CN103525491A - Method and device for removing hydrogen sulfide in shale gas with high sulfur content - Google Patents
Method and device for removing hydrogen sulfide in shale gas with high sulfur content Download PDFInfo
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- CN103525491A CN103525491A CN201310496883.5A CN201310496883A CN103525491A CN 103525491 A CN103525491 A CN 103525491A CN 201310496883 A CN201310496883 A CN 201310496883A CN 103525491 A CN103525491 A CN 103525491A
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Abstract
The invention relates to a method and device for removing hydrogen sulfide in shale gas with high sulfur content, and particularly relates to a method for removing hydrogen sulfide in shale gas with high sulfur content. The method comprises the following steps of (1) filtering and separating the shale gas with high sulfur content to remove contained solid particles and liquid drops in the shale gas; (2) sequentially carrying out primary amine desulfuration and secondary amine desulfuration on the filtered shale gas with high sulfur content, wherein the desulfuration process intensification and amine solution removal coupling operation is realized by using a rotational flow field provided by a micro rotational flow in an amine desulfuration process, and a desulfurized shale gas product which does not contain amine liquid drops is obtained; (3) carrying out flash distillation on an amine rich solution to remove light hydrocarbon, and then, regenerating an amine solution to ensure that the amine solution can be recycled, wherein the amine solution is obtained in the amine desulfuration process. The invention also provides a device for removing hydrogen sulfide in shale gas with high sulfur content.
Description
Technical field
The invention belongs to chemical industry environmental protection field, relate to the method and apparatus that a kind of high sulfur-bearing shale gas removes hydrogen sulfide.
Background technology
Shale gas be take methane as main, is a kind of clean energy, as unconventional Sweet natural gas, has caused various countries' extensive concern.Along with the continuous progress of horizontal well and fracturing technique level, shale gas exploratory development is forming upsurge.Along with the large-scale development of the U.S., shale gas has become the focus that world energy sources field is paid close attention to simultaneously.And China's shale gas workable reserve reaches 25.08 billion cubic meters, occupy the first in the world, therefrom on long terms, shale gas will provide the sufficient energy for China.
Investigation according to U.S. NRDC to Chinese shale gas field, the shale structure of China contains the hydrogen sulfide that reaches harmful concentration level (1% or more).Hydrogen sulfide is a kind of flammable poisonous gas.The Weiyuan shale gas block hydrogen sulfide content concentration in the Sichuan Basin is between 0.8% to 1.4%, and carbon isotopic piece hydrogen sulfide content concentration is up to 15%.Therefore, in shale gas pre-treatment hydrogen sulfide remove very important.
Yet the hydrogen sulfide content of general shale gas is at hundreds of mg/Nm
3purifying method adopts MDEA(methyldiethanolamine conventionally) hydraulic performance of solution in absorption tower absorb, in absorption tower, except pressure drop and liquid flooding are calculated, in gas processing technique, the actual hydromechanics that gas processing slip-stick artist does not pay special attention to tower conventionally flows.Yet the composition of the gas-liquid mixture of tray surfaces but has significant impact to column plate selectivity.Therefore, in shale gas processing new way, explore a kind of new strategy, by device column plate is carried out to special design, processed shale gas, and understood the mobile radially mass transport properties different from the column plate of jet flow state of foam.
Bar Nat shale gas is processed and is adopted single overflow valve tray, and the plate efficiency of balance state model and hypothesis, utilizes after desulfurization promotor strengthening absorption agent MDEA solvent absorbing, has realized 73% design production capacity.According to modeling determining, shale gas hydrogen sulfide content can be reduced to 4ppmv.Yet this method cannot continue to improve production capacity because device internals limit, and therefore need to transform absorption tower, or build a higher new absorption tower, will cause investment more thus, and the utilization of resources increases.Yet this method is tens ppm for shale gas sulphur content, this shale gas for Chinese high hydrogen sulfide content is improper, therefore need to upgrade purifying method.
Natural gas desulfur method for the high-hydrogen sulfide of current China, Chinese patent application CN101082007A discloses a kind of method of removing gaseous state organosulfur compound in fuel gas stream, the method mainly utilizes gas stream to contact with sorbent material, carry out gas-solid separating method and carry out desulfurization processing, the sorbent material utilizing is the clay mineral from fiber rod stone class.The processing of the organosulfur that comprises in Sweet natural gas has mainly been considered in this patent application, and does not take into full account for inorganic sulfur hydrogen sulfide and sulfurous gas etc., and adopts solid adsorbent will increase the degree of difficulty of regenerative operation.
Chinese patent application CN102477331A discloses a kind of desulphurization system for natural gas containing high-content sulfur, and this system mainly comprises raw natural gas storing unit, interchanger, desulfurizer, filtration equipment for clarifying and retrieving arrangement etc.This system has been carried out effective desulfurization to raw natural gas, and whole facility investment is low, flow process simple, sweetening agent number of dropouts is little.Yet the desulfurization precision of this patent application is lower, the sweetening agent adopting is that common alkali lye sweetening effectiveness is relatively general.
Chinese patent application CN101831333A disclose a kind of for oil-gas field development the method for desulphurizing natural gas in oil and gas fields to hydrogen sulfide bearing gas and oil well associated gas desulfurization, mainly utilize the effect of a plurality of series connection thionizer reinforcing mass transfer to carry out desulfurization processing, this patent application is by the classification processing mode of connecting, the height that has lowered tower, has improved mass-transfer efficiency.Yet it is bulky to use merely desulfuration absorbing tower to carry out desulfurization treatment facility, and sorbent consumption is large, and desulfurization precision is low.
Chinese patent application CN102977964A discloses a kind of Sweet natural gas and has removed desulfurization solvent consumption-reducing method and device in organic and inorganic sulfur process, by increase the micro-cyclonic separation of solution-air between absorbing hydrogen sulphide and tempreture organic sulphur hydrolysis process for the first time, to remove the rich amine liquid of carrying secretly in raw natural gas, after tempreture organic sulphur hydrolysis, hydrogen sulfide absorption tower top inside adopts the micro-cyclonic separation of solution-air simultaneously, remove amine liquid, reached the object lowering consumption in selexol process process.Chinese patent application CN103031171A discloses solvent foaming prevention method and device in Natural Gas Amine method sweetening process, and first this application utilizes entrained solid granulometric impurity and C in cyclonic separation gas
4and above heavy hydrocarbon, purified natural gas, and then before leaving absorption tower, adopt the micro-cyclone separation process of solution-air by the solvent recuperation of carrying secretly in Sweet natural gas.These patent applications have taken into full account that the micro-cyclonic separation of solution-air reclaims for amine liquid or to gas cleaning, but integrated artistic can not meet due to the new demand for turndown ratio and desulfurization precision of the high sulphur property of high sulfur-bearing shale gas.
Above patent documentation only relates to the method and apparatus of low sulfur-bearing shale gas processing and gas conditioning, about the high sulfur-bearing shale gas processing in China's part gas field, there is no patent documentation relates to, and the patent application of at present domestic relevant shale gas also only limits to develop volume increase aspect, and process application aspect for shale gas, also do not have and relate to.Therefore, researching and developing method and apparatus that a kind of high sulfur-bearing shale gas removes hydrogen sulfide has high economic society and is worth.
Summary of the invention
The high sulfur-bearing shale gas that the invention provides a kind of novelty removes the method and apparatus of hydrogen sulfide, adopt the method for the micro-cyclonic separation combination of two-stage amine absorption and two-stage, by absorption tower, operate, abundant absorbing hydrogen sulphide gas, at absorbing tower top, divide swirler part is set simultaneously, the further desulfurization of gas is processed, the amine liquid droplet of while cyclonic separation gas entrainment, the shale gas that makes to process reaches the requirement of product specification, realize green low-carbon and produce, thereby solved problems of the prior art.
On the one hand, the invention provides a kind of method that high sulfur-bearing shale gas removes hydrogen sulfide, the method comprises the following steps:
(1) high sulfur-bearing shale gas is implemented to filtering separation, to remove wherein entrained solid particle and drop;
(2) the high sulfur-bearing shale gas after filtering is implemented to the desulfurization of primary amine method and the desulfurization of secondary amine method successively, wherein, the rotational flow field that utilizes micro-eddy flow to provide in amine method sweetening process is realized the coupling operation that sweetening process is strengthened and amine liquid removes, and obtains the desulfurization shale gas product that does not contain amine liquid drop; And
(3) the rich amine liquid obtaining in amine method sweetening process is implemented to the de-lighter hydrocarbons of flash distillation, carry out afterwards the regeneration of amine liquid, so that amine liquid recycles.
One preferred embodiment in, the concentration of hydrogen sulfide that described high sulfur-bearing shale gas contains is greater than 5000mg/Nm
3, service temperature is 30-70 ℃.
Another preferred embodiment in, the absorption agent that described amine method sweetening process adopts is the MDEA solution of concentration 20-50 % by weight, by the column plate in amine absorption tower or filler, provides reacting environment to realize the mass transfer of MDEA solution and gas.
Another preferred embodiment in, the desulfurization of described primary amine method and the desulfurization of secondary amine method are serial operation, the rich amine liquid of described secondary amine method desulfurization gained, for the thick absorption of described primary amine method desulfurization, is realized amine liquid and is used by rich or poor grade classification.
On the other hand, the invention provides the device that a kind of high sulfur-bearing shale gas removes hydrogen sulfide, this device comprises:
Charging filter separator, for high sulfur-bearing shale gas is implemented to filtering separation, to remove wherein entrained solid particle and drop;
The primary amine liquid absorption tower being connected with the outlet of charging filter separator, for implementing the desulfurization of primary amine method to the high sulfur-bearing shale gas after filtering;
The secondary amine liquid absorption tower being connected with the gaseous phase outlet on primary amine liquid absorption tower, for implementing the desulfurization of secondary amine method;
Middle amine liquid pump with the rich amine liquid outlet on secondary amine liquid absorption tower is connected, uses for the rich amine liquid pump on secondary amine liquid absorption tower being delivered to the classification of primary amine liquid absorption tower;
With the rich amine liquid flash tank that the rich amine liquid outlet on primary amine liquid absorption tower is connected, for the rich amine liquid that amine method sweetening process is obtained, implement the de-lighter hydrocarbons of flash distillation;
The middle amine liquid pump being connected with the liquid-phase outlet of rich amine liquid flash tank, carries out the regeneration of amine liquid for rich amine liquid is evacuated to amine liquid regenerator column, and the poor amine liquid of gained is delivered to the absorption tower recycle of secondary amine liquid, and high-concentration acidic wastewater pneumatic transmission reclaims to sulphur recovery unit;
Wherein, described primary amine liquid absorption tower and top, secondary amine liquid absorption tower arrange micro-a cluster cyclone, for the rotational flow field that utilizes micro-eddy flow to provide in amine method sweetening process, realize the coupling operation that sweetening process is strengthened and amine liquid removes, obtain the desulfurization shale gas product that does not contain amine liquid drop.
One preferred embodiment in, high sulfur-bearing shale gas and amine liquid complete after mass transfer on amine absorption tower column plate or filler, carry the amine liquid drop being atomized secretly and enter the coupling operation that micro-swirler completes the de-amine of cyclone desulfuration and eddy flow; The cyclone desulfuration efficiency of described micro-a cluster cyclone is not less than 90%, and drop separation efficiency is not less than 90%.
Another preferred embodiment in, described primary amine liquid absorption tower adopts tray column structure, desulfurization degree is not less than 95%; Described secondary amine liquid absorption tower adopts packing tower structure, and desulfurization degree is not less than 95%.
Accompanying drawing explanation
According to carrying out following detailed description by reference to the accompanying drawings, it is more obvious that object of the present invention and feature will become, in accompanying drawing:
Fig. 1 is according to the schematic diagram of the high sulfur-bearing shale gas desulfurization process of an embodiment of the invention.
Embodiment
Present inventor finds after having passed through extensive and deep research: shale gas sulphur content is higher, if adopt traditional desulfurization technology, required equipment volume is large, and energy waste is higher; And under Elevated Gravity, microcosmic mixes and mass transfer process is greatly strengthened, the traditional tower (packing tower or tray column) of interphase mass transfer speed ratio improves 1-3 the order of magnitude; High gravity technology is considered to a new technology of strengthening transmission and heterogeneous reaction process; Hypergravity can be accomplished in several ways, and one of them is to adopt micro-swirler; In addition,, in the rotational flow field forming in micro-swirler, drop is subject to the effect of shearing force and high speed rotation, fragmentation, constantly updates the surface in contact with hydrogen sulfide molecule, carries out absorption reaction, has also realized the strengthening for sweetening process; Meanwhile, due in rotational flow field, particle is subject to the effect of centrifugal force simultaneously, makes drop that the revolution motion around swirler axis occur, and can realize again drop (amine liquid) is trapped, separated from gas; By the use of micro-swirler, can reach the coupling operation of the de-amine of cyclone desulfuration and eddy flow, greatly strengthened sweetening process, desulfuration efficiency improves 0.2-5% compared with traditional technology, can avoid again the amine liquid of sweetening process simultaneously for the secondary pollution of desulfurization shale gas product, the race of reduction amine liquid is damaged.Based on above-mentioned discovery, the present invention is accomplished.
In a first aspect of the present invention, provide a kind of high sulfur-bearing shale gas to remove the method for hydrogen sulfide, to obtain, meet the shale gas product that sulphur content requires, the method comprises:
High sulfur-bearing shale gas is implemented to filtering separation, to remove entrained solid particle and drop, guarantee subsequent technique equipment not because solid particulate affects the operation efficiency of equipment or the working time of reducing device;
High sulfur-bearing shale gas after filtering is implemented to one-level, the desulfurization of secondary amine method successively, improve sulfur removal technology for turndown ratio and the desulfurization precision of high sulfur-bearing shale gas, realize the object of deep desulfuration, obtain meeting the desulfurization shale gas product of product specification, wherein, the rotational flow field that utilizes micro-swirler to provide in two-stage amine method sweetening process is realized the coupling operation that cyclone desulfuration and amine liquid remove, by the particle rotation behavior in the rotational flow field forming in micro-swirler, constantly upgrade amine liquid with surface in contact and the Elevated Gravity reinforcing desulfuration process of hydrogen sulfide molecule, utilize the revolution behavior for amine liquid drop in rotational flow field to complete the trapping for amine liquid simultaneously, separated, finally realize the raising of desulfurization precision and avoid desulfurization shale gas product carrying secretly for amine liquid, obtain the desulfurization shale gas product that does not contain amine liquid drop, also avoided the race of amine liquid to damage,
Rich amine liquid in amine method sweetening process is implemented, after the de-lighter hydrocarbons of flash distillation, to carry out the regeneration of amine liquid, amine liquid be can be recycled.
In the present invention, the sulphur content of described high sulfur-bearing shale gas is greater than 5000mg/Nm
3, the service temperature of system is about 30-70 ℃.
In the present invention, the absorption agent that described amine method sweetening process adopts is the MDEA solution of concentration 20-50 % by weight, in amine absorption tower, MDEA solution contacts with back flow of gas, by the column plate in absorption tower or filler, provides reacting environment to realize the mass transfer of MDEA solution and gas.
In the present invention, described one-level, the desulfurization of secondary amine method are serial operation, to improve desulfurization precision, realize deep desulfuration, guarantee that the concentration of hydrogen sulfide of outlet desulfurization shale gas product is up to standard; Meanwhile, the rich amine liquid of described secondary amine method desulfurization, for the thick absorption of described primary amine method desulfurization, is realized amine liquid and is used by rich or poor grade classification, the whole amine liquid usage quantity of reduction system, the energy consumption that amine liquid is regenerated that reduced.
In a second aspect of the present invention, provide a kind of high sulfur-bearing shale gas to remove the device of hydrogen sulfide, to realize, the high precision desulfurization of high sulfur-bearing shale gas to be processed, this device comprises:
For removing drop that gas carries and the charging filter separator of solid particulate;
The primary amine liquid absorption tower connecting with the outlet of charging filter separator, for realizing primary amine method desulfurization operations;
The secondary amine liquid absorption tower connecting with the gaseous phase outlet of one-level amine absorption tower, for realizing secondary amine method desulfurization operations;
Rich amine liquid with secondary amine liquid absorption tower exports the middle amine liquid pump connecting, and for the rich amine liquid pump on secondary amine liquid absorption tower being delivered to the classification of primary amine liquid absorption tower, uses;
Rich amine liquid with one-level amine absorption tower exports the rich amine liquid flash tank connecting, and for the lighter hydrocarbons that rich amine liquid is carried, flashes off;
The middle amine liquid pump connecting with the liquid-phase outlet of rich amine liquid flash tank, carries out amine liquid manipulation of regeneration for rich amine liquid is evacuated to amine liquid regenerator column, and the poor amine liquid of gained is delivered to the absorption tower recycle of secondary amine liquid, and high-concentration acidic wastewater pneumatic transmission reclaims to sulphur recovery unit.
In the present invention, because tray column is applicable to easy fouling, stops up system, and packing tower is applicable to foaming system, high sulfur-bearing shale gas through charging filter separator and primary amine liquid absorption tower still may carry small particle, thereby have influence on the long-term operation of device, therefore, secondary amine liquid absorption tower is stricter for the requirement of desulfurization.
In the present invention, described primary amine liquid absorption tower adopts tray column structure, and desulfurization degree is not less than 95%; Described secondary amine liquid absorption tower adopts packing tower structure, and desulfurization degree is not less than 95%.
In the present invention, the top on described primary amine liquid absorption tower and secondary amine liquid absorption tower arranges micro-a cluster cyclone, high sulfur-bearing shale gas and amine liquid complete after mass transfer on column plate or filler, carry the amine liquid drop being atomized secretly and enter the coupling operation that micro-swirler completes cyclone desulfuration and the de-amine of eddy flow, the cyclone desulfuration efficiency of described micro-a cluster cyclone is not less than 90%, drop separation efficiency is not less than 90%, realize the raising of desulfurization precision and avoid desulfurization shale gas product carrying secretly for amine liquid, obtain the desulfurization shale gas product that does not contain amine liquid drop, and reduced the race damage amount of amine liquid.
In the present invention, by cyclone desulfuration and the de-amine coupling operation of eddy flow, strengthened mass transfer process, having reduced amine absorption tower front and back may need minute flow container equipment arranging, and has reduced facility investment.
Below describe with reference to the accompanying drawings apparatus structure of the present invention and method in detail.
Fig. 1 is according to the schematic diagram of the high sulfur-bearing shale gas desulfurization process of an embodiment of the invention.As shown in Figure 1, shale gas charging enters charging filter separator 1 and the charging filter separator 2 being connected in series, the drop and the solid particulate that to remove gas, carry, and sour water is expelled to battery limit (BL) by the bottom of charging filter separator 1 and charging filter separator 2; High sulfur-bearing shale gas after filtration enters primary amine liquid absorption tower 3 and the secondary amine liquid absorption tower 4 being connected in series successively, to carry out the desulfurization of primary amine method and the desulfurization of secondary amine method, wherein, the top on described primary amine liquid absorption tower 3 and secondary amine liquid absorption tower 4 arranges micro-a cluster cyclone, with the rotational flow field that utilizes micro-swirler to provide, realize the coupling operation that sweetening process is strengthened and amine liquid removes, obtain the desulfurization shale gas that does not contain amine liquid drop; The desulfurization shale gas of gained is discharged by the top on secondary amine liquid absorption tower 4, and rich amine liquid is pumped to 3 classifications of primary amine liquid absorption tower by the rich amine liquid outlet on secondary amine liquid absorption tower 4 through middle amine liquid pump 7 and uses; The rich amine liquid of gained is delivered to rich amine liquid flash tank 5 by the rich amine liquid outlet on primary amine liquid absorption tower 3, with the lighter hydrocarbons that rich amine liquid is carried, flashes off; Through the rich amine liquid of flash distillation, by the liquid-phase outlet of rich amine liquid flash tank 5, through middle amine liquid pump 8, be evacuated to amine liquid regenerator column 6 and carry out amine liquid manipulation of regeneration, the poor amine liquid of gained returns to amine liquid regenerator column 6 regeneration through amine liquid regenerator column reboiler 11 rear section of heavily boiling, part is through middle amine liquid pump 9, and together enter 4 recycles of secondary amine liquid absorption tower with external poor amine liquid after interchanger 10 heat exchange, high-concentration acidic wastewater gas returns to 6 regeneration of amine liquid regenerator column after 12 condensations of amine liquid regeneration overhead condenser, and part is delivered to sulphur recovery unit and reclaimed.
Major advantage of the present invention is:
1) the present invention adopts two-stage amine method desulfurization serial operation, makes shale gas sulphur content reach product specification requirement, has effectively improved turndown ratio and desulfurization precision for the desulfurization of high sulfur-bearing shale gas, realizes the object of deep desulfuration; The rich amine liquid of secondary amine method desulfurization simultaneously, for the thick absorption of primary amine method desulfurization, has been realized the rich or poor grade classification of amine liquid and has been used, and has reduced the usage quantity of amine liquid, reduces the whole energy consumption of system;
2) by the application of micro-swirler, realized the coupling operation of the de-amine of cyclone desulfuration and eddy flow, both strengthen mass-transfer progress, improved desulfurization precision, what completed again amine liquid drop removes, avoids in sweetening process amine liquid for the secondary pollution of desulfurization shale gas product, also reduce simultaneously amine liquid race damage amount, reduced the running cost of desulfurization.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.But, should be understood that these embodiment only do not form limitation of the scope of the invention for the present invention is described.The test method of unreceipted actual conditions in the following example, conventionally 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:
At 50,000 m
3the high sulfur-bearing shale gas of/h is produced in treatment process, the device that employing is implemented according to method of the present invention, in order to carry out absorption extraction to containing the acid shale gas of hydrogen sulfide, make shale gas reach the requirement of product specification, its concrete operation and effect are described below:
1. the character of pending gas and operational condition
Pending gas is high sulfur-bearing shale gas, and main component is alkane, and wherein methane accounts for the overwhelming majority, and a small amount of ethane, propane and butane, generally also contain in addition hydrogen sulfide, carbonic acid gas, nitrogen and aqueous vapor, and the rare gas element of trace, as helium and argon etc., concrete sulphur content is about 1%.Gas conditioning amount is 50,000 m
3/ h, density of gas phase service temperature is 50 ℃.Absorption agent is N-methyl glycol amine aqueous solution (methyldiethanolamine), and concentration is 50%.
2. implementation process
As shown in Figure 1.
High sulfur-bearing shale gas removes liquid and the solid particulate carrying through charging filter separator; Then enter two-stage amine absorption tower and carry out the desulfurization of amine method; Amine absorption top of tower arranges a cluster cyclone, utilizes micro-swirler by the desulfurization of amine liquid, cyclone desulfuration, the de-amine coupling of eddy flow, carries out the absorption of hydrogen sulfide and removing of amine liquid; Gained low-sulfur shale gas enters dewatering unit to be continued to process, and to regenerator column, regenerates after the flash distillation of rich amine liquid, and the middle amine liquid pump of regeneration lean solution utilization returns to desulphurization system and recycles.
3. interpretation of result
3.1 the method for sampling
Respectively at primary amine liquid absorption tower gas phase entrance, primary amine liquid absorption tower gaseous phase outlet, gaseous phase outlet place, secondary amine liquid absorption tower, utilize sebific duct sampling valve and alkali cleaning bottle, syringe to sample.
3.2 analytical procedure
Adopt SN/T2943-2011 " the painted length method of mensuration detector tube of hydrogen sulfide in natural gas content " to carry out hydrogen sulfide content detection.
3.3 interpretation of result
The hydrogen sulfide content of separator gaseous phase outlet is not more than 4.5mg/Nm
3(3ppm), as shown in table 1 below.Firsts and seconds amine absorption tower tradition absorption portion desulfurization degree is greater than 95%, and swirler partial desulfurization rate is greater than 90%, and separation efficiency is about 90%.
Table 1
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (7)
1. high sulfur-bearing shale gas removes a method for hydrogen sulfide, and the method comprises the following steps:
(1) high sulfur-bearing shale gas is implemented to filtering separation, to remove wherein entrained solid particle and drop;
(2) the high sulfur-bearing shale gas after filtering is implemented to the desulfurization of primary amine method and the desulfurization of secondary amine method successively, wherein, the rotational flow field that utilizes micro-eddy flow to provide in amine method sweetening process is realized the coupling operation that sweetening process is strengthened and amine liquid removes, and obtains the desulfurization shale gas product that does not contain amine liquid drop; And
(3) the rich amine liquid obtaining in amine method sweetening process is implemented to the de-lighter hydrocarbons of flash distillation, carry out afterwards the regeneration of amine liquid, so that amine liquid recycles.
2. the method for claim 1, is characterized in that, the concentration of hydrogen sulfide that described high sulfur-bearing shale gas contains is greater than 5000mg/Nm
3, service temperature is 30-70 ℃.
3. the method for claim 1, is characterized in that, the absorption agent that described amine method sweetening process adopts is the MDEA solution of concentration 20-50 % by weight, by the column plate in amine absorption tower or filler, provides reacting environment to realize the mass transfer of MDEA solution and gas.
4. the method for claim 1, it is characterized in that, the desulfurization of described primary amine method and the desulfurization of secondary amine method are serial operation, and the rich amine liquid of described secondary amine method desulfurization gained, for the thick absorption of described primary amine method desulfurization, is realized amine liquid and used by rich or poor grade classification.
5. high sulfur-bearing shale gas removes a device for hydrogen sulfide, and this device comprises:
Charging filter separator (1,2), for high sulfur-bearing shale gas is implemented to filtering separation, to remove wherein entrained solid particle and drop;
The primary amine liquid absorption tower (3) being connected with the outlet of charging filter separator (2), for implementing the desulfurization of primary amine method to the high sulfur-bearing shale gas after filtering;
The secondary amine liquid absorption tower (4) being connected with the gaseous phase outlet on primary amine liquid absorption tower (3), for implementing the desulfurization of secondary amine method;
Middle amine liquid pump (7) with the rich amine liquid outlet on secondary amine liquid absorption tower (4) is connected, uses for the rich amine liquid pump on secondary amine liquid absorption tower (4) being delivered to primary amine liquid absorption tower (3) classification;
With the rich amine liquid flash tank (5) that the rich amine liquid outlet on primary amine liquid absorption tower (3) is connected, for the rich amine liquid that amine method sweetening process is obtained, implement the de-lighter hydrocarbons of flash distillation;
The middle amine liquid pump (8) being connected with the liquid-phase outlet of rich amine liquid flash tank (5), for being evacuated to amine liquid regenerator column (6), rich amine liquid carries out the regeneration of amine liquid, the poor amine liquid of gained is delivered to secondary amine liquid absorption tower (4) recycle, and high-concentration acidic wastewater pneumatic transmission reclaims to sulphur recovery unit
Wherein, described primary amine liquid absorption tower (3) and top, secondary amine liquid absorption tower (4) arrange micro-a cluster cyclone, for the rotational flow field that utilizes micro-eddy flow to provide in amine method sweetening process, realize the coupling operation that sweetening process is strengthened and amine liquid removes, obtain the desulfurization shale gas product that does not contain amine liquid drop.
6. device as claimed in claim 5, is characterized in that, high sulfur-bearing shale gas and amine liquid complete after mass transfer on amine absorption tower column plate or filler, carries the amine liquid drop being atomized secretly and enters the coupling operation that micro-swirler completes cyclone desulfuration and the de-amine of eddy flow; The cyclone desulfuration efficiency of described micro-a cluster cyclone is not less than 90%, and drop separation efficiency is not less than 90%.
7. device as claimed in claim 5, is characterized in that, described primary amine liquid absorption tower (3) adopts tray column structure, and desulfurization degree is not less than 95%; Described secondary amine liquid absorption tower adopts packing tower structure, and desulfurization degree is not less than 95%.
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| CN108367231A (en) * | 2015-10-27 | 2018-08-03 | 氟石科技公司 | The structures and methods for processing high pressure sour gas with zero-emission |
| CN109652641A (en) * | 2018-11-19 | 2019-04-19 | 北京汉唐环保科技股份有限公司 | Ilmenite cleaning device |
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| CN102051244A (en) * | 2009-10-28 | 2011-05-11 | 中国石油化工股份有限公司 | High-efficiency purification desulfurizer for high-acid oil and gas |
| CN101721861A (en) * | 2009-12-18 | 2010-06-09 | 上海华畅环保设备发展有限公司 | Method and device for desulphurization of recycle hydrogen |
| CN101831333A (en) * | 2010-04-18 | 2010-09-15 | 胜利油田胜利勘察设计研究院有限公司 | Method for desulphurizing natural gas in oil and gas fields |
| CN102977964A (en) * | 2012-12-26 | 2013-03-20 | 上海华畅环保设备发展有限公司 | Method and device for reducing consumption of desulfurization solvent during natural gas organic and inorganic sulfur-removing process |
| CN103031171A (en) * | 2012-12-26 | 2013-04-10 | 上海华畅环保设备发展有限公司 | Solvent foaming control method and device in amine desulfuration process of natural gas |
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| CN108367231A (en) * | 2015-10-27 | 2018-08-03 | 氟石科技公司 | The structures and methods for processing high pressure sour gas with zero-emission |
| CN109652641A (en) * | 2018-11-19 | 2019-04-19 | 北京汉唐环保科技股份有限公司 | Ilmenite cleaning device |
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