CN1161175C - Vacuum pressure-variable process for removing ethane or hydrocarbons over ethane from gas-state hydrocarbon - Google Patents
Vacuum pressure-variable process for removing ethane or hydrocarbons over ethane from gas-state hydrocarbon Download PDFInfo
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- CN1161175C CN1161175C CNB001130676A CN00113067A CN1161175C CN 1161175 C CN1161175 C CN 1161175C CN B001130676 A CNB001130676 A CN B001130676A CN 00113067 A CN00113067 A CN 00113067A CN 1161175 C CN1161175 C CN 1161175C
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Abstract
The present invention provides a pressure-variable adsorption method for removing ethane and hydrocarbons over the ethane from gaseous hydrocarbon in a vacuum desorption way, namely that when the pressure of an adsorption bed is reduced to the normal pressure in the desorption processes of the adsorption bed, the adsorption bed is regenerated by a vacuum pumping method instead of a method that the adsorption bed is flushed by a product methane under the normal pressure; thereby, the recovery ratio of the product methane can be greatly improved. The vacuum degree of the desorption is between-0.05 and 0.095(g); meanwhile, the present invention provides an adsorption bed layer which adopts silica gel and activated carbon; the silica gel is filled in a gas outlet end of a product of the adsorption bed; thereby, the recovery ratio of the product methane is improved.
Description
The invention relates to the method for using vacuum pressure varying adsorption technology rejecting ethane and above hydrocarbons of ethane from Sweet natural gas or oil field gas.
The main component of Sweet natural gas or oil field gas is a methane, also has the above hydrocarbons of small amount of nitrogen, carbonic acid gas, ethane and ethane in addition.It is concrete form because of different gas fields or oil field different.Classical group becomes:
Sweet natural gas (V%) oil field gas (V%)
CH
4 92～98 86～93
CO
2 0.1～0.5 0.1～0.5
N
2 1.5～2.0 1.5～2.0
C
2H
6 0.25～3.5 3.0～6.5
C
3～C
6 0.15～2.0 0.5～5.0
H
2S ～500ppm ～500ppm
H
2O is saturated
When Sweet natural gas or oil field gas are used as many chemical process raw materials, all can carry out restriction to the above hydrocarbon component content of ethane and ethane in Sweet natural gas or the oil field gas.As by Sweet natural gas being raw material when producing the methane chlorination series product, be to guarantee the chlorization product quality, require ethane in the Sweet natural gas and the above hydrocarbon content of ethane are removed to below the 100ppm; By Sweet natural gas is raw material when producing hydrogen cyanide product or dithiocarbonic anhydride product, also requires ethane in the Sweet natural gas and the above hydrocarbon content of ethane are removed to below 0.1%.
The above hydrocarbons of rejecting ethane and ethane is industrial at present from Sweet natural gas or oil field gas
What use mainly is membranes, cryogenic fractionation, alternating temperature absorption method and pressure swing adsorption process.Characteristics to the whole bag of tricks in patent ZL1069670A compare, and describe multitower pressure swing adsorption technique and flow process that gac and molecular sieve bed are loaded in employing by a certain percentage in detail.The pressure swing adsorption technique of introducing in patent ZL1069670A can be removed to ethane in Sweet natural gas or the oil field gas and the above hydro carbons of ethane below the 100ppm.This process using forward step-down product gas of discharging reduces to reverse that sorbent material washes the regenerated method in the non-pressurized adsorption tower.Owing to be subjected to the influence of product component methane and non-product component ethane separation factor on sorbent material in Sweet natural gas or the oil field gas, when absorption ethane and the above hydro carbons of ethane, also to adsorb a considerable amount of methane, the above component of ethane adsorptive power on sorbent material is stronger relatively simultaneously, product methane as purge gas is close with the physico-chemical property of the impurity such as ethane that are rinsed, so desorb is difficulty relatively, need the product gas of flushing more, and this part product gas will be discharged as stripping gas with the ethane and the above component of ethane of desorb, thereby make that the methane recovery of this technology is lower, have only 40%～60% usually.
The objective of the invention is to adopt the method that vacuumizes to replace among Deutsches Reichs-Patent DE2624346 and the Chinese patent ZL1069670A process of washing and regenerate, methane recovery is brought up to more than 80% adsorbent bed.
Another object of the present invention is to provides the sorbent material kind and proportioning and the filling method of these sorbent materials in adsorption bed that are suitable for for methane recovery in the raising sepn process.
Many pressure swing adsorption techniques are described in patent ZL1069670A.The present invention is applicable to the pressure swing adsorption technique of 2 and 2 above adsorption beds; Adopt pressure swing adsorption technique of the present invention, each adsorption bed comprises following algorithm:
1. absorption: gaseous mixture by adsorption bed, wherein easily adsorbs the impurity component and is adsorbed by selectivity under the process top pressure, and the product component that is difficult for absorption obtains from gas phase, and adsorptive pressure can be 0.1～3.0MPa (g).
2. all pressure drops: adsorption bed stops absorption, and bed internal pressure air current flow direction when adsorption step is carried out step-down step by step, forward puts and presses expellant gas to be respectively applied for boosting of other adsorption bed; When the absorb leading-edge of easy absorption impurity component reaches the adsorption bed outlet, forward put to press and end.
3. the reverse pressure of putting: the adsorption bed internal pressure during against adsorption step the air current flow direction reduce near barometric point, the partial impurities gas of adsorption bed internal adsorption descends with pressure and discharges discharge; When forward the step-down end pressure is near or below barometric point, do not carry out this step.
4. vacuumize: utilize to vacuumize machinery (as vacuum pump etc.) adsorption bed that is under the barometric point is found time, further reduce the adsorption bed internal pressure to vacuum state (0.05～-0.095MPa (g)), make the foreign gas that is adsorbed be drawn out of adsorption bed, sorbent material obtains regeneration.
5. all voltage rises: regeneration adsorption bed well utilized other adsorption bed forward to put the product gas component of the higher part of pressure pressure respectively before carrying out next step absorption, and low earlier back height boosts step by step until balance.
6. finally boost: directly adsorption bed is boosted to adsorptive pressure at last with product gas component.Then repeat the above-mentioned steps cyclical operation.
In patent ZL1069670A, proposition in product gas ethane content greater than 0.5% o'clock, its sorbent material can adopt gac, yet the present invention reaches full scale plant by experiment and uses proof, only adopt acticarbon in above-mentioned pressure-swing adsorption process, will make in Sweet natural gas or the oil field gas ethane be removed to 0.5% when above, methane recovery is also unsatisfactory, its major cause is that gac is bigger than normal to the adsorptive capacity of methane component in Sweet natural gas or the oil field gas, promptly when charcoal absorption ethane and the above hydro carbons of ethane, also adsorb a large amount of methane simultaneously.
The present invention has determined that when adopting above-mentioned technology the above hydrocarbon component requirement of ethane or ethane is in the product component, can adopt the combination of gac and silica type sorbent material at 0.1%～2.0% o'clock.Compare with gac, the silica type sorbent material wants big to the separation factor of methane and other component in Sweet natural gas or the oil field gas, thereby improves the rate of recovery of methane.
The present invention points out, adopt pressure swing adsorption technique from Sweet natural gas or oil field gas when rejecting ethane or the above hydro carbons of ethane, can adopt the method that vacuumizes with replace traditional with product gas component under normal pressure to the adsorbent bed process of washing of carrying out, the vacuum desorption pressure after adsorption bed vacuumizes and finishes can-0.05MPa (g)～-0.095MPa (g) scope.And the present invention does not add any restriction to adsorptive pressure.Adsorption bed filled with adsorbent kind is not added any restriction yet.
The present invention points out, adopts pressure swing adsorption technique from Sweet natural gas or oil field gas when rejecting ethane or the above hydro carbons of ethane, and ethane content can adopt the combination of gac and silica type sorbent material at 0.1%～2% o'clock in product.Its gac and silica gel ratio range are 1: 0.5～6 (weight ratios).Gac fills in adsorption bed unstripped gas inlet end, and silica gel fills in the adsorption bed exit end.
Example one:
Sweet natural gas is formed (v%): CH
493.7 C
2H
61.63 C
3H
80.38 C
4H
100.28C
5H
120.06 C
6 +0.02 N
23.47 CO
20.38 H
2S 100mg/m
3, H
2O is saturated.
Gas pressure 0.40MPa (g), 28 ℃ of flow 3300Nm of temperature
3/ h.
The secondary that employing is made up of six adsorption beds is all pressed the vacuum desorption pressure swing adsorption technique.Inlet end loads a small amount of aluminium sesquioxide in the adsorption bed, and exit end filling 13X molecular sieve loads gac between aluminium sesquioxide and molecular sieve.Gac and 13X molecular sieve filling ratio are 1: 3.2 (weight), and adsorptive pressure is 0.38MPa (g).Vacuum desorption pressure-0.08MPa (g).
Forming (V%) by the Sweet natural gas after the pressure-swing adsorption process acquisition purification is CH
496.32, C
2H
6＜100ppm, C
3 +Trace, N
23.65, CO
20.03, product atmospheric pressure～0.30MPa (g), 29 ℃ of temperature, product flow 2600Nm
3/ h.Methane recovery 81%.
Example two:
Sweet natural gas is formed (v%): CH
487.16 C
2H
61.88 C
3H
80.95 C
4H
100.61C
5H
120.25 C
6 +0.01 N
28.64 CO
20.49 H
2S 400mg/m
3H
2O is saturated.
Gas pressure 1.30MPa (g), 28 ℃ of flow 3300Nm of temperature
3/ h.
The secondary that employing is made up of four adsorption beds is all pressed the vacuum desorption pressure swing adsorption technique.Inlet end loads a small amount of aluminium sesquioxide in the adsorption bed, and exit end filling silica gel loads gac between aluminium sesquioxide and silica gel.Gac and silica gel filling ratio are 1: 5.44 (weight), and adsorptive pressure is 0.8MPa (g).Vacuum desorption pressure-0.08MPa (g).
Forming (V%) by the Sweet natural gas after the pressure-swing adsorption process acquisition purification is CH
493.10, C
2H
60.47, C
3H
80.08, C
4H
10Trace, N
26.24, CO
20.11.
Product atmospheric pressure～0.25MPa (g), 29 ℃ of temperature, product flow 2600Nm
3/ h.
Methane recovery 89%.
Claims (3)
1, the pressure swing adsorption process of rejecting ethane and the above hydro carbons of ethane from Sweet natural gas or oil field gas, in the system that has at least 2 adsorption beds to form, select ethane and the above hydrocarbon impurities component of ethane in absorbed natural gas or the oil field gas with being filled in sorbent material in the adsorption bed, acquisition has removed the product methane component of ethane and the above hydro carbons of ethane, it is characterized in that each adsorption bed is once experiencing absorption in the circulation successively, all pressure drops, reverse step-down, vacuumize, all voltage rises, the step of finally boosting, absorption bed vacuum desorption pressure in gauge pressure is-0.05MPa～-0.095Mpa, sorbent material is the compound adsorbent of gac and silica gel, and its gac and silica gel weight ratio proportioning are gac: silica gel=1: 0.5～6.
2,, it is characterized in that sorbent material also has at least a in zeolite molecular sieve, the activated alumina according to the pressure swing adsorption process of claim 1.
3,, it is characterized in that at adsorption bed products export end filling silica gel absorber according to the pressure swing adsorption process of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001130676A CN1161175C (en) | 2000-06-28 | 2000-06-28 | Vacuum pressure-variable process for removing ethane or hydrocarbons over ethane from gas-state hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001130676A CN1161175C (en) | 2000-06-28 | 2000-06-28 | Vacuum pressure-variable process for removing ethane or hydrocarbons over ethane from gas-state hydrocarbon |
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| Publication Number | Publication Date |
|---|---|
| CN1330974A CN1330974A (en) | 2002-01-16 |
| CN1161175C true CN1161175C (en) | 2004-08-11 |
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ID=4582884
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001130676A Expired - Lifetime CN1161175C (en) | 2000-06-28 | 2000-06-28 | Vacuum pressure-variable process for removing ethane or hydrocarbons over ethane from gas-state hydrocarbon |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329103C (en) * | 2004-08-27 | 2007-08-01 | 四川天一科技股份有限公司 | Pressure-varying adsorption method for recovering vinyl chloride and acetylene from gas mixture |
| CN100400142C (en) * | 2005-10-01 | 2008-07-09 | 四川天一科技股份有限公司 | Stripped gas method for recovering C2 and higher carbon content hydrocarbon constituent |
| CN102921271B (en) * | 2012-11-07 | 2015-04-29 | 四川天一科技股份有限公司 | Improved process for recovering non-methane alkane in polyolefin tail gas by adsorption method |
| US9944872B2 (en) * | 2014-02-27 | 2018-04-17 | Dow Global Technologies Llc | Method for regenerating adsorbent media used for extracting natural gas liquids from natural gas |
| CN105586089B (en) * | 2014-10-22 | 2017-10-31 | 中国石化扬子石油化工有限公司 | A kind of method that utilization VPSA technologies reclaim C2 and its above hydro carbons |
| CN104357118B (en) * | 2014-10-28 | 2017-02-01 | 四川天一科技股份有限公司 | Method for increasing recycling rate of liquefied natural gas |
| CN104624017B (en) * | 2015-01-23 | 2019-04-30 | 四川省达科特能源科技股份有限公司 | The method of lighter hydrocarbons is recycled in a kind of natural gas, associated gas |
| CN107789949B (en) * | 2016-08-30 | 2020-06-16 | 四川天采科技有限责任公司 | Gas separation method by negative pressure swing adsorption |
-
2000
- 2000-06-28 CN CNB001130676A patent/CN1161175C/en not_active Expired - Lifetime
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