CN104178217A - Liquid phase hydrogenation method and reactor thereof - Google Patents
Liquid phase hydrogenation method and reactor thereof Download PDFInfo
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- CN104178217A CN104178217A CN201310206899.8A CN201310206899A CN104178217A CN 104178217 A CN104178217 A CN 104178217A CN 201310206899 A CN201310206899 A CN 201310206899A CN 104178217 A CN104178217 A CN 104178217A
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Abstract
The invention discloses a liquid phase hydrogenation method and a reactor thereof. The method is as below: stripping feedstock oil by a stripping medium in a stripping distributor of a hydrogenation reactor; discharging exhaust gas from the stripping out of the reactor; introducing the feedstock oil after stripping into a mixer and mixing the feedstock oil with hydrogen; subjecting the feedstock oil with hydrogen dissolved therein to a hydrogenation reaction in a catalyst bed layer; and discharging the reaction products out of the reactor. The invention also discloses a liquid phase hydrogenation reactor, which comprises a reactor tube, a mixer, a stripping distributor, a catalyst bed layer, a reactor outlet and a reactor inlet. The invention has the advantages of flexible operation and low investment.
Description
Technical field
The present invention relates to hydrocarbon oil refining field, particularly a kind of liquid phase hydrogenating method and reactor thereof.
Background technology
The sustainable development of world economy at present and the increasingly stringent of environmental regulation, need to produce a large amount of light clean fuels, and these all require existing oil Refining Technologies to improve, and produce satisfactory product with minimum cost.Along with worsening shortages and heaviness, the in poor quality of crude resources develop, catalytic cracking and coking become the important means of producing light Fuel product, but the quality product that these two kinds of techniques obtain is generally difficult to the product quality indicator requirement that reaches strict.In light Fuel quality product system, sulphur content is most important index, because fuel medium sulphide content can be transformed into SO in its combustion processes
x, SO
xbe to cause topsoil, form the arch-criminal of acid rain, more seriously SO
xwith the synergistic effect of other pollutents, form secondary pollution, how to reduce sulphur content in 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 applied widely in Clean Fuel Production taking desulfurization and upgrading as main purpose hydrogenation technique.
Hydrogen addition technology is to improve one of conventional technology of hydrocarbon ils quality, along with global crude oil market supply is tending towards the crude oil of higher sulfur content, refinery need process the hydrocarbon ils inferior that sulfur-bearing is higher, 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 meet code requirement.The hydrogen that in fact hydrocarbon oil hydrogenation process participates in reaction only has the hydrogen for chemical hydrogen consumption, and traditional trickle-bed reactor hydrogen addition technology need to have excessive hydrogen to exist, and maintains the exess of H2 gas and need to use circulating hydrogen compressor.
In traditional hydrogenation technique, hydrogen need to be delivered to liquid phase from gas phase, and then co-absorbed, on the surface of catalyzer, is reacted under the effect of catalyst active center.Because hydrogenation reaction is a strong exothermal reaction, conventionally utilize a large amount of hydrogen and reaction feed oil to take away by beds the heat that reaction produces, and the hydrogen of actual needs is fewer in hydrogenation process, the hydrogen that major part is not participated in reaction is recycled to hydrogenator continuation participation reaction; It is the hydrogen dividing potential drop that maintains hydrocarbon oil hydrogenation reaction that tradition hydrocarbon oil hydrogenation technology adopts another major cause of excessive hydrogen, maintains higher hydrogen and divides to be pressed on thermodynamics and be conducive to hydrofining and hydrocracking reaction, suppresses to generate the condensation reaction of coke.
The hydrogen of not participating in reaction is by separator and liquid phase separation and remove after impurity, by circulating hydrogen compressor, its pressure is elevated to the required pressure of reaction and delivers to reactor and continue to participate in hydrogenation reaction.The effect of circulating hydrogen compressor is exactly the hydrogen that does not participate in hydrogenation reaction to be improved to pressure it is recycled, and therefore circulating hydrogen compressor becomes requisite equipment in existing hydrogen addition technology, is called in the industry the heart of hydrogenation unit.
In traditional fixed bed hydrogenation reactor, be gas, liquid, solid three-phase and deposit, gas phase is the steam of hydrogen and hydrocarbon raw material, and liquid phase is the hydrocarbon raw material of not vaporizing, and solid phase is 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, the actual reaction feed of reacting of participating in is oily relevant with liquid hourly space velocity, and air speed has reflected the processing power of device, and industrial hope adopts larger air speed operation, but air speed is subject to the restriction of speed of response.Air speed is unusual at 0.5～10h according to catalyst activity, feedstock property, reaction depth
-1between fluctuation.The unifining process of industrial application can improve olefin saturated rate, hydrogenating desulfurization rate and hydrodenitrification rate at certain temperature of reaction condition decline low-speed at present.
The object that adopts the exess of H2 gas is strengthen mass transfer and take away the amount of heat producing 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 start to consider to utilize hydrogen supply agent to provide hydrogen source for hydrocarbon oil hydrogenation process, USP4698147 discloses and has utilized hydrogen supply agent to reduce the residence time, and after reaction, hydrogen supply agent utilizes hydrogen to regenerate, and after regeneration, recycles.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, CN200810141293.X has proposed a kind of two-phase hydrogenation method, recycle hydrogen and circulating hydrogen compressor are cancelled, hydrogen is mixed to form to mixture flow with fresh reactant feed oil and part turning oil under the existence of solvent or thinner, mixture flow in separating tank by after gas delivery, liquid phase enters reactor and contacts and react with catalyzer, a reaction effluent part is as turning oil, another part degass after liquid/gas separator separates and obtains product, but the inner member of liquid phase hydrogenation reactor is not yet mentioned, and liquid phase hydrogenation reactor inner member is the core of reactor, determining mass transfer and the speed of response of hydrogenation reaction, and the efficiency of hydrogenation.
Summary of the invention
The object of the present invention is to provide a kind of liquid phase hydrogenating method, reaction feed oil is carried out contacting with catalyzer and carrying out hydrogenation reaction after stripping mixes with hydrogen again.Remove the hydrogen sulfide carrying in reaction feed oil, the restraining effect of removal of hydrogen sulfide to deep desulfuration reaction.
The present invention also provides a kind of liquid phase hydrogenation reactor, be provided with vapour-liquid contact separation tower tray or filler on catalyzer top, stripping sparger is established in separation tray or filler below, the hydrogen sulfide carrying for removing out reaction feed oil, the restraining effect of removal of hydrogen sulfide to deep desulfuration reaction.This reactor liquid-phase hydrogenatin is simple in structure, promotes reaction, greatly improves the efficiency of hydrogenation.
A kind of liquid phase hydrogenating method of the present invention, comprising:
Reaction feed oil enters the stripper of hydrogenator after stripping medium stripping, the waste gas that stripping goes out is discharged outside reactor, reaction feed oil after stripping enters mixing dissolver to be mixed with hydrogen, the reaction feed oil of molten hydrogen enters beds and carries out hydrogenation reaction, and reaction product is discharged reactor.
Described a kind of liquid phase hydrogenating method, is characterized in that: stripping medium is hydrogen.
Described a kind of liquid phase hydrogenating method, is characterized in that: liquid reacting product is discharged reactor from reactor lower part, and gaseous product is discharged reactor from reactor catalyst bed top.
Described a kind of liquid phase hydrogenating method, is characterized in that: among reactor catalyst bed dipping liquid phase.
Described a kind of liquid phase hydrogenating method, is characterized in that: at least remove in reaction feed oil a kind of pollutent in sulphur, nitrogen, oxygen, metallic impurity, and saturated aromatic hydrocarbons, change hydrocarbon ils molecular structure.
The liquid reacting product part that described liquid reacting product is discharged reactor from reactor lower part turns back to reactor inlet as turning oil, and another part is as product.
The present invention proposes a kind of liquid phase hydrogenation reactor, comprise reactor shell, mixing dissolver, stripping sparger, beds, reactor outlet, reactor inlet, be characterised in that: mixing dissolver, stripping sparger and catalyzer mixed bed layer are arranged in reactor shell.
Described mixing dissolver is arranged on stripping sparger below, and the top of beds, in the time that beds is two or more, also arranges mixing dissolver between beds.
Described mixing dissolver is provided with mixing oil opening for feed and hydrogen inlet, and mixing dissolver also has molten hydrogen mixture and pneumatic outlet, and the molten hydrogen mixture outlet of mixing dissolver is inserted in reactor liquid phase.
Described reactor inlet is arranged on reactor top, particularly top or upper side, and reactor outlet is arranged on reactor lower part, particularly in bottom or lower side.
Described a kind of liquid phase hydrogenation reactor, is characterized in that: reactor head is provided with gas discharge outlet.
Described a kind of liquid phase hydrogenation reactor, is characterized in that: in reactor, be provided with liquid distributor.
Described a kind of liquid phase hydrogenation reactor, is characterized in that: reactor top is provided with separation tray or filler.
Described a kind of liquid phase hydrogenation reactor, is characterized in that: in reactor, be provided with gas distributor.
Described a kind of liquid phase hydrogenation reactor, is characterized in that: mixing dissolver is provided with mixing oil opening for feed, hydrogen inlet and discharge port.
Described a kind of liquid phase hydrogenation reactor, is characterized in that: the molten hydrogen mixture outlet of mixing dissolver is immersed in reactor liquid phase.
In described a kind of liquid phase hydrogenation reactor, be provided with segregation section, can remove most of hydrogen sulfide and rare gas element in charging, be conducive to deep desulfuration reaction.Reactor catalyst can be single bed or the filling of many beds, in reactor, establish mixing dissolver, make reaction feed and the abundant mixed dissolution of hydrogen after stripping, after discharge section gas, molten hydrogen mixture enters beds and contacts and react with catalyzer, concerning many bed reactors, between bed, be also provided with mixing dissolver, entering bed mixing dissolver from first paragraph beds effluent out dissolves wherein the hydrogen injecting between bed, after discharge section gas, liquid enters second segment beds, contact with catalyzer and proceed reaction, the rest may be inferred, reaction effluent is drawn from reactor outlet.
Reaction feed oil of the present invention is the mixture of fresh feed and reacted liquid product, or hydrocarbon ils or hydrocarbon ils distillate, as petroleum fractions, distillate, diesel oil, deasphalted oil, residual oil, lubricating oil, liquefied coal coil and shale oil or its product.
The medium that a kind of liquid phase hydrogenation reactor of the present invention utilizes segregation section to remove to be unfavorable for reaction to carry out.
A kind of liquid phase hydrogenation reactor of the present invention utilizes mixing dissolver to make hydrogen be dissolved in the hydrogenation reaction for hydrocarbon ils in hybrid reaction feed oil hydrogen source is provided.
A kind of liquid phase hydrogenation reactor of the present invention can be used for straight run oil, FCC turning oil, coker gas oil CGO, or it mixes kerosene and diesel oil hydrogenation processing, also can be used for FCC raw materials pretreatment, for new device and mild hydrocracking transformation, for the production of ULSD, for the aftertreatment of raw materials pretreatment or product.
A kind of liquid phase hydrogenating method of the present invention and reactor thereof have following advantage:
1) catalyst levels is few;
2) hydrogen loss is less;
3) lower process cost;
4) liquid yield is higher;
5) larger flexibility of operation;
6) product of production super low sulfur nitrogen content;
7) lower investment;
8) reduced reactor volume;
9) for plant modification to produce for ultra-low-sulphur diesel, improvement expenses is very low.
Compared with the prior art of trickle bed hydrogenator, the present invention: can desulfurization 98%～99%, and hydrogen consumption is only 70%～90% of trickle bed hydrogenator.
Brief description of the drawings
Fig. 1 is a kind of single bed liquid phase hydrogenation reactor schema of the present invention,
Fig. 2 is a kind of many beds liquid phase hydrogenation reactor schema.
In figure: 1. reaction feed oil, 2. stripping medium, 3. waste gas, 4. variable valve, 5. reactant gases product, 6. liquid distributor, 7. stripping stage, 8. gas distributor, 9. mixing dissolver, 10. variable valve, 11. beds, 12. reactor shells, 13. liquid phase reaction things, 14. turning oils.
Embodiment
As shown in Figure 1, reaction feed oil enters the liquid phase distributor of hydrogenator, then at stripper after stripping medium hydrogen stripped, the H of hydrogenation reaction that what stripping went out affect
2s, NH
3discharge outside reactor Deng waste gas, reaction feed oil after stripping enters mixing dissolver to be mixed with hydrogen, the reaction feed oil of molten hydrogen enters beds and carries out hydrogenation reaction, product liquid in reaction product is discharged reactor from reactor lower part, gaseous product is discharged reactor from reactor catalyst bed top, product liquid can be partly as turning oil, part goes out device as product, reactor catalyst bed is immersed among liquid phase, remove less sulphur in reaction feed oil, nitrogen, oxygen, a kind of pollutent in metallic impurity, and saturated aromatic hydrocarbons, change hydrocarbon ils molecular structure.
As shown in Figure 2, in reactor shell, be provided with a segregation section and two-stage catalytic agent bed, reaction feed oil enters reactor segregation section and contacts with hydrogen and carry out stripping, stripping goes out waste gas and is discharged by reactor head, reaction feed oil after gas mixes in mixing dissolver with hydrogen, hydrogen is dissolved in reaction feed oil, the reaction feed oil of molten hydrogen enters reactor catalyst bed and carries out hydrogenation reaction, maintaining beds is immersed in reaction feed oil, catalyst bed interlayer is provided with bed mixing dissolver, hydrogen is dissolved in oil in bed mixing dissolver, between bed after Exhaust Gas, liquid enter the second bed contact with catalyzer proceed reaction, from reactor lower part reaction effluent out separates, obtain product and go out device.
Claims (10)
1. a liquid phase hydrogenating method, reaction feed oil enters the stripper of hydrogenator after stripping medium stripping, the waste gas that stripping goes out is discharged outside reactor, reaction feed oil after stripping enters mixing tank to be mixed with hydrogen, the reaction feed oil of molten hydrogen enters beds and carries out hydrogenation reaction, and reaction product is discharged reactor.
2. according to a kind of liquid phase hydrogenating method claimed in claim 1, it is characterized in that: stripping medium is hydrogen.
3. according to a kind of liquid phase hydrogenating method claimed in claim 1, it is characterized in that: in reaction product, product liquid is discharged reactor from reactor lower part, gaseous product is discharged reactor from reactor catalyst bed top.
4. according to a kind of liquid phase hydrogenating method claimed in claim 1, it is characterized in that: among reactor catalyst bed dipping liquid phase.
5. according to a kind of liquid phase hydrogenating method claimed in claim 1, it is characterized in that: at least remove in reaction feed oil a kind of pollutent in sulphur, nitrogen, oxygen, metallic impurity, and saturated aromatic hydrocarbons, change hydrocarbon ils molecular structure.
6. according to a kind of liquid phase hydrogenating method claimed in claim 1, it is characterized in that: the liquid reacting product part that described liquid reacting product is discharged reactor from reactor lower part turns back to reactor inlet as turning oil, and another part is as product.
7. a liquid phase hydrogenation reactor, comprises reactor shell, mixing tank, stripping sparger, beds, reactor outlet, reactor inlet, is characterised in that: mixing tank, stripping sparger and catalyzer mixed bed layer are arranged in reactor shell.
8. according to a kind of liquid phase hydrogenation reactor claimed in claim 7, it is characterized in that: described mixing tank is arranged on stripping sparger below, the top of beds, in the time that beds is two or more, also arranges mixing tank between beds.
9. according to a kind of liquid phase hydrogenation reactor claimed in claim 7, it is characterized in that: described mixing tank is provided with mixing oil opening for feed and hydrogen inlet, mixing tank also has molten hydrogen mixture and pneumatic outlet, and the molten hydrogen mixture outlet of mixing tank is inserted in reactor liquid phase.
10. according to a kind of liquid phase hydrogenation reactor claimed in claim 7, it is characterized in that: described reactor inlet is arranged on reactor top, particularly top or upper side, reactor outlet is arranged on reactor lower part, particularly in bottom or lower side.It is characterized in that: reactor head is provided with gas discharge outlet, in reactor, be provided with liquid distributor and gas distributor, reactor top is provided with separation tray or filler.It is characterized in that: mixing tank is provided with mixing oil opening for feed, hydrogen inlet and discharge port.It is characterized in that: the molten hydrogen mixture outlet of mixing tank is immersed in reactor liquid phase.
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| CN201310206899.8A CN104178217A (en) | 2013-05-22 | 2013-05-22 | Liquid phase hydrogenation method and reactor thereof |
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| CN201310206899.8A CN104178217A (en) | 2013-05-22 | 2013-05-22 | Liquid phase hydrogenation method and reactor thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203599A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | A kind of method of synthetic oil Porous deproteinized bone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428686B1 (en) * | 1997-06-24 | 2002-08-06 | Process Dynamics, Inc. | Two phase hydroprocessing |
| 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 |
| CN102029128A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Hydrotreating method of product circulation |
| CN102660321A (en) * | 2012-05-08 | 2012-09-12 | 南京化工职业技术学院 | Diesel hydrogenation device and production process |
-
2013
- 2013-05-22 CN CN201310206899.8A patent/CN104178217A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428686B1 (en) * | 1997-06-24 | 2002-08-06 | Process Dynamics, Inc. | Two phase hydroprocessing |
| 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 |
| CN102029128A (en) * | 2009-09-28 | 2011-04-27 | 中国石油化工股份有限公司 | Hydrotreating method of product circulation |
| CN102660321A (en) * | 2012-05-08 | 2012-09-12 | 南京化工职业技术学院 | Diesel hydrogenation device and production process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108203599A (en) * | 2016-12-16 | 2018-06-26 | 中国石油天然气股份有限公司 | A kind of method of synthetic oil Porous deproteinized bone |
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Application publication date: 20141203 |