CN1970697A - Method for refining circulating hydrogen in hydrocracking process - Google Patents
Method for refining circulating hydrogen in hydrocracking process Download PDFInfo
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- CN1970697A CN1970697A CN 200510123389 CN200510123389A CN1970697A CN 1970697 A CN1970697 A CN 1970697A CN 200510123389 CN200510123389 CN 200510123389 CN 200510123389 A CN200510123389 A CN 200510123389A CN 1970697 A CN1970697 A CN 1970697A
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Abstract
The invention discloses an extracting method of dense circulating hydrogen in the hydrogenating cracking technique, which comprises the following steps: separating extracted dense circulating hydrogen from high-pressure separator; removing drip in the separatory tank; entering into hydrated-method purifying unit; removing light hydrocarbon component in the circulating hydrogen; blending purified circulating hydrogen and new hydrogen into hydrogenating reactor.
Description
Technical field
The present invention relates to a kind of method of in hydrocracking process, carrying dense recycle hydrogen, belong to the Petroleum Processing Technology field.
Background technology
Hydrogen is the indispensable raw material of hydroeracking unit ordinary production, and the height of its hydrogen purity is to manufacturing cost, the running cost of hydroeracking unit and concern that the reactivity worth of target product productive rate and catalyst operation etc. has material impact.The system of conventional high-tension hydrocracking as shown in Figure 1, wherein major equipment comprises hydrofining reactor 1, hydrocracking reactor 2, high-pressure separator 3 is divided flow container 4, make-up hydrogen compressor 5, circulating hydrogen compressor 6, recycle hydrogen process furnace 7, stock oil feeding pump 12 etc.
As can be seen from Figure 1, the purity that enters the hydrogen of hydrofining reactor 1 and hydrocracking reactor 2 depends on the purity of new hydrogen 8 and the purity of recycle hydrogen 9.In the process of hydrogenation reaction, to produce light hydrocarbon components such as methane, because they can not separate with recycle hydrogen in high-pressure separator 3 effectively, thereby can add up to reduce the purity of recycle hydrogen gradually, current at present method is to bleed off a part of recycle hydrogen (being that what is called speeds to put hydrogen 10), replenish the highly purified new hydrogen 8 of a part simultaneously, to keep recycle hydrogen concentration stabilize basic like this level about 85%.If can effectively the recycle hydrogen concentration that obtains in the high-pressure separator 3 be brought up to more than 95%, then not only can avoid speeding to put hydrogen, also can significantly save cost, as reducing the design pressure of relevant device in others.
From Fig. 2-5 as can be seen, the raising of hydrogen dividing potential drop can improve the decreasing ratio of sulphur, nitrogen, improves the crude oil transformation efficiency, increases the yield of light-end products.
The recycle hydrogen pressure of hydroeracking unit is generally very high, and present mature pressure swing adsorption is because working pressure is low and inapplicable.Though the technology-membrane separation technique of another kind of separating gas mixture is fit to separate high pressure gas, obtain to carry dense hydrogen pressure too low, need could circulate after a large amount of superchargings hydrogenator, so energy consumption is very high also inapplicable.
Chinese patent 00100279.1 discloses a kind of generation hydrate or its precursor utilized the Hydrogen Separation in the hydrogeneous gas mixture has been put forward dense method, it is-20 ℃～10 ℃ in temperature range that this method will contain hydrogen mixed gas, pressure is under the operational condition of 0.1～20MPa, making non-hydrogen generate hydrate exists with solid form, and hydrogen can not generate hydrate and still exists with the form of gas, then by gas, the solid separation realizing gas delivery.But do not see that this method is used to carry the report of dense recycle hydrogen in hydrogenation catalyst technology.
Summary of the invention
The objective of the invention is to solve the problem that is difficult for improving recycle hydrogen concentration in the existing hydrocracking process.
In order to achieve the above object, the invention provides a kind of method of in hydrocracking process, carrying dense recycle hydrogen, this method comprises: from the high-pressure separator of hydroeracking unit come out wait that carrying dense recycle hydrogen removes institute's droplets entrained minute flow container after, enter monohydrate method hydrogen purifier units, remove light hydrocarbon component in the recycle hydrogen at this, purify the back recycle hydrogen with enter hydrogenator again after newly hydrogen mixes.
The hydrate hydrogen purifier units that adopts in the aforesaid method comprises hydration reactor and decomposition of hydrate device, described hydration reactor be used for the described light hydrocarbon component of waiting to carry dense recycle hydrogen and liquid, aqueous generation hydrate and and Hydrogen Separation, the decomposition of hydrate that described decomposition of hydrate device is used for generating generates gas light hydrocarbon component and liquid, aqueous, liquid, aqueous recycling.Described liquid, aqueous can be the emulsion that tetrahydrofuran aqueous solution or tetrahydrofuran aqueous solution and hydrocarbon liquids form, can also be the emulsion that water and the hydrocarbon liquids that contains pentamethylene, propane, Trimethylmethane or fluorine Lyons form.Described hydrocarbon liquids comprises crude oil fractions such as gasoline, kerosene, diesel oil.The preparation of emulsion is by adding any or several emulsifying agent, the aqueous solution and hydrocarbon liquids mixed stir and get.The add-on of emulsifying agent is decided according to the quality of emulsifying agent.
The working pressure of the hydration reactor of hydrate hydrogen purifier units is the pressure of waiting to carry dense recycle hydrogen that described high-pressure separator is come out, and service temperature is 1～10 ℃; Working pressure 0.2～the 3MPa of described decomposition of hydrate device, service temperature is 10～25 ℃; Described flow rate volume ratio liquid, aqueous and that wait to carry dense recycle hydrogen is 1/50 to 1/300.
The present invention has made full use of hydrate Hydrogen Separation concentrating method and has been fit to the characteristics that dense hydrogen pressure is carried in high top pressure operation and not obvious reduction, and it is dense to be used for carrying of High-pressure Hydrogenation Unit recycle hydrogen.
The present invention has improved the hydrogenation reaction performance, reduced equipment cost and operation power consumption and has avoided discharging hydrogen by improving hydrogen partial pressure in the hydrogenator.
For new device, the density of hydrogen of recycle hydrogen improves, and can reduce the design pressure of equipment.Owing to react under the certain situation of needed hydrogen dividing potential drop, the raising hydrogen concentration means can reduce the reaction stagnation pressure, reduces the facility investment (reactor, process furnace, interchanger, water cooler, high-pressure separator and pipeline) of entire reaction system.After recycle hydrogen concentration improved, the operation stagnation pressure of reactive moieties can select for use lift than low pump, the compressor that compression ratio is little after reducing.For for the working unit, after the density of hydrogen of recycle hydrogen improves,,, be one of important expansionary measures to desiring to improve the device of throughput with the throughput of entire reaction system is improved.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Description of drawings
Fig. 1 is existing hydroeracking unit hydrogenation reaction cell process flow process and equipment synoptic diagram;
Fig. 2 is the synoptic diagram of hydrogen dividing potential drop to the influence of desulfurization degree;
Fig. 3 is the synoptic diagram of hydrogen dividing potential drop to the influence of denitrification percent;
Fig. 4 is the synoptic diagram of hydrogen dividing potential drop to the influence of refining section denitrogenation;
Fig. 5 is the synoptic diagram of hydrogen dividing potential drop to the influence of cracking conversion rate;
Fig. 6 is hydroeracking unit hydrogenation reaction cell process flow process of the present invention and equipment synoptic diagram;
Fig. 7 is the industrialization flow process and the equipment synoptic diagram of hydrate hydrogen purifier units of the present invention.
Embodiment
Referring to Fig. 6, the gas that allows high-pressure separator 3 come out, it is the recycle hydrogen in the traditional process, after in minute flow container 4, removing institute's droplets entrained, enter hydrate hydrogen purifier units 11, here light hydrocarbon component such as methane, ethene contacts with water and generates hydrate, and hydrogen can not generate hydrate and still exists with the form of gas, thereby, density of hydrogen is brought up to more than 95% (V) with other gas delivery that can generate hydrate; Leave the dense hydrogen of carrying of hydration separating unit 11 as recycle hydrogen 9 through recycle compressor 6 pressurization, with return hydrofining reactor 1 and hydrocracking reactor 2 after new hydrogen 8 mixes, make two reactors interior density of hydrogen and dividing potential drop remain on high level.
Wherein hydration separation carry dense hydrogen operating process as shown in Figure 7.Wait to carry dense recycle hydrogen 28 at first with hydrate slurry 29 heat exchange of flowing out hydration reactor 20, temperature drops to the back hydration reactor 20 that enters from the bottom below 10 ℃, most of light hydrocarbon component in up process and descending through ammonia circulating cooling system 23 refrigerative liquid, aqueous 30 contact the generation solid hydrate and and Hydrogen Separation, the recycle hydrogen of carrying after dense 24 leaves hydrate hydrogen purifier units 11 from the top of hydration reactor 20, and enter hydrofining reactor 1 and hydrocracking reactor 2 (see figure 6)s again after new hydrogen mixes; Solid hydrate that generates in the hydration reactor 20 and unconverted liquid, aqueous form with slurries 29 are discharged from the bottom of hydration reactor 20, at first and wait to propose dense recycle hydrogen 28 heat exchange, be heated to 10～25 ℃, again through the hydraulic turbine energy-recuperation system 22 0.2～3MPa that reduces pressure, enter decomposition of hydrate device 21 at last, here hydrate thoroughly is decomposed to form light hydrocarbon gas component 25 and liquid, aqueous two bursts of logistics, light hydrocarbon gas component 25 is discharged by the top of decomposition of hydrate device 21 and is left hydration purifier units 11, liquid, aqueously after liquid circulating pump 31 superchargings, return hydration reactor 20 tops, form descending liquid, aqueous 30 through ammonia circulating cooling system 23.Partially aqueous liquid replenishes into liquid, aqueous working cycle by pipeline 27 after liquid circulating pump 31 superchargings.The working pressure of hydration reactor 20 is the pressure that high-pressure separator 3 (see figure 6)s are come gas, and service temperature is 1～10 ℃; 0.2～3MPa is pressed in the operation of decomposition of hydrate device 21, and service temperature is 15～25 ℃; The flow rate ratio liquid, aqueous and that wait to carry dense recycle hydrogen that circulates is that 1/50 (V/V) is to 1/300 (V/V).
Adopt the inventive method, can obviously reduce the equipment requirements and the equipment power dissipation of hydrocracking process, following table has provided equipment contrast and the power consumption contrast before and after the hydrogen purification.
| Device name | Parameter name | Carry dense before | Carry dense after |
| The stock oil feeding pump | Top hole pressure/MPa | 18.5 | 15.5 |
| Shaft power/kW | 1717.4 | 1441.8 | |
| Make-up hydrogen compressor | Top hole pressure/MPa | 18.5 | 15.5 |
| Shaft power/kW | 2600 | 2180 | |
| Circulating hydrogen compressor | Top hole pressure/MPa | 18.6 | 15.6 |
| Shaft power/kW | 2212 | 2005 |
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the spirit and scope of technical solution of the present invention.
Claims (6)
1, a kind of method of in hydrocracking process, carrying dense recycle hydrogen, comprising: from the high-pressure separator of hydroeracking unit come out wait that carrying dense recycle hydrogen removes institute's droplets entrained minute flow container after, enter monohydrate method hydrogen purifier units, remove light hydrocarbon component in the recycle hydrogen at this, purify the back recycle hydrogen with enter hydrogenator again after newly hydrogen mixes.
2, the method that in hydrocracking process, improves recycle hydrogen concentration according to claim 1, wherein the hydrate hydrogen purifier units of Cai Yonging comprises hydration reactor and decomposition of hydrate device, described hydration reactor be used for the described light hydrocarbon component of waiting to carry dense recycle hydrogen and liquid, aqueous generation hydrate and and Hydrogen Separation, the decomposition of hydrate that described decomposition of hydrate device is used for generating generates gas light hydrocarbon component and liquid, aqueous.
3, the method for in hydrocracking process, carrying dense recycle hydrogen according to claim 2, wherein said liquid, aqueous be the emulsion that tetrahydrofuran aqueous solution, tetrahydrofuran aqueous solution and the hydrocarbon liquids emulsion or the water that form and the hydrocarbon liquids that contains pentamethylene, propane, Trimethylmethane or fluorine Lyons form.
4, the method for carrying dense recycle hydrogen in hydrocracking process according to claim 3, wherein said hydrocarbon liquids is gasoline, kerosene or diesel oil.
5, the method for in hydrocracking process, carrying dense recycle hydrogen according to claim 2, the working pressure of the hydration reactor of wherein said hydrate hydrogen purifier units is the pressure of waiting to carry dense recycle hydrogen that described high-pressure separator is come out, and service temperature is 1～10 ℃; Working pressure 0.2～the 3MPa of described decomposition of hydrate device, service temperature is 10～25 ℃; Described flow rate volume ratio liquid, aqueous and that wait to carry dense recycle hydrogen is 1/50 to 1/300.
6, the method for carrying dense recycle hydrogen in hydrocracking process according to claim 1, recycle hydrogen mixes with new hydrogen and pressurizes through a circulating hydrogen compressor before after the wherein said purification.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200510123389XA CN100489064C (en) | 2005-11-25 | 2005-11-25 | Method for refining circulating hydrogen in hydrocracking process |
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| CNB200510123389XA CN100489064C (en) | 2005-11-25 | 2005-11-25 | Method for refining circulating hydrogen in hydrocracking process |
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| CN1970697A true CN1970697A (en) | 2007-05-30 |
| CN100489064C CN100489064C (en) | 2009-05-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531347B (en) * | 2008-03-11 | 2011-05-11 | 中国石油大学(北京) | Method for recycling and synthesizing nitrogen and hydrogen in off-gases of ammonia and device thereof |
| CN101723325B (en) * | 2008-10-29 | 2011-09-21 | 中国石油化工股份有限公司 | Method for recovering low-concentration hydrogen |
| CN106957681A (en) * | 2017-03-31 | 2017-07-18 | 北京中科诚毅科技发展有限公司 | A kind of method and its method for designing and purposes for improving hydrogenation reaction system hydrogen dividing potential drop |
| CN108828135A (en) * | 2018-03-09 | 2018-11-16 | 惠州大亚湾伊科思新材料科技发展有限公司 | A method of saving nine hydrogenation plant hydrogen gas consumption of carbon |
-
2005
- 2005-11-25 CN CNB200510123389XA patent/CN100489064C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531347B (en) * | 2008-03-11 | 2011-05-11 | 中国石油大学(北京) | Method for recycling and synthesizing nitrogen and hydrogen in off-gases of ammonia and device thereof |
| CN101723325B (en) * | 2008-10-29 | 2011-09-21 | 中国石油化工股份有限公司 | Method for recovering low-concentration hydrogen |
| CN106957681A (en) * | 2017-03-31 | 2017-07-18 | 北京中科诚毅科技发展有限公司 | A kind of method and its method for designing and purposes for improving hydrogenation reaction system hydrogen dividing potential drop |
| WO2018177401A1 (en) * | 2017-03-31 | 2018-10-04 | 北京中科诚毅科技发展有限公司 | Method for increasing hydrogen partial pressure in hydrogenation reaction system, design method therefor and use thereof |
| CN108828135A (en) * | 2018-03-09 | 2018-11-16 | 惠州大亚湾伊科思新材料科技发展有限公司 | A method of saving nine hydrogenation plant hydrogen gas consumption of carbon |
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| Publication number | Publication date |
|---|---|
| CN100489064C (en) | 2009-05-20 |
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Granted publication date: 20090520 Termination date: 20121125 |