenation, adopt trickle bed as the two anti-deep hydrogenations that carry out, solved hydrogen sulfide and be dissolved in the hydrocarbon ils, be unfavorable for the problem that desulphurization reaction carries out.But there is the limited problem of hydrocarbon ils dissolve hydrogen capacity in this technique, has difficulties for processing the larger stock oil of chemical hydrogen consumption.
Summary of the invention
Prior art is to enter reactor after hydrogen, hydrocarbon ils and reactor effluent are mixed outside reactor, the carrying out that the hydrogen that dissolves in dependence hydrocarbon ils and the reactor effluent is kept hydrogenation reaction.Reactor effluent partly circulates, and this part effluent not only can dissolve hydrogen supplies with hydrogenation reaction, can also take away the heat that hydrogenation process produces, and avoids the beds temperature rise excessive.Consider that from this angle the internal circulating load of reactor effluent is larger, more be conducive to the carrying out of hydrogenation reaction.Yet in actual production process, restricted by the factor such as energy consumption, the reactor effluent internal circulating load is unsuitable excessive, is generally 1～5 times of stock oil inlet amount, more optimizedly 1.5～2.5 times.For the larger hydrocarbon oil hydrogenation process of chemical hydrogen consumption, the hydrogen deficient that dissolves in the hydrocarbon ils is required to supply with hydrogenation reaction, causes the hydrogenation degree of depth not even causes catalyst deactivation.
Prior art is for solving this contradiction, in the reactor stage casing hydrocarbon ils extracted out to mix with hydrogen or add the mixing that mixing tank carries out hydrocarbon ils and hydrogen at inside reactor, so that hydrocarbon ils can repeatedly mix with hydrogen, increased the total amount that hydrocarbon ils carries hydrogen.But, the hybrid position of hydrocarbon ils and hydrogen is not investigated in these prior aries.Hybrid position is selected incorrect will cause mixing number of times too much, quality product descends or catalyst deactivation.
The purpose of this invention is to provide a kind of and conventional trickle bed method of hydrotreating and compare, can cancel the hydrotreatment that the hydrogen recycle compressor is realized hydrocarbon ils, the method can under the condition than the circulation of low reactor effluent, realize the hydrotreatment of different material oil.
Method provided by the invention comprises:
N beds is set in the reactor, be provided with mixing tank between the adjacent catalyst bed layer, in mixing tank, logistics mixes with external hydrogen in the reactor, the n-1 of a reactor mixing tank does not use simultaneously, but according to the concentration of hydrogen in the logistics in the reactor, be chosen in the different mixing tanks and mix with the hydrogen that passes into, wherein 2≤n≤10.
The concentration of hydrogen is greater than 5 * 10 in logistics in the reactor
-4GH
2During/g, it does not need to mix in mixing tank with the external hydrogen that passes into.Only have in the reactor in the logistics concentration of hydrogen to be lower than and to a certain degree just need to pass through mixing tank.In the situation of the catalyst stability that keeps high hydrogenation reaction speed to become reconciled, so that logistics reaches minimum with the number of times that mixes of hydrogen in the reactor, thereby pressure drop is low, and energy consumption is low, has reduced tooling cost.
In the preferred embodiment of the present invention, comprise the steps:
(1) before entering reactor, in the environment of constant pressure, stock oil, reactor effluent and hydrogen are mixed, mixed material is introduced the reactor that hydrogenation catalyst is housed;
(2) in the described reactor of step (1) n beds arranged, along the reactor stream direction, be followed successively by the 1st, the 2nd ... n beds, between the adjacent catalyst bed layer, be provided with n-1 mixing tank, along the reactant flow direction, be followed successively by the 1st, the 2nd ... n-1 mixing tank, the 1st to n-1 beds bottom thief hatch is set, can extract the interior logistics of partial reaction device in beds exit, carry out determining hydrogen gas concentration
(3) concentration of hydrogen is in 2 * 10 in logistics in the reactor in determination step (2) the m layer beds exit of extracting out
-4GH
2/ g～5 * 10
-4GH
2/ g then mixes logistics in this reactor in m mixing tank with hydrogen, 1≤m＜n wherein,
(4) in logistics in the reactor in determination step (2) the m layer beds exit of extracting out the concentration of hydrogen less than 2 * 10
-4GH
2/ g then mixes logistics in this reactor in m-1 mixing tank with hydrogen,
(5) in logistics in the reactor in determination step (2) the m layer beds exit of extracting out the concentration of hydrogen greater than 5 * 10
-4GH
2During/g, logistics does not need to mix with hydrogen in this reactor, then directly flows to m+1 beds.
Adopt method provided by the invention, do not need recycle compressor, according to the concentration of hydrogen in the hydrocarbon ils, control hydrocarbon ils and hydrogen hybrid position can under the condition than the circulation of low reactor effluent, be processed straight-run diesel oil or secondary processing diesel oil inferior.The present invention compares with traditional trickle bed technique, does not need recycle compressor, and facility investment and process cost are all lower.Compare with existing two-phase hydrogenation technique, adaptability to stock oil is stronger, can the hydrogenation reaction in guaranteeing whole reactor have higher speed of reaction and catalyst stability, hydrocarbon ils reaches minimum with the number of times that mixes of hydrogen simultaneously, thereby has reduced tooling cost.
Description of drawings
Accompanying drawing is liquid-phase hydrogenatin treatment process synoptic diagram provided by the invention.
Embodiment
The present invention fully mixes stock oil, reactor effluent and hydrogen, and the mixture that has dissolved hydrogen enters reactor.Whole reactor is provided with a plurality of beds, and mixing tank is arranged between the bed, mixture can be mixed with hydrogen, and each bed bottom is provided with thief hatch, can measure the concentration of hydrogen in the interior logistics of this bed exit reactor.A plurality of mixing tanks in the reactor might not use in actual production process simultaneously, but according to the requirement of processing raw material oil properties and product, logistics is chosen in the different mixing tanks and mixes with the external hydrogen that passes in the reactor, and the specific embodiment of the present invention is as follows:
In step (1), before entering reactor, in the environment of constant pressure, stock oil, reactor effluent and hydrogen are mixed, mixed material is introduced the reactor that hydrogenation catalyst is housed.
In step (2), according to the stock oil composition and property with to the different mass requirement of product, hydrogenation catalyst can be divided into n bed, along the reactor stream direction, be followed successively by the 1st, the 2nd ... n beds, between the adjacent catalyst bed layer, be provided with n-1 mixing tank, along the reactant flow direction, be followed successively by the 1st, the 2nd ... n-1 mixing tank, the 1st to n-1 beds bottom thief hatch is set, can extract the interior logistics of partial reaction device in beds exit, carry out determining hydrogen gas concentration.What measure is the concentration of hydrogen in the liquid phase part of resultant behind the described compounding substances of step (1) and the said mixture matter generation chemical reaction.
(3) concentration of hydrogen is in 2 * 10 in logistics in the reactor in determination step (2) the m layer beds exit of extracting out
-4GH
2/ g～5 * 10
-4GH
2/ g then mixes logistics in this reactor in m mixing tank with hydrogen, namely in the mixing tank of the most contiguous thief hatch, mixes, and 1≤m＜n wherein,
(4) in logistics in the reactor in determination step (2) the m layer beds exit of extracting out the concentration of hydrogen less than 2 * 10
-4GH
2/ g then mixes logistics in this reactor in m-1 mixing tank with hydrogen, namely mix at the most adjacent mixing tank place of the mixing tank upstream of contiguous thief hatch.
(5) in logistics in the reactor in determination step (2) the m layer beds exit of extracting out the concentration of hydrogen greater than 5 * 10
-4GH
2During/g, logistics does not need to mix with hydrogen in this reactor, then directly flows to m+1 beds.Do not pass through bypass by mixing tank and enter next bed.
Selecting of above-mentioned mixing tank is that concentration according to hydrogen in the logistics in the reactor is determined.Because the hydrogen saturation solubility of hydrocarbon ils is lower, when the concentration of dissolving hydrogen in the hydrocarbon ils was larger, hydrocarbon ils was subject to the restriction of saturation solubility when again mixing with hydrogen, and the concentration amplification of dissolving hydrogen is very little in the hydrocarbon ils, does not have the actually operating meaning.Yet when the concentration of hydrogen that hydrocarbon ils dissolves was low, hydrogenation reaction speed was slow, when the concentration of hydrogen that hydrocarbon ils dissolves less than 2 * 10
-4GH
2During/g, the catalyzer rapid deactivation.By research as can be known, the concentration of hydrogen is 2 * 10 in the liquid phase of said mixture and resultant of reaction
-4GH
2/ g～5 * 10
-4GH
2It is mixed again with hydrogen in the scope of/g, can realize mixing that number of times is few, quality product is high and catalyst stability is good.
The present invention in time monitors the concentration of the hydrogen in the logistics in the reactor, when the concentration of hydrogen 2 * 10
-4GH
2/ g～5 * 10
-4GH
2With the mixing of logistics in the reactor and hydrogen, guarantee that the hydrogenation reaction in the whole reactor has higher speed of reaction and catalyst stability in the scope of/g, the while hydrocarbon ils reaches minimum with the number of times that mixes of hydrogen.The present invention can under the condition than the circulation of low reactor effluent, realize the hydrotreatment of different material oil.
Stock oil carries out the reactions such as hydrogenating desulfurization, hydrodenitrification, olefin saturated, aromatic saturation and cracking under the effect of hydrogenation catalyst.Reaction conditions is: 250～450 ℃ of temperature of reaction, preferred 280～430 ℃, system pressure 1.0～18.0MPa, preferred 3.0～15.0MPa, volume space velocity 0.1～9.0h during liquid
-1, preferred 0.3～6.0h
-1, the reactor effluent of circulation: stock oil charging=1: 1～10: 1, preferred 1: 1～3: 1.
Described stock oil is selected from one or more in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil, the vacuum gas oil.
Hydrogenation catalyst can be load hydrogenation catalyst for the conventional catalyzer with hydrofining or hydro-upgrading function, also can be non-supported hydrogenation catalyst.
The reactor bottom effluent enters high-pressure separator and carries out gas-liquid separation, obtain the first gas phase and the first liquid phase, the first gas phase of gained obtains the second gas phase and second liquid phase through after the heat exchange, the second gas phase emission wherein, second liquid phase can be used as reactor effluent to be mixed with raw material and hydrogen; The first liquid phase part mixes with raw material and hydrogen as the reactor ejecta, and remainder goes out device through after the heat exchange as product.
In one of them preferred embodiment of the present invention, the miscellany of stock oil, reactor effluent and hydrogen can enter from reactor bottom.
Below by accompanying drawing, method of the present invention is illustrated further, but not thereby limiting the invention.
As shown in drawings, stock oil is through pipeline 1, the new hydrogen of part mixes with stock oil through pipeline 2, through process furnace 4 heating, then with from the reactor effluent of pipeline 5 and from the high score air cooling lime set (second liquid phase) of pipeline 6 mix in mixing tank 7, mixed material enters hydrogenator 9 by pipeline 8.React under the hydrogenation catalyst effect at hydrogenator Raw oil and hydrogen, two beds are arranged in the reactor 9, in the first beds bottom thief hatch 10 is arranged.By density of hydrogen in the logistics in the thief hatch 10 sampling analysis reactors, to judge that logistics is to mix in the reactor in mixing tank 11 with from pipeline 3 new hydrogen, still do not mix with hydrogen, directly enter the second beds.The rear logistics of reaction enters high-pressure separator 15 and carries out gas-liquid separation, the air-flow at high-pressure separator top (the first gas phase) enters condenser 17 by pipeline 16, top gaseous stream at the bottom of the condenser (the second gas phase) is discharged as waste gas, and the liquid phase stream of bottom (second liquid phase) enters mixing tank 7 through pipeline 6.High-pressure separator bottom liquid phases logistics (the first liquid phase) part is by pipeline 18 dischargers, and another part enters mixing tank 7 through pipeline 5.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
The trade names of the load hydrogenation catalyst for refining that embodiment and Comparative Examples are used are RS-1000, and the trade names of used hydrocracking catalyst are RHC-5, are Sinopec catalyzer branch office and produce.
Embodiment 1
Take a kind of Middle East high-sulfur straight(-run) diesel distillate as stock oil 1, stock oil 1 mixes under the pressure of 6.5MPa with reactor effluent, hydrogen, mixed material is introduced the reactor that the load hydrogenation catalyst for refining is housed, carry out the deep hydrodesulfurizationof reaction at this, reaction conditions is: 355 ℃ of temperature of reaction, reactor pressure 6.4MPa, volume space velocity 1.5h during raw material fluid
-1Reactor evenly is divided into three beds, in 2 bed exits, records in the reactor that density of hydrogen is 5 * 10 in the logistics
-4GH
2/ g, the second mixing tank that logistics and the external hydrogen that passes into enter between 2 beds and 3 beds in the reactor mixes, and enters 3 beds after the mixing and proceeds reaction, records in the reactor in the logistics concentration of hydrogen in 1 bed exit greater than 5 * 10
-4GH
2Therefore/g need to not mix with hydrogen in the first mixing tank.Logistics is with external to pass into the number of times that hydrogen mixes be 1 time in the present embodiment reactor.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and after the separating obtained gas phase of process high-pressure separator was partly passed through heat exchange, with the gas phase partial discharge, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; The liquid phase part of high-pressure separator gained is mixed with raw material and hydrogen as the reactor ejecta, and another part goes out device through after the heat exchange as product, and two-part mass ratio is 1: 1.The resultant of reaction of caterpillar enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Stock oil 1 main character of present embodiment is as shown in table 1, and reaction conditions and product main character are as shown in table 2.
Comparative Examples 1
Stock oil 1 mixes under the pressure of 6.5MPa with reactor effluent, hydrogen, and mixed material is introduced reactor that Hydrobon catalyst is housed, carried out the deep hydrodesulfurizationof reaction, and reaction conditions is with embodiment 1.Reactor evenly is divided into three beds, mixes in logistics and first mixing tank of the external hydrogen that passes between 1 bed and 2 beds in the reactor, and mixed material enters interior next bed of reactor and reacts.The concentration concentration that records hydrogen in the interior logistics of 1 bed exit reactor is 8 * 10
-4GH
2/ g.Logistics is with external to pass into the number of times that hydrogen mixes be 1 time in this Comparative Examples reactor.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and after the separating obtained gas phase of process high-pressure separator was partly passed through heat exchange, with the gas phase partial discharge, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; The liquid phase part of high-pressure separator gained is mixed with raw material and hydrogen as the reactor ejecta, and another part goes out device through after the heat exchange as product, and two-part mass ratio is 1: 1.The resultant of reaction of caterpillar enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Reaction conditions and product main character are as shown in table 2.
Table 1 stock oil character
| Stock oil | Stock oil 1 | |
|
| Type of feed | Straight-run diesel oil | Catalytic diesel oil | Husky light VGO |
| Density (20 ℃), g/cm 3 | 0.8321 | 0.8921 | 0.9098 |
| Sulphur content, μ g/g | 9700 | 7700 | 18000 |
| Nitrogen content, μ g/g | 97 | 536 | 986 |
| Boiling range ASTM D-86, ℃ | |||
| IBP | 188 | 177 | 255 |
| 10％ | 224 | 210 | 386 |
| 50％ | 277 | 267 | 443 |
| 90％ | 338 | 343 | 496 |
| FBP | 365 | 374 | 550 |
Table 2
As can be seen from Table 1, stock oil 1 is a kind of high-sulfur straight(-run) diesel distillate, and sulphur content is 9700 μ g/g, and nitrogen content is 97 μ g/g.As can be seen from Table 2, adopt the method for embodiment 1, the sulphur content of product is 9 μ g/g, and sulphur content satisfies Europe V diesel oil emission standard, can be used as the clean diesel blend component of high-quality.Adopt the hydrogen addition technology of Comparative Examples 1 under identical processing condition, the sulphur content of the product that obtains is 38 μ g/g.As 100, relatively desulphurizing activated, the relative denitrification activity that calculates embodiment 1 is respectively 259 and 274 with the desulfurization of Comparative Examples 1, denitrification activity.The method that provides of the present invention (embodiment 1) is controlled logistics in the reactor and the decomposite position of hydrogen, and existing hydrogen addition technology (Comparative Examples 1) is not controlled logistics in the reactor and the decomposite position of hydrogen.Contrasting both can find, under the condition of identical mixed hydrogen number of times, adopts the method that provides of the present invention can obtain sulphur content, the product that meets the clean diesel standard that nitrogen content is lower.
A kind of secondary processing catalytic cracking diesel oil cut is stock oil 2, stock oil 2 mixes under the pressure of 8.2MPa with reactor effluent, hydrogen, mixed material introduced carry out the deep hydrodesulfurizationof reaction in the reactor that the load hydrogenation catalyst for refining is housed, reaction conditions is: 370 ℃ of temperature of reaction, reactor pressure 8.0MPa, volume space velocity 1.5h during raw material fluid
-1Reactor evenly is divided into five beds, records in 1 bed exit in the reactor that density of hydrogen is 3 * 10 in the logistics
-4GH
2Logistics and hydrogen mix in the first mixing tank in/the g, reactor, enter 2 beds after the mixing and react; Record in 3 bed exits in the reactor that density of hydrogen is 3 * 10 in the logistics
-4GH
2Logistics and hydrogen mix in the 3rd mixing tank in/the g, reactor, enter reactor 4 beds after the mixing and react, and whole process need be mixed 2 times.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and after the separating obtained gas phase of process high-pressure separator was partly passed through heat exchange, with the gas phase partial discharge, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; The liquid phase part of high-pressure separator gained is mixed with raw material and hydrogen as the reactor ejecta, and another part goes out device through after the heat exchange as product, and two-part mass ratio is 1.5: 1.The resultant of reaction of caterpillar enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Stock oil 2 main character of present embodiment are as shown in table 1, and reaction conditions and product main character are as shown in table 3.
Comparative Examples 2a
Reactor effluent carries out gas-liquid separation in high-pressure separator, and after the separating obtained gas phase of process high-pressure separator was partly passed through heat exchange, with the gas phase partial discharge, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; The liquid phase part of high-pressure separator gained is mixed with raw material and hydrogen as the reactor ejecta, and another part goes out device through after the heat exchange as product, and two-part mass ratio is 1.5: 1.The resultant of reaction of caterpillar enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.The stock oil main character of this Comparative Examples is as shown in table 1, and reaction conditions and product main character are as shown in table 3.
Comparative Examples 2b
Reactor effluent carries out gas-liquid separation in high-pressure separator, and after the separating obtained gas phase of process high-pressure separator was partly passed through heat exchange, with the gas phase partial discharge, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; The liquid phase part of high-pressure separator gained is mixed with raw material and hydrogen as the reactor ejecta, and another part goes out device through after the heat exchange as product, and two-part mass ratio is 1.5: 1.The resultant of reaction of caterpillar enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.The stock oil main character of this Comparative Examples is as shown in table 1, and reaction conditions and product main character are as shown in table 3.
Table 3
As can be seen from Table 1, stock oil 2 is a kind of catalytic cracking diesel oil cut, and sulphur content is 7700 μ g/g, and nitrogen content is 536 μ g/g.As can be seen from Table 3, adopt the method for embodiment 2, the sulphur content of product is 45 μ g/g, and sulphur content satisfies Europe IV diesel oil emission standard, can be used as the clean diesel blend component of high-quality.Adopt the method for Comparative Examples 2a under identical processing condition, the sulphur content of the product that obtains is 103 μ g/g.Adopt the method for Comparative Examples 2b under identical processing condition, increase once mixed hydrogen, the sulphur content of the product that obtains is 42 μ g/g.As 100, relatively desulphurizing activated, the relative denitrification activity that calculates embodiment 2 is respectively 175 and 119 with the desulfurization of Comparative Examples 2a, denitrification activity, and relatively desulphurizing activated, the relative denitrification activity of Comparative Examples 2b is respectively 183 and 121.Method provided by the present invention is controlled logistics in the reactor and the decomposite position of hydrogen, and existing method is not controlled logistics in the reactor and the decomposite position of hydrogen and number of times.The contrast three can find, under the condition of identical mixed hydrogen number of times, adopts hydrogen addition technology of the present invention can obtain sulphur content, the product that meets the clean diesel standard that nitrogen content is lower; Perhaps when reaching the product of identical clean diesel standard, adopt the mixed hydrogen number of times of the present invention still less.
Take a kind of Saudi Arabia lightweight VGO as stock oil 3, stock oil 3 mixes under the pressure of 15MPa with reactor effluent, hydrogen, mixed material is introduced the reactor that hydrogenation catalyst is housed.The first reactor charge load hydrogenation catalyst for refining, the second reactor charge load hydrogenation cracking catalyst.Reaction conditions is: 380 ℃ of the first temperature of reactor, 395 ℃ of the second temperature of reactor, reactor pressure 14.5MPa, volume space velocity 1.2h during raw material fluid
-1Each reactor was according to 1.5: 2: 1.5: 2: 3 filling ratio is divided into five beds, records in 2 bed exits of the first reactor in the reactor that density of hydrogen is 4.0 * 10 in the logistics
-4GH
2/ g, logistics mixes at the second mixing tank with hydrogen in the reactor, enters the first reactor 3 beds after the mixing and reacts, and records in the reactor in the logistics concentration of hydrogen in the first reactor 1 bed, 3 beds, 4 bed exits greater than 5 * 10
-4GH
2Therefore/g need to not mix with hydrogen in mixing tank.Record in 2 bed exits of the second reactor in the reactor that density of hydrogen is 3.0 * 10 in the logistics
-4GH
2Logistics and hydrogen mix at the second mixing tank in/the g, reactor, enter interior 3 beds of the second reactor after the mixing and react.Record in the reactor in the logistics concentration of hydrogen in the second reactor 1 bed, 3 beds, 4 bed exits greater than 5 * 10
-4GH
2Therefore/g need to not mix with hydrogen in mixing tank.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and after the separating obtained gas phase of process high-pressure separator was partly passed through heat exchange, with the gas phase partial discharge, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; The liquid phase part of high-pressure separator gained is mixed with raw material and hydrogen as the reactor ejecta, and another part goes out device through after the heat exchange as product, and two-part mass ratio is 3: 1.The resultant of reaction of caterpillar enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Stock oil 3 main character of present embodiment are as shown in table 1, and reaction conditions and product main character are as shown in table 4.
Comparative Examples 3
Reactor effluent carries out gas-liquid separation in high-pressure separator, and after the separating obtained gas phase of process high-pressure separator was partly passed through heat exchange, with the gas phase partial discharge, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; The liquid phase part of high-pressure separator gained is mixed with raw material and hydrogen as the reactor ejecta, and another part goes out device through after the heat exchange as product, and two-part mass ratio is 3: 1.The resultant of reaction of caterpillar enters fractionating system, is cut into naphtha fraction, fine-quality diesel oil cut.Stock oil 3 main character of this Comparative Examples are as shown in table 1, and reaction conditions and product main character are as shown in table 4.
Table 4
As can be seen from Table 1, stock oil 3 is Saudi Arabia lightweight VGO, and density is 0.9098g/cm
3, sulphur content is 18000 μ g/g, nitrogen content is 986 μ g/g.As can be seen from Table 4, adopt the method for embodiment 3 and Comparative Examples 3, initial reaction stage both＞350 ℃ of transformation efficiencys are identical.Yet the method for employing embodiment 3 is kept this transformation efficiency operation 1000 hours, needs 1.5 ℃ of equalising temps; Adopt the method for Comparative Examples 3, keep this transformation efficiency operation 1000 hours, need 6 ℃ of equalising temps.This is to be reduced to 1 * 10 because of liquid phase density of hydrogen in the compounding substances in the Comparative Examples 3
-4GH
2/ g just mends hydrogen, and excessively low density of hydrogen can't stop hydrocarbon ils at the catalyst surface carbon deposit, causes catalyst activity reduction.As seen, adopt hydrogen addition technology of the present invention to compare with existing hydrogen addition technology, can under the prerequisite of same process condition, like products quality, improve catalyst life.
Claims (10)
1. Continuous Liquid Phase method for hydrotreating hydrocarbon oil, it is characterized in that, n beds is set in the reactor, be provided with mixing tank between the adjacent catalyst bed layer, in mixing tank, logistics mixes with external hydrogen in the reactor, the n-1 of a reactor mixing tank does not use simultaneously, but according to the concentration of hydrogen in the logistics in the reactor, be chosen in the different mixing tanks and mix with the hydrogen that passes into, wherein 2≤n≤10.
2. in accordance with the method for claim 1, it is characterized in that the concentration of hydrogen is greater than 5 * 10 in logistics in the reactor
-4GH
2During/g, it does not need to mix in mixing tank with the external hydrogen that passes into.
3. in accordance with the method for claim 1, it is characterized in that, comprise the steps:
(1) before entering reactor, in the environment of constant pressure, stock oil, reactor effluent and hydrogen are mixed, mixed material is introduced the reactor that hydrogenation catalyst is housed;
(2) in the described reactor of step (1) n beds arranged, along the reactor stream direction, be followed successively by the 1st, the 2nd ... n beds, between the adjacent catalyst bed layer, be provided with n-1 mixing tank, along the reactant flow direction, be followed successively by the 1st, the 2nd ... n-1 mixing tank, the 1st to n-1 beds bottom thief hatch is set, can extract the interior logistics of partial reaction device in beds exit, carry out determining hydrogen gas concentration
(3) concentration of hydrogen is in 2 * 10 in logistics in the reactor in determination step (2) the m layer beds exit of extracting out
-4GH
2/ g～5 * 10
-4GH
2/ g then mixes logistics in this reactor in m mixing tank with hydrogen, 1≤m＜n wherein,
(4) in logistics in the reactor in determination step (2) the m layer beds exit of extracting out the concentration of hydrogen less than 2 * 10
-4GH
2/ g then mixes logistics in this reactor in m-1 mixing tank with hydrogen,
(5) in logistics in the reactor in determination step (2) the m layer beds exit of extracting out the concentration of hydrogen greater than 5 * 10
-4GH
2During/g, logistics does not need to mix with hydrogen in this reactor, then directly flows to m+1 beds.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that, the reactor bottom effluent enters high-pressure separator and carries out gas-liquid separation, obtain the first gas phase and the first liquid phase, the first gas phase of gained is through after the heat exchange, obtain the second gas phase and second liquid phase, the second gas phase emission wherein, second liquid phase can be used as reactor effluent to be mixed with raw material and hydrogen; The first liquid phase part mixes with raw material and hydrogen as the reactor ejecta, and remainder goes out device through after the heat exchange as product.
5. according to claim 1 or 2 or 3 described methods, it is characterized in that reaction conditions is: 250～450 ℃ of temperature of reaction, system pressure 1.0～18.0MPa, volume space velocity 0.1～9.0h during liquid
-1
6. according to claim 1 or 2 or 3 described methods, it is characterized in that reaction conditions is: 280～430 ℃ of temperature of reaction, system pressure 3.0～15.0MPa, volume space velocity 0.3～6.0h during liquid
-1
7. in accordance with the method for claim 3, it is characterized in that the reactor effluent of circulation: stock oil charging=1: 1～10: 1.
8. in accordance with the method for claim 3, it is characterized in that the reactor effluent of circulation: stock oil charging=1: 1～3: 1.
9. in accordance with the method for claim 3, it is characterized in that described stock oil is selected from one or more in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil, the vacuum gas oil.
10. in accordance with the method for claim 3, it is characterized in that the miscellany of stock oil, reactor effluent and hydrogen enters from reactor bottom.
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