CN102002395A - Method and device for dissolving gas in liquid-phase circulating hydrodesulfurization system - Google Patents
Method and device for dissolving gas in liquid-phase circulating hydrodesulfurization system Download PDFInfo
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Abstract
The invention relates to a method and a device for dissolving gas in a liquid-phase circulating hydrodesulfurization system, and provides a method for dissolving gas in a liquid-phase circulating hydrodesulfurization system, which comprises the following steps of: introducing new hydrogen, raw oil and circulating saturated oil refluxed from a hydrogenation reactor into a gas-liquid mixing pump, and fully mixing under the strong turbulence state; introducing the mixed materials into a gas-liquid separation tank, collecting big bubbles, removing the big bubbles, and introducing the mixed materials into the hydrogenation reactor for hydrogenation; and introducing the circulating saturated oil refluxed from the hydrogenation reactor into the gas-liquid mixing pump again, mixing with the raw oil and the new hydrogen entering the gas-liquid mixing pump, and introducing the mixture into the hydrogenation reactor again. The invention also provides a device for dissolving gas in the liquid-phase circulating hydrodesulfurization system.
Description
Technical field
The invention belongs to petrochemical complex and environmental protection field, relate to a kind of gas-liquid mixing pump technology that adopts liquid-phase hydrogenatin field oil gas hybrid technique link is optimized the method for transformation, be applicable to and handle liquid phase circulation hydrogenation process.Specifically, the invention provides the optimization method and the device of the molten gas of liquid phase circulation hydrogenating desulfurization system.
Background technology
At present, refining main single hop and the two-stage process technology that adopts hydrogen recycle of diesel oil deepness hydrogenation.There is defective in these technology at aspects such as investment cost, economic benefits, therefore are badly in need of the diesel oil deepness hydrogenation technology that the development device investment is little, process cost is low.Liquid phase circulation hydrogen addition technology can not be provided with hydrogen gas circulating system, rely on the liquid-phase product circulation time to carry the dissolved hydrogen of reactive system into as the needed hydrogen of hydrogenation reaction, plant investment and process cost have not only been reduced, eliminated also that therefore hydrogen sulfide and ammonia be the research focus of modernized hydrogenation technique to the disadvantageous effect of reaction in the wetting factor of catalyzer and the recycle hydrogen.
Fig. 1 shows the liquid phase circulation hydrogenation technique flow process without transformation of prior art.As shown in Figure 1, the oil-feed air inlet that is pumped to process furnace 2 heating back and compressed machine 6 superchargings through pump 8 is together sent into and is carried out hybrid reaction in the mixing tank 7; The blended material enters two-stage hydrogenator 5-1,5-2 and carries out hydrogenation reaction, the saturated material of circulation of discharging from hydrogenator 5-2 underflow opening flow to mixing tank through recycle pump 10 pumped back, all the other ejectas enter stripping tower 9 to be separated, diesel oil goes out device from stripping tower 9 bottoms, gas goes out stripping tower 9 and enters separating tank 11, and gas separated is gone gas train; The reactant that comes out from hydrogenator 5-1,5-2 top enters separating tank 11 after water filling, separating obtained gas goes gas train, and all the other materials go the further processing and utilizing of follow-up system.
In liquid phase circulation hydrogenation technique, adopt hydrogen and stock oil before entering reactor, to carry out pre-mixing and pre-reaction, and by the recycle stock supply of hydrogen, thereby need find a kind of suitable oil gas blending means.Gas-liquid mixed process before this is the cost height not only, and system complex.Air compressor machine, pressurized vessel, general-purpose centrifugal pump and Controlling System are absolutely necessary.Method commonly used is fluid jet, diffuser plate method.
Fluid jet is that the air cavity of ejector forms negative pressure under the effect of high velocity liquid stream, and inspiration gas, high velocity liquid stream are pulverized gas again, forms microbubble and fully contacts mixing with liquid.Its advantage is to mix, lack duration of contact, and its shortcoming is the energy consumption height.
The diffuser plate method is that pressurized air disperses by microwell plate.Its advantage is that energy consumption is lower, and gas distribution was inhomogeneous when its shortcoming was the shower nozzle obstruction, and it is poor to mix, and needs large-scale air compressor machine and expensive oxidizing reaction tower.
It is above-mentioned that both solve the gas-liquid mixed process and have the cost height, the shortcoming of system complex.
Therefore, this area presses for a kind of can reducing cost of exploitation, and simplified system improves the gas-liquid mixed method of effect simultaneously.
Summary of the invention
The invention provides a kind of new molten gas method of liquid phase circulation hydrogenating desulfurization system and device, overcome the defective that exists in the prior art.
The objective of the invention is to propose to transform in a kind of hydrogenation catalyst cracking technical process oil plant and two-phase or multiphase blended method and apparatus of hydrogen.Primary technical problem to be solved by this invention is to solve system complex in the existing hydrogenation oil gas hybrid technique process, and cost is too high, and the not good problem of mixed effect, and a kind of new oil gas blending means is provided.Another technical problem to be solved by this invention provides the isolated plant of a cover in the above-mentioned treatment process, and its system is simple, implements easily, invest little, easy to operate, and suitable long-term operation.
On the one hand, the invention provides the molten gas method of a kind of liquid phase circulation hydrogenating desulfurization system, this method comprises:
New hydrogen and stock oil are sent into gas-liquid mixing pump, thorough mixing under the strong turbulence state with the saturated oil plant of circulation that hydrogenator refluxes;
The blended material enters knockout drum, and air pocket is collected, and removes blended material behind the air pocket and enters hydrogenator and carry out hydrogenation reaction;
The saturated oil plant of circulation that refluxes from hydrogenator enters gas-liquid mixing pump once more, enters hydrogenator once more with the stock oil that enters gas-liquid mixing pump with after newly hydrogen mixes.
One preferred embodiment in, described hydrogenator be single-stage or plural serial stage.
Another preferred embodiment in, described gas-liquid mixing pump be single-stage or plural serial stage or in parallel being used in combination.
Another preferred embodiment in, the median size of regulating hydrogen in the described blended material is to 0-60 μ m, and the liquor ratio of working off one's feeling vent one's spleen of gas-liquid mixing pump is to 20-45%.
On the other hand, the invention provides a kind of liquid phase circulation hydrogenating desulfurization system air-dissolving apparatus, this device comprises:
Gas-liquid mixing pump is used for new hydrogen and the saturated oil plant of the circulation thorough mixing under the strong turbulence state that refluxes of stock oil and hydrogenator that will send into wherein;
The knockout drum that is connected with gas-liquid mixing pump is used for the blended material of sending into is wherein carried out the air pocket collection;
With the tank connected hydrogenator of gas-liquid separation, be used for the blended material of removing behind the air pocket is carried out hydrogenation reaction.
One preferred embodiment in, described gas-liquid mixing pump uses unshrouded impeller.
Another preferred embodiment in, the high-temperature resistant of the material of described gas-liquid mixing pump reaches 400 ℃, the highest withstand voltage 15MPa that reaches.
Description of drawings
Fig. 1 is the liquid phase circulation hydrogenation technique schematic flow sheet without transformation of prior art.
Fig. 2 optimizes process flow diagram according to the liquid phase circulation hydrogenation of the transformation of an embodiment of the invention.
Fig. 3 is the device synoptic diagram according to liquid phase circulation hydrogenation gas-liquid mixing pump of the present invention.
Embodiment
The present inventor replaces the mixing tank of prior art to carry out the oil gas pre-mixing through finding after the extensive and deep research by gas-liquid mixing pump is set before hydrogenator, can improve the reaction efficiency that enters behind the reactor; Simultaneously, knockout drum is set at the gas-liquid mixed pump discharge, bubble diameter in the control outlet liquid, the stock oil of avoiding entering hydrogenator is carried the too much air pocket that influences high efficient mixed and effecting reaction secretly; In addition, adopt recycle hydrogen to be back in the gas-liquid mixing pump and mix the method that adds the hydrogen make-up supply of hydrogen simultaneously, keep certain reaction heat, produce certain pre-reaction with stock oil, improve final reaction effect, thereby improved the liquid phase circulation hydrogenation technique of prior art.Based on above-mentioned discovery, the present invention is accomplished.
In the air dissolving system of present air-float technology, begun to use in a large number a kind of gas-liquid mixing pump, as the centrifugal Airfloat pump of the EDUR of famous German company production.Negative pressure by the gas-liquid mixing pump admission port sucks gas-liquid two-phase, by impeller gas-liquid mixed is smashed mutually then, promptly reaches the molten gas effect of liquid phase.In addition, its impeller is an open architecture, can avoid producing air pocket in ingress, influences the steady operation and the gas-liquid mixed effect of pump.Expection can produce the bubble of 20-40 micron in the outlet liquid, vapour-liquid ratio 1-20%, and through after the pressurization once more, bubble diameter will further reduce, and bubble is even, intensive, and air flotation effect is stable, tolerance abundance, so gas-liquid dissolved efficiency height, stable performance.And its production technique is simple: alternative four equipment of mixing pump, system is simple, processing ease, convenient management, is the equipment that investment is minimum at present, mixed effect is best.In addition,, solved the reliever blocking problem, reduced the maintenance work amount because of without reliever.
Technical conceive of the present invention is as follows:
Saturated oil plant of the recycle hydrogen that stock oil and hydrogenator come out and raw hydrogen enter pump housing simultaneously automatically by inlet mouth on the gas-liquid mixing pump and the formed negative pressure of fluid inlet, vapour-liquid ratio is controlled by the setting device on the inlet ductwork, high velocity effect at pump swing-in impeller is issued to the turbulent flow mixing, hydrogen partial is dissolved in the oil plant with molecular level, all the other hydrogen mix with stock oil with the particle diameter level of 0-60 μ m, discharge from pump discharge after under High Temperature High Pressure, producing certain pre-reaction, at pump discharge knockout drum is set, bubble diameter in the control outlet liquid, the stock oil of avoiding entering hydrogenator is carried the too much air pocket that influences high efficient mixed and effecting reaction secretly.At last, the gas-oil mixture material of good mixing enters the hydrogenator reaction.The saturated recycle hydrogen oil plant that refluxes from the hydrogenator bottom enters in the gas-liquid mixing pump once more by return line, and said process is carried out in circulation.
In a first aspect of the present invention, a kind of liquid phase circulation hydrogenation oil gas blending means of optimization is provided, this method comprises:
After the saturated oil plant of hydrogen that new hydrogen and stock oil reflux with hydrogenator (or last step of multistage hydrogenator) by the adjusting pipeline respectively feeds gas-liquid mixing pump, be issued to thorough mixing at the strong turbulence state, reach certain pre-reaction effect simultaneously and enter hydrogenator (or first step of multistage hydrogenator) from the pump discharge discharge;
The saturated oil plant of circulation that refluxes from hydrogenator (or last step of multistage hydrogenator) liquid phase outlet enters in the gas-liquid mixing pump once more, mixes the back and discharges from pump discharge and enter hydrogenator (or first step of multistage hydrogenator) once more with stock oil and new hydrogen in entering pump;
At the pump discharge pipeline knockout drum is set the air pocket of gas-liquid mixed pump discharge is collected, remove the air pocket that export pipeline influences high efficient mixed.
In the present invention, gas-liquid mixing pump both used as mixing tank, used as recycle pump again, also used as the hydrogenation pre-reactor simultaneously.New hydrogen passes through pump steam inlet, entering pump housing by fluid inlet simultaneously after stock oil heats the back and the saturated oil plant of hydrogen of hydrogenator backflow converges mixes, and certain pre-reaction takes place under High Temperature High Pressure, vapour-liquid ratio can be provided with valve by inlet ductwork and regulate.
In the present invention, the required hydrogen of stock oil is mainly by the saturated raw material supplying of hydrogen, and insufficient part is replenished by new hydrogen, and new hydrogen magnitude of recruitment is determined by reactive hydrogen consumption and discharge amount of exhaust gas.
In the present invention, hydrogen and stock oil reach thorough mixing by the comprehensive action of gas-liquid mixed pump impeller and runner, hydrogen partial can be dissolved in stock oil by molecular level, all the other hydrogen gas bubbles median sizes are by regulating the level that can reach 0-60 μ m, and the liquor ratio of working off one's feeling vent one's spleen is adjustable, reaches as high as 45%.
In the present invention, by bubble diameter in the control outlet liquid, the oil plant that can avoid entering reactor is carried the too much air pocket that influences high efficient mixed and hydrogenation reaction effect secretly, and its method is to collect above-mentioned air pocket by knockout drum is set at export pipeline.
In a second aspect of the present invention, a kind of liquid phase circulation hydrogenation oil gas blended device is provided, this device comprises:
Be used for before the hydrogenation reaction stock oil, new hydrogen and the saturated oil plant of reactor backflow hydrogen being carried out gas-liquid mixed, and produce the gas-liquid mixing pump of certain pre-reaction effect;
With the knockout drum that the gas-liquid mixed pump discharge is connected, be used to remove the air pocket that influences high efficient mixed and hydrogenation reaction effect after mixing.
In the present invention, the unshrouded impeller that gas-liquid mixing pump is special is not easy to stop up, and also is difficult for cavitating, the impeller concussion that can avoid bubble to cause in addition effectively.
In the present invention, the material that gas-liquid mixing pump adopts is a high temperature high-pressure resistant material, and high-temperature resistant can reach 400 ℃, the highest withstand voltage 15MPa that reaches.
In the present invention, described gas-liquid mixing pump uses in the mode of single-stage or plural serial stage combination, improving the solubleness of pump discharge gas phase in liquid phase, and/or uses in the mode of single-stage or plural parallel stage combination, to satisfy the engineering treatment capacity.
Method and apparatus of the present invention can also be used for other occasion that comprises the gas-liquid mixed process, comprises all kinds of hydrogenation catalyst cracking reactions, all kinds of air-float technologies etc.
Below referring to accompanying drawing.
Fig. 2 optimizes process flow diagram according to the liquid phase circulation hydrogenation of the transformation of an embodiment of the invention.As shown in Figure 2, stock oil enters the saturated material of recycle hydrogen that reflux with the new hydrogen of regulating flow through valve 1-1 and hydrogenator 5-2 in process furnace 2 heating backs, that regulate flow through valve 1-3 and enters in the pump housing simultaneously by inlet mouth on the gas-liquid mixing pump 3 and fluid inlet regulating flow through valve 1-2; Reaching turbulent flow by impeller and pump housing effect mixes, hydrogen partial is dissolved in the oil plant with molecular level, hydrogen partial and oil plant reach thorough mixing in addition, and median size is in 0～60 μ m level, and all the other blended air pockets not yet in effect are effectively removed through the knockout drum 4 of pump discharge setting; Through the oil plant of said process with the hydrogen high efficient mixed, average vapour-liquid ratio is adjustable by demand, generally about 20%; Then, gas-oil mixture enters hydrogenator 5-1,5-2 and carries out hydrogenation reaction, and the product of gained enters the follow up device processing, utilizes from the top of hydrogenator 5-1,5-2 and the bottom of hydrogenator 5-2 respectively.
Fig. 3 is the device synoptic diagram according to liquid phase circulation hydrogenation gas-liquid mixing pump of the present invention.As shown in Figure 3, stock oil and new hydrogen are entered in the pump by the pumping hole negative pressure by the inlet mouth 32 and the fluid inlet 31 of pump respectively automatically with the saturated hydrogen feed that refluxes together, are issued to turbulent flow in the effect of impeller and pump housing and mix, simultaneously outside the overboard pump; At pump discharge 33 knockout drum is set and collects and not have well-mixed bubble, guarantee to work off one's feeling vent one's spleen the liquid mixture composition evenly and the effect of subsequent reactions.
The major advantage of method and apparatus of the present invention is:
The present invention transforms hydrogenation mode in the liquid-phase hydrogenatin technical process, gas-liquid mixed degree height in the pump, and outlet gas-liquid degree of mixing is even, and bubble diameter is less, can improve hydrogenation reaction efficient well; Because gas-liquid mixing pump promptly can be used as recycle pump and uses, can be used as Liqiud-gas mixing device again and use, and its gas-liquid mixed process itself is simpler than traditional static mixing tank, thus simplified system significantly, the reduction cost of investment; Method technology advanced person of the present invention, equipment investment cost is lower, and floor space is little, and failure rate is low, and reaction effect is good, and energy consumption is low, can effectively improve the technological process of liquid phase circulation hydrogenation, improves mixed effect.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.But, should be understood that these embodiment only are used to the present invention is described and do not constitute limitation of the scope of the invention.The test method of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Except as otherwise noted, all per-cent and umber are by weight.
Embodiment 1:
In one 200,000 tons/year liquid phase circulation hydrogenation units, according to the present invention's transformation oil gas mixing process wherein.
Technical process:
Concrete technical process as shown in Figure 2, the raw material parameter is as shown in table 1 below, main operational condition is as shown in table 2 below:
Table 1
Table 2
Technique effect:
Because the immixture of pump has improved the air-fuel mixture degree that enters before the reactor, and the recycle hydrogen mixed material that refluxes kept certain reaction heat, can greatly improve hydrogenation reaction efficient. Compare with other gas-liquid mixed method, adopt gas-liquid mixing pump as mixed media, can use as the circulating pump in the system simultaneously again, played the simplification system, saved the effect of cost. The employing of the method can produce huge economic benefit.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference. Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (7)
1. molten gas method of liquid phase circulation hydrogenating desulfurization system, this method comprises:
New hydrogen and stock oil are sent into gas-liquid mixing pump, thorough mixing under the strong turbulence state with the saturated oil plant of circulation that hydrogenator refluxes;
The blended material enters knockout drum, and air pocket is collected, and removes blended material behind the air pocket and enters hydrogenator and carry out hydrogenation reaction;
The saturated oil plant of circulation that refluxes from hydrogenator enters gas-liquid mixing pump once more, enters hydrogenator once more with the stock oil that enters gas-liquid mixing pump with after newly hydrogen mixes.
2. the method for claim 1 is characterized in that, described hydrogenator be single-stage or plural serial stage.
3. the method for claim 1 is characterized in that, described gas-liquid mixing pump be single-stage or plural serial stage or in parallel being used in combination.
4. the method for claim 1 is characterized in that, the median size of regulating hydrogen in the described blended material is to 0-60 μ m, and the liquor ratio of working off one's feeling vent one's spleen of gas-liquid mixing pump is to 20-45%.
5. liquid phase circulation hydrogenating desulfurization system air-dissolving apparatus, this device comprises:
Gas-liquid mixing pump (3) is used for new hydrogen and the saturated oil plant of the circulation thorough mixing under the strong turbulence state that refluxes of stock oil and hydrogenator that will send into wherein;
The knockout drum (4) that is connected with gas-liquid mixing pump (3) is used for the blended material of sending into is wherein carried out the air pocket collection;
With the hydrogenator that knockout drum (4) is connected, be used for the blended material of removing behind the air pocket is carried out hydrogenation reaction.
6. device as claimed in claim 5 is characterized in that, described gas-liquid mixing pump (3) uses unshrouded impeller.
7. device as claimed in claim 5 is characterized in that, the high-temperature resistant of the material of described gas-liquid mixing pump (3) reaches 400 ℃, the highest withstand voltage 15MPa that reaches.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104212483A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Method for controlling mixing ratio of hydrogen and oil selectively hydrogenated in catalytic gasoline |
| CN105623769A (en) * | 2016-03-28 | 2016-06-01 | 南京工业大学 | Process for co-producing nano calcium carbonate by biogas purification |
| CN106701173A (en) * | 2015-11-18 | 2017-05-24 | 中国石油天然气股份有限公司 | liquid phase hydrogenation device and method |
| CN106701179A (en) * | 2015-11-18 | 2017-05-24 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation device and method |
| CN106701180A (en) * | 2015-11-18 | 2017-05-24 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation device and method |
| CN106701174B (en) * | 2015-11-18 | 2018-08-14 | 中国石油天然气股份有限公司 | liquid phase hydrogenation device and method |
| CN111359556A (en) * | 2019-03-15 | 2020-07-03 | 南京延长反应技术研究院有限公司 | Micro-interface enhanced hydrogenation reaction system |
| CN111686665A (en) * | 2019-03-15 | 2020-09-22 | 南京延长反应技术研究院有限公司 | Micro-interface enhanced reaction system |
| CN112169720A (en) * | 2019-07-04 | 2021-01-05 | 南京延长反应技术研究院有限公司 | Nano-micro interface enhanced reaction system |
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| CN101653706A (en) * | 2009-08-12 | 2010-02-24 | 华东理工大学 | Circumferential direction mixer and gas-liquid/liquid-liquid mixing method using the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101653706A (en) * | 2009-08-12 | 2010-02-24 | 华东理工大学 | Circumferential direction mixer and gas-liquid/liquid-liquid mixing method using the same |
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| CN104212483A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Method for controlling mixing ratio of hydrogen and oil selectively hydrogenated in catalytic gasoline |
| CN106701173A (en) * | 2015-11-18 | 2017-05-24 | 中国石油天然气股份有限公司 | liquid phase hydrogenation device and method |
| CN106701179A (en) * | 2015-11-18 | 2017-05-24 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation device and method |
| CN106701180A (en) * | 2015-11-18 | 2017-05-24 | 中国石油天然气股份有限公司 | Liquid phase hydrogenation device and method |
| CN106701173B (en) * | 2015-11-18 | 2018-08-10 | 中国石油天然气股份有限公司 | liquid phase hydrogenation device and method |
| CN106701174B (en) * | 2015-11-18 | 2018-08-14 | 中国石油天然气股份有限公司 | liquid phase hydrogenation device and method |
| CN106701180B (en) * | 2015-11-18 | 2018-09-04 | 中国石油天然气股份有限公司 | liquid phase hydrogenation device and method |
| CN106701179B (en) * | 2015-11-18 | 2018-09-04 | 中国石油天然气股份有限公司 | liquid phase hydrogenation device and method |
| CN105623769A (en) * | 2016-03-28 | 2016-06-01 | 南京工业大学 | Process for co-producing nano calcium carbonate by biogas purification |
| CN111359556A (en) * | 2019-03-15 | 2020-07-03 | 南京延长反应技术研究院有限公司 | Micro-interface enhanced hydrogenation reaction system |
| CN111686665A (en) * | 2019-03-15 | 2020-09-22 | 南京延长反应技术研究院有限公司 | Micro-interface enhanced reaction system |
| CN112169720A (en) * | 2019-07-04 | 2021-01-05 | 南京延长反应技术研究院有限公司 | Nano-micro interface enhanced reaction system |
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