CN102732299A - Hydrocarbon oil two-phase hydrogenation method - Google Patents
Hydrocarbon oil two-phase hydrogenation method Download PDFInfo
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- CN102732299A CN102732299A CN2011100899451A CN201110089945A CN102732299A CN 102732299 A CN102732299 A CN 102732299A CN 2011100899451 A CN2011100899451 A CN 2011100899451A CN 201110089945 A CN201110089945 A CN 201110089945A CN 102732299 A CN102732299 A CN 102732299A
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Abstract
The invention discloses a hydrocarbon oil two-phase hydrogenation method. According to the invention, a mixer is arranged on the top of a hydrogenation reactor, a cycle oil tube is arranged in the hydrogenation reactor, hydrogen is mixed with fresh raw oil and cycle oil in the mixer to form a mixture flow, the mixture flow contacts with a catalyst and is hydrogenated, parts of the resulting reaction effluent are used as the cycle oil, and the other parts of the reaction effluent are separated. The cycle oil is cycled in the hydrogenation reactor through the cycle oil tube, one end of the cycle oil tube is connected with the mixer, and the other end of the cycle oil tube is connected with the outlet of the hydrogenation reactor through a cycle oil pump. The method which allows the mixer and the cycle oil tube to be arranged in the hydrogenation reactor has the advantages of simple structure, substantial space saving, and investment reduction.
Description
Technical field
The present invention relates to the hydrocarbon oil hydrogenation technology, particularly liquid-phase hydrogenatin technology.
Background technology
The sustainable development of world economy and the increasingly stringent of environmental regulation need to produce a large amount of light clean fuels at present, and these all require existing oil Refining Technologies is improved, and produce satisfactory product with minimum cost.Along with the worsening shortages of crude resources and heaviness, poor qualityization development, catalytic cracking and coking become the important means of producing the light Fuel product, but the quality product that these two kinds of technologies obtain generally is difficult to the quality index requirement that reaches strict.In the light Fuel quality product system; Sulphur content is most important index; How to reduce sulphur content in the petroleum products and be one of most significant problems that current petroleum chemical industry faces, the cetane value of diesel product receives publicity always in addition, and its specification requirement is also more and more stricter.At present, be that the main purpose hydrogenation technique has obtained widespread use in Clean Fuel Production with desulfurization and upgrading.
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 through 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 drum 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 raw oil to take away the heat that reaction produces through beds; And the hydrogen of actual needs (chemical hydrogen consumption) is fewer in hydrogenation process, does not participate in the hydrogen of reaction, is recycled to hydrogenator and continues 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 unifining and hydrocracking reaction on the thermodynamics, suppresses to generate the condensation reaction of coke.
The hydrogen of not participating in reaction is elevated to the required pressure of reaction through circulating hydrogen compressor with its pressure and delivers to reactor drum continuation participation hydrogenation reaction through separator and liquid phase separation and after removing impurity.The hydrogen pressurize that hydrogenation reaction will not be participated in the effect of circulating hydrogen compressor 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 raw oil is generally 50～2000: 1, so the hydrogenator design is bigger; And the actual raw oil that reacts of participating in is relevant with liquid hourly space velocity; Air speed has reflected the processing power of device, hope in the industry to adopt bigger air speed operation, but air speed receives 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, and investment and process cost are all higher, in order to cancel circulating hydrogen compressor; People begin to consider to utilize hydrogen supply agent for the hydrocarbon oil hydrogenation process hydrogen source to be provided; 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 for heavy-oil hydrogenation the heavy-oil hydrogenation cracking method of hydrogen source to be provided, 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, and CN200810141293.X has proposed a kind of two-phase hydrogenation method, has cancelled recycle hydrogen and circulating hydrogen compressor; Hydrogen is mixed the formation mixture flow with fresh feed oil and part turning oil in the presence of solvent or thinner; With after the gas delivery, liquid phase entering reactor drum contacts with catalyzer and reacts mixture flow in separating tank, and a reaction effluent part is as turning oil; Another part degass and obtains product after liquid/gas separator separates; But plant investment is still higher, the turning oil HTHP, and the equipment pipe investment is bigger.
Summary of the invention
The object of the present invention is to provide a kind of two-phase hydrogenation method for hydrocarbon oil, this method is arranged on mixing tank and circulating pipe in the hydrogenator, and is simple in structure, practiced thrift the space greatly, reduced investment.
A kind of two-phase hydrogenation method for hydrocarbon oil of the present invention, hydrogen and fresh feed oil mixes the formation mixture flow with turning oil in mixing tank, contact with catalyzer after the mixture flow and carry out hydrogenation reaction, and a reaction effluent part is as turning oil, and another part separates.It is characterized in that: mixing tank is arranged on the hydrogenator top, and circulating pipe is arranged on hydrogenator inside, and turning oil circulates in hydrogenator through circulating pipe.Circulating pipe one end links to each other with mixing tank, and the other end links to each other with the hydrogenator outlet through circulating oil pump.
Circulating pipe is arranged on inside reactor; The mixture flow that forms gets into reactor bed, and after reactor head was isolated little of gas, liquid contacted with catalyzer and reacts; Gas is discharged from reactor head; A reaction effluent part is squeezed into circulating pipe by circulating oil pump and is circulated as turning oil, and another part gets into light pressure separator after the dropping valve step-down carries out gas-liquid separation and obtain product.
A kind of two-phase hydrogenation method for hydrocarbon oil of the present invention, a reaction effluent part are squeezed into circulating pipe by circulating oil pump and are circulated as turning oil.Circulating pipe is arranged in the reactor drum, and turning oil and hydrogen get into mixing tank from bottom to top.
A kind of two-phase hydrogenation method for hydrocarbon oil of the present invention, reaction effluent another part get into light pressure separator and carry out gas-liquid separation after the dropping valve step-down.
A kind of two-phase hydrogenation method for hydrocarbon oil according to the invention removes a kind of pollutent in its sulphur, nitrogen, oxygen, the metallic impurity at least, and saturated aromatic hydrocarbons, changes the hydrocarbon ils molecular structure.
A kind of two-phase hydrogenation method for hydrocarbon oil catalyst reactor according to the invention can be single bed or the filling of many beds, and the reactor head end socket is provided with mixing tank, makes fresh feed, turning oil and hydrogen mixed dissolution; Behind the discharge section gas; Molten hydrogen mixture entering beds contacts with catalyzer and reacts, and concerning many bed reactors, also is provided with mixing tank between bed; The elute entering bed mixing tank that comes out from first section beds dissolves wherein the hydrogen that injects between bed; Behind the discharge section gas, liquid gets into second section beds, contacts with catalyzer to proceed reaction; The rest may be inferred; Reaction effluent is drawn from reactor outlet, and the partial reaction elute turns back in the reactor head mixing tank through circulating pipe as turning oil and mixes with fresh feed, and another part gets into light pressure separator and carries out gas-liquid separation after the dropping valve step-down.
The fresh feed oil of a kind of two-phase hydrogenation method for hydrocarbon oil according to the invention is hydrocarbon ils or hydrocarbon ils distillate, like petroleum fractions, distillate, diesel oil, deasphalted oil, residual oil, lubricating oil, liquefied coal coil and shale oil or its product.
A kind of two-phase hydrogenation method for hydrocarbon oil according to the invention utilizes mixing tank that hydrogen is dissolved in the mixing raw material oil and for the hydrogenation reaction of hydrocarbon ils hydrogen source is provided.
A kind of two-phase hydrogenation method for hydrocarbon oil according to the invention can be used for straight run oil, 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 hydrogen cracking transformation, be used to produce ULSD, be used for the aftertreatment of raw materials pretreatment or product.
A kind of two-phase hydrogenation method for hydrocarbon oil 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) reduced reactor volume;
9) for producing ultra-low-sulphur diesel, improvement expenses is very low.
Compare the present invention with the prior art of traditional trickle bed hydrogenation: but desulfurization 90%～98%, and the hydrogen consumption only is 70%～90% of a trickle bed hydrogenator, the total consumption of catalyzer is merely 15%～30%.
Description of drawings
Fig. 1 is a kind of two-phase hydrogenation method for hydrocarbon oil schema of the present invention.
Fig. 2 is the another kind of embodiment schema of a kind of two-phase hydrogenation method for hydrocarbon oil of the present invention.
Among the figure: 1. fresh feed, 2. mixing tank, 3. reactor head gas, 4. beds; 5. hydrogenator, 6. hydrogen make-up, 7. hydrogen make-up between bed, 8. gas between bed; 9. reaction effluent, 10. circulating oil pump, 11. turning oils, 12. circulating pipes; 13. light pressure separator, 14. light pressure separator gases, 15. light pressure separator liquid
Embodiment
Shown in Figure 1 is first kind of embodiment of the present invention.Reactor drum shown in Fig. 1 is a two-stage catalytic agent bed.Form by equipment such as mixing tank 2, hydrogenator 5, circulating oil pump 10, light pressure separators 13.
Fresh feed oil 1 forms mixture flow with hydrogen 6 and turning oil 11 mixed dissolution in mixing tank 2; After reactor head is isolated gas 3; Mixture flow gets into first section beds of reactor drum 4 and catalyzer contact reacts from reactor head, also is provided with mixing tank between bed, and the elute entering bed mixing tank that comes out from first section beds dissolves wherein the hydrogen that injects between bed; Behind the discharge section gas; Liquid gets into second section beds, contacts with catalyzer to proceed reaction, reaction effluent 9 separated into two parts that come out from reactor drum 5 bottoms; A part is squeezed into circulating pipe 12 as turning oil 11 by circulating oil pump 10 and is turned back in the reactor head mixing tank with hydrogen and fresh feed are oily and mix; Another part gets into light pressure separator 13 and carries out gas-liquid separation after the dropping valve step-down, the gas 14 that light pressure separator obtains after separating gets into the fractionation part with liquid 15, obtains product after the separation and goes out device.
Shown in Figure 2 is another embodiment of the present invention; Just be that with the difference of first kind of embodiment circulating pipe 12 also links to each other with catalyst bed interlayer mixing tank 2; Reaction effluent 9 separated into two parts that come out from reactor drum 5 bottoms; A part is squeezed into circulating pipe 12 as turning oil 11 by circulating oil pump 10 and is turned back to simultaneously in reactor head mixing tank and the catalyst bed interlayer mixing tank, mixes with hydrogen and fresh feed oil, and another part gets into light pressure separator 13 and carries out gas-liquid separation after the dropping valve step-down; The gas 14 that light pressure separator obtains after separating gets into the fractionation part with liquid 15, obtains product after the separation and goes out device.
Claims (7)
1. two-phase hydrogenation method for hydrocarbon oil; Hydrogen and fresh feed oil (1) carries out hydrogenation reaction with contacting with catalyzer turning oil (11) mixes the formation mixture flow in mixing tank (2) after in hydrogenator; A reaction effluent part is as turning oil (11); Another part separates, and it is characterized in that: mixing tank (2) is arranged in the reactor head, and circulating pipe (12) is arranged on inside reactor; Circulating pipe (12) one ends link to each other with mixing tank (2), and the other end links to each other with reactor outlet (9) through circulating oil pump (10).
2. a kind of two-phase hydrogenation method for hydrocarbon oil according to claim 1 is characterized in that: catalyst reactor is single bed or the filling of many beds.
3. a kind of two-phase hydrogenation method for hydrocarbon oil according to claim 2 is characterized in that: between reactor catalyst bed (4), be provided with mixing tank (2).
4. a kind of two-phase hydrogenation method for hydrocarbon oil according to claim 3 is characterized in that: said turning oil gets into catalyst bed interlayer mixing tank (2) through circulating pipe (12).
5. a kind of two-phase hydrogenation method for hydrocarbon oil according to claim 1 is characterized in that: said raw oil is the distillate of hydrocarbon ils or hydrocarbon ils.
6. a kind of two-phase hydrogenation method for hydrocarbon oil according to claim 1 is characterized in that: said mixing tank (2) is arranged in the reactor head end socket.
7. a kind of two-phase hydrogenation method for hydrocarbon oil according to claim 1 is characterized in that: said mixture flow is after reactor head is isolated little of gas, and liquid contacts with catalyzer and reacts, and gas is discharged from reactor head.
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| CN2011100899451A CN102732299A (en) | 2011-04-12 | 2011-04-12 | Hydrocarbon oil two-phase hydrogenation method |
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| CN2011100899451A CN102732299A (en) | 2011-04-12 | 2011-04-12 | Hydrocarbon oil two-phase hydrogenation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992816A (en) * | 2013-02-19 | 2014-08-20 | 中石化洛阳工程有限公司 | Gas phase-liquid phase hydrogenation combined process and device |
| CN104178206A (en) * | 2013-05-22 | 2014-12-03 | 中石化洛阳工程有限公司 | Liquid-solid two-phase hydrogenation process and device thereof |
| US20150361357A1 (en) * | 2013-01-30 | 2015-12-17 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
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| EP1394237A1 (en) * | 1997-06-24 | 2004-03-03 | Process Dynamics, Inc. | Two phase hydroprocessing |
| CN201644076U (en) * | 2010-04-13 | 2010-11-24 | 中国石油化工集团公司 | Liquid-phase hydrogenated reactor |
| CN101992047A (en) * | 2009-08-11 | 2011-03-30 | 中国石化集团洛阳石油化工工程公司 | Reactor and application thereof to hydrocarbon oil two-phase hydrogenation |
| CN101992048A (en) * | 2009-08-11 | 2011-03-30 | 中国石化集团洛阳石油化工工程公司 | Reactor and application thereof to hydrocarbon oil liquid-solid two-phase hydrogenation |
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2011
- 2011-04-12 CN CN2011100899451A patent/CN102732299A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1394237A1 (en) * | 1997-06-24 | 2004-03-03 | Process Dynamics, Inc. | Two phase hydroprocessing |
| CN101992047A (en) * | 2009-08-11 | 2011-03-30 | 中国石化集团洛阳石油化工工程公司 | Reactor and application thereof to hydrocarbon oil two-phase hydrogenation |
| CN101992048A (en) * | 2009-08-11 | 2011-03-30 | 中国石化集团洛阳石油化工工程公司 | Reactor and application thereof to hydrocarbon oil liquid-solid two-phase hydrogenation |
| CN201644076U (en) * | 2010-04-13 | 2010-11-24 | 中国石油化工集团公司 | Liquid-phase hydrogenated reactor |
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| 徐春明等: "《石油炼制工程》", 30 September 2009, 石油工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150361357A1 (en) * | 2013-01-30 | 2015-12-17 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
| US9534178B2 (en) * | 2013-01-30 | 2017-01-03 | Petrochina Company Limited | Distillate two-phase hydrogenation reactor and hydrogenation method |
| CN103992816A (en) * | 2013-02-19 | 2014-08-20 | 中石化洛阳工程有限公司 | Gas phase-liquid phase hydrogenation combined process and device |
| CN103992816B (en) * | 2013-02-19 | 2016-05-11 | 中石化洛阳工程有限公司 | A kind of gas phase and liquid-phase hydrogenatin group technology and device |
| CN104178206A (en) * | 2013-05-22 | 2014-12-03 | 中石化洛阳工程有限公司 | Liquid-solid two-phase hydrogenation process and device thereof |
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Application publication date: 20121017 |