CN100387691C - Method for generating aqua compound - Google Patents
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- CN100387691C CN100387691C CNB2005100016744A CN200510001674A CN100387691C CN 100387691 C CN100387691 C CN 100387691C CN B2005100016744 A CNB2005100016744 A CN B2005100016744A CN 200510001674 A CN200510001674 A CN 200510001674A CN 100387691 C CN100387691 C CN 100387691C
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Abstract
The present invention relates to a method for generating hydrate. Gas or gas mixture generates hydrate in a water/ oil emulsification system, and the water/oil emulsification system is formed by that water is added with hydrocarbon liquid and hydrate inhibitor. The method is applied in a process of separating gas mixture by a hydrate method, on one hand, the generating speed of the hydrate is improved, on the other hand, the hydrate generated in a hydration reactor can successfully flow out of the reactor, enters a dissolver, and does not block equipment, and which ensures that the separation process is continuously carried out.
Description
Invention field
The present invention relates to generate the method for hydrate, relate in particular to a kind of formation speed that can improve hydrate, improve the method for the flowability of the hydrate that generates.
Background technology
At present, the refinery is a large amount of dry gas of by-product all generally, and as catalytic cracked dry gas, cracking dry gas etc., the composition complexity of these dry gas, main component wherein are H
2, N
2, CH
4, C
2H
4, C
2H
6, CO
2Deng, belong to the low-boiling point gas mixture, H wherein
2And C
2Component (C
2H
4, C
2H
6) all be the higher component of economic worth, though oil refining enterprise all has their demand of very strong recycling, but because the separation method (low temperature separation process, transformation absorption, membrane sepn etc.) that uses needs very big input at present, it is all uneconomical economically to be applied to these systems, so the present technique means that also is not well suited for for the separation of this class low-boiling point gas mixture can realize.
The another kind of dry gas of refinery as hydrogenation unit discharge tail gas, reformation dry gas etc., is formed simply relatively, is mainly light hydrocarbon components such as hydrogen and a small amount of methane.These rich hydrogen dry gas will obtain utilizing, and need remove light hydrocarbon component and make hydrogen reach sufficiently high purity; This is the separation problem of low-boiling point gas mixture equally.Though have more sophisticated transformation absorption and membrane separation technique can realize that carrying of hydrogen is dense at present, also exist and employ new technology with the demand of energy efficiency.
Ethylene industry always occupies critical role as the mainstay industry of petrochemical industry in national economy.There is expansion energy synergic pressure mostly in existing ethylene unit.The most complicated part of ethylene unit is exactly a deep cooling demethanizing workshop section, is that whole device expands energy synergic bottleneck.Address this problem the isolation technique that also needs a kind of economy, effective low-boiling point gas mixture.
The hydrate isolation technique can just satisfy the separation needs of above-described these low-boiling point gas mixtures.In addition, the hydrate isolation technique also can be used for the reaction product (conversion gas) of water vapor reforming hydrogen manufacturing, CO
2+ H
2The separation of mixture removes H from sour natural gas or acid refinery gas
2Acidic components such as S etc.
Hydrate is water and micro-molecular gas (CH
4, C
2H
6, CO
2, N
2Deng) a kind of cage modle material (water molecules constitutes the cage that is connected with each other aloft by hydrogen bond, and gas molecule is in the cage to keep the stability of cage) of under certain temperature, pressure condition, forming.The complexity that forms hydrate owing to gas with various is different, therefore can make the component of easy generation hydrate preferentially enter the hydrate phase and realize separation of gaseous mixture by generating the method for hydrate.Owing to generally have only micro-molecular gas could generate hydrate, so hydrate is applicable to separation low-boiling point gas mixture usually.The sharpest edges of hydrate are can be in the separation that realizes the low-boiling point gas mixture more than 0 ℃, and the conventional rectification rule need be carried out under very low temperature, for example, adopt the conventional rectification method, need the separating of methane and hydrogen carry out about-160 ℃, methane and need about-110 ℃, carry out separating of ethane.
Yet also there is inborn defective in hydrate: one, because the solubleness of gas in water is generally very little, hydrate generally can only generate at liquid-vapo(u)r interface, makes the natural formation speed of hydrate lower, can not satisfy the needs of large-scale industrial application; Its two, hydrate is a solid, deposits coalescently easily, occluding device be difficult for to be realized operate continuously.And the formation speed of hydrate is crossed low and flowability is bad, has all directly influenced the separating effect to mixed gas.Therefore, hydrate preservation and delivering gas and hydrate separating gas mixture technology will obtain large-scale industrial application, all must solve low and easy these two key technical problems of occluding device of hydrate formation speed.These two key issues propose in order to solve just in the present invention.
Summary of the invention
The present invention has mainly proposed a kind of method of new generation hydrate, by changing the state of reaction system, can effectively improve the formation speed and the hydrate flowability of hydrate.
The method according to this invention, make gas or gaseous mixture in water/oily emulsification system, generate hydrate, described water/oily emulsification system is to form by adding hydrocarbon liquids and hydrate stopper in water, wherein the volume ratio of hydrocarbon liquids and water is 2: 1-5: 1, and the stopper add-on is the 0.5-4% of the quality of water in the emulsification system.
This case contriver finds on the basis of carrying out big quantity research, if in the reaction system that generates hydrate, add an amount of oil (hydrocarbon liquids), make water and oil form the emulsion of water-in-oil-type, then can improve the formation speed of hydrate, reason is that the solubleness of gas in oil is much larger than the solubleness in water, with water/when oily emulsification system contacts with gas, gas dissolving is equivalent to greatly increase the air-water contact area in the dispersive oil droplet, thereby the formation speed of hydrate is improved greatly.Simultaneously, in reaction system, add an amount of hydrate stopper with emulsification and dissemination, the hydrate particle of generation can be dispersed in have good flowability in the moving phase, reduce the deposition agglomeration phenomena does not even take place, thereby can solve low and these two the gordian technique difficult problems of easy coalescent occluding device of the hydrate formation speed that runs in traditional hydrate separating gas mixture technology implementation.
According to preferred version of the present invention, can be oil or the hydrocarbon mixture liquid or the liquid alkane that obtain by refining of petroleum in order to the hydrocarbon liquids that forms emulsification system.Indefiniteness ground, described oil or can be selected from gasoline, diesel oil, kerosene, condensate oil or former wet goods by the hydrocarbon mixture liquid that refining of petroleum obtains, described liquid alkane is selected from liquid alkanes such as the liquid alkane of C5-C10 or its mixed alkanes, for example normal hexane, normal heptane, octane etc.
For making water and oil (hydrocarbon liquids) in the hydrate reaction system form emulsion better, need to add a certain amount of emulsifying agent as the hydrate stopper with emulsifying effect, this emulsifying agent should have the dual function of oil in water emulsion and water and disperse water compound.The stopper that the present invention preferably uses can be the serial emulsifying agent of this dish (Span) and polyoxyethylene nonylphenol ether emulsifying agent and forms than mixed preparing by 1: 1 to 4: 1 quality.Wherein, described this coils serial emulsifying agent and is meant sorbitan mono-laurate (Span-20), anhydrous sorbitol monopalmitate (Span-40), sorbitan monostearate (Span-60), anhydrous sorbitol tristearate (Span-65), sorbitan monooleate (Span-80), sorbitan sesquioleate (Span-83), Witconol AL 69-66 (Span-85) etc.Preferred use a kind of among Span-20, Span-40, Span-60 and the Span-80.And employed polyoxyethylene nonylphenol ether has comprised OP series, TX series and NP series emulsifying agent, preferably uses OP series and TX series product, wherein o π-10 (perhaps TX-10) etc. more preferably.
According to method provided by the invention, when making water and oil form emulsification system since the existence of stopper also can make the hydrate particle of quick generation be dispersed in uniformly and stably fluid mutually in and not sedimentation is coalescent, can flow mutually with fluid.Like this, when method of the present invention is applied to the hydrate separating gas mixture, can guarantee that gas (mixed gas) generates hydrate with higher speed in reaction system, and the hydrate that generates can not deposit coalescent and occluding device, help carrying out continuously of sepn process, satisfy the needs of large-scale industrial application.
The contriver finds in experiment, after in the hydrate reaction system, adding oil (hydrocarbon liquids), can form emulsification (liquid) system, dispersiveness and flowability to the hydrate that generated are favourable, generally speaking, the dispersiveness of hydrate and mobile meeting improve along with the increase of the volume ratio of oil and water, but the increase of water oil ratio will reduce the isolating efficient of hydrate, the economy variation, therefore, for the present invention, the control of oil/water ratio is very crucial, take all factors into consideration, oil/water volume ratio more suitable among the present invention should be controlled between 2: 1 to 5: 1.
For inhibitor action, test-results shows, if use span series emulsifying agent separately, though hydrate can be dispersed into small-particle, can not be uniform and stable fluid mutually in, can sink to the reactor bottom gradually, can caking after long-time the placement; If use o π or TX separately, the hydrate of generation floats on can be rapidly above the liquid and lumps, and is mobile bad; Therefore, the present invention uses span series emulsifying agent and emulsifying agents such as o π or TX simultaneously, makes it remain on a suitable proportioning, has effectively improved hydrate in the dispersiveness of fluid in mutually, and the quality proportioning of span and o π or TX preferably was controlled at 1: 1 to 4: 1; And the add-on of stopper is not The more the better, add-on is too big, though hydrate still can uniform and stablely disperse, the viscosity of hydrate slurry increases, mobile can variation, among the present invention the usage quantity of stopper be preferably water in the system quality 0.5% to 4% between.
The concrete operations that relevant gas generation hydrate reaches the mixed gas separating and concentrating are ordinary method well known in the art, do not repeat them here.
The method of generation hydrate of the present invention can be applied to the especially separation of low-boiling point gas mixture of various gas mixtures, various low-boiling point gas mixtures such as Sweet natural gas, various refinery gas, ethylene unit splitting gas for example, can improve the hydrate formation speed on the one hand, make on the other hand the hydrate that generates in the hydration reactor smoothly outflow reactor, enter by pipeline and to dissolve device, and occluding device not, guarantee that sepn process can carry out continuously, obtain good separating effect.
Particularly, when the method for generation hydrate of the present invention is applied to separation of gaseous mixture, be to mix among stopper is joined the aqueous solution (can comprise conventional promotor tetrahydrofuran (THF) (THF) in this aqueous solution) by a certain percentage, add a certain proportion of oil (liquefied hydrocarbon) then, thorough mixing makes system become stable emulsion.This emulsion is transferred in the hydration reactor, reactor is installed in the adjustable airbath of temperature again.The temperature of regulation system is to claimed range and after stablizing, the mixed gas of known composition (is preferably the lower boiling mixed gas, the for example mixing of methane and hydrogen) charge in the reactor, the temperature, pressure condition in the reactor should satisfy mixed gas and generate the hydrate needs.After gas charged into reactor, system can begin to generate hydrate in stirring.If the reactor that uses is a transparent material, can clearly observe the flowing property that generates formed hydrate slurry behind the hydrate and the particle form of hydrate.When generate hydrate in the system and reach balance each other after, can get the analysis of gas sample and form and change, to estimate the dense effect of putting forward of gas in certain (for example hydrogen).
In specific embodiments of the invention, the contriver has also carried out a series of experiment according to the method described above, use the method for generation hydrate of the present invention hydrogen+methane gas mixture separated, experiment condition and the results are shown in table 1 and Fig. 1 in.Simultaneously, experiment when the contriver has also carried out not adding stopper and oil as a comparison, the method of using the generation hydrate behind adding stopper of the present invention and the oil with reflection is listed among table 1 and Fig. 1 equally to the isoparametric effect of improving of low-boiling point gas mixture separation effect, hydrate flowing property and formation speed.A series of experimental result can clearly be seen that from table 1 and Fig. 1: the method for using generation hydrate of the present invention is separated mixed gas, after in the reaction system that generates hydrate, adding oil of the present invention and stopper, can improve the formation speed and the flowability of hydrate, thereby improve the separation of gaseous mixture effect.
In a word, method of the present invention is primarily aimed at that the hydrate formation speed that hydrate separating gas mixture new technology exists is not high enough, the hydrate that generates easily in equipment key technical problem such as coalescent obstruction propose, guaranteed hydrate separating gas mixture process can high-efficiency and continuous operation, the industrialization of hydrate is had critical meaning.
Description of drawings
Fig. 1 is the comparison diagram of the formation speed of water+THF+ gas mixture system (hydrogen+methane) and water+THF+ gas mixture system+stopper+oil body system.Among the figure, gas reaction amount-time relation in curve (1) expression water+THF+ gas mixture system+2.5wt% stopper (Span20 and o π-10 (or TX-10) mass ratio are 4: 1)+oil (oil/water was than 4.0: 1) system, gas reaction amount-time relation in curve (2) expression water+THF+ gas mixture system.
Embodiment
Stopper added in the aqueous solution contain promotor tetrahydrofuran (THF) (THF) by designated ratio mix, add the diesel oil of designated ratio then, thorough mixing makes system become stable emulsion.Emulsion is transferred in the bright hydration reactor of full impregnated, reactor is installed in the adjustable airbath of temperature again.The temperature of regulation system to a certain value and stable after, the methane and the hydrogen mixed gas of known composition charged in the reactor.The mixed gas that temperature, pressure condition in the reactor should satisfy methane and hydrogen generates the hydrate needs, is controlled at 0-10 ℃ and 1-5Mpa.After gas charged into reactor, system can begin to generate hydrate.Reactor adopts transparent material, in a magnetic stir bar is arranged, by magnetic stir bar moving up and down, can clearly observe the flowing property that generates formed hydrate slurry behind the hydrate and the particle form of hydrate.When generate hydrate in the system and reach balance each other after, get the gas sample and analyze it and form and change, to estimate the hydrogen upgrading effect.
One group of result of experiment of carrying out is according to the method described above listed among table 1 and Fig. 1.For reflection adds stopper and oil back to the isoparametric effect of improving of separating effect, flowing property and formation speed, provided the experimental result when not adding stopper and oil among table 1 and Fig. 1 simultaneously.The contrast and experiment that provides from table 1 and Fig. 1 can clearly be seen that: (1) does not add stopper, can lump rapidly after hydrate generates, and can not flow; (2) use span series emulsifying agent separately, though hydrate can be dispersed into small-particle, can not be uniform and stable fluid mutually in, can sink to the reactor bottom gradually, can caking after long-time the placement; (3) use o π separately, the hydrate of generation floats on can be rapidly above the liquid and lumps, and is mobile bad; (4) use span series emulsifying agent and o π can improve hydrate in the dispersiveness of fluid in mutually simultaneously, but need to keep a suitable proportioning, it is more suitable that the quality proportioning of span and o π is controlled between 1: 1 to 4: 1; (5) add-on of stopper is not The more the better, and add-on is too big, though hydrate still can uniform and stablely disperse, the hydrate slurry fluid viscosity increases, mobile variation; (6) select for use span20 and span60 effect best in the span series emulsifying agent; (7) dispersiveness of hydrate and flowability improve along with the increase of the volume ratio of oil and water, but the increase of water oil ratio has reduced the isolating efficient of hydrate, the economy variation, and more suitable oil/water is than between 2: 1 to 5: 1; (8) add stopper and can improve the hydrate formation speed, also can improve separation of gaseous mixture effect (increase of vapor phase hydrogen concentration increase rate), and the hydrate that forms discharges through dissolving device, also can be carried dense methane relatively.
Table 1 water+THF+ gas mixture system (hydrogen+methane) and water+THF+ gas mixture system+stopper+diesel oil system separating effect and flowing property contrast; Operational condition: 4Mpa, 5 ℃, the gas/water volume ratio is 100: 1, and the concentration of THF is 20%, and unstripped gas is formed H
275%+CH
425%.
| Sequence number | Oil/water ratio | Stopper is at water mass concentration and set of dispense ratio | Put forward dense back gas phase and form (H 2) | Dispersed | Mobile | The hydrate shape |
| 1 | 0 | 0 | 90.76％ | Become piece | Stop up | The coalescent ice cube that is |
| 2 | 4.0∶1 | 2.0% (using Span20 separately) | 91.43％ | Hydrate sinks to not luming | Can flow but can not keep | Fine granularity |
| 3 | 4.0∶1 | 2.0% (using o π-10 separately) | 91.67％ | Hydrate come-up caking | Mobile poor | Block |
| 4 | 4.0∶1 | 0.5% (Span20 and o π-10 mass ratio are 4: 1) | 92.37％ | Can disperse but long-time back layering | Can flow but cannot not hold time longly | Fine granularity |
| 5 | 4.0∶1 | 2.0% (Span20 and o π-10 mass ratio are 4: 1) | 93.07％ | Uniform distribution and stable | Mobile fine | The fine particle shape |
| 6 | 4.0∶1 | 2.5% (Span20 and o π-10 mass ratio are 4: 1) | 93.58％ | Uniform distribution and stable | Mobile fine | The fine particle shape |
| 7 | 4.0∶1 | 3.0% (Span20 and o π-10 mass ratio are 4: 1) | 93.20％ | Uniform distribution and stable | Good fluidity | Particulate |
| 8 | 4.0∶1 | 4.0% (Span20 and o π-10 mass ratio are 4: 1) | 93.31％ | Distributivity is fine and stable | Than thickness, can flow | Particulate |
| 9 | 4.0∶1 | 2.0% (Span20 and TX-10 mass ratio are 1: 1) | 92.67％ | Uniform distribution | Can flow | The fine particle shape |
| 10 | 4.0∶1 | 2.0% (Span20 and o π-10 mass ratio are 2: 1) | 92.79％ | Uniform distribution | Better mobile | The fine particle shape |
| 11 | 4.0∶1 | 2.0% (Span20 and o π-10 mass ratio are 3: 1) | 92.91％ | Uniform distribution | Good fluidity | Particulate |
| 12 | 4.0∶1 | 2.0% (Span20 and o π-10 mass ratio are 4: 1) | 93.07％ | Distributivity is fine | Mobile fine | Particulate |
| 13 | 4.0∶1 | 2.0% (Span20 and o π-10 mass ratio are 5: 1) | 93.47％ | Hydrate sinks to not luming | Mobile general | Particulate |
| 14 | 4.0∶1 | 2.0% (Span40 and o π-10 mass ratio are 4: 1) | 92.07％ | Can disperse | Can flow | The fine particle shape |
| 15 | 4.0∶1 | 2.0% (Span60 and o π-10 mass ratio are 4: 1) | 92.87％ | Uniform distribution | Mobile fine | The fine particle shape |
| 16 | 4.0∶1 | 2.0% (Span80 and o π-10 mass ratio are 4: 1) | 92.56％ | Uniform distribution | Can flow | Particulate |
| 17 | 5.0∶1 | 2.0% (Span20 and o π-10 mass ratio are 4: 1) | 93.66％ | Uniform distribution | Mobile fine | Particulate |
| 18 | 4.5∶1 | 2.0% (Span20 and o π-10 mass ratio are 4: 1) | 93.34％ | Uniform distribution | Mobile fine | Particulate |
| 19 | 3.5∶1 | 2.0% (Span20 and o π-10 mass ratio are 4: 1) | 92.94％ | Uniform distribution | Viscosity is bigger, flows better | The fine particle shape |
| 20 | 3.0∶1 | 2.0% (Span20 and o π-10 mass ratio are 4: 1) | 92.56％ | Can disperse | Viscosity is big, can flow | The fine particle shape |
| 21 | 2.5∶1 | 2.0% (Span20 and o π-10 mass ratio are 4: 1) | 92.07％ | Can disperse | Thickness, mobile relatively poor | Fine granularity |
| 22 | 4.0∶1 | 2.0% (Span20 and 0P-8 mass ratio are 4: 1) | 92.14％ | Uniform distribution | Can flow | Fine granularity |
| 23 | 4.0∶1 | 2.0% (Span80 and TX-11 mass ratio are 4: 1) | 92.06％ | Uniform distribution | Can flow | Fine granularity |
| 24 | 4.0∶1 | 2.0% (Span20 and NP-9 mass ratio are 4: 1) | 92.10％ | Uniform distribution | Can flow | Fine granularity |
Claims (8)
1. method that generates hydrate, it is characterized in that making gas or gaseous mixture in water/oily emulsification system, to generate hydrate, described water/oily emulsification system is to form by add oil or hydrocarbon liquids and hydrate stopper in water, the volume ratio of its PetroChina Company Limited. or hydrocarbon liquids and water is 2: 1-5: 1, the stopper add-on is the 0.5-4% of the quality of water in the emulsification system, and stopper forms than mixed preparing by 1: 1 to 4: 1 quality for this coils serial emulsifying agent and polyoxyethylene nonylphenol ether emulsifying agent.
2. the method for the described generation hydrate of claim 1, wherein, the hydrocarbon mixture liquid of described hydrocarbon liquids for obtaining by refining of petroleum.
3. the method for the described generation hydrate of claim 1, wherein, the liquid alkane of described hydrocarbon liquids for obtaining by refining of petroleum.
4. the method for the described generation hydrate of claim 2, wherein, the described hydrocarbon mixture liquid that is obtained by refining of petroleum is selected from gasoline, diesel oil, kerosene or condensate oil.
5. the method for the described generation hydrate of claim 3, wherein, described liquid alkane is selected from the liquid alkane of C5-C10 or the mixed alkanes of C5-C10.
6. the method for the described generation hydrate of claim 1, wherein, it is a kind of in sorbitan mono-laurate, anhydrous sorbitol monopalmitate, sorbitan monostearate and the sorbitan monooleate that described this coils serial emulsifying agent.
7. the method for each described generation hydrate of claim 1-6, wherein said gaseous mixture comprises Sweet natural gas, refinery gas or ethylene unit splitting gas.
8. the method for a separating mixed gas comprises according to each described method of claim 1-6 making mixed gas form hydrate, carries out gas, solid phase separating process then.
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| CN101531337B (en) * | 2008-03-13 | 2011-11-30 | 中国石油大学(北京) | Method and device for low-pressure processing of coal coking gas |
| CN101554560B (en) * | 2008-04-09 | 2011-06-22 | 中国石油大学(北京) | Method for treating coal bed gas at low pressure |
| CN101732987B (en) * | 2008-11-21 | 2011-11-16 | 中国石油大学(北京) | Method for photocatalytic reduction of carbon oxide |
| CN108003952B (en) * | 2017-11-30 | 2020-10-13 | 湘南学院 | Method for preparing hydrate and application of phytic acid |
| CN109266414A (en) * | 2018-09-29 | 2019-01-25 | 湘南学院 | A kind of application of the method for preparing hydrate and oleic acid potash soap |
| CN109666504A (en) * | 2019-01-25 | 2019-04-23 | 中国石油大学(华东) | A method of enhancing gas solubility behavior in viscous crude |
| CN110375146A (en) * | 2019-08-07 | 2019-10-25 | 华孚油气工程技术成都有限公司 | Plumber's skill is changed in a kind of closure of oil pipeline hydrate |
| CN114558424A (en) * | 2022-03-25 | 2022-05-31 | 中海石油气电集团有限责任公司 | Method for separating carbon dioxide in flue gas of gas power plant |
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| CN1181806A (en) * | 1996-01-18 | 1998-05-13 | Bg公开有限公司 | Method of producing gas hydrate |
| RU2125033C1 (en) * | 1997-09-05 | 1999-01-20 | Открытое акционерное общество "Капролактам" | Antihydrate addition agent to gases |
| CN1272618A (en) * | 2000-01-13 | 2000-11-08 | 石油大学(北京) | Method for extracting concentrated hydrogen gas by utilizing separation of aqua compound |
| WO2004033598A1 (en) * | 2002-10-08 | 2004-04-22 | Bp Chemicals Limited | Process for the removal of oxygen from olefin-containing process streams |
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2005
- 2005-02-03 CN CNB2005100016744A patent/CN100387691C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1181806A (en) * | 1996-01-18 | 1998-05-13 | Bg公开有限公司 | Method of producing gas hydrate |
| RU2125033C1 (en) * | 1997-09-05 | 1999-01-20 | Открытое акционерное общество "Капролактам" | Antihydrate addition agent to gases |
| CN1272618A (en) * | 2000-01-13 | 2000-11-08 | 石油大学(北京) | Method for extracting concentrated hydrogen gas by utilizing separation of aqua compound |
| WO2004033598A1 (en) * | 2002-10-08 | 2004-04-22 | Bp Chemicals Limited | Process for the removal of oxygen from olefin-containing process streams |
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