CN103773532B - The purifying treatment method of sour gas in a kind of Sweet natural gas - Google Patents
The purifying treatment method of sour gas in a kind of Sweet natural gas Download PDFInfo
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- CN103773532B CN103773532B CN201410040345.XA CN201410040345A CN103773532B CN 103773532 B CN103773532 B CN 103773532B CN 201410040345 A CN201410040345 A CN 201410040345A CN 103773532 B CN103773532 B CN 103773532B
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- sweet natural
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Abstract
The invention discloses the purifying treatment method of sour gas in a kind of Sweet natural gas, comprise the following steps: the soft solid gel with porous specific surface area to fill in purification reactor and adds hydration accelerator by (1); (2) pass into the Sweet natural gas that need purify in purification reactor, control intake pressure is 2.5 ~ 7.5MPa, and temperature of reaction is 0 ~ 10 DEG C, carries out hydration purifying treatment.The purifying treatment method reaction times of the present invention is short, and reaction process is without the need to stirring, and soft solid gelatinous material can in-situ regeneration be cycled to repeat use, and have the double effects of energy-saving and environmental protection, economic benefit and Environmental Effect Yidu are significantly improved.
Description
Technical field
The present invention relates to natural gas conditioning separating treatment field, particularly the purifying treatment method of sour gas in a kind of Sweet natural gas.
Background technology
Sweet natural gas, as a kind of energy of clean and effective, has become one of mainstay of current energy industry.Sweet natural gas main component is methane, the difference in this external cause place of production and containing a small amount of C
2h
6, C
3h
8and the H of trace
2s, CO
2, N
2and the foreign gas such as CO, the existence of foreign gas has had a strong impact on accumulating and the use of Sweet natural gas.With sour gas H
2s and CO
2for example, not only in transporting, corrode handling equipment, reduce throughput of pipeline, reduce heating value of natural gas simultaneously, bring serious harm in the deep cooling secondary industrys such as natural gas liquefaction, therefore, it is very necessary and necessary for implementing purifying treatment to Sweet natural gas.
Conventional processes for sour gas in Sweet natural gas is a lot, and mainly comprise wet method and the large class of dry method two, wet method has chemical absorption method, physical absorption method and direct oxidation method etc., and dry method has sieve method and sponge iron processes etc.Although existing multiple purifying treatment method technology is comparatively ripe, ubiquity technical process is complicated, the serious and high deficiency of methane waste of environmental pollution.
The development of gas hydrate technology gas separation an is striden forward step, less energy-consumption low cost gas delivery is purified becomes possibility.The method is mainly different with complexity based on the phase balance condition of gas with various when forming hydrate and realize gas delivery, the gas being easy to be formed hydrate preferentially forms hydrate, the gas being difficult to be formed hydrate then keeps gaseous state, so just achieves the hydration separation of mixed gas.The advantage of this technology is that technical process is simple, process environmental protection and energy saving, and is difficult to because methane has higher vapor pressure form hydrate, hardly loss methane gas in sepn process.
Patent CN103055676A proposes a kind of natural gas refining method that normal temperature ionic liquid adds low temperature hydration reaction, and this method mainly based on hydration separation principle, compares conventional purge technique in principle, has good economic benefit and environmental benefit.But the shortcoming adopting normal temperature ionic liquid to carry out low temperature hydration is that hydration is insufficient, needs to carry out repeatedly stage trapping and purify, also need to stir in hydro-combination process simultaneously, adds additional energy consumption, therefore still have some deficits and part to be modified.
Obviously, improve existing natural gas conditioning techniques and methods, reduce the energy consumption in Sweet natural gas isolation of purified process and cost energetically, be the trend and direction of Sweet natural gas isolation of purified technical development, need the new type purification method of active development energy-conserving and environment-protective on this basis.
Summary of the invention
In order to overcome the above-mentioned shortcoming of prior art with not enough, the object of the present invention is to provide the purifying treatment method of sour gas in a kind of Sweet natural gas, reaction times is short, reaction process is without the need to stirring, soft solid gelatinous material can in-situ regeneration be cycled to repeat use, have the double effects of energy-saving and environmental protection, economic benefit and Environmental Effect Yidu are significantly improved.
Object of the present invention is achieved through the following technical solutions:
A purifying treatment method for sour gas in Sweet natural gas, comprises the following steps:
(1) the soft solid gel with porous specific surface area is filled in purification reactor, and add hydration accelerator;
(2) pass into the Sweet natural gas that need purify in purification reactor, control intake pressure is 2.5 ~ 7.5MPa, and temperature of reaction is 0 ~ 10 DEG C, carries out hydration purifying treatment.
The described soft solid gel with porous specific surface area is made up through chemical gel technique by following mass percent of following raw material:
2 hydroxyethyl meth acrylates 10% ~ 40%
Linking agent ethylene glycol bisthioglycolate (methacrylic acid) ester 0.1 ~ 1%
Initiator ammonium persulfate 0.5 ~ 5%
Catalyzer Tetramethyl Ethylene Diamine 0.1 ~ 1%
Surplus is water.
Described hydration accelerator is sodium dodecyl sulfate solution, tetrabutyl phosphonium bromide ammonium solution or pentamethylene solution, but is not limited to above-mentioned three kinds.
Described soft solid gel adopts the decoration form of layered multi-stage to fill in purification reactor.
The filling ratio of described soft solid gel in purification reactor is 0.75 ~ 0.90.
The air outlet place at described purification reactor top is provided with gaseous constituent proofing unit.
When gaseous constituent proofing unit detects that the Sweet natural gas of discharging from air outlet is below standard, the Sweet natural gas of discharging from air outlet is passed in purification reactor, re-starts step (2).
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) purifying treatment method of sour gas in Sweet natural gas of the present invention, topping-up pump system is used to carry out supercharging by needing the natural air-air source of purification, because intake pressure is below methane vapor pressure, methane does not generate hydrate with this understanding, by discharging from reactor top in a gaseous form after reactor; H
2s and CO
2be captured with the form of solid water compound, reaction process is without the need to stirring, and realize the high-efficient purification of single step, the reaction times is short.
(2) soft solid gel of the present invention can in-situ regeneration repeat to recycle, manipulation of regeneration can be carried out to it when gas purification efficiency step-down, reactor temperature is maintained 40 ~ 50 DEG C, adopt type of heating that the decomposition of hydrate in gel is discharged, its intrinsic absorption hydration performance can be recovered.
(3) soft solid gel of the present invention adopts the decoration form of layered multi-stage to fill in purification reactor, guarantees that gas to be clean has sufficient reaction times and reaction contact area in reactor, increases gas purification efficiency.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the purification reactor of embodiments of the invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Figure 1 shows that the purification reactor 4 of the purifying treatment method of sour gas in the Sweet natural gas realizing the present embodiment, the top of purification reactor 4 is provided with pressure transmitter 5, temperature sensor 6, the air outlet at purification reactor 4 top is also connected with gas chromatographicanalyzer 7, and the air outlet place bottom purification reactor 4 is provided with gas boosting pump system 1.V1 ~ V6 is operate control valve.Soft solid gel 3 and hydration accelerator 2 have been housed in purification reactor 4, and soft solid gel 3 adopts the decoration form of layered multi-stage to fill in purification reactor, and the hydration accelerator of the present embodiment is sodium lauryl sulphate.
The soft solid gel with porous specific surface area of the present embodiment is made up through chemical gel technique by following mass percent of following raw material:
2 hydroxyethyl meth acrylates 10%
Linking agent ethylene glycol bisthioglycolate (methacrylic acid) ester 1%
Initiator ammonium persulfate 5%
Catalyzer Tetramethyl Ethylene Diamine 1%
Surplus is water.
The purification reactor of the purifying treatment of sour gas in the Sweet natural gas of the present embodiment, operating process is as follows:
A () starts purification reactor cooling recirculation system, make temperature in purification reactor be reduced to the scope of 0 ~ 10 DEG C, temperature-fall period is by temperature sensor monitors record;
B () opens valve V1, open gas boosting pump system 1, by the reaction pressure (being generally 2.5 ~ 7.5MPa) needed for pending gas boosting to purification reactor, then pass in purification reactor;
C () valve-off V1 ~ V4, makes purification reactor keep airtight under intake pressure, the temperature and pressure condition now in purification reactor meets H
2s and CO
2hydrating condition, and the main component methane in Sweet natural gas does not participate in hydration reaction, after keeping certain reaction times (being generally more than 10h), determine whether hydration reaction terminates by interpretation reactor temperature and pressure data change, and open valve V3 and carry out gas sampling and chromatographically instrument is analyzed.If analytical results meets index request, directly exported by valve V6, if discontented sufficient index request, then reentered again in topping-up pump system and purification reactor by valve V5 and again process.
D () is when soft solid gel uses its purification efficiency of for some time to reduce, the in-situ regeneration of the soft gel of conducting self-heating functional realiey solid of purification reactor can be utilized, the hydrate solids retained in gel is discharged, heating temperature range is 40 ~ 50 DEG C, time length 1 ~ 2h, can recover the intrinsic absorption hydration properties of soft solid gel.
Choose Sweet natural gas gas sample, wherein CH
4, CO
2, H
2s volume percent is respectively 91.6%, 7.6%, 0.8%, input to after topping-up pump system boost to 2.5MPa in purification reactor, the filling ratio of soft solid gel in purification reactor is 0.7, hydration accelerator selects sodium dodecyl sulfate solution, hydration purifying treatment temperature is 1 DEG C, reaction times is 10h, and reaction terminates rear gas chromatographicanalyzer and carries out sampling analysis, the CH after purification
4and CO
2volume percent is respectively 98.6% and 1.4%, does not detect H
2s component.
Embodiment 2
Purification reactor and the embodiment 1 of the present embodiment employing are same.
The soft solid gel with porous specific surface area of the present embodiment is made up through chemical gel technique by following mass percent of following raw material:
Raw material is made through chemical gel technique by following mass percent:
2 hydroxyethyl meth acrylates 40%
Linking agent ethylene glycol bisthioglycolate (methacrylic acid) ester 1%
Initiator ammonium persulfate 5%
Catalyzer Tetramethyl Ethylene Diamine 1%
Surplus is water.
Choose Sweet natural gas gas sample, wherein CH
4, CO
2, H
2s volume percent is respectively 88.3%, 10.5%, 1.2%, input after topping-up pump system boost to 7.5MPa in purification reactor, the filling ratio of soft solid gel in purification reactor is 0.90, hydration accelerator selects tetrabutyl phosphonium bromide ammonium solution, hydration purifying treatment temperature is 10 DEG C, reaction times is 10h, and reaction terminates rear gas chromatographicanalyzer and carries out sampling analysis, the CH after purification
4and CO
2volume percent is respectively 98.6% and 1.4%, does not detect H
2s component.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not limited by the examples; as hydration accelerator also can adopt pentamethylene solution etc.; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. the purifying treatment method of sour gas in Sweet natural gas, is characterized in that, comprise the following steps:
(1) the soft solid gel with porous specific surface area is filled in purification reactor, and add hydration accelerator; The described soft solid gel with porous specific surface area is made up through chemical gel technique by following mass percent of following raw material:
2 hydroxyethyl meth acrylates 10% ~ 40%
Linking agent ethylene glycol bisthioglycolate (methacrylic acid) ester 0.1 ~ 1%
Initiator ammonium persulfate 0.5 ~ 5%
Catalyzer Tetramethyl Ethylene Diamine 0.1 ~ 1%
Surplus is water;
(2) pass into the Sweet natural gas that need purify in purification reactor, control intake pressure is 2.5 ~ 7.5MPa, and temperature of reaction is 0 ~ 10 DEG C, carries out hydration purifying treatment.
2. the purifying treatment method of sour gas in Sweet natural gas according to claim 1, it is characterized in that, described hydration accelerator is sodium dodecyl sulfate solution, tetrabutyl phosphonium bromide ammonium solution or pentamethylene solution.
3. the purifying treatment method of sour gas in Sweet natural gas according to claim 1, is characterized in that, described soft solid gel adopts the decoration form of layered multi-stage to fill in purification reactor.
4. the purifying treatment method of sour gas in Sweet natural gas according to claim 1, it is characterized in that, the filling ratio of described soft solid gel in purification reactor is 0.75 ~ 0.90.
5. the purifying treatment method of sour gas in Sweet natural gas according to claim 1, it is characterized in that, the air outlet place at described purification reactor top is provided with gaseous constituent proofing unit.
6. the purifying treatment method of sour gas in Sweet natural gas according to claim 5, it is characterized in that, when gaseous constituent proofing unit detects that the Sweet natural gas of discharging from air outlet is below standard, the Sweet natural gas of discharging from air outlet is passed in purification reactor, re-starts step (2).
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| CN103773532B true CN103773532B (en) | 2015-12-09 |
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Citations (8)
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|---|---|---|---|---|
| JP2003105361A (en) * | 2001-09-27 | 2003-04-09 | Mitsubishi Rayon Co Ltd | Gas hydrate formation control agent |
| CN1488331A (en) * | 2003-08-13 | 2004-04-14 | 复旦大学 | Ultra porous hydrogel complex substance, preparing method and use in pharmaceutics thereof |
| CN1587289A (en) * | 2004-07-09 | 2005-03-02 | 浙江大学 | Process for preparing high water absorption resin |
| CN101045773A (en) * | 2006-03-29 | 2007-10-03 | 株式会社日本触媒 | Method of producing polyacrylic acid (salt) water-absorbent resin |
| GB2457464A (en) * | 2008-02-13 | 2009-08-19 | Univ Liverpool | Use of clathrates in gas storage |
| CN101703885A (en) * | 2009-11-13 | 2010-05-12 | 华南理工大学 | Method and device for solid phase separation of mixed gas by using hydrate method |
| CN101785949A (en) * | 2010-03-19 | 2010-07-28 | 华南理工大学 | Application of high water absorbability macromolecular material in separating mixed gas by using hydrate method |
| EP2596849A1 (en) * | 2011-11-24 | 2013-05-29 | Shell Internationale Research Maatschappij B.V. | Method of removing a gaseous contaminant, preferably H2S, from a contaminated gas stream |
-
2014
- 2014-01-27 CN CN201410040345.XA patent/CN103773532B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003105361A (en) * | 2001-09-27 | 2003-04-09 | Mitsubishi Rayon Co Ltd | Gas hydrate formation control agent |
| CN1488331A (en) * | 2003-08-13 | 2004-04-14 | 复旦大学 | Ultra porous hydrogel complex substance, preparing method and use in pharmaceutics thereof |
| CN1587289A (en) * | 2004-07-09 | 2005-03-02 | 浙江大学 | Process for preparing high water absorption resin |
| CN101045773A (en) * | 2006-03-29 | 2007-10-03 | 株式会社日本触媒 | Method of producing polyacrylic acid (salt) water-absorbent resin |
| GB2457464A (en) * | 2008-02-13 | 2009-08-19 | Univ Liverpool | Use of clathrates in gas storage |
| CN101703885A (en) * | 2009-11-13 | 2010-05-12 | 华南理工大学 | Method and device for solid phase separation of mixed gas by using hydrate method |
| CN101785949A (en) * | 2010-03-19 | 2010-07-28 | 华南理工大学 | Application of high water absorbability macromolecular material in separating mixed gas by using hydrate method |
| EP2596849A1 (en) * | 2011-11-24 | 2013-05-29 | Shell Internationale Research Maatschappij B.V. | Method of removing a gaseous contaminant, preferably H2S, from a contaminated gas stream |
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