CN103074102B - A kind of Continuous Liquid Phase method for hydrotreating hydrocarbon oil - Google Patents
A kind of Continuous Liquid Phase method for hydrotreating hydrocarbon oil Download PDFInfo
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- CN103074102B CN103074102B CN201110326866.8A CN201110326866A CN103074102B CN 103074102 B CN103074102 B CN 103074102B CN 201110326866 A CN201110326866 A CN 201110326866A CN 103074102 B CN103074102 B CN 103074102B
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Abstract
A kind of Continuous Liquid Phase method for hydrotreating hydrocarbon oil, has multiple beds, is provided with mixing tank between bed, logistics in reactor can be mixed with hydrogen in reactor.Multiple mixing tanks of reactor do not use simultaneously, but according to the character of processed stock oil and the requirement of product, select to pass into hydrogen in different mixing tanks and mix.Compare with existing two-phase hydrogenation technique, the adaptability of the present invention to stock oil is stronger, hydrogenation reaction in the whole reactor of guarantee can have higher speed of reaction and catalyst stability, hydrocarbon ils reaches minimum with the number of times that mixes of hydrogen simultaneously, thus reduces tooling cost.
Description
Technical field
The invention belongs to hydrocarbon oil treatment process in the presence of hydrogen, more particularly, is the method for hydrotreating hydrocarbon oil of a kind 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 country such as the U.S., Japan has also promulgated respective vapour, diesel product index.China has also come into effect the state III standard being equivalent to Europe III emission standard from 2010, in Beijing, Shanghai come into effect the local vapour, the diesel product index that are equivalent to Europe IV emission standard.
The hydrotreating techniques that current production meets Europe IV, the vapour of Euro V emissions, diesel oil adopt is mostly trickle bed hydrogenator, and the gas phase namely in reactor is external phase, liquid phase surround by gas-phase space and exist with the form of drop or liquid film.Research shows, in trickle-bed reactor, hydrogen is from gas phase diffusion and the speed be dissolved into oil is the rate-determining steps of whole hydrogenation reaction.Traditional trickle bed reaction adopts one of reason of higher hydrogen-oil ratio to be exactly strengthen gas-liquid mass transfer, accelerates the dissolving of hydrogen, thus improves the speed of reaction of hydrogenating desulfurization, denitrification reaction.In addition, hydrogenation reaction is a strong exothermal reaction, in order to maintain reaction bed temperature, needs to utilize a large amount of excessive hydrogens to take away the heat of reaction generation by beds.Therefore, the original volume of hydrogen and stock oil larger (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 not participating in chemical reaction need constantly to recycle, and this just causes the investment cost of hydro-refining unit and running cost to increase substantially.
In order to solve the problem that hydrogen circulates in a large number, each patent business starts consideration and utilizes hydrocarbon ils to be 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 by limit coke formation on a catalyst, and can eliminate the formation of coke substantially or completely.But thinner needs constantly to regenerate, regeneration needs to carry out in the reactor that another contains catalyzer.
US6123835 discloses two-phase hydrogenation treatment process.Stock oil, thinner and hydrogen fully mix by this technique, make stock oil and thinner all with mix, and hydrogen is fully 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 mixes with stock oil as thinner, and part enters subsequent cell, and both ratio is called recycle ratio, and the recycle ratio of this technique is 1: 1 ~ 2.5: 1.The method, without the need to hydrogen recycle, avoids the use of circulating hydrogen compressor.But because the dissolve hydrogen capacity of stock oil and thinner is limited, the stock oil larger for process chemical hydrogen consumption has difficulties.
US6428686, US6881326, US7291257 and US7569136 content to US6123835 is supplemented, and these patents are pointed out to be extracted out by hydrocarbon ils in the middle part of reactor, after fully mixing, hydrocarbon ils Returning reactor are continued reaction with hydrogen; Or increase Liqiud-gas mixing device at inside reactor, after hydrocarbon ils fully mixes with hydrogen in this device, then allow hydrocarbon ils enter beds continuation reaction.This design makes stock oil and thinner repeatedly fully to mix with hydrogen, and hydrocarbon ils can dissolve more hydrogen, and this technique can process the larger stock oil of chemical hydrogen consumption, has widened the range of application of this technique.But there is no the clear and definite position that hydrocarbon ils mixes with hydrogen of pointing out in these patents, hybrid position select incorrect may cause mixing number of times too much, quality product declines or catalyst deactivation.
US2009/0321310A1 discloses the three-phase hydroprocessing process not having gas circulating compressor.The method adopts two reactors in series operations, and the high pressure separating tank of stock oil and a part hydrocarbon ils instead exported and two anti-afterbodys is separated the hydrogen-rich gas obtained and mixes, and mixed hydrocarbon ils enters one and instead carries out hydrogenation reaction.One instead exports hydrocarbon ils component loops mixes with stock oil, and another part hydrocarbon ils and new hydrogen together enter two instead, and two is anti-the trickle-bed reactors that gas-liquid-solid three-phase coexists, and in this reactor, hydrocarbon ils deep hydrogenation obtains product.The method without the need to circulating hydrogen compressor, saves investment compared with traditional trickle bed technique; Compared with pure two-phase hydrogenation, adopt trickle bed instead to carry out deep hydrogenation as two, solve hydrogen sulfide and be dissolved in hydrocarbon ils, be unfavorable for the problem that desulphurization reaction carries out.But this technique exists the limited problem of hydrocarbon ils dissolve hydrogen capacity, the stock oil larger for process chemical hydrogen consumption has difficulties.
Summary of the invention
Prior art is that hydrogen, hydrocarbon ils and reactor effluent are entered reactor outward after reactor mixes, and relies on the hydrogen dissolved in hydrocarbon ils and reactor effluent to maintain the carrying out of hydrogenation reaction.Reactor effluent component loops, this part effluent not only can dissolve hydrogen supply hydrogenation reaction, can also take away the heat that hydrogenation process produces, avoid beds temperature rise excessive.Consider from this angle, the internal circulating load of reactor effluent is larger, is more conducive to the carrying out of hydrogenation reaction.But in actual production process, restrict by factors such as energy consumptions, 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 hydrocarbon oil hydrogenation process that chemical hydrogen consumption is larger, the hydrogen deficient dissolved in hydrocarbon ils, to supply needed for hydrogenation reaction, causes hydrogenation depth not even to cause catalyst deactivation.
Prior art is for solving this contradiction, and hydrocarbon ils extraction mixes with hydrogen or adds at inside reactor the mixing that mixing tank carries out hydrocarbon ils and hydrogen by section in the reactor, hydrocarbon ils repeatedly can be mixed with hydrogen, increase 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 select incorrect will cause mixing number of times too much, quality product decline or catalyst deactivation.
The object of this invention is to provide a kind of compared with conventional trickle bed method of hydrotreating, can cancel the hydrotreatment that hydrogen recycle compressor realizes hydrocarbon ils, the method under the condition circulated compared with low reactor effluent, can realize the hydrotreatment of different material oil.
Method provided by the invention comprises:
N beds is set in reactor, mixing tank is provided with between adjacent catalyst bed, in mixing tank, in reactor, logistics mixes with external hydrogen, n-1 mixing tank of reactor does not use simultaneously, but according to the concentration of hydrogen in logistics in reactor, select to mix with the hydrogen passed in different mixing tanks, wherein 2≤n≤10.
When in logistics in reactor, the concentration of hydrogen is greater than 5 × 10
-4gH
2during/g, it does not need to mix in mixing tank with the external hydrogen passed into.The concentration when hydrogen in logistics in reactor is only had to pass through mixing tank lower than to a certain degree just needing.When the catalyst stability keeping high hydrogenation reaction speed to become reconciled, make logistics in reactor reach minimum with the number of times that mixes of hydrogen, thus pressure drop is low, energy consumption is low, reduces tooling cost.
In the preferred embodiment of the present invention, comprise the steps:
(1) in the environment of constant pressure, stock oil, reactor effluent and hydrogen are mixed before entering the reactor, mixed material is introduced the reactor that hydrogenation catalyst is housed;
(2) n beds is had in the reactor described in step (1), along reactor stream direction, be followed successively by the 1st, the 2nd ... the n-th beds, n-1 mixing tank is provided with between adjacent catalyst bed, along reactant flow direction, be followed successively by the 1st, the 2nd ... (n-1)th mixing tank, bottom the 1st to (n-1)th beds, thief hatch is set, logistics in the partial reaction device that can extract beds exit, carry out determining hydrogen gas concentration
(3) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be in 2 × 10
-4gH
2/ g ~ 5 × 10
-4gH
2/ g, then mix logistics in this reactor with hydrogen in m mixing tank, wherein 1≤m < n,
(4) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be less than 2 × 10
-4gH
2/ g, then mix logistics in this reactor with hydrogen in m-1 mixing tank,
(5) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be greater than 5 × 10
-4gH
2during/g, in this reactor, logistics does not need to mix with hydrogen, then directly flow to m+1 beds.
Adopt method provided by the invention, do not need recycle compressor, according to the concentration of hydrogen in hydrocarbon ils, control hydrocarbon ils and hydrogen hybrid position, can under the condition circulated compared with low reactor effluent, process 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, stronger to the adaptability of stock oil, hydrogenation reaction in the whole reactor of guarantee can have higher speed of reaction and catalyst stability, hydrocarbon ils reaches minimum with the number of times that mixes of hydrogen simultaneously, thus reduces tooling cost.
Accompanying drawing explanation
Accompanying drawing is liquid-phase hydrogenatin treatment process schematic diagram provided by the invention.
Embodiment
Stock oil, reactor effluent and hydrogen fully mix by the present invention, and the mixture having dissolved hydrogen enters reactor.Whole reactor is provided with multiple bed, has mixing tank between bed, mixture can be mixed with hydrogen, is provided with thief hatch bottom each bed, can measure the concentration of hydrogen in logistics in this bed exit reactor.Multiple mixing tanks in reactor might not use in actual production process simultaneously, but according to the character of processed stock oil and the requirement of product, in reactor, logistics is selected to mix with the external hydrogen passed in different mixing tanks, and the specific embodiment of the present invention is as follows:
In step (1), in the environment of constant pressure, stock oil, reactor effluent and hydrogen are mixed before entering the reactor, mixed material is introduced the reactor that hydrogenation catalyst is housed.
In step (2), according to stock oil composition and property and the different mass requirement to product, hydrogenation catalyst can be divided into n bed, along reactor stream direction, be followed successively by the 1st, the 2nd ... the n-th beds, n-1 mixing tank is provided with between adjacent catalyst bed, along reactant flow direction, be followed successively by the 1st, the 2nd ... (n-1)th mixing tank, bottom the 1st to (n-1)th beds, thief hatch is set, logistics in the partial reaction device that can extract beds exit, carries out determining hydrogen gas concentration.What measure is the concentration of hydrogen in the liquid phase part of resultant after compounding substances described in step (1) and said mixture matter generation chemical reaction.
(3) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be in 2 × 10
-4gH
2/ g ~ 5 × 10
-4gH
2/ g, then mix logistics in this reactor with hydrogen, namely mix in the mixing tank of the most contiguous thief hatch, wherein 1≤m < n in m mixing tank,
(4) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be less than 2 × 10
-4gH
2/ g, then mix logistics in this reactor with hydrogen in m-1 mixing tank, namely mixes at the adjacent mixing tank place of the mixing tank upstream of the most contiguous thief hatch.
(5) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be greater than 5 × 10
-4gH
2during/g, in this reactor, logistics does not need to mix with hydrogen, then directly flow to m+1 beds.Next bed is not entered through bypass by mixing tank.
Selecting of above-mentioned mixing tank is that concentration according to hydrogen in logistics in reactor is determined.Because the hydrogen saturation solubility of hydrocarbon ils is lower, when the concentration of dissolving hydrogen in hydrocarbon ils is larger, be subject to the restriction of saturation solubility when hydrocarbon ils mixes again with hydrogen, the concentration amplification of dissolving hydrogen in hydrocarbon ils is very little, does not have actually operating meaning.But, hydrocarbon ils dissolve the concentration of hydrogen lower time, hydrogenation reaction speed is slow, when hydrocarbon ils dissolve hydrogen concentration be less than 2 × 10
-4gH
2during/g, rapid catalyst deactivation.Known by studying, in the liquid phase of said mixture and resultant of reaction, the concentration of hydrogen is 2 × 10
-4gH
2/ g ~ 5 × 10
-4gH
2in the scope of/g, it is mixed again with hydrogen, can realize mixing that number of times is few, quality product is high and catalyst stability good.
The present invention in time monitors the concentration of the hydrogen in reactor in logistics, when the concentration of hydrogen is 2 × 10
-4gH
2/ g ~ 5 × 10
-4gH
2mixing by logistics in reactor and hydrogen in the scope of/g, ensure that the hydrogenation reaction in whole reactor has higher speed of reaction and catalyst stability, while hydrocarbon ils reach minimum with the number of times that mixes of hydrogen.The present invention under the condition circulated compared with low reactor effluent, can 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: temperature of reaction 250 ~ 450 DEG C, preferably 280 ~ 430 DEG C, system pressure 1.0 ~ 18.0MPa, preferably 3.0 ~ 15.0MPa, volume space velocity 0.1 ~ 9.0h during liquid
-1, preferably 0.3 ~ 6.0h
-1, the reactor effluent of circulation: stock oil charging=1: 1 ~ 10: 1, preferably 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, vacuum gas oil.
Hydrogenation catalyst is the conventional catalyzer with hydrofining or hydro-upgrading function, can be load hydrogenation catalyst, also can be non-supported hydrogenation catalyst.
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, after heat exchange, obtains the second gas phase and second liquid phase, wherein the second gas phase emission, second liquid phase can be used as reactor effluent and mixes with raw material and hydrogen; First liquid phase part mixes with raw material and hydrogen as reactor ejecta, and remainder goes out device as product after heat exchange.
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, heat through process furnace 4, then mix in mixing tank 7 with the reactor effluent from pipeline 5 and the high score air cooling lime set (second liquid phase) from pipeline 6, mixed material enters hydrogenator 9 by pipeline 8.React under hydrogenation catalyst effect at hydrogenator Raw oil and hydrogen, have two beds in reactor 9, bottom the first beds, have thief hatch 10.By density of hydrogen in logistics in thief hatch 10 sampling analysis reactor, to judge that in reactor, logistics mixes in mixing tank 11 with from the new hydrogen of pipeline 3, 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 (the first gas phase) at high-pressure separator top enters condenser 17 by pipeline 16, top gas phase logistics at the bottom of condenser (the second gas phase) is discharged as waste gas, and the liquid phase stream (second liquid phase) of bottom enters mixing tank 7 through pipeline 6.High-pressure separator bottom liquid phases logistics (the first liquid phase) part is by pipeline 18 discharger, and another part enters mixing tank 7 through pipeline 5.
The following examples to method provided by the invention, will be further described, but not thereby limiting the invention.
The trade names of embodiment and comparative example load hydrogenation catalyst for refining used are RS-1000, and the trade names of hydrocracking catalyst used are RHC-5, are Sinopec catalyzer branch office and produce.
Embodiment 1
With a kind of Middle East high-sulfur straight(-run) diesel distillate for stock oil 1, stock oil 1 mixes under the pressure of 6.5MPa with reactor effluent, hydrogen, mixed material is introduced the reactor that load hydrogenation catalyst for refining is housed, deep hydrodesulfurizationof reaction is carried out at this, reaction conditions is: temperature of reaction 355 DEG C, reactor pressure 6.4MPa, volume space velocity 1.5h during raw material fluid
-1.Reactor is evenly divided into three beds, and in 2 bed exits, recording in reactor density of hydrogen in logistics is 5 × 10
-4gH
2/ g, the second mixing tank that in reactor, logistics and the external hydrogen passed into enter between 2 beds and 3 beds mixes, and enters 3 beds and proceed reaction after mixing, to record in reactor the concentration of hydrogen in logistics be greater than 5 × 10 in 1 bed exit
-4gH
2/ g, does not therefore need to mix with hydrogen in the first mixing tank.In the present embodiment reactor, logistics is with external to pass into the number of times that hydrogen mixes be 1 time.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and through the separating obtained gas phase portion of high-pressure separator after heat exchange, discharged by gas phase portion, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; A liquid phase part for high-pressure separator gained mixes with raw material and hydrogen as reactor ejecta, and another part goes out device as product after heat exchange, 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 the present embodiment is as shown in table 1, reaction conditions and product main character as shown in table 2.
Comparative example 1
Stock oil 1 mixes under the pressure of 6.5MPa with reactor effluent, hydrogen, and mixed material introducing is equipped with the reactor of Hydrobon catalyst, carries out deep hydrodesulfurizationof reaction, reaction conditions is with embodiment 1.Reactor is evenly divided into three beds, mixes in reactor in logistics and the external hydrogen passed into the first mixing tank between 1 bed and 2 beds, and mixed material enters next bed in reactor and reacts.The concentration recording hydrogen in logistics in 1 bed exit reactor is 8 × 10
-4gH
2/ g.In this comparative example reactor, logistics is with external to pass into the number of times that hydrogen mixes be 1 time.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and through the separating obtained gas phase portion of high-pressure separator after heat exchange, discharged by gas phase portion, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; A liquid phase part for high-pressure separator gained mixes with raw material and hydrogen as reactor ejecta, and another part goes out device as product after heat exchange, 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 as shown in table 2.
Table 1 stock oil character
| Stock oil | Stock oil 1 | Stock oil 2 | Stock oil 3 |
| Type of feed | Straight-run diesel oil | Catalytic diesel oil | Husky light VGO |
| Density (20 DEG C), 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, DEG C | |||
| 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 meets Europe V Diesel Emissions standard, can be used as the clean diesel blend component of high-quality.Under identical processing condition, adopt the hydrogen addition technology of comparative example 1, the sulphur content of the product obtained is 38 μ g/g.Using the desulfurization of comparative example 1, denitrification activity as 100, relatively desulphurizing activated, the relative denitrification activity calculating embodiment 1 is respectively 259 and 274.The method (embodiment 1) provided of the present invention is controlled logistics in reactor and the decomposite position of hydrogen, and existing hydrogen addition technology (comparative example 1) does not control logistics in reactor and the decomposite position of hydrogen.Both contrasts can find, under the condition of identical mixed hydrogen number of times, adopt the method provided of the present invention can obtain sulphur content, the product meeting clean diesel standard that nitrogen content is lower.
Embodiment 2
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 is introduced to be equipped with in the reactor of load hydrogenation catalyst for refining and carries out deep hydrodesulfurizationof reaction, reaction conditions is: temperature of reaction 370 DEG C, reactor pressure 8.0MPa, volume space velocity 1.5h during raw material fluid
-1.Reactor is evenly divided into five beds, and recording in reactor density of hydrogen in logistics in 1 bed exit is 3 × 10
-4gH
2/ g, in reactor, logistics and hydrogen mix in the first mixing tank, enter 2 beds and react after mixing; Recording in reactor density of hydrogen in logistics in 3 bed exits is 3 × 10
-4gH
2/ g, in reactor, logistics and hydrogen mix in the 3rd mixing tank, and enter reactor 4 bed after mixing and react, whole process need mix 2 times.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and through the separating obtained gas phase portion of high-pressure separator after heat exchange, discharged by gas phase portion, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; A liquid phase part for high-pressure separator gained mixes with raw material and hydrogen as reactor ejecta, and another part goes out device as product after heat exchange, 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 the present embodiment is as shown in table 1, reaction conditions and product main character as shown in table 3.
Comparative example 2a
Mixed under the pressure of 8.2MPa with reactor effluent, hydrogen by stock oil 2, introduced to be equipped with in the reactor of load hydrogenation catalyst for refining by mixed material and carry out deep hydrodesulfurizationof reaction, reaction conditions is identical with embodiment 2.Reactor is evenly divided into five beds, and recording logistics density of hydrogen in reactor in 2 bed exits is 1 × 10
-4gH
2/ g, in reactor, logistics and hydrogen enter the second mixing tank and mix, and enter 3 beds and react after mixing; Recording logistics density of hydrogen in reactor in 3 bed exits is 6 × 10
-4gH
2/ g, in reactor, logistics and hydrogen enter the 3rd mixing tank and mix, and enter 4 beds after mixing and react, whole process need mix 2 times.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and through the separating obtained gas phase portion of high-pressure separator after heat exchange, discharged by gas phase portion, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; A liquid phase part for high-pressure separator gained mixes with raw material and hydrogen as reactor ejecta, and another part goes out device as product after heat exchange, 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 example is as shown in table 1, reaction conditions and product main character as shown in table 3.
Comparative example 2b
Mixed under the pressure of 8.2MPa with reactor effluent, hydrogen by stock oil 2, introduced to be equipped with in the reactor of load hydrogenation catalyst for refining by mixed material and carry out deep hydrodesulfurizationof reaction, reaction conditions is identical with embodiment 2.Reactor is evenly divided into five beds, and recording in reactor density of hydrogen in logistics in 1 bed exit is 3 × 10
-4gH
2/ g, in reactor, logistics and hydrogen mix at the first mixing tank, enter 2 beds and react after mixing; Recording in reactor density of hydrogen in logistics in 2 bed exits is 7.5 × 10
-4gH
2/ g, in reactor, logistics and hydrogen enter the second mixing tank and mix, and enter 3 beds in reactor and react after mixing, and recording in reactor density of hydrogen in logistics in 4 bed exits is 2 × 10
-4gH
2/ g, in reactor, logistics and hydrogen enter the 4th mixing tank and mix, and enter 5 beds in reactor after mixing and react, whole process need mix 3 times.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and through the separating obtained gas phase portion of high-pressure separator after heat exchange, discharged by gas phase portion, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; A liquid phase part for high-pressure separator gained mixes with raw material and hydrogen as reactor ejecta, and another part goes out device as product after heat exchange, 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 example is as shown in table 1, reaction conditions and product main character 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 meets Europe IV Diesel Emissions standard, can be used as the clean diesel blend component of high-quality.Under identical processing condition, adopt the method for comparative example 2a, the sulphur content of the product obtained is 103 μ g/g.Under identical processing condition, adopt the method for comparative example 2b, increase once mixed hydrogen, the sulphur content of the product obtained is 42 μ g/g.Using the desulfurization of comparative example 2a, denitrification activity as 100, relatively desulphurizing activated, the relative denitrification activity calculating embodiment 2 is respectively 175 and 119, and relatively desulphurizing activated, the relative denitrification activity of comparative example 2b is respectively 183 and 121.Method provided by the present invention is controlled logistics in reactor and the decomposite position of hydrogen, and existing method does not control logistics in reactor and the decomposite position of hydrogen and number of times.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 meeting clean diesel standard that nitrogen content is lower; Or when reaching the product of identical clean diesel standard, adopt the present invention to mix hydrogen number of times less.
Embodiment 3
With a kind of Saudi Arabia lightweight VGO for 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.First reactor charge load hydrogenation catalyst for refining, the second reactor charge load hydrogenation cracking catalyst.Reaction conditions is: the first temperature of reactor 380 DEG C, the second temperature of reactor 395 DEG C, reactor pressure 14.5MPa, volume space velocity 1.2h during raw material fluid
-1.Each reactor is divided into five beds according to the filling ratio of 1.5: 2: 1.5: 2: 3, and recording in reactor density of hydrogen in logistics in 2 bed exits of the first reactor is 4.0 × 10
-4gH
2/ g, in reactor, logistics mixes at the second mixing tank with hydrogen, enters the first reactor 3 bed and react after mixing, to record in reactor the concentration of hydrogen in logistics be greater than 5 × 10 in the first reactor 1 bed, 3 beds, 4 bed exits
-4gH
2/ g, does not therefore need to mix with hydrogen in mixing tank.Recording in reactor density of hydrogen in logistics in 2 bed exits of the second reactor is 3.0 × 10
-4gH
2/ g, in reactor, logistics and hydrogen mix at the second mixing tank, enter 3 beds in the second reactor and react after mixing.To record in reactor the concentration of hydrogen in logistics in the second reactor 1 bed, 3 beds, 4 bed exits and be greater than 5 × 10
-4gH
2/ g, does not therefore need to mix with hydrogen in mixing tank.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and through the separating obtained gas phase portion of high-pressure separator after heat exchange, discharged by gas phase portion, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; A liquid phase part for high-pressure separator gained mixes with raw material and hydrogen as reactor ejecta, and another part goes out device as product after heat exchange, 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 the present embodiment is as shown in table 1, reaction conditions and product main character as shown in table 4.
Comparative example 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.First reactor charge load hydrogenation catalyst for refining, the second reactor charge load hydrogenation cracking catalyst.Reaction conditions is identical with embodiment 3.Each reactor is divided into five beds according to the filling ratio of 1.5: 2: 1.5: 2: 3, at the first reactor, mix in logistics and hydrogen the 3rd mixing tank between 3 beds and 4 beds in reactor, recording in 3 bed exit reactors density of hydrogen in logistics is 1.3 × 10
-4gH
2/ g, enters the first reactor 4 bed and reacts after mixing; At the second reactor, in reactor, logistics and hydrogen mix in the 3rd mixing tank between 3 beds and 4 beds, and recording in 3 bed exit reactors density of hydrogen in logistics is 0.8 × 10
-4gH
2/ g, enters 4 beds in the second reactor and reacts after mixing.
Reactor effluent carries out gas-liquid separation in high-pressure separator, and through the separating obtained gas phase portion of high-pressure separator after heat exchange, discharged by gas phase portion, the liquid phase that condensation is got off can be used as reactor effluent and mixes with raw material and hydrogen; A liquid phase part for high-pressure separator gained mixes with raw material and hydrogen as reactor ejecta, and another part goes out device as product after heat exchange, 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 example is as shown in table 1, reaction conditions and product main character 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, and nitrogen content is 986 μ g/g.As can be seen from Table 4, adopt the method for embodiment 3 and comparative example 3, identical at both initial reaction stage > 350 DEG C of transformation efficiencys.But, adopt the method for embodiment 3, maintain this transformation efficiency and run 1000 hours, need equalising temp 1.5 DEG C; Adopt the method for comparative example 3, maintain this transformation efficiency and run 1000 hours, need equalising temp 6 DEG C.This is because in comparative example 3 in compounding substances liquid phase density of hydrogen be reduced to 1 × 10
-4gH
2/ g just carries out benefit hydrogen, and too low density of hydrogen cannot stop hydrocarbon ils at catalyst surface carbon deposit, causes catalyst activity reduction.Visible, adopt hydrogen addition technology of the present invention compared with existing hydrogen addition technology, under the prerequisite of same process condition, like products quality, catalyst life can be improved.
Claims (7)
1. a Continuous Liquid Phase method for hydrotreating hydrocarbon oil, it is characterized in that, n beds is set in reactor, mixing tank is provided with between adjacent catalyst bed, in mixing tank, in reactor, logistics mixes with external hydrogen, n-1 mixing tank of reactor does not use simultaneously, but according to the concentration of hydrogen in logistics in reactor, select to mix with the hydrogen passed in different mixing tanks, wherein 2≤n≤10, when extract m layer beds exit out reactor in logistics the concentration of hydrogen be greater than 5 × 10
-4gH
2during/g, in this reactor, logistics does not need to mix with hydrogen, then directly flow to m+1 beds, wherein 1≤m < n,
In reactor, reaction conditions is: temperature of reaction 250 ~ 450 DEG C, system pressure 1.0 ~ 18.0MPa, volume space velocity 0.1 ~ 9.0h during liquid
-1,
Stock oil is selected from one or more in straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, visbreaking diesel oil, vacuum gas oil.
2. in accordance with the method for claim 1, it is characterized in that, comprise the steps:
(1) in the environment of constant pressure, stock oil, reactor effluent and hydrogen are mixed before entering the reactor, mixed material is introduced the reactor that hydrogenation catalyst is housed;
(2) n beds is had in the reactor described in step (1), along reactor stream direction, be followed successively by the 1st, the 2nd ... the n-th beds, n-1 mixing tank is provided with between adjacent catalyst bed, along reactant flow direction, be followed successively by the 1st, the 2nd ... (n-1)th mixing tank, bottom the 1st to (n-1)th beds, thief hatch is set, logistics in the partial reaction device that can extract beds exit, carry out determining hydrogen gas concentration
(3) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be in 2 × 10
-4gH
2/ g ~ 5 × 10
-4gH
2/ g, then mix logistics in this reactor with hydrogen in m mixing tank, wherein 1≤m < n,
(4) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be less than 2 × 10
-4gH
2/ g, then mix logistics in this reactor with hydrogen in m-1 mixing tank,
(5) when determination step (2) extract m layer beds exit out reactor in logistics the concentration of hydrogen be greater than 5 × 10
-4gH
2during/g, in this reactor, logistics does not need to mix with hydrogen, then directly flow to m+1 beds.
3. according to the method described in claim 1 or 2, it is characterized in that, reactor bottom effluent enters high-pressure separator and carries out gas-liquid separation, obtain the first gas phase and the first liquid phase, first gas phase of gained is after heat exchange, obtain the second gas phase and second liquid phase, wherein the second gas phase emission, second liquid phase can be used as reactor effluent and mixes with raw material and hydrogen; First liquid phase part mixes with raw material and hydrogen as reactor ejecta, and remainder goes out device as product after heat exchange.
4. according to the method described in claim 1 or 2, it is characterized in that, reaction conditions is: temperature of reaction 280 ~ 430 DEG C, system pressure 3.0 ~ 15.0MPa, volume space velocity 0.3 ~ 6.0h during liquid
-1.
5. in accordance with the method for claim 2, it is characterized in that, the reactor effluent of circulation: stock oil charging=1: 1 ~ 10: 1.
6. in accordance with the method for claim 2, it is characterized in that, the reactor effluent of circulation: stock oil charging=1: 1 ~ 3: 1.
7. in accordance with the method for claim 2, it is characterized in that, the mixture of stock oil, reactor effluent and hydrogen enters from reactor bottom.
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| CN105861046B (en) * | 2015-01-23 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of Ultra-deep Desulfurization of Diesel Fuels system |
| CN105861037B (en) * | 2015-01-23 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of Continuous Liquid Phase diesel oil hydrotreating method |
| CN107267198A (en) * | 2017-08-11 | 2017-10-20 | 南京康鑫成生物科技有限公司 | A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil |
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