CN101275083A - Hydrogenation method for hydrocarbon oils - Google Patents
Hydrogenation method for hydrocarbon oils Download PDFInfo
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- CN101275083A CN101275083A CNA2008100498134A CN200810049813A CN101275083A CN 101275083 A CN101275083 A CN 101275083A CN A2008100498134 A CNA2008100498134 A CN A2008100498134A CN 200810049813 A CN200810049813 A CN 200810049813A CN 101275083 A CN101275083 A CN 101275083A
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Abstract
The present invention provides a method of hydrocarbon oil hydrogenation, the method cancels recycle hydrogen and recycle hydrogen compressor, hydrogen is mixed with fresh raw oil and partial cycle oil in the presence of solvent or thinner, the separated gas enters in the reactor, contacting reaction with the catalyst, another part cycle oil is mixed with hydrogen, entering between catalyst beds in one path or several directions, the reaction effluent is extracted from the bottom of the reactor to process separation, cycling use the separated solvent or the thinner, the liquid product is used as product and cycle oil, the solubility of the hydrogen in the solvent or the thinner is higher than the solubility of the hydrogen in the mixer of the fresh raw material oil and the solvent or the thinner.
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 is fewer in hydrogenation process, it is chemical hydrogen consumption, 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 hydrogenation method for hydrocarbon oils, 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 hydrogenation method for hydrocarbon oils of the present invention is: hydrogen mixes the formation mixture flow with fresh feed oil and part or zero turning oil in the presence of solvent or thinner, mixture flow enters first section beds of reactor and catalyzer contact reacts from reactor head after isolating gas, another part or whole turning oil mix with hydrogen, 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 goes out device 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.
The another kind of hydrogenation method for hydrocarbon oils of the present invention is: fresh feed oil with in the presence of solvent or thinner, mix the formation mixture flow after part or zero turning oil mix again with hydrogen, mixture flow enters first section beds of reactor and catalyzer contact reacts from reactor head after isolating gas, another part or whole turning oil mix with hydrogen, 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 goes out device 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.
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 a kind of hydrogenation method for hydrocarbon oils 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.
A kind of hydrogenation method for hydrocarbon oils 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.
A kind of hydrogenation method for hydrocarbon oils 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.
A kind of hydrogenation method for hydrocarbon oils of the present invention: utilize the ratio of mixture of turning oil and fresh feed oil to control the temperature that mixture flow enters reactor, utilize the circulation oil mass controlling reactor temperature that enters between the beds.
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 be deposited on catalyst surface, the present invention is owing to adopt the turning oil circulation, and it is saturated that turning oil obtains many aromatic hydrocarbons through hydrogenation, has the function of hydrogen supply.
A kind of hydrogenation method for hydrocarbon oils 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.
Hydrogenation method for hydrocarbon oils 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 the present invention with the prior art of trickle bed hydrogenator: 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 hydrocarbon oil hydrogenation processing flow chart of the present invention.
Fig. 2 is the another kind of hydrocarbon oil hydrogenation processing flow chart of the present invention.
Fig. 3 is a diesel oil hydrogenation processing flow chart of the present invention.
Fig. 4 is the another kind of diesel oil hydrogenation processing flow chart of the present invention.
Among the figure: 1-fresh feed oil, 2-hydrogen, 3-first mixing tank, the 4-separating tank, 5-reactor, 6-second mixing tank, the 7-reactor feed, 8-first separator, 9-second separator, the 11-first separator waste gas, 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.
Embodiment
As shown in Figure 1, reactor shown in the figure is four sections beds.Fresh feed oil 1 mixes in first mixing tank 3 with hydrogen 2 and part or zero turning oil in the presence of solvent or 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 or whole turning oil mix with hydrogen 2 makes it saturated, saturated molten hydrogen turning oil 15 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.A part or zero 17 times first mixing tanks 3 of turning oil, another part or all turning oil 17 enter second mixing tank 6 and mix with hydrogen 2 and make it saturatedly become saturated molten hydrogen turning oil 15.
As shown in Figure 2, it is with the difference of Fig. 1: fresh feed oil 1 with in the presence of solvent or thinner 13, mix the formation mixture flow after part or zero turning oil 17 mix again with hydrogen 2.
As shown in Figure 3, reactor shown in the figure is four sections beds.Fresh feed oil 1 mixes in first mixing tank 3 with hydrogen 2 and part or zero turning oil, mixture flow enters separating tank 4, become reactor feed 7 after isolating separating tank waste gas 14, enter 5 first sections beds of reactor and catalyzer contact reacts from reactor 5 tops, another part or whole turning oil mix with hydrogen 2 makes it saturated, saturated molten hydrogen turning oil 15 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 goes out device as product, another part is as turning oil 17, a part or zero turning oil 17 loop back first mixing tank 3, another part or all turning oil 17 enter second mixing tank 6 and mix with hydrogen 2 and make it become saturated molten hydrogen turning oil 15.
Fig. 4 is with the difference of Fig. 3: fresh feed oil 1 with mix the formation mixture flow again with hydrogen 2 after part or zero turning oil 17 mix.
Claims (10)
1, a kind of hydrogenation method for hydrocarbon oils, it is characterized in that: hydrogen mixes the formation mixture flow with fresh feed oil and part or zero turning oil in the presence of solvent or thinner, mixture flow enters first section beds of reactor and catalyzer contact reacts from reactor head after isolating gas, another part or whole turning oil mix with hydrogen, 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 goes out device 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.
2, a kind of hydrogenation method for hydrocarbon oils, it is characterized in that: fresh feed oil with in the presence of solvent or thinner, mix the formation mixture flow after part or zero turning oil mix again with hydrogen, mixture flow enters first section beds of reactor and catalyzer contact reacts from reactor head after isolating gas, another part or whole turning oil mix with hydrogen, 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 goes out device 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.
3, according to the described hydrogenation method for hydrocarbon oils of claim 1, it is characterized in that: hydrogen mixes the formation mixture flow with fresh feed oil and part or zero turning oil.
4, according to the described hydrogenation method for hydrocarbon oils of claim 2, it is characterized in that: mix forming mixture flow after fresh feed oil and part or zero turning oil mix again with hydrogen.
5, according to claim 1 or 2 described hydrogenation method for hydrocarbon oils, 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.
6, according to claim 1 or 2 described hydrogenation method for hydrocarbon oils, it is characterized in that: utilize the ratio of mixture of turning oil and fresh feed oil to control the temperature that mixture flow enters reactor, utilize the circulation oil mass controlling reactor temperature that enters between the beds.
7, according to claim 1 or 2 described hydrogenation method for hydrocarbon oils, it is characterized in that: the catalyzer in the reactor divides two sections fillings at least.
8, according to claim 1 or 2 described hydrogenation method for hydrocarbon oils, it is characterized in that: fresh feed oil is the distillate of hydrocarbon ils or hydrocarbon ils.
9, according to claim 1 or 2 described hydrogenation method for hydrocarbon oils, it is characterized in that: fresh feed oil is petroleum fractions, distillate, diesel oil, deasphalted oil, residual oil, lubricating oil, liquefied coal coil, shale oil or its product.
10, according to claim 1 or 2 described hydrogenation method for hydrocarbon oils, it is characterized in that: fresh feed oil is deviate from a kind of of sulphur, nitrogen, oxygen and metallic impurity at least in hydrogenator, and saturated aromatic hydrocarbons.
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| CNA2008100498134A CN101275083A (en) | 2008-05-20 | 2008-05-20 | Hydrogenation method for hydrocarbon oils |
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| CNA2008100498134A CN101275083A (en) | 2008-05-20 | 2008-05-20 | Hydrogenation method for hydrocarbon oils |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993721A (en) * | 2009-08-25 | 2011-03-30 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method and reaction system for liquid phase cycling hydrotreatment |
| CN102039105B (en) * | 2009-10-21 | 2012-06-27 | 中国石油化工股份有限公司 | Gas-liquid reverse flow reactor and gas-liquid reverse flow hydrogenation process method |
| CN102039104B (en) * | 2009-10-21 | 2012-08-29 | 中国石油化工股份有限公司 | Reactor and liquid-phase hydrogenation processing method |
| CN103131461A (en) * | 2013-03-11 | 2013-06-05 | 中国寰球工程公司辽宁分公司 | Hydrocarbon oil hydrogenation method |
| CN104099127A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Distillate oil hydrotreatment process |
-
2008
- 2008-05-20 CN CNA2008100498134A patent/CN101275083A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993721A (en) * | 2009-08-25 | 2011-03-30 | 中国石油化工股份有限公司抚顺石油化工研究院 | Method and reaction system for liquid phase cycling hydrotreatment |
| CN101993721B (en) * | 2009-08-25 | 2016-04-13 | 中国石油化工股份有限公司 | Method of liquid phase circulation hydrotreatment and reactive system |
| CN102039105B (en) * | 2009-10-21 | 2012-06-27 | 中国石油化工股份有限公司 | Gas-liquid reverse flow reactor and gas-liquid reverse flow hydrogenation process method |
| CN102039104B (en) * | 2009-10-21 | 2012-08-29 | 中国石油化工股份有限公司 | Reactor and liquid-phase hydrogenation processing method |
| CN103131461A (en) * | 2013-03-11 | 2013-06-05 | 中国寰球工程公司辽宁分公司 | Hydrocarbon oil hydrogenation method |
| CN104099127A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Distillate oil hydrotreatment process |
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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: 20081001 |