CN105502289A - Separation method of hydrogen from catalytic cracking dry gas and system therefor - Google Patents
Separation method of hydrogen from catalytic cracking dry gas and system therefor Download PDFInfo
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Abstract
The invention provides a separation method of hydrogen from catalytic cracking dry gas and a system therefor. The separation method includes the steps of: performing a hydration reaction to the catalytic cracking dry gas and collecting hydrogen-rich gas. A hydration reactor for the hydration reaction includes the following structures: a chamber, in the flowing direction of a hydrate working fluid, of the hydration reactor comprises an inlet section, a throat pipe section and a stable section, wherein the flowing area of the throat pipe section is less than those in both the inlet section and the stable section. An air inlet is arranged on the side wall, which is relative to the throat pipe section, of the chamber of the hydration reactor. The separation method is free of a step of compressing and pressurizing the catalytic cracking dry gas in a process of separating the hydrogen from the catalytic cracking dry gas through a hydrate separation method in the prior art, so that the separation method is reliable in operation and has strong practical industrial application aviliability.
Description
Technical field
The present invention relates to separation method and the system thereof of hydrogen in a kind of catalytic cracked dry gas, belong to chemical technology field.
Background technology
Owing to containing a large amount of hydrogen and ethene in catalytic cracked dry gas, therefore, ethylene cracking material and the hydrogen feedstock of millions of ton can be saved their comprehensive utilization every year, there is billions of economic benefits.In recent years, many investigators to hydrogen in catalytic cracked dry gas and ethene be separated and large quantifier elimination has been carried out in recovery, the existing method for separating of hydrogen in catalytic cracked dry gas and ethene has separation by deep refrigeration, absorption extraction method, membrane separation process and hydrate separation method.But aforesaid method but exists different defects, constrain the recovery of hydrogen and ethene in catalytic cracked dry gas.
Such as, although cold separation technology is comparatively ripe, but the shortcoming that energy consumption is higher but governs applying of this technology always, general only in the larger refinery for the treatment of capacity, the more area of oil catalytic cracking unit, or oil refining-chemical industry integration firm just can be considered to use cold separation technology separation catalytic cracked dry gas; Membrane separation process is also in conceptual phase in ethene extraction, easily damages by the impact of impurity, there is again the higher problem of masking cost simultaneously, thus fail to be widely used always owing to being separated the film used; Absorption extraction method has the advantage that technique is simple, equipment and materials is common, operational condition is gentle and energy consumption is low, efficiency is high, but usually can only process the gas of lower concentration, and impurity remove more difficult.Absorption extraction method can be divided into physical absorption and chemical absorption by the mode absorbed.Wherein, typical technology in physical absorption method is cold oil absorption process, this cold oil absorption process is the conventional art being separated ethene in catalytic cracked dry gas, has strong adaptability, investment cost is low, process scale is little advantage, but this technique exists energy consumption is high, ethylene loss amount is large defect; Chemical absorption method is again π Absorptive complex wave isolation technique, and it is large that the method has absorptive capacity, the advantage that Recovery rate of ethylene is high, but industrial application is actually rare at present.
Hydrate separation method is a kind of isolation technique of separation lower boiling mixed gas newly, and principle is the complexity forming hydrate according to gas with various, thus realizes the separation of each component in mixed gas.Relative to above-mentioned gas partition method, the advantage of hydrate separation method is that condition is gentleer, can realize the isolation andpurification of mixed gas, all have obvious advantage in energy consumption or in facility investment between temperature 0-15 DEG C.But prior art, when utilizing hydrate separation method to be separated hydrogen and ethene in catalytic cracked dry gas, usually will be implemented compression boosting process, then send in gas hydrate reactor and mix with hydrate working fluid to the catalytic cracked dry gas as unstripped gas.Be limited to execute-in-place space, and the reason of the aspect such as the energy consumption of gas compressor, current hydrate separation technology is not yet used widely being separated in the hydrogen in catalytic cracked dry gas.Therefore, study the hydrogen in new hydrate separation catalytic cracked dry gas, studied person paid close attention to always.
Summary of the invention
Technical problem solved by the invention is, separation method and the system thereof of hydrogen in a kind of catalytic cracked dry gas are provided, the method does not need existing hydrate separation method to be separated hydrogen in catalytic cracked dry gas and needs, to the step of catalytic cracked dry gas compression boosting, to have the advantage that operation is reliable, practical application in industry feasibility is strong.
The invention provides the separation method of hydrogen in a kind of catalytic cracked dry gas, comprise and make catalytic cracked dry gas generation hydration reaction, and collect the process of hydrogen-rich gas, wherein,
The hydration reactor realizing hydration reaction has following structure: hydration reactor cavity has entrance, trunnion section and stable section along hydrate working fluid flow direction, and the circulation area of trunnion section is all less than the circulation area of entrance and stable section, the sidewall that this hydration reactor cavity corresponds to trunnion section offers inlet mouth;
Described separation method comprises: send into described hydration reactor by hydrate working fluid from entrance, catalytic cracked dry gas is communicated with hydration reactor by inlet mouth, catalytic cracked dry gas to be separated is sucked hydration reactor by the suction utilizing the hydrate working fluid flowing through trunnion section to produce, and make the two flowing to mixed in stable section process, hydration reaction occur, generate hydrate slurry and hydrogen-rich gas;
Described hydrate slurry and hydrogen-rich gas are sent into hydrate separator, is separated and collects hydrogen-rich gas.
The separation method of hydrogen in above-mentioned catalytic cracked dry gas, mainly make use of hydromechanical principle, utilize the flowing of the different positions of hydrate working fluid in hydration reactor and the Changing Pattern of pressure, achieve the process of the suction of catalytic cracked dry gas, certainly boosting and hydration separation.Be in particular in: the entrance of hydrate working fluid from hydration reactor is injected, when it arrives the trunnion section of hydration reactor, because actual internal area sharply reduces, thus its flow velocity is increased suddenly, static pressure in hydration reactor is reduced fast, under the effect of pressure difference, catalytic cracked dry gas has been inhaled in hydration reactor and has mixed with hydrate working fluid, when catalytic cracked dry gas and hydrate working fluid arrive the stable section of hydration reactor, due to the expansion of actual internal area, thus the static pressure of fluid is raised, the pressure of system enters the pressure of hydration reactor higher than catalytic cracked dry gas, when the static pressure of fluid is greater than the generation pressure of hydrate, methane in catalytic cracked dry gas, ethane, the component such as ethene and carbonic acid gas and hydrate working fluid generation hydration reaction, form hydrate slurry, and a part of gas phase of institute's hydrogen obtains enrichment formation hydrogen-rich gas in catalytic cracked dry gas.
In the specific embodiment of the present invention, described hydrogen-rich gas is made to discharge from the top exit of hydrate separator and be collected, described hydrate slurry is sent into hydrate through the outlet at bottom of hydrate separator dissolve device and implement to dissolve, dissolve the hydrate working fluid removing gas that for hydration reaction cycle.
In the specific embodiment of the present invention, temperature when making hydrate working fluid enter hydration reactor is 4-15 DEG C, and pressure is 1.0-5.1MPa.It is poor that hydrate working fluid under this temperature and pressure is more conducive to flowing through trunnion section mineralization pressure at it, thus be conducive to the stable section that cracking catalysis dry gas is inhaled into hydration reactor, makes it to carry out hydration reaction with hydrate working fluid, forms hydrate slurry.
In the specific embodiment of the present invention, the internal diameter of the pipeline of the entrance of described hydration reactor is 15-50mm, the internal diameter of described trunnion section and the internal diameter of the pipeline ratio of described entrance are 0.05-0.5, and the diameter of described inlet mouth and the internal diameter ratio of described trunnion section are 0.2-0.5;
The length of described entrance and the internal diameter of the pipeline ratio of described entrance are 1-3, and the ratio of described trunnion segment length and described trunnion section internal diameter is 1-2.5, and the length of described stable section and the internal diameter of the pipeline ratio of described entrance are 3-5.
In the specific embodiment of the present invention, the service temperature of described hydrate separator is 4-15 DEG C, and working pressure is 1.1-5.1MPa.In hydrate separator, control aforesaid operations temperature can make hydrate slurry and the hydrogen in catalytic cracked dry gas be separated as much as possible completely with working pressure, realizes being separated of gas phase and liquid phase.
In the specific embodiment of the present invention, the service temperature that described hydrate dissolves device is 8-23 DEG C, and working pressure is 0.1-2.1MPa.Hydrate dissolve in device control aforesaid operations temperature and pressure can make hydrate slurry as much as possible Completion solution obtain hydrogen depleted gas and hydrate working fluid, realize being separated of hydrogen depleted gas and hydrate working fluid.
In the specific embodiment of the present invention, it is 0.6-1.6MPa that catalytic cracked dry gas to be separated is inhaled into the pressure before hydration reactor.
Present invention also offers the system of the separation method realizing hydrogen in above-mentioned catalytic cracked dry gas, described system comprises hydrate working fluid storage tank, hydration reactor, hydrate separator, hydrate dissolve device, well heater and/or reducing valve;
Wherein, hydration reactor cavity has entrance, trunnion section and stable section along hydrate working fluid flow direction, and the circulation area of trunnion section is all less than the circulation area of entrance and stable section, the sidewall that this hydration reactor cavity corresponds to trunnion section offers inlet mouth;
Described hydrate working fluid storage tank is provided with entrance and exit, and the outlet of described hydrate working fluid storage tank is communicated with the entrance of described hydration reactor;
Described hydration reactor stable section is provided with the outlet for discharging hydrate slurry and hydrogen-rich gas, and it is communicated with the entrance of described hydrate separator, and the top of described hydrate separator is provided with hydrogen-rich gas discharge outlet, and bottom is provided with hydrate slurry outlet;
The entrance that hydrate slurry outlet and the hydrate of described hydrate separator dissolve device is communicated with, and between the two, being provided with well heater and/or reducing valve, the hydrate working fluid outlet removing gas that described hydrate dissolves device is communicated with the entrance of described hydrate working fluid storage tank.
In said system, the internal diameter of the pipeline of the entrance of described hydration reactor is 15-50mm, and the internal diameter of described trunnion section and the internal diameter of the pipeline ratio of described entrance are 0.05-0.5, and the diameter of described inlet mouth and the internal diameter ratio of described trunnion section are 0.2-0.5;
The length of described entrance and the internal diameter of the pipeline ratio of described entrance are 1-3, and the internal diameter ratio of described trunnion segment length and described trunnion section is 1-2.5, and the length of described stable section and the internal diameter of the pipeline ratio of described entrance are 3-5.
The separation method of hydrogen in catalytic cracked dry gas provided by the invention, have employed structually improved hydration reactor, change by circulation area in hydration reactor dexterously and the hydrating condition required for catalytic cracked dry gas (hydration generation pressure) is provided, namely, after catalytic cracked dry gas is sucked hydration reactor by the Pressure Drop (even reaching parital vacuum) flowing through trunnion section utilizing hydrate working fluid and produce, and impel the components such as the alkane in catalytic cracked dry gas and alkene that hydration as far as possible all occurs due to pressure increase and the two abundant mixing under pressure-driven flowing in stable section process, reach the object of separating hydrogen gas.Compared to the current technique be separated catalytic cracked dry gas, separation method of the present invention does not need to carry out compression boosting to catalytic cracked dry gas to be separated, not only eliminate the input of gas booster compressor, significantly reduce energy consumption, also without the need to extra stirring mechanism during hydration reaction, and the requirement of operating space and operation sequence is all significantly reduced, achieve the separation of hydrogen in catalytic cracked dry gas, for the industrial applications of this technology provides possibility.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention is separated hydrogen in catalytic cracked dry gas.
Fig. 2 is the hydration reactor that the present invention is separated in catalytic cracked dry gas in hydrogen gas system.
Reference numeral:
1-hydrate working fluid storage tank; 2-hydration reactor; 3-hydrate separator; 4-hydrate dissolves device; 5-high-pressure pump; 6-water cooler; 7-well heater; 8-reducing valve; 9-hydrate working fluid; 10-catalytic cracked dry gas;
01-entrance; 02-trunnion section; 03-expanding reach; 04-inlet mouth.
Embodiment
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, be clearly and completely described below to the technical scheme in the embodiment of the present invention, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The separation method of hydrogen in catalytic cracked dry gas of the present invention, comprises and makes catalytic cracked dry gas generation hydration reaction, and collect the process of hydrogen-rich gas, wherein,
Realize the hydration reactor of hydration reaction as shown in Figure 2, there is following structure: hydration reactor cavity has entrance 01, trunnion section 02 and stable section 03 along hydrate working fluid flow direction, and the circulation area of trunnion section 02 is all less than the circulation area of entrance 01 and stable section 03, the sidewall that this hydration reactor cavity corresponds to trunnion section 02 offers inlet mouth 04; Wherein, the internal diameter of the pipeline of the entrance 01 of hydration reactor is 15-50mm, and the internal diameter of trunnion section 02 and the internal diameter of the pipeline ratio of entrance 01 are 0.05-0.5, and the diameter of inlet mouth 04 and the internal diameter ratio of trunnion section 02 are 0.2-0.5; The length of entrance 01 and the internal diameter of the pipeline ratio of entrance 01 are 1-3, and the internal diameter ratio of trunnion section 02 length and trunnion section 02 is 1-2.5, and the length of stable section 03 and the internal diameter of the pipeline ratio of entrance 01 are 3-5.
As shown in Figure 1, in catalytic cracked dry gas of the present invention, the separation method of hydrogen comprises: by the hydrate working fluid 9 in hydrate working fluid storage tank 1 after high-pressure pump 5 and water cooler 6, send into hydration reactor 2 from entrance 01, temperature when making hydrate working fluid 9 enter hydration reaction 2 is 4-15 DEG C, and pressure is 1.0-5.1MPa.Catalytic cracked dry gas 10 is communicated with hydration reactor 2 by inlet mouth 04, catalytic cracked dry gas 10 to be separated is inhaled into the pressure 0.6-1.6MPa before hydration reactor 2, catalytic cracked dry gas 10 to be separated is sucked hydration reactor 2 by the suction utilizing the hydrate working fluid 9 flowing through trunnion section 02 to produce, and make the two flowing to mixed in stable section 03 process, hydration reaction occur, generate hydrate slurry and hydrogen-rich gas;
Hydrate slurry and hydrogen-rich gas are sent into hydrate separator 3, and the service temperature of hydrate separator 3 is 4-15 DEG C, and working pressure is 1.1-5.1Mpa, is separated and collects hydrogen-rich gas.
Hydrogen-rich gas is made to discharge from the top exit of hydrate separator 3 and be collected, by the outlet at bottom of hydrate slurry through hydrate separator 3, heater via 7 and reducing valve 8 rear feeding hydrate are dissolved device 4 and are implemented to dissolve, the service temperature that hydrate dissolves device 4 is 8-23 DEG C, working pressure is 0.1-2.1Mpa, dissolves the hydrate working fluid removing gas and returns in hydrate working liquid tank 1 for hydration reaction cycle.
In the present invention, the selection of hydrate working fluid can be selected according to the height of concentration of component each in catalytic cracked dry gas, can be the aqueous solution of Tetrabutyl amonium bromide or tetrabutyl ammonium fluoride, can be with the addition of other chemical substance that can improve hydrate formation speed, whether adding of these materials all affect technical scheme of the present invention with the height of concentration yet.
Embodiment 1
Hydrate working fluid is Tetrabutyl amonium bromide (english abbreviation: TBAB), and its concentration is 10wt%;
Shown in the table 1 composed as follows of catalytic cracked dry gas:
The composition of table 1 catalytic cracked dry gas
| Composition | CH 4 | C 2H 6 | C 2H 4 | C 3H 6 | CO 2 | H 2 |
| Content, mol% | 23.79 | 7.65 | 21.61 | 0.24 | 2.85 | 44.86 |
Adopt the technical process of hydrogen and the hydration reactor of Fig. 2 in separation catalytic cracked dry gas as shown in Figure 1, its detailed process please refer to the explanation of above-mentioned separation method, and the processing parameter related to is as follows:
1) pressure of catalytic cracked dry gas is 1.6MPa.
2) temperature when hydrate working fluid enters hydration reactor is 8 DEG C, and pressure is 5MPa.
3) hydrate working fluid through the pressure of the trunnion section of hydration reactor be 1.2MPa.
4) fluid that the hydrogen in hydrate working fluid and catalytic cracked dry gas is formed is 4.5MPa at the pressure of the stable section of hydration reactor.
5) service temperature of hydrate separator is 9 DEG C, and working pressure is 4.3MPa.
6) hydrate dissolves the service temperature of device is 9 DEG C, and working pressure is 0.2MPa.
Technical process through Fig. 1 is separated the composition of hydrogen-rich gas and the hydrogen depleted gas obtained, as shown in table 2 below:
The composition of table 2 hydrogen-rich gas and hydrogen depleted gas
| Composition | CH 4 | C 2H 6 | C 2H 4 | C 3H 6 | CO 2 | H 2 |
| The content of hydrogen-rich gas, mol% | 11.25 | 3.52 | 5.08 | 0.27 | 1.89 | 77.99 |
| The content of hydrogen depleted gas, mol% | 27.38 | 14.93 | 41.59 | 0.10 | 4.48 | 11.50 |
As shown in Table 2, in hydrogen-rich gas, the mole fraction of hydrogen is 77.99%, and the rate of recovery of hydrogen reaches 73%, and this result shows: hydrogen in catalytic cracked dry gas can effectively be separated by above-mentioned hydration separation method.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (9)
1. the separation method of hydrogen in catalytic cracked dry gas, is characterized in that, comprise and make catalytic cracked dry gas generation hydration reaction, and collect the process of hydrogen-rich gas, wherein,
The hydration reactor realizing hydration reaction has following structure: hydration reactor cavity has entrance, trunnion section and stable section along hydrate working fluid flow direction, and the circulation area of trunnion section is all less than the circulation area of entrance and stable section, the sidewall that this hydration reactor cavity corresponds to trunnion section offers inlet mouth;
Described separation method comprises: send into described hydration reactor by hydrate working fluid from entrance, catalytic cracked dry gas is communicated with hydration reactor by inlet mouth, catalytic cracked dry gas to be separated is sucked hydration reactor by the suction utilizing the hydrate working fluid flowing through trunnion section to produce, and make the two flowing to mixed in stable section process, hydration reaction occur, generate hydrate slurry and hydrogen-rich gas;
Described hydrate slurry and hydrogen-rich gas are sent into hydrate separator, is separated and collects hydrogen-rich gas.
2. separation method according to claim 1, it is characterized in that, described hydrogen-rich gas is made to discharge from the top exit of hydrate separator and be collected, described hydrate slurry is sent into hydrate through the outlet at bottom of hydrate separator dissolve device and implement to dissolve, dissolve the hydrate working fluid removing gas that for hydration reaction cycle.
3. separation method according to claim 1, is characterized in that, temperature when making hydrate working fluid enter hydration reactor is 4-15 DEG C, and pressure is 1.0-5.1MPa.
4. the separation method according to claim 1 or 3, it is characterized in that, the internal diameter of the pipeline of the entrance of described hydration reactor is 15-50mm, the internal diameter of described trunnion section and the internal diameter of the pipeline ratio of described entrance are 0.05-0.5, and the diameter of described inlet mouth and the internal diameter ratio of described trunnion section are 0.2-0.5;
The length of described entrance and the internal diameter of the pipeline ratio of described entrance are 1-3, and the internal diameter ratio of described trunnion segment length and described trunnion section is 1-2.5, and the length of described stable section and the internal diameter of the pipeline ratio of described entrance are 3-5.
5. separation method according to claim 1, is characterized in that, the service temperature of described hydrate separator is 4-15 DEG C, and working pressure is 1.1-5.1MPa.
6. separation method according to claim 2, is characterized in that, the service temperature that described hydrate dissolves device is 8-23 DEG C, and working pressure is 0.1-2.1MPa.
7. the separation method according to claim 1 or 3, is characterized in that, it is 0.6-1.6MPa that catalytic cracked dry gas to be separated is inhaled into the pressure before hydration reactor.
8. realize the system of the separation method of hydrogen in the catalytic cracked dry gas described in any one of claim 1-7, it is characterized in that, described system comprises hydrate working fluid storage tank, hydration reactor, hydrate separator, hydrate dissolve device, well heater and/or reducing valve;
Wherein, hydration reactor cavity has entrance, trunnion section and stable section along hydrate working fluid flow direction, and the circulation area of trunnion section is all less than the circulation area of entrance and stable section, the sidewall that this hydration reactor cavity corresponds to trunnion section offers inlet mouth;
Described hydrate working fluid storage tank is provided with entrance and exit, and the outlet of described hydrate working fluid storage tank is communicated with the entrance of described hydration reactor;
Described hydration reactor stable section is provided with the outlet for discharging hydrate slurry and hydrogen-rich gas, and it is communicated with the entrance of described hydrate separator, and the top of described hydrate separator is provided with hydrogen-rich gas discharge outlet, and bottom is provided with hydrate slurry outlet;
The entrance that hydrate slurry outlet and the hydrate of described hydrate separator dissolve device is communicated with, and between the two, being provided with well heater and/or reducing valve, the hydrate working fluid outlet removing gas that described hydrate dissolves device is communicated with the entrance of described hydrate working fluid storage tank.
9. system according to claim 8, it is characterized in that, the internal diameter of the pipeline of the entrance of described hydration reactor is 15-50mm, the internal diameter of described trunnion section and the internal diameter of the pipeline ratio of described entrance are 0.05-0.5, and the diameter of described inlet mouth and the internal diameter ratio of described trunnion section are 0.2-0.5;
The length of described entrance and the internal diameter of the pipeline ratio of described entrance are 1-3, and the internal diameter ratio of described trunnion segment length and described trunnion section is 1-2.5, and the length of described stable section and the internal diameter of the pipeline ratio of described entrance are 3-5.
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| CN1301684A (en) * | 1999-12-30 | 2001-07-04 | 中国科学院广州能源研究所 | Method and device for separating and reclaiming ethylene from catalytic cracked dry gas |
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| CN1301684A (en) * | 1999-12-30 | 2001-07-04 | 中国科学院广州能源研究所 | Method and device for separating and reclaiming ethylene from catalytic cracked dry gas |
| US20050274258A1 (en) * | 2004-06-15 | 2005-12-15 | Spencer Dwain F | Methods and systems for selectively separating CO2 from a multicomponent gaseous stream to produce a high pressure CO2 product |
| CN103623766A (en) * | 2013-12-10 | 2014-03-12 | 中国科学院广州能源研究所 | Spraying device for rapidly forming gas hydrate |
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