CN101338219A - Two-phase hydrogenation process - Google Patents
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- CN101338219A CN101338219A CNA2008101409903A CN200810140990A CN101338219A CN 101338219 A CN101338219 A CN 101338219A CN A2008101409903 A CNA2008101409903 A CN A2008101409903A CN 200810140990 A CN200810140990 A CN 200810140990A CN 101338219 A CN101338219 A CN 101338219A
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Abstract
The present invention discloses a biphase hydrogenation method, which cancels circulating hydrogen and a circulating hydrogen compressor. Hydrogen is mixed with fresh crude oil and circulating oil under the existence of a solvent or a diluting agent so as to form a mixture flow; the mixture flows into a reactor to contact a catalyst; after the other part of the circulating oil is mixed with hydrogen for gas discharging, a circuit or a shunt circuit enters the reactor between reactor catalyst bed layers; after the solvent or the diluting agent is mixed with hydrogen for gas discharging, a circuit or a shunt circuit enters the reactor between reactor catalyst bed layers; the reacted effluent is used for gas-liquid separation and the liquid phase further separates the solvent or the diluting solvent for recycling use; a part of the separated liquid product is used as the product and the other part is used as the circulating oil.
Description
Technical field
The present invention relates to the hydrocarbon oil hydrogenation technology, particularly liquid-solid two-phase hydrocarbon oil hydrogenation technology.
Background technology
In the hydrocarbon ils processing technology, hydrogen addition technology is to improve one of hydrocarbon ils quality technology commonly used, the crude oil that is tending towards higher sulfur content along with the global crude oil market supply, the refinery need process the higher hydrocarbon ils inferior of sulfur-bearing, sulphur, nitrogen, oxygen and metal impurities are removed in refining process, change its quality by the molecular structure that changes hydrocarbon ils, thereby make various products satisfy code requirement.The hydrogen that in fact the hydrocarbon oil hydrogenation process participates in reacting only is useful on the hydrogen of chemical hydrogen consumption, and traditional trickle-bed reactor hydrogen addition technology, need excessive hydrogen and exist, make that the volume ratio of reactor is bigger, and keep the exess of H2 gas and need use circulating hydrogen compressor.
Hydrogen need be delivered to liquid phase from gas phase in traditional hydrogenation technique, and co-absorbed is reacted under the effect of catalyst active center on the surface of catalyzer then.Because hydrogenation reaction is a strong exothermal reaction, in order to keep temperature of reaction, utilize a large amount of hydrogen and stock oil to take away the heat that reaction produces by beds, and the hydrogen of actual needs (chemical hydrogen consumption) is fewer in hydrogenation process, do not participate in the hydrogen of reaction, be recycled to hydrogenator and continue to participate in reaction; It is to keep the hydrogen dividing potential drop of hydrocarbon oil hydrogenation reaction that tradition hydrocarbon oil hydrogenation technology adopts another major cause of excessive hydrogen, keeps higher hydrogen branch and is pressed in and helps hydrofining and hydrocracking reaction on the thermodynamics, suppresses to generate the condensation reaction of coke.
The hydrogen of participating in reaction is not elevated to the required pressure of reaction by circulating hydrogen compressor with its pressure and delivers to reactor continuation participation hydrogenation reaction by separator and liquid phase separation and after removing impurity.The hydrogen pressurize that the effect of circulating hydrogen compressor will not participate in hydrogenation reaction exactly recycles it, so the circulating hydrogen compressor becomes imperative equipment in existing hydrogen addition technology, is called the heart of hydrogenation unit in the industry.
Be the gas, liquid, solid three-phase in traditional fixed bed hydrogenation reactor and deposit that gas phase is the steam of hydrogen and hydrocarbon raw material, liquid phase is the hydrocarbon raw material of vaporization not, and solid phase is a catalyzer.Gas-liquid two-phase is to pass through beds with the form of drip, therefore also claims trickle-bed reactor.
In trickle-bed reactor, in order to strengthen the mass transfer dynamics, the volume ratio of hydrogen and stock oil is generally 50～2000: 1, therefore the hydrogenator design is bigger, and the actual stock oil that reacts of participating in is relevant with liquid hourly space velocity, air speed has reflected the processing power of device, and bigger air speed operation is adopted in industrial hope, but air speed is subjected to the restriction of speed of response.Air speed is unusual at 0.5～10h according to catalyst activity, feedstock property, reaction depth
-1Between the fluctuation.The unifining process of industrial application can improve alkene saturation exponent, hydrogenating desulfurization rate and hydrodenitrification rate at certain temperature of reaction condition decline low-speed at present.Under hydrocracking condition, it is little to total transformation efficiency influence to improve air speed, but the decline of the light constituent content in the reaction product is more.
The purpose that adopts the exess of H2 gas is to strengthen mass transfer and take away a large amount of heats that produce because of hydrogenation reaction, circulating hydrogen compressor is as the heart of hydrogenation process, investment and process cost are all higher, in order to cancel circulating hydrogen compressor, people begin to consider to utilize hydrogen supply agent to provide hydrogen source for the hydrocarbon oil hydrogenation process, USP4698147 promptly discloses and has utilized hydrogen supply agent to reduce the residence time, and reaction back hydrogen supply agent utilizes hydrogen to regenerate, and recycles after the regeneration.In order to strengthen cracking reaction, USP4857168 discloses and has utilized hydrogen supply agent and hydrogen to provide the heavy-oil hydrogenation cracking method of hydrogen source for heavy-oil hydrogenation, and hydrogen supply agent mainly works to suppress to generate the condensation reaction of coke.
Above-mentioned improvement still needs recycle hydrogen and circulating hydrogen compressor, US6428686 has proposed a kind of two-phase hydrogenation method, before reactor, be dissolved in hydrogen in the stock oil, recycle hydrogen and circulating hydrogen compressor have been cancelled, the investment and the process cost of hydrogenation unit have been reduced, this technology adopts the liquid phase circulation of reaction product, improve the meltage of hydrogen, to satisfy in the hydrogenation process requirement to hydrogen, and take reaction heat out of, this technology be with turning oil with enter hydrogenator after stock oil and hydrogen mix, its shortcoming is the speed of response that the existence of a large amount of turning oil can influence fresh feed and hydrogen, because fresh feed is relatively fiercer with hydrogen reaction when beginning contacts with catalyzer, the existence of turning oil has suppressed the touch opportunity of fresh feed oil and hydrogen and catalyzer, has reduced the mass transfer and the speed of response of fresh feed oil and hydrogen.
Summary of the invention
The present invention proposes a kind of two-phase hydrogenation method, cancelled recycle hydrogen and circulating hydrogen compressor, strengthen the touch opportunity of fresh feed oil and hydrogen and catalyzer, improve mass transfer and speed of response.
A kind of two-phase hydrogenation method of the present invention is: hydrogen mixes the formation mixture flow with fresh feed oil and turning oil in the presence of solvent or thinner, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent carries out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, part is as turning oil, hydrogen in solvent or thinner solubleness greater than the solubleness of hydrogen in fresh feed oil and solvent or diluent mixture.
Described and fresh feed oil and hydrogen blended turning oil are part turning oil, another part turning oil mixes discharge gas with hydrogen after, the one tunnel or shunt between the reactor catalyst bed, enter reactor.
Described mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation.
Described mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
Described mixture flow enters reactor after isolating gas.
Described mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
Described a kind of two-phase hydrogenation method, its feature also is: from going out the laggard mixture flow of going into reactor of gas, liquid contacts with catalyzer from the mixing tank top portion, and gas is got rid of from reactor head.
The present invention proposes another kind of two-phase hydrogenation method, it is characterized in that: fresh feed oil with in the presence of solvent or thinner, mix the formation mixture flow after turning oil mixes again with hydrogen, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent is drawn from reactor bottom and is carried out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, part is as turning oil, and the solubleness of hydrogen in solvent or thinner is greater than the solubleness of hydrogen in fresh feed oil and solvent or diluent mixture.
Described and fresh feed oil blended turning oil is part turning oil, another part turning oil mixes discharge gas with hydrogen after, the one tunnel or shunt between the reactor catalyst bed, enter reactor.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor after isolating gas.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
Described another kind of two-phase hydrogenation method, its feature also is: from the mixing tank top portion from going out the laggard mixture flow of going into reactor of gas, liquid and catalyzer contact reacts, gas is got rid of from reactor head.
The present invention proposes another kind of two-phase hydrogenation method, it is characterized in that: mix the formation mixture flow after fresh feed oil and turning oil and solvent or the mixing diluents with hydrogen, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent is drawn from reactor bottom and is carried out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, part is as turning oil, and the solubleness of hydrogen in solvent or thinner is greater than the solubleness of hydrogen in fresh feed oil and solvent or diluent mixture.
Described and fresh feed oil blended turning oil is part turning oil, another part turning oil mixes discharge gas with hydrogen after, the one tunnel or shunt between the reactor catalyst bed, enter reactor.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor after isolating gas.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
Described another kind of two-phase hydrogenation method, its feature also is: from the mixing tank top portion from going out the laggard mixture flow of going into reactor of gas, liquid and catalyzer contact reacts, gas is got rid of from reactor head.
The another kind of two-phase hydrogenation method of the present invention, it is characterized in that: mix the formation mixture flow after fresh feed oil and solvent or the mixing diluents with turning oil and hydrogen, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent is drawn from reactor bottom and is carried out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, and part is as turning oil.
Described and fresh feed oil blended turning oil is part turning oil, another part turning oil mixes discharge gas with hydrogen after, the one tunnel or shunt between the reactor catalyst bed, enter reactor.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow enters reactor after isolating gas.
Described another kind of two-phase hydrogenation method, its feature also is: mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
Described another kind of two-phase hydrogenation method, its feature also is: from the mixing tank top portion from going out the laggard mixture flow of going into reactor of gas, liquid and catalyzer contact reacts, gas is got rid of from reactor head.
Catalyzer divides two sections bed fillings at least in the hydrogenator of the present invention, form two-stage catalytic agent bed at least, the effluent that comes out from first section beds and the turning oil of introducing are mixed into second section beds, contact with catalyzer and to proceed reaction, the effluent that comes out from second section beds with enter the 3rd section beds after the turning oil of introducing mixes, the rest may be inferred, and reaction effluent is drawn from reactor bottom.
Solvent of the present invention or thinner are at least a in the hydrocarbon ils behind heavy naphtha, petroleum naphtha, lighter hydrocarbons, benzoline, diesel oil, VGO and the hydrogenation.
The fresh feed oil of two-phase hydrogenation method of the present invention is the distillate of hydrocarbon ils or hydrocarbon ils, as petroleum fractions, distillate, diesel oil, deasphalted oil, residual oil, lubricating oil, liquefied coal coil and shale oil or its product.
Two-phase hydrogenation method of the present invention removes a kind of pollutent in its sulphur, nitrogen, oxygen, the metallic impurity at least, and saturated aromatic hydrocarbons, changes the molecular structure of hydrocarbon ils.
Two-phase hydrogenation method of the present invention has been cancelled recycle hydrogen and circulating hydrogen compressor, utilize hydrocarbon ils, solvent or thinner that hydrogen is dissolved in wherein, for hydrocarbon oil hydrogenation provides hydrogen source, wherein solvent or thinner to the dissolving power of hydrogen greater than hydrocarbon ils, the addition of solvent or thinner is according to the amount of the required hydrogen of hydrocarbon oil hydrogenation process reaction, and promptly chemical hydrogen consumes and regulates.
Two-phase hydrogenation method of the present invention: the temperature of utilizing the ratio of mixture control mixture flow of turning oil and solvent or thinner and fresh feed oil to enter reactor, utilize to enter the turning oil that is dissolved with hydrogen between the beds and the amount controlling reactor temperature of solvent or thinner.
The problem of a maximum of hydrogenation process is the beds coking, the coking reaction can take place under the reaction conditions, if there is not enough hydrogen, the cracking reaction meeting causes coke to form, and is deposited on catalyst surface, and the present invention is owing to adopt the turning oil circulation, it is saturated that turning oil obtains many aromatic hydrocarbons through hydrogenation, function with hydrogen supply can suppress coke and form, and prolongs life of catalyst.
Two-phase hydrogenation method of the present invention can be used for straight run, FCC turning oil, coker gas oil CGO, perhaps it mixes kerosene and diesel oil hydrogenation processing, also can be used for the FCC raw materials pretreatment, be used for new device and relax the hydrocracking transformation, be used to produce ULSD, be used for the pre-treatment of raw material or the aftertreatment of product.
Two-phase hydrogenation method of the present invention has following advantage:
1) catalyst levels is few;
2) hydrogen loss is less;
3) lower process cost;
4) liquid yield is higher;
5) bigger flexibility of operation;
6) the sulphur nitrogen content of product is very low;
7) lower investment;
8) for producing ultra-low-sulphur diesel, improvement expenses is very low.
Compare with the prior art of trickle bed hydrogenator, advantage of the present invention is: but desulfurization 90%～98%, and the hydrogen consumption only is 70%～90% of a trickle bed hydrogenator, the total consumption of catalyzer only is 15%～30%.
Description of drawings
Fig. 1 is a two-phase hydrogenation processing flow chart of the present invention.
Fig. 2 is the another kind of two-phase hydrogenation processing flow chart of the present invention.
Fig. 3 is the third two-phase hydrogenation processing flow chart of the present invention.
Fig. 4 is the 4th kind of two-phase hydrogenation processing flow chart of the present invention.
Fig. 5 is the 5th kind of two-phase hydrogenation processing flow chart of the present invention.
Fig. 6 is the 6th kind of two-phase hydrogenation processing flow chart of the present invention.
Fig. 7 is the 7th kind of two-phase hydrogenation processing flow chart of the present invention.
Fig. 8 is the 8th kind of two-phase hydrogenation processing flow chart of the present invention.
Fig. 9 is the 9th kind of two-phase hydrogenation processing flow chart of the present invention.
Figure 10 is the tenth kind of two-phase hydrogenation processing flow chart of the present invention.
Figure 11 is the 11 kind of two-phase hydrogenation processing flow chart of the present invention.
Figure 12 is the 12 kind of two-phase hydrogenation processing flow chart of the present invention.
Figure 13 is the 13 kind of two-phase hydrogenation processing flow chart of the present invention.
Figure 14 is the 14 kind of two-phase hydrogenation processing flow chart of the present invention.
Figure 15 is the 15 kind of two-phase hydrogenation processing flow chart of the present invention.
Figure 16 is the 16 kind of two-phase hydrogenation processing flow chart of the present invention.
Among the figure: 1-fresh feed oil, 2-hydrogen, 3-first mixing tank, 4-separating tank, 5-reactor, 6-second mixing tank, 7-reactor feed, 8-first separator, 9-second separator, 10-the 3rd mixing tank; The 11-first separator waste gas, molten hydrogen solvent of 12-or thinner; 13-solvent or thinner, 14-separating tank waste gas, the molten hydrogen turning oil of 15-, the 16-first separator separated product, 17-turning oil, 18-the 3rd mixing tank waste gas, the 19-second mixing tank waste gas.
Embodiment
As shown in Figure 1, reactor shown in the figure is four sections beds.Fresh feed oil 1 is mixing in first mixing tank 3 with hydrogen 2 and turning oil 17 in the presence of partial solvent or the thinner 13, mixture flow enters separating tank 4, become reactor feed 7 after isolating separating tank waste gas 14, reactor feed 7 enters first section beds of reactor and catalyzer contact reacts from reactor 5 tops, another part solvent or thinner 13 mix in the 3rd mixing tank 10 with hydrogen 2 and discharge the 3rd mixing tank waste gas 18, molten hydrogen solvent or thinner 12 respectively from first section of reactor 5 with second section beds, enter reactor 5 between second section and the 3rd section beds and the 3rd section and the 4th section beds, the reaction effluent that comes out from reactor 5 bottoms enters first separator 8 to be separated, isolate the first separator waste gas 11, the separated product separated into two parts that comes out from first separator, 8 bottoms, a part is as the first separator separated product 16, another part is as turning oil 17, the first separator separated product 16 enters second separator 9 again to be separated, the logistics of coming out from second separator, 9 tops is as solvent or thinner 13, and the separated product that comes out from second separator, 9 bottoms goes out device as product.
Fig. 2, the difference of itself and Fig. 1 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and the reaction effluent of reactor 5 comes out to enter first separator 8 from the top of reactor 5.
Fig. 3, the difference of itself and Fig. 1 is: turning oil 17 separated into two parts, part turning oil 17 enters first mixing tank 3, another part turning oil 17 and hydrogen 2 mix in second mixing tank 6 discharges the second mixing tank waste gas 19 and becomes molten hydrogen turning oil 15, enters reactor 5 respectively between first section of reactor 5 and second section beds, second section and the 3rd section beds and the 3rd section and the 4th section beds.
Fig. 4, the difference of itself and Fig. 3 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and the reaction effluent of reactor 5 comes out to enter first separator 8 from the top of reactor 5.
Fig. 5, it is with the difference of Fig. 1: fresh feed oil 1 with in the presence of partial solvent or thinner 13, in first mixing tank 3, mix the formation mixture flow again after turning oil 17 mixes with hydrogen 2.
Fig. 6, the difference of itself and Fig. 5 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and the reaction effluent of reactor 5 comes out to enter first separator 8 from the top of reactor 5.
Fig. 7, the difference of itself and Fig. 5 is: turning oil 17 separated into two parts, part turning oil 17 enters first mixing tank 3, another part turning oil 17 and hydrogen 2 mix in second mixing tank 6 discharges the second mixing tank waste gas 19 and becomes molten hydrogen turning oil 15, enters reactor 5 respectively between first section of reactor 5 and second section beds, second section and the 3rd section beds and the 3rd section and the 4th section beds.
Fig. 8, the difference of itself and Fig. 7 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and reactor exhaust 4 is discharged at reactor 5 tops, and the reaction effluent that comes out in reactor 5 tops enters first separator 8 to be separated.
Fig. 9, it is with the difference of Fig. 1: mix forming mixture flow after fresh feed oil 1 and partial solvent or thinner 13 mix again in first mixing tank with turning oil 17 and hydrogen 2.
Figure 10, the difference of itself and Fig. 9 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and reactor exhaust 4 is discharged at reactor 5 tops, and the reaction effluent that comes out in reactor 5 tops enters first separator 8 to be separated.
Figure 11, the difference of itself and Fig. 9 is: turning oil 17 separated into two parts, part turning oil 17 enters first mixing tank 3, another part turning oil 17 and hydrogen 2 mix in second mixing tank 6 discharges the second mixing tank waste gas 19 and becomes molten hydrogen turning oil 15, enters reactor 5 respectively between first section of reactor 5 and second section beds, second section and the 3rd section beds and the 3rd section and the 4th section beds.
Figure 12, the difference of itself and Figure 11 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and reactor exhaust 4 is discharged at reactor 5 tops, and the reaction effluent that comes out in reactor 5 tops enters first separator 8 to be separated.
Figure 13, it is with the difference of Fig. 1: fresh feed oil 1, turning oil and mix in first mixing tank 3 with hydrogen 2 after partial solvent or thinner 13 mix again and form mixture flow.
Figure 14, the difference of itself and Figure 13 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and reactor exhaust 4 is discharged at reactor 5 tops, and the reaction effluent that comes out in reactor 5 tops enters first separator 8 to be separated.
Figure 15, the difference of itself and Figure 13 is: turning oil 17 separated into two parts, part turning oil 17 enters first mixing tank 3, another part turning oil 17 and hydrogen 2 mix in second mixing tank 6 discharges the second mixing tank waste gas 19 and becomes molten hydrogen turning oil 15, enters reactor 5 respectively between first section of reactor 5 and second section beds, second section and the 3rd section beds and the 3rd section and the 4th section beds.
Figure 16, the difference of itself and Figure 15 is: reactor feed 7 enters reactor 5 from reactor 5 bottoms, and reactor exhaust 4 is discharged at reactor 5 tops, and the reaction effluent that comes out in reactor 5 tops enters first separator 8 to be separated.
Claims (36)
1 one kinds of two-phase hydrogenation methods, it is characterized in that: hydrogen mixes the formation mixture flow with fresh feed oil and turning oil in the presence of solvent or thinner, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent carries out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, and part is as turning oil.
2, according to the described a kind of two-phase hydrogenation method of claim 1, it is characterized in that: with fresh feed oil and hydrogen blended turning oil be part turning oil, another part turning oil mix with hydrogen discharge gas after, the one tunnel or between the reactor catalyst bed, enter reactor along separate routes.
3, according to claim 1 or 2 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation; Perhaps mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
4, according to claim 1 or 2 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor after isolating gas.
5, according to claim 1 or 2 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
6, according to claim 1 or 2 described a kind of two-phase hydrogenation methods, it is characterized in that: from the mixing tank top portion from going out the laggard mixture flow of going into reactor of gas, liquid and catalyzer contact reacts, gas is got rid of from reactor head.
7, according to claim 1 or 2 described a kind of two-phase hydrogenation methods, it is characterized in that: solvent or thinner are at least a in the hydrocarbon ils behind heavy naphtha, petroleum naphtha, lighter hydrocarbons, benzoline, diesel oil, VGO and the hydrogenation.
8, according to claim 1 or 2 described a kind of two-phase hydrogenation methods, it is characterized in that: the temperature of utilizing the ratio of mixture control mixture flow of turning oil and solvent or thinner and fresh feed oil to enter reactor, utilize to enter the turning oil that is dissolved with hydrogen between the beds and the amount controlling reactor temperature of solvent or thinner.
9, according to claim 1 or 2 described a kind of two-phase hydrogenation methods, it is characterized in that: the catalyzer in the reactor divides two sections fillings at least.
10, a kind of two-phase hydrogenation method, it is characterized in that: fresh feed oil with in the presence of solvent or thinner, mix the formation mixture flow after turning oil mixes again with hydrogen, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent carries out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, and part is as turning oil.
11, according to the described a kind of two-phase hydrogenation method of claim 10, it is characterized in that: with fresh feed oil blended turning oil be part turning oil, another part turning oil mix with hydrogen discharge gas after, the one tunnel or between the reactor catalyst bed, enter reactor along separate routes.
12, according to claim 10 or 11 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation; Perhaps mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
13, according to claim 10 or 11 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor after isolating gas.
14, according to claim 10 or 11 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
15, according to claim 10 or 11 described a kind of two-phase hydrogenation methods, it is characterized in that: from the mixing tank top portion from going out the laggard mixture flow of going into reactor of gas, liquid and catalyzer contact reacts, gas is got rid of from reactor head.
16, according to claim 10 or 11 described a kind of two-phase hydrogenation methods, it is characterized in that: solvent or thinner are at least a in the hydrocarbon ils behind heavy naphtha, petroleum naphtha, lighter hydrocarbons, benzoline, diesel oil, VGO and the hydrogenation.
17, according to claim 10 or 11 described a kind of two-phase hydrogenation methods, it is characterized in that: the temperature of utilizing the ratio of mixture control mixture flow of turning oil and solvent or thinner and fresh feed oil to enter reactor, utilize to enter the turning oil that is dissolved with hydrogen between the beds and the amount controlling reactor temperature of solvent or thinner.
18, according to claim 10 or 11 described a kind of two-phase hydrogenation methods, it is characterized in that: the catalyzer in the reactor divides two sections fillings at least.
19, a kind of two-phase hydrogenation method, it is characterized in that: mix the formation mixture flow after fresh feed oil and turning oil and solvent or the mixing diluents with hydrogen, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent is drawn from reactor bottom and is carried out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, and part is as turning oil.
20, according to the described a kind of two-phase hydrogenation method of claim 19, it is characterized in that: with fresh feed oil blended turning oil be part turning oil, another part turning oil mix with hydrogen discharge gas after, the one tunnel or between the reactor catalyst bed, enter reactor along separate routes.
21, according to claim 19 or 20 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation; Perhaps mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
22, according to claim 19 or 20 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor after isolating gas.
23, according to claim 19 or 20 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
24, according to claim 19 or 20 described a kind of two-phase hydrogenation methods, it is characterized in that: from the mixing tank top portion from going out the laggard mixture flow of going into reactor of gas, liquid and catalyzer contact reacts, gas is got rid of from reactor head.
25, according to claim 19 or 20 described a kind of two-phase hydrogenation methods, it is characterized in that: solvent or thinner are at least a in the hydrocarbon ils behind heavy naphtha, petroleum naphtha, lighter hydrocarbons, benzoline, diesel oil, VGO and the hydrogenation.
26, according to claim 19 or 20 described a kind of two-phase hydrogenation methods, it is characterized in that: the temperature of utilizing the ratio of mixture control mixture flow of turning oil and solvent or thinner and fresh feed oil to enter reactor, utilize to enter the turning oil that is dissolved with hydrogen between the beds and the amount controlling reactor temperature of solvent or thinner.
27, according to claim 19 or 20 described a kind of two-phase hydrogenation methods, it is characterized in that: the catalyzer in the reactor divides two sections fillings at least.
28, a kind of two-phase hydrogenation method, it is characterized in that: mix the formation mixture flow after fresh feed oil and solvent or the mixing diluents with turning oil and hydrogen, mixture flow enters reactor and contacts with catalyzer, solvent or thinner mix discharge gas with hydrogen after, one the tunnel or along separate routes between the reactor catalyst bed, enter reactor, reaction effluent is drawn from reactor bottom and is carried out gas-liquid separation, liquid phase further isolates solvent or thinner recycles, isolated product liquid part is as product, and part is as turning oil.
29, according to the described a kind of two-phase hydrogenation method of claim 28, it is characterized in that: with fresh feed oil, solvent or thinner and hydrogen blended turning oil be part turning oil, another part turning oil mix with hydrogen discharge gas after, the one tunnel or between the reactor catalyst bed, enter reactor along separate routes.
30, according to claim 28 or 29 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor from reactor head, and reaction effluent flows out from reactor bottom and carries out gas-liquid separation; Perhaps mixture flow enters reactor from reactor bottom, and reaction effluent flows out from reactor head and carries out gas-liquid separation.
31, according to claim 28 or 29 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow enters reactor after isolating gas.
32, according to claim 28 or 29 described a kind of two-phase hydrogenation methods, it is characterized in that: mixture flow is mixed in mixing tank, and gas is laggard goes into reactor from going out from the mixing tank top portion.
33, according to claim 28 or 29 described a kind of two-phase hydrogenation methods, it is characterized in that: from the mixing tank top portion from going out the laggard mixture flow of going into reactor of gas, liquid and catalyzer contact reacts, gas is got rid of from reactor head.
34, according to claim 28 or 29 described a kind of two-phase hydrogenation methods, it is characterized in that: solvent or thinner are at least a in the hydrocarbon ils behind heavy naphtha, petroleum naphtha, lighter hydrocarbons, benzoline, diesel oil, VGO and the hydrogenation.
35, according to claim 28 or 29 described a kind of two-phase hydrogenation methods, it is characterized in that: the temperature of utilizing the ratio of mixture control mixture flow of turning oil and solvent or thinner and fresh feed oil to enter reactor, utilize to enter the turning oil that is dissolved with hydrogen between the beds and the amount controlling reactor temperature of solvent or thinner.
36, according to claim 28 or 29 described a kind of two-phase hydrogenation methods, it is characterized in that: the catalyzer in the reactor divides two sections fillings at least.
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| CN201210032397.3A Division CN102585894B (en) | 2008-08-11 | 2008-08-11 | Hydrocarbon oil hydrogenation method |
| CN201210032299.XA Division CN102618320B (en) | 2008-08-11 | 2008-08-11 | Method for biphase hydrogenation of hydrocarbon oil |
| CN2012100323653A Division CN102634367A (en) | 2008-08-11 | 2008-08-11 | Double-phase hydrogenating method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102120934A (en) * | 2010-01-12 | 2011-07-13 | 中国石油化工集团公司 | Circulating liquid phase hydrogenation method |
| CN102358847A (en) * | 2011-09-16 | 2012-02-22 | 中国海洋石油总公司 | Method for producing clean diesel by full liquid phase hydrogenation |
| CN103965953A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Distillate oil two-phase hydrogenation reactor and hydrogenation process |
| US8926826B2 (en) | 2011-04-28 | 2015-01-06 | E I Du Pont De Nemours And Company | Liquid-full hydroprocessing to improve sulfur removal using one or more liquid recycle streams |
| CN104321411A (en) * | 2012-05-25 | 2015-01-28 | 纳幕尔杜邦公司 | Process for direct hydrogen injection in liquid full hydroprocessing reactors |
| CN107400534A (en) * | 2016-05-20 | 2017-11-28 | 中石化洛阳工程有限公司 | A kind of Clean Fuel Production method |
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| AU2003200780B2 (en) * | 1997-06-24 | 2006-02-23 | E.I. Du Pont De Nemour And Company | Two phase hydroprocessing |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120934A (en) * | 2010-01-12 | 2011-07-13 | 中国石油化工集团公司 | Circulating liquid phase hydrogenation method |
| CN102120934B (en) * | 2010-01-12 | 2014-01-15 | 中国石油化工集团公司 | Circulating liquid phase hydrogenation method |
| US8926826B2 (en) | 2011-04-28 | 2015-01-06 | E I Du Pont De Nemours And Company | Liquid-full hydroprocessing to improve sulfur removal using one or more liquid recycle streams |
| CN102358847A (en) * | 2011-09-16 | 2012-02-22 | 中国海洋石油总公司 | Method for producing clean diesel by full liquid phase hydrogenation |
| CN102358847B (en) * | 2011-09-16 | 2014-05-07 | 中国海洋石油总公司 | Method for producing clean diesel by full liquid phase hydrogenation |
| CN104321411A (en) * | 2012-05-25 | 2015-01-28 | 纳幕尔杜邦公司 | Process for direct hydrogen injection in liquid full hydroprocessing reactors |
| CN104321411B (en) * | 2012-05-25 | 2016-08-24 | 纳幕尔杜邦公司 | The method being directly injected into hydrogen in full liquid hydrotreating reactor |
| CN103965953A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Distillate oil two-phase hydrogenation reactor and hydrogenation process |
| WO2014117310A1 (en) * | 2013-01-30 | 2014-08-07 | 中国石油天然气股份有限公司 | Distillate two-phase hydrogenation reactor and hydrogenation process method |
| CN103965953B (en) * | 2013-01-30 | 2015-07-22 | 中国石油天然气股份有限公司 | Distillate oil two-phase hydrogenation reactor and hydrogenation process |
| US9534178B2 (en) | 2013-01-30 | 2017-01-03 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
| CN107400534A (en) * | 2016-05-20 | 2017-11-28 | 中石化洛阳工程有限公司 | A kind of Clean Fuel Production method |
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Address after: 100029 Beijing City, Chaoyang District Hui Street No. 6 Applicant after: China Petrochemical Group Corp. Co-applicant after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100029 Beijing City, Chaoyang District Hui Street No. 6 Applicant before: China Petrochemical Group Corp. Co-applicant before: Luoyang Petrochemical Engineering Co., China Petrochemical Group |
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Application publication date: 20090107 |