CN101348235B - Hydrogen recovery method for hydrogenation plant - Google Patents
Hydrogen recovery method for hydrogenation plant Download PDFInfo
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- CN101348235B CN101348235B CN 200710119255 CN200710119255A CN101348235B CN 101348235 B CN101348235 B CN 101348235B CN 200710119255 CN200710119255 CN 200710119255 CN 200710119255 A CN200710119255 A CN 200710119255A CN 101348235 B CN101348235 B CN 101348235B
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Abstract
The invention provides a hydrogen recovering method for a hydrogenation unit. The method comprises the following steps that: products of a hydrogenation unit reaction system(2) enter a hot high-pressure separator(3) for gas-liquid separation; the gases obtained from the hot high-pressure separator(3) enter a cold high-pressure separator(4), the liquid phase obtained from the cold high-pressure separator(4) is decompressed and enters a cold low-pressure separator(5), the hydrogen rich gases obtained from the cold low-pressure separator(5) return back to the reaction system(2) through a hydrogen recovering system(8); the liquids obtained from the hot high-pressure separator(3) are decompressed and enter a hot low-pressure separator(6), the gases obtained from the hot low-pressure separator(6) are cooled and enter a flash tank(7), and the flash vapor directly returns back to the reaction system(2). The method of the invention reduces the hydrogen loss during the hydrogen recovering process and lowers the investments of the hydrogen recovering system and the hydrogenation unit.
Description
Technical field
The present invention relates to a kind of hydrogen recycling method, more particularly, relate to the hydrogen recycling method of hydrogenation unit in a kind of petrochemical complex/petroleum refining process.
Background technology
Petrochemical complex/petroleum refining process generally comprises: hydrogenating desulfurization, hydrodenitrification, hydrogenation take off impurity (oxygen, metal etc.), hydrogenation units such as aromatic hydrocarbons is saturated, alkene is saturated, hydrocracking.
The technical process of hydrogenation unit is according to the difference of hydrogen addition technology and varied, but its component units is basic identical, mainly comprises: raw materials pretreatment system, reactive system, reaction product heat exchange, separation system, recycle hydrogen system and hydrogen make-up system.
In hydrogenation unit, hydrogen is through reactive system, and hydrogen partial is reacted utilization, and unreacted hydrogen reclaims through hydrogen recovery system, and recover hydrogen is mixed with hydrogen make-up, recycles as the hydrogen feed of hydrogenation unit.
At present, the hydrogen recycling method of hydrogenation unit is normally: the recover hydrogen that the hydrogen make-up outside the system and hydrogen recovery system obtain enters the hydrogen make-up suction port of compressor respectively and divides flow container or inter-stage to divide flow container, enters the reactive system of hydrogenation unit after boosting through the hydrogen make-up compressor; In reactive system, hydrogen, stock oil are through heating and reacting under the effect of catalyzer, the reaction product that obtains enters separation system separates, and separation system is generally by high pressure hot separator, thermal low-pressure separators, and cold high pressure separator and cold low separator are formed.
The flow process of separation system generally is: the reaction product of process heat exchange at first enters high pressure hot separator and carries out preliminary gas-liquid flash distillation; The gas (hot high score gas) that is obtained by the high pressure hot separator top enters cold high pressure separator through heat exchange with after cooling off, and in order to prevent ammonium salt crystallization occurring in heat exchange and process of cooling, needs to carry out water filling before interchanger or water cooler; (contain hydrogen sulfide, ammonia owing in this gas, also muriate may be arranged sometimes, if in the process of cooling, there is not the existence of free-water, just have the amine salt crystallization in the water cooler, stop up and the corrosion water cooler, therefore need water filling before cooling, guarantee in the process of cooling, to have the existence of free-water.) in cold high pressure separator, carry out the three phase separation of vapour, liquid and water, the gas at cold high pressure separator top boosts by circulating hydrogen compressor and is back in the reactive system, according to different process condition, between circulating hydrogen compressor and cold high pressure separator the desulphurization of recycle hydrogen tower can be set and the circulating hydrogen compressor entrance divides facilities such as flow container, the liquid phase that cold high pressure separator obtains enters the cold low separator after through decompression.
The liquid that is obtained by the high pressure hot separator bottom carries out gas-liquid separation through entering thermal low-pressure separators after reducing pressure; The gas (the low gas that divides of heat) that is got by the thermal low-pressure separators top enters the cold low separator or enters the low gas flash tank that divides of heat after overcooling (also can cool off after the first heat exchange).
In the cold low separator, carry out gas-liquid water three phase separation, isolated gas (the cold low minute gas) hydrogen recovery system that access to plant is interior or device is outer usually.If the low gas that divides of heat enters the low gas flash tank that divides of heat, the gas of flash tank with enter hydrogen recovery system after cold low minute gas mixes.
Hydrogen recovery system generally adopts the method recover hydrogen of membrane sepn and transformation/alternating temperature fractionation by adsorption, and the recover hydrogen that obtains is back to the hydrogen pipe network or the hydrogen make-up compressor divides the flow container entrance.
The main drawback that above-mentioned prior art exists is: the investment of the hydrogenation unit rate of recovery big, the hydrogen recovery process is lower.
Chinese patent CN1642860A provides " a kind of method that is used for the hydrogen feed fluid in hydrotreating reactor ", this feed fluid contains heavy hydrocarbon liquid ingredient and hydrogen feed component, this hydrogen feed component contains recycle gas and make-up gas fluid, reactor produces a kind of effluent liquid stream and a kind of effluent stream, this effluent stream contains unreacted hydrogen and methane and the hydrocarbon of heavy more, this method contacts with a kind of lean solution body solvent fluid eluting gas cooling back in the uptake zone, solvent fluid absorbs methane and the hydrocarbon of heavy more, prepare a kind of hydrogen-rich gas fluid and a kind of liquid-rich solvent fluid, the hydrogen-rich gas fluid uses as recycle gas.
This method is by the absorption tower, removes methane in the recycle hydrogen and heavier hydro carbons, improves the purity of recycle hydrogen, do not improve hydrogen recovery rate, reduces the purpose that hydrogenation unit is invested but reach.
Summary of the invention
In order to improve the investment of hydrogen recovery rate, reduction hydrogenation unit, the invention provides a kind of hydrogen recycling method of hydrogenation unit, this recovery method is achieved in that
A kind of hydrogen recycling method of hydrogenation unit, this method may further comprise the steps:
A. the hydrogen make-up of being come by the hydrogen pipe network enters the reactive system 2 of hydrogenation unit, and reaction product enters high pressure hot separator 3 and carries out gas-liquid separation;
B. separate the gas that obtains by step a high pressure hot separator 3 and go into cold high pressure separator 4 through overcooling is laggard; The gas that is obtained by cold high pressure separator 4 is back to reactive system 2 through after boosting, and the liquid phase that obtains enters cold low separator 5 after reducing pressure; The hydrogen-rich gas that is obtained by cold low separator 5 enters hydrogen recovery system 8, and the recover hydrogen that obtains is back to reactive system 2 or is back to the hydrogen pipe network;
C. separate the liquid that obtains by step a high pressure hot separator 3 and entering thermal low-pressure separators 6 after through decompression, the gas that is obtained by thermal low-pressure separators 6 is gone into flash tank 7 through overcooling is laggard, and the flashed vapour that obtains is back to reactive system 2.
In the specific implementation, the service temperature of high pressure hot separator 3 is 150～400 ℃, and working pressure is 4.0～20MPa; The service temperature of cold high pressure separator 4 is 35～60 ℃, and working pressure is 3.5～20MPa; The service temperature of cold low separator 5 is 35～60 ℃, and working pressure is 0.70～5.0MPa; The service temperature of thermal low-pressure separators 6 is 150～400 ℃, and working pressure is 0.70～5.0MPa; The service temperature of flash tank 7 is 35～60 ℃, and working pressure is 0.70～5.0MPa.
In the specific implementation, the recover hydrogen that is obtained by step b and directly be back to the hydrogen make-up suction port of compressor by the flashed vapour that step c obtains and divide between flow container or hydrogen make-up compressor stage and divide flow container.
In the specific implementation, hydrogen recovery system 8 adopts membrane sepn or transformation/alternating temperature adsorption separating method recover hydrogen; Separated the gas water filling before cooling that obtains by high pressure hot separator 3; Cooling separates the gas that obtains by high pressure hot separator 3, adopts air-cooler or/and watercooler.
Compared with prior art, hydrogen recycling method of the present invention is: heat is low divides gas to go into the low gas flash tank that divides of heat through overcooling is laggard, and flashed vapour directly is back to reactive system; Existing hydrogen recycling method is: heat is low divides gas to enter the cold low separator after cooling or enters the low gas flash tank that divides of heat, flashed vapour with enter hydrogen recovery system after cold low minute gas mixes, recover hydrogen is back to reactive system or is back to the hydrogen pipe network.
Compared with prior art, hydrogen recycling method of the present invention, the investment that the hydrogen loss of hydrogenation unit hydrogen recovery process reduces 20-90%, liquefied gas loss minimizing 10-85%, petroleum naphtha loss minimizing 10-85%, hydrogen recovery system reduces 10-85%.
This be because: existing hydrogen recovery system generally adopts the method recover hydrogen of membrane sepn or transformation/alternating temperature fractionation by adsorption, hydrogen recovery system not only needs facility investment, working cost, and the efficient of recovery system can not reach 100%, part high value material (as hydrogen, liquefied gas, petroleum naphtha) is converted into the low value material in recovery system, has reduced the income of hydrogenation unit integral body.The present invention has changed flow process, and the hydrogen of higher concentration no longer directly is back to hydrogenation reaction system through hydrogen recovery system, has reduced facility investment and loss of material.
The low hydrogen purity of gas flashed vapour of dividing of heat has only 50～88 (mole) % usually, is lower than the hydrogen purity (88～99.99 (mole) %) of hydrogen make-up; It is generally acknowledged: the direct Returning reacting system of flashed vapour, can reduce the hydrogen partial pressure of reactive system, be unfavorable for hydrogenation reaction; The present invention is in order to guarantee the hydrogen partial pressure of hydrogenation reaction, and the corresponding reaction pressure that improves hydrogenation reaction system reduces the influence that brings to overcome hydrogen purity.
Can increase the part investment though improve the pressure of hydrogenation reaction system, but the investment that the investment that hydrogen recovery system reduces increases much larger than hydrogenation reaction system, the hydrogen recovery process has reduced hydrogen, liquefied gas, light naphthar loss simultaneously, guaranteeing obviously to have improved the integral benefit of hydrogenation unit under the constant prerequisite of hydrogenation reaction system effect.Method of the present invention can be applied in utilizes High Purity Hydrogen as a supplement on the various hydrogenation units of hydrogen.
Description of drawings
Fig. 1: hydrogenation unit hydrogen recovery schematic flow sheet of the present invention.
Fig. 2: existing hydrogenation unit hydrogen recovery schematic flow sheet.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment and accompanying drawing, protection scope of the present invention is not limited to following embodiment.
Certain 150x10 of company
4The t/a hydroeracking unit.
Enter the hydrogen make-up compressor by the next new hydrogen of hydrogen pipe network and divide flow container 1, enter reactive system 2 after boosting through compressor, reaction product enters high pressure hot separator 3 and carries out gas-liquid separation;
The gas that high pressure hot separator 3 obtains is gone into cold high pressure separator 4 through overcooling is laggard, and mode and the water-cooled mode of air-cooler adopted in cooling, and water filling before cooling; The gas that cold high pressure separator 4 obtains is back to reactive system 2 through after boosting; The liquid phase that cold high pressure separator 4 obtains enters cold low separator 5 after reducing pressure; The hydrogen-rich gas that cold low separator 5 obtains enters hydrogen recovery system 8; Recover hydrogen is back to the hydrogen make-up compressor and divides flow container 1.
Liquid that high pressure hot separator 3 obtains enters thermal low-pressure separators 6 after through decompression, and the gas that thermal low-pressure separators 6 obtains is gone into flash tank 7 through overcooling is laggard, and flashed vapour directly is back to the hydrogen make-up compressor and divides flow container 1 without hydrogen recovery system 8.
The pressure of hydrogen make-up (new hydrogen) is 2.1MPa, and hydrogen purity is 99.9 (mole) %; The pressure of flashed vapour is 2.1MPa, and hydrogen purity is 80 (mole) %; The hydrogen purity that enters reactive system 2 after the mixing is 97.2 (mole) %;
The inlet pressure of reactor 2 is 16.94MPa; The working pressure of high-pressure separator 3 is: 15.72MPa, service temperature are 260 ℃; The working pressure of cold high pressure separator 4 is that 15.5MPa, service temperature are 50 ℃; The working pressure of cold low separator 5 is that 2.3MPa, service temperature are 50 ℃; The working pressure of thermal low-pressure separators 6 is that 2.4MPa, service temperature are 260 ℃; The working pressure of flash tank 7 is that 2.3MPa, service temperature are 50 ℃; The inlet pressure of hydrogen recovery system 8 is 2.2MPa, and it is 2.1MPa that recover hydrogen is returned the pressure that the hydrogen make-up compressor divides flow container 1, and recover hydrogen purity is 99.9 (mole) %.
The hydrogen make-up that hydrogenation unit needs (new hydrogen) flow is 4568.5kg/h, and the actual chemistry consumption of device hydrogen is 4481kg/h; The nominal scale of hydrogen recovery system 8 is 1000x10
4Nm
3/ a, actual recovered hydrogen 105.7kg/h; The liquefied gas product is 6484.4kg/h, and light naphtha product is 14078kg/h.
Comparative Examples 1
Certain 150x10 of company
4The t/a hydroeracking unit.(not implementing the flashed vapour flow process transforms preceding)
Enter the hydrogen make-up compressor by the next new hydrogen of hydrogen pipe network and divide flow container 1, enter reactive system 2 after boosting through compressor, reaction product enters high pressure hot separator 3 and carries out gas-liquid separation;
The gas that high pressure hot separator 3 obtains is gone into cold high pressure separator 4 through overcooling is laggard, and mode and the water-cooled mode of air-cooler adopted in cooling, and water filling before cooling; The gas that cold high pressure separator 4 obtains is back to reactive system 2 through after boosting; The liquid phase that cold high pressure separator 4 obtains enters cold low separator 5 after reducing pressure; The hydrogen-rich gas that cold low separator 5 obtains enters hydrogen recovery system 8.
Liquid that high pressure hot separator 3 obtains enters thermal low-pressure separators 6 after through decompression, and the gas that thermal low-pressure separators 6 obtains is gone into flash tank 7 through overcooling is laggard, and flashed vapour enters hydrogen recovery system 8, and recover hydrogen is back to the hydrogen make-up compressor and divides flow container 1.
The pressure of hydrogen make-up (new hydrogen) is 2.1MPa, and hydrogen make-up purity is 99.9 (mole) %.
The inlet pressure of reactor 2 is 16.44MPa; The working pressure of high-pressure separator 3 is: 15.22MPa, service temperature are 260 ℃; The working pressure of cold high pressure separator 4 is that 15.0MPa, service temperature are 50 ℃; The working pressure of cold low separator 5 is that 2.3MPa, service temperature are 50 ℃; The working pressure of thermal low-pressure separators 6 is that 2.4MPa, service temperature are 260 ℃; The working pressure of flash tank 7 is that 2.3MPa, service temperature are 50 ℃; The inlet pressure of hydrogen recovery system 8 is 2.2MPa, and it is 2.1MPa that recover hydrogen is returned the pressure that the hydrogen make-up compressor divides flow container 1, and recover hydrogen purity is 99.9 (mole) %.
The hydrogen make-up that hydrogenation unit needs (new hydrogen) flow is 4635kg/h, and the actual chemistry consumption of device hydrogen is 4481kg/h; The nominal scale of hydrogen recovery system 8 is 12100x10
4Nm
3/ a, actual recovered hydrogen 641.3kg/h; The liquefied gas product is 5799.4kg/h, and light naphtha product is 13518kg/h.
Embodiment compares with Comparative Examples, and it is about 3% that the pressure of hydrogenation reaction system improves, and the investment of hydrogenation reaction system increases by 1,000,000 yuan, and hydrogen recovery system is reduced investment outlay 1,000 ten thousand yuan, and the gross investment of hydrogenation unit is saved 9,000,000 yuan; Simultaneously, hydrogen loss reduces 558.6 tons/year, and the liquefied gas loss reduces 5754 tons/year, and the petroleum naphtha loss reduces 4704 tons/year.
Claims (5)
1. the hydrogen recycling method of a hydrogenation unit, this method may further comprise the steps:
A. the hydrogen make-up of being come by the hydrogen pipe network enters the reactive system [2] of hydrogenation unit, and reaction product enters high pressure hot separator [3] and carries out gas-liquid separation;
B. separate the gas obtain by step a high pressure hot separator [3] and go into cold high pressure separator [4] through overcooling is laggard; The gas that is obtained by cold high pressure separator [4] is back to reactive system [2] through after boosting, and the liquid phase that obtains enters cold low separator [5] after reducing pressure; The hydrogen-rich gas that is obtained by cold low separator [5] enters hydrogen recovery system [8], and the recover hydrogen that obtains is back to reactive system [2] or is back to the hydrogen pipe network;
C. separate the liquid obtain by step a high pressure hot separator [3] and entering thermal low-pressure separators [6] after through decompression, the gas that is obtained by thermal low-pressure separators [6] is gone into flash tank [7] through overcooling is laggard, and the flashed vapour that obtains is back to reactive system [2];
The service temperature of described high pressure hot separator [3] is 150～400 ℃, and working pressure is 4.0～20MPa; The service temperature of described cold high pressure separator [4] is 35～60 ℃, and working pressure is 3.5～20MPa; The service temperature of described cold low separator [5] is 35～60 ℃, and working pressure is 0.70～5.0MPa; The service temperature of described thermal low-pressure separators [6] is 150～400 ℃, and working pressure is 0.70～5.0MPa; The service temperature of described flash tank [7] is 35～60 ℃, and working pressure is 0.70～5.0MPa.
2. hydrogen recycling method according to claim 1 is characterized in that:
The recover hydrogen that is obtained by step b and directly be back to the hydrogen make-up suction port of compressor by the flashed vapour that step c obtains and divide between flow container or hydrogen make-up compressor stage and divide flow container.
3. hydrogen recycling method according to claim 1 is characterized in that:
Hydrogen recovery system [8] adopts membrane sepn or transformation/alternating temperature adsorption separating method recover hydrogen.
4. hydrogen recycling method according to claim 1 is characterized in that:
Separated the gas water filling before cooling that obtains by high pressure hot separator [3].
5. hydrogen recycling method according to claim 1 is characterized in that:
Cooling separates the gas that obtains by high pressure hot separator [3], adopts air-cooler or/and watercooler.
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| CN102863985A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Combined hydrogenation method |
| CN102399584B (en) * | 2011-10-12 | 2014-06-25 | 中国石油化工股份有限公司 | Hydrogen combined optimized utilization technology of hydrogenation apparatus |
| US20160038854A1 (en) * | 2013-01-30 | 2016-02-11 | East China University Of Science And Technology | Method and apparatus for improving hydrogen utilization rate of hydrogenation apparatus |
| CN103320161B (en) * | 2013-06-17 | 2015-04-15 | 华东理工大学 | Method and apparatus for improving hydrogen utilization rate of hydrogenation equipment |
| CN105712814A (en) * | 2014-12-05 | 2016-06-29 | 中国石油化工股份有限公司 | Improved separation method |
| CN104845664A (en) * | 2015-05-08 | 2015-08-19 | 北京中科诚毅科技发展有限公司 | Multiple-optimizing separator combined systems as well as use method and design method |
| FR3039562B1 (en) * | 2015-07-28 | 2017-07-28 | Ifp Energies Now | OPTIMIZATION OF THE USE OF HYDROGEN FOR THE HYDROTREATMENT OF HYDROCARBON LOADS |
| CN107141196A (en) * | 2017-06-27 | 2017-09-08 | 查都（上海）科技有限公司 | A kind of 1,4 butynediols two-stage hydrogenation systems |
| CN111378474B (en) * | 2018-12-28 | 2021-03-05 | 中国石油化工股份有限公司 | Treatment system and method for improving hydrogen partial pressure of hydrogenation device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1923972A (en) * | 2006-09-06 | 2007-03-07 | 中国石油化工集团公司 | Hydrocarbons hydrocracking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1923972A (en) * | 2006-09-06 | 2007-03-07 | 中国石油化工集团公司 | Hydrocarbons hydrocracking method |
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Address after: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Patentee after: SINOPEC Group Patentee after: Sinopec Engineering Construction Co., Ltd Address before: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: Sinopec Engineering Incorporation |