CN1538105A - Method of using hydrate to storage ethylene under normal pressure - Google Patents
Method of using hydrate to storage ethylene under normal pressure Download PDFInfo
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- CN1538105A CN1538105A CNA031218342A CN03121834A CN1538105A CN 1538105 A CN1538105 A CN 1538105A CN A031218342 A CNA031218342 A CN A031218342A CN 03121834 A CN03121834 A CN 03121834A CN 1538105 A CN1538105 A CN 1538105A
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- ethene
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Abstract
A method for using hydrate to store ethylene under ordinary pressure includes such steps as generating ethylene hydrate at 3-10 deg.C under 2-4 MPa, cooling the hydrate to lowe than -5 deg.C, making ethylene in contact with the hydrate for capillary condensing of ethylene in hydrate, exhausting residual gas, lowering pressure, and storing ethylene at -10-0 deg.C. Its advantages are high storage density and safety and less energy consumption.
Description
Technical field
The present invention relates to the method that a kind of normal pressure stores ethene, particularly relate to a kind of method that stores ethene by the generation hydrate, with solid-state form high density, high security under normal pressure.
Background technique
Ethene adopts usually at low temperature (about 30 ℃) in the actual production at present, and middle pressure (about 2MPa) condition is stored in large-size spherical tank with the form of liquid state.Because ethene belongs to the height flammable and explosive substance, therefore the Security of this storing mode is not high.Owing to the low temperature that will keep about-30 ℃, need continue to provide cold in addition in storage process, energy consumption is also bigger.Therefore there is the demand that adopts safer, economic technological method to store ethene in petroleum chemical enterprise.
The hydrate storing technology is a kind of stored-gas technology that at home and abroad draws attention at present.Relevant hydrate storing technology in the bibliographical information is primarily aimed at the storage of rock gas (methane is main) at present, and relevant technical paper with hydrate storage ethene does not retrieve as yet.
The liquid working condition that stores ethene is-30 ℃, 2MPa.Ethene density is 0.44g/cm3 under this operating mode, is equivalent to 0.0157mol/cm3, convert for the per unit volume gas-storing capacity be 350 normal volumes.The theoretical value of the per unit volume gas-storing capacity of hydrate is 135 volumes, and promptly storing ethene with hydrate is 2.6 times of liquid reservoir volume.The working condition that hydrate stores ethene be roughly (5-0 ℃, 0.1-0.5MPa).
The production operation condition of ethylene hydrate is 10 ± 2 ℃, 2-4MPa, and the conditions of manufacture and the condition of storage of liquid ethylene are basic identical.The ethene of equal quality is converted into liquid institute chilling requirement from gaseous state and is about 1/3 with the ratio that is converted into hydrate institute chilling requirement, but because the potential temperature difference differs more than 40 ℃, the coefficient of refrigeration of producing hydrate significantly liquefies greater than ethene, loss of refrigeration capacity makes that then less than liquefaction process both refrigeration power consumptions are approaching.
Reservoir manufacture cost aspect because the storage temperature of hydrate exceeds nearly 30 ℃ of liquefaction storage temperature, greatly reduces the difficulty of insulation aspect.Because hydrate is preserved at normal pressure or near under the normal pressure, make the wall thickness of reservoir significantly reduce on the other hand, the volume of reservoir can do more, the also corresponding reduction of manufacture difficulty, and the equivalent carrying capacity during transportation also can be along with reduction.
The energy consumption of insulation aspect and equipment cost also can be minimized because of the storage temperature height of hydrate in the storage process.The advantage of storage safe aspect hydrate is apparent in view.
The solid-state storing method of hydrate is compared with liquid storing method more as can be seen from above, and advantage is that significantly deficiency is that storage density will hang down.Hydrate is 135V/V to the storage density maximum value of ethene, but water and ethene directly reacts, and the storage density that does not add the hydrate that other ancillary method generates has only about 80V/V.Therefore the amount (and storage density) that how to improve per unit volume hydrate storage ethene becomes and improves the key that hydrate stores the ethene Technological Economy.
Summary of the invention
The technical problem to be solved in the present invention is to propose a kind of method with hydrate normal pressure storage ethene, adopts the solid-state storage ethene of hydrate, makes the gas storage density and the formation speed of ethylene hydrate improve greatly, has Technological Economy preferably.
The objective of the invention is to be achieved through the following technical solutions, described method with hydrate normal pressure storage ethene, its step comprises:
(1) 3～10 ℃ of temperature, generates ethylene hydrate under the condition of pressure 2～4MPa;
(2) under reaction pressure, hydrate is cooled to below-5 ℃ and keeps ethene contact, make ethene in hydrate, produce capillary condensation, further improve gas storage density with hydrate;
(3) residual gas is got rid of, made system pressure reduce to normal pressure, or a little more than normal pressure;
(4) in the environment below-10--0 ℃, store ethylene hydrate.
It is at present general in low temperature (30 ℃), the down liquid method that stores ethene of middle pressure (2MPa) to adopt the method for the invention to replace, can improve amount and storage density that the per unit volume hydrate stores ethene, improve the Security that stores and transport and reduced energy consumption.The present invention utilizes hydrate can obtain the effect of ethene storage preferably, and condition of storage is much more superior than conventional method, has reduced the energy consumption of related process, has guaranteed the present invention's self Security and validity.This shows that the present invention has obvious using value to the energy-efficient storage of ethene in petroleum gas processing and the petrochemical field ethylene production.
Embodiment
Main purpose of the present invention is to improve the gas storage density and the formation speed of ethylene hydrate, makes the solid-state storage ethene of hydrate have Technological Economy preferably.The hydrate that generates when the reaction of ethene and pure water be a bulk, cover gas-liquid interface, hinder gas and continue to contact the generation hydrate with water, therefore formation speed is very slow, water is difficult for all being converted into hydrate, that is to say in the hydrate of last generation also to be mixed with more not reacted moisture, therefore the apparent gas-storing capacity that obtains is undesirable.After attempting in water, adding surface active agent, find that the hydrate that generates is Powdered, hydrate is very fast to develop in depth from the gas-liquid surface of contact, and water transforms very complete, thereby has obtained comparatively ideal gas-storing capacity.Because the hydrate that generates is Powdered, has a large amount of small-sized gaps, may the capillary condensation phenomenon take place so analyze at ethene under the lower temperature in these gaps, can increase the additional gas-storing capacity of a part like this.Experimental result has proved the correctness of above-mentioned analysis.After soaking a period of time in the ethene lime set of hydrate about-5 ℃, the ethene lime set is volatilized fully at the constant temperature normal pressure.Again hydrate is heated up and decompose, the situation that the apparent gas-storing capacity of the hydrate that records does not more soak has had and has significantly improved, the desirable gas-storing capacity that surpasses ethylene hydrate, therefore, its part that surpasses can only be thought owing to capillarity is stayed lime set in the hydrate powder gap.
Integrate, the technical problem to be solved in the present invention has two key technology points, the one, by in water, adding formation speed and the gas storage density that surface active agent improves hydrate, the 2nd, under lower temperature (storage temperature of ethylene hydrate just), allow ethene in the hydrate gap, capillary condensation take place, further improve the apparent gas-storing capacity of hydrate.
The surface active agent that is used for improving hydrate gas-storing capacity formation speed is not special, and the most cheap alkyl sulfate and alkylbenzene sulfonate just can reach good effect.Addition can be no more than 500PPM, and is very economical.Surface active substance used in the present invention comprises that ten alkyl sulfates are (as lauryl sodium sulfate, sodium tetradecyl sulfate, sodium hexadecyl sulfate), alkylbenzene sulfonate is (as neopelex, sodium n-alkylbenzenesulfonate) anionic surfactant and amphoteric surfactant (comprising class of department 80, class of department 20 etc.) such as.
Because the adding of surface active agent makes the hydrate of generation be Powdered, gas can continue to keep contacting with unreacted water, therefore the hydrate formation speed is very fast, and need not to adopt mechanical agitation to strengthen the contact of gas-liquid, the structure of hydration reactor is greatly simplified, even can in reservoir, directly be generated hydrate.Be three specific embodiments of the present invention below.
Embodiment 1: experimentize with ethene and pure water
In the laboratory, make ethene and pure water generate hydrate at the reactor internal reaction of stirring type variable-volume.Keep system temperature constant by air bath in the course of reaction.Along with the carrying out of reaction, the pressure in the reactor can reduce, and the volume that needs to reduce reaction system with piston makes the pressure substantially constant.After reaction reaches balance, system temperature is reduced to-5 ℃ of freezing half an hour after, under the constant voltage residual gas is released reactor.Heating up then dissolves the hydrate in the reactor fully, and assaying reaction device internalization separates the volume of gas, that is the ethene reserves under this experimental condition.Experimental result is listed in table 1.
Table 1 stores experimental result (with the pure water experiment) for the ethylene hydrate method
Table 1
| Reaction pressure (MPa) | ????P＝3.0 | ????P＝4.0 |
| Reaction temperature (℃) | ????7.0 | ????5.0 |
| Storage volume (V/V) | ????83 | ????71 |
Annotate: storage volume in the table (V/V) is the stored volume of ethylene number (under the normal temperature and pressure) of per unit volume hydrate
By data in the table 1 as can be seen, when using pure water to experimentize, the generation of hydrate is longer induction period, makes the generation difficulty comparatively of hydrate, and formation speed and gas storage effect are all not ideal enough.
Embodiment 2: experimentize with the ethene and the aqueous solution that contains surface active agent (SAA)
Preparation contains the aqueous solution of finite concentration surface active agent (SAA) in the laboratory, makes itself and ethene generate hydrate at the reactor internal reaction of a stirring type variable-volume.Keep system temperature constant by air bath in the course of reaction.Along with the carrying out of reaction, reactor pressure can reduce, and the volume that needs to reduce reaction system with piston makes the pressure substantially constant.After reaction reaches balance, system temperature is reduced to-5 ℃ of freezing half an hour after, under the constant voltage residual gas is released reactor.Heating up then dissolves the hydrate in the reactor fully, and assaying reaction device internalization separates the volume of gas, that is the ethene reserves under this experimental condition.Experimental result is listed in table 2.
Table 2 stores experimental result (with pure water+surface active agent SAA experiment reaction pressure 4MPa) for the ethylene hydrate method
Table 2
| SAA concentration (ppm) | ???????????100 | |
| Reaction temperature (℃) | ????5 | ????7 |
| Storage volume (V/V) | ????120.0 | ????127 |
Annotate: storage volume in the table (V/V) is the stored volume of ethylene number (under the normal temperature and pressure) of per unit volume hydrate
By data in the table 2 as can be seen, after the aqueous solution that has used the adding surface active agent,, reduced the difficulty that ethene and water generate hydrate owing to the interfacial resistance effect that has reduced between gas-liquid two-phase, make the growth velocity of hydrate obviously accelerate, and the gas storage effect also significantly strengthen.
Embodiment 3: experimentize with the ethene and the aqueous solution that contains surface active agent (SAA), and soak the solid hydrate that has generated in the reactor with liquid ethylene
Preparation contains the aqueous solution of finite concentration surface active agent (SAA) in the laboratory, makes itself and ethene generate hydrate at the reactor internal reaction of a stirring type variable-volume.Keep system temperature constant by air bath in the course of reaction.Along with the carrying out of reaction, reactor pressure can reduce, and the volume that needs to reduce reaction system with piston makes the pressure substantially constant.After reaction reaches balance, after system temperature being reduced to-5 ℃ of freezing half an hour, the piston of driving a reaction device increases the pressure of reaction system, makes ethene liquefaction, soak the solid hydrate that has generated in the reactor repeatedly with liquid ethylene, under the constant voltage residual gas is released reactor then.Heating up dissolves the hydrate in the reactor fully again, and assaying reaction device internalization separates the volume of gas, that is the ethene reserves under this experimental condition.Several groups of experimental results are listed in table 3.
Table 3 stores experimental result (with pure water+surface active agent SAA experiment, reaction pressure 4MPa) for the ethylene hydrate method
Table 3
| SAA concentration (ppm) | ?????????500 | |
| Reaction temperature (℃) | ????7 | ????9 |
| Storage volume (V/V) | ????185 | ????186 |
Annotate: storage volume in the table (V/V) is the stored volume of ethylene number (under the normal temperature and pressure) of per unit volume hydrate
Data as can be seen from table 3: in the experimentation, after hydrate generates fully, the piston of driving a reaction device increases the pressure of reaction system, soak the solid hydrate that has generated in the reactor with the ethene that has liquefied, utilize the suction-operated of hydrate hole, can obtain the higher ethene storage volume of storage volume (135V/V) than theoretical calculation.
Contrast above example as can be seen, add the storage effect of ethene in hydrate that surface active agent (SAA) experimentizes and obtains, obviously be better than pure water, and higher surface activity agent (SAA) concentration (seeing Table 3) helps promoting ethene to generate hydrate more, improve the formation speed of hydrate, increase the hydrate storage volume of middle ethene mutually.Simultaneously as can be seen, ethene stores effect to utilize hydrate can obtain preferably, and the condition of storage of this method is much more superior than conventional method, has also reduced the energy consumption of related process, and has guaranteed the Security and the validity of this method self.This shows that the present invention has obvious using value to the energy-efficient storage of ethene in petroleum gas processing and the petrochemical field ethylene production.
It should be noted last that: above embodiment is the unrestricted technological scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that: the present invention is made amendment or is equal to replacement, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (5)
1, a kind of method with hydrate normal pressure storage ethene is characterized in that, may further comprise the steps:
(1) 3～10 ℃ of temperature, generates ethylene hydrate under the condition of pressure 2～4MPa;
(2) under reaction pressure, hydrate is cooled to below-5 ℃ and keeps ethene contact, make ethene in hydrate, produce capillary condensation, further improve gas storage density with hydrate;
(3) residual gas is got rid of, made system pressure reduce to normal pressure, or a little more than normal pressure;
(4) in the environment below-10--0 ℃, store ethylene hydrate.
2, a kind of method that stores ethene with the hydrate normal pressure according to claim 1, it is characterized in that, generate in the process of ethylene hydrate in step (1), add surface active agent and generate hydrate to promote ethene in water, the hydrate that makes water all be converted into hydrate, raising per unit volume stores the amount of ethene.
3, a kind of method with hydrate normal pressure storage ethene according to claim 2 is characterized in that the surfactant concentrations of described interpolation is the aqueous solution of (100-800) ppm.
4, a kind of method with hydrate normal pressure storage ethene according to claim 3 is characterized in that the optium concentration of the surface active agent of described interpolation is the aqueous solution of 500ppm.
5, according to claim 2,3 or 4 described a kind of methods, it is characterized in that described surface active agent comprises alkyl sulfate, anionic surfactant and amphoteric surfactantes such as alkylbenzene sulfonate with hydrate normal pressure storage ethene.
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| CN 03121834 CN1228563C (en) | 2003-04-14 | 2003-04-14 | Method of using hydrate to storage ethylene under normal pressure |
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| CN 03121834 CN1228563C (en) | 2003-04-14 | 2003-04-14 | Method of using hydrate to storage ethylene under normal pressure |
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| CN1538105A true CN1538105A (en) | 2004-10-20 |
| CN1228563C CN1228563C (en) | 2005-11-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430459C (en) * | 2005-11-10 | 2008-11-05 | 中国石油大学(北京) | Method for storing and/or transporting fluid fuel |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430459C (en) * | 2005-11-10 | 2008-11-05 | 中国石油大学(北京) | Method for storing and/or transporting fluid fuel |
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