CN1111708C - Method for extracting concentrated hydrogen gas by utilizing separation of aqua compound - Google Patents
Method for extracting concentrated hydrogen gas by utilizing separation of aqua compound Download PDFInfo
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- CN1111708C CN1111708C CN 00100279 CN00100279A CN1111708C CN 1111708 C CN1111708 C CN 1111708C CN 00100279 CN00100279 CN 00100279 CN 00100279 A CN00100279 A CN 00100279A CN 1111708 C CN1111708 C CN 1111708C
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- Prior art keywords
- hydrogen
- gas
- hydrates
- hydrate
- precursors
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000000926 separation method Methods 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title 1
- 239000007789 gas Substances 0.000 claims abstract description 62
- 239000001257 hydrogen Substances 0.000 claims abstract description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- 238000005336 cracking Methods 0.000 claims abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 150000004677 hydrates Chemical class 0.000 claims abstract 12
- 239000000203 mixture Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 2
- 239000003245 coal Substances 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 7
- 210000000952 spleen Anatomy 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000013022 venting Methods 0.000 description 5
- 238000007630 basic procedure Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
利用水合物及前身物对氢气选择性为零的特点对含氢的混合气(如煤层气、乙烯裂解气、含氢炼厂气、加氢尾气等)进行分离、提浓，并可利用多级分离技术提高终级氢气浓度，进而替代现有的膜分离、变压吸附工艺，其基本流程为混合气进入水合器生成水合物，难生成水合物的气体仍为气态，而易生成水合物的气体以水合物或其前身物的形式进入化解池化解。
Utilize the characteristics of zero selectivity of hydrates and precursors to hydrogen to separate and concentrate hydrogen-containing mixed gases (such as coal bed methane, ethylene cracking gas, hydrogen-containing refinery gas, hydrogenation tail gas, etc.), and can use multiple Stage separation technology increases the final hydrogen concentration, and then replaces the existing membrane separation and pressure swing adsorption processes. The basic process is that the mixed gas enters the hydrator to form hydrates. The gas that is difficult to form hydrates is still in the gaseous state, and hydrates are easy to form. The gas in the form of hydrates or their precursors enters the dissolution pool for dissolution.
Description
Relate to the field
The present invention relates to a kind ofly be applicable to recovery, put forward dense technology, generate hydrate or its precursor comes the hydrogen in the hydrogeneous gas mixture is carried out separating and concentrating by utilizing such as hydrogen in coal-seam gas, refinery's splitting gas, hydrogeneous refinery gas or the hydrogenation tail gas.
Background technology
To produce hydrogen in the cracking of ethylene process, this is an important hydrogen source, general recovery method is: in the demethanizing cat head, the mixture of hydrogen and methane is realized separating of hydrogen and methane in very low temperature (-160 ℃ approximately) by ice chest, and this operation will consume a large amount of colds and use complicated compression, changes cold technology.
Also contain hydrogen partial in hydrogenation tail gas, oil refinery dry gas, the coal-seam gas, the technology of recover hydrogen had pressure swing adsorption and membrane separation technique in the past, and the former needs the logotype of 7-10 bed, the facility investment height, high material consumption, latter's working pressure are more than 15Mpa, and hydrogen dividing potential drop pressure reduction is more than 10Mpa, working pressure is higher, and energy consumption is big.
Summary of the invention
The objective of the invention is to: generate the bigger phenomenon of pressure difference based on the gas with various hydrate, generate hydrate or its precursor and come the hydrogen in the hydrogeneous gas mixture is carried out the method that separating and concentrating provides a kind of high efficiency, recover hydrogen that energy consumption is low by utilizing.
The present invention is achieved in that the method for utilizing hydrate separating and concentrating hydrogen, it is characterized in that: it is dense to utilize the method that generates hydrate or its precursor that hydrogen is carried from contain hydrogen mixture, separate, to contain hydrogen mixed gas and be-20 ℃-10 ℃ in temperature range, pressure is under the operational condition of 0.1-20MPa, making non-hydrogen generate hydrate exists with solid form, or generation hydrate precursor exists with liquid form, and can not generating hydrate, hydrogen still exists with the form of gas, pass through gas then, Gu after separating, the solid phase hydration materialization is separated and is realized gas delivery.
Hydrate is small molecules gas (N
2, CO
2, CH
4, C
2H
6, C
3H
8Deng) and a kind of crystalline substance of under certain temperature and pressure, generating of water, generally between 0 ℃ and 15 ℃, difference is very big with the difference of the gas that generates hydrate and generate pressure for the generation temperature of hydrate.During as 1 ℃, the generation pressure of methane is up to 30 normal atmosphere, and propane can generate hydrate below normal pressure, and the gas separation of hydrate just is being based on the gas with various hydrate and is generating realizing than big difference of pressure.
The hydrate precursor is meant that gas combines with water but do not reach the state of solid crystals as yet, and it still is liquid.
Utilize generating hydrate or its precursor, to come recover hydrogen be exactly to make other component in the gas mixture form hydrate and remove, and hydrogen can not form hydrate because molecule is too little.Because hydrate is zero to the selectivity of hydrogen, thereby can be with more than the hydrogen upgrading to 95% by an equilibrium stage.
The invention has the advantages that: absorption is compared with transformation, present technique can significantly improve the rate of recovery of hydrogen, reduce facility investment and materials consumption, compare working pressure and pressure falls and can reduce with membrane sepn, the isolating affected pressure of Hydrate Technology can be about 3MPA, pressure drop more than 0.1MPA, thereby cut down the consumption of energy.Can above zero finish with hydrate separating hydrogen gas and methane in the cracking of ethylene process, this can save a large amount of colds and number of compression stages, thereby increases economic efficiency.
Description of drawings
Fig. 1 utilizes hydrate to separate, carry the single-stage tripping device process schematic representation of dense hydrogen;
Fig. 2 utilizes hydrate to separate, carry the multi-stage separation device process schematic representation of dense hydrogen.
Concrete enforcement
The basic procedure of single equilibrium stage is: gas mixture at first enters in the hydrator, with the hydrator temperature at-20 ℃-10 ℃, pressure is under the 0.1-20Mpa condition, select concrete operational condition generally between light key ingredient (hydrogen) and heavy key (methane or ethene etc.) formation condition, make gas mixture be easy to generate the heavy key generation hydrate of hydrate and do not reach the condition that light key ingredient generates hydrate, so just can make the gas of hydration in hydrate or its precursor tangible difference be arranged, the awkward gas of hydrate and the hydrate of generation of generating of mixed gas separation in hydrator with the gas composition that does not generate hydrate.The hydrate that generates or its precursor flow into to dissolve in the pond to be dissolved by heating or step-down, and the water cycle after dissolving is returned hydrator, dissolves gas for easily generating the part of hydrate.
The basic procedure of many equilibrium stages is: adopt a plurality of equilibrium stages, the difficult gas that generates hydrate among the single-stage charging equilibrium stage A is entered next equilibrium stage B (operational condition and then change into the higher operational condition of selectivity) as charging, the difficult gas that generates hydrate returns in the charging of A equilibrium stage among the balance B, among the same equilibrium stage A the difficult gas that generates hydrate enter easily generate hydrate among the equilibrium stage C among the equilibrium stage C gas also as the charging of equilibrium stage A.Like this, just can utilize many equilibrium stages that the weight component is all had better selectivity.
Embodiment:
The basic procedure of single equilibrium stage:
Gas mixture at first enters hydrator, and hydrator temperature, pressure are controlled at respectively :-20 ℃-10 ℃, 0.1-20.0MPa.Mixed gas partly generates hydrate in hydrator, and remainder is product (hydrogen that contains high density).The hydrate that generates or its precursor flow into to dissolve utilizes heating or step-down to dissolve (general temperature is no more than 28 ℃, and pressure is lower than hydrator and gets final product) in the pond, the water cycle after dissolving is returned hydrator, and dissolving the gas that is byproduct (containing small quantity of hydrogen).
Example 1: operational condition: 3.0MPa, 1.0 ℃
| Mol percentage ratio | H 2 | CH 4 | C 3H 8 |
| Feeding gas is formed | 78.4178 | 13.3206 | 8.2615 |
| The immobilization composition of venting one's spleen | 5.8741 | 63.5567 | 30.5692 |
| Gas phase is formed | 88.1822 | 9.5629 | 2.2549 |
Example 2: operational condition: 4.0MPa, 1.0 ℃
| Mol percentage ratio | H 2 | CH 4 | C 3H 8 |
| Feed composition | 78.4178 | 13.3206 | 8.2615 |
| The immobilization composition of venting one's spleen | 31.7696 | 44.8745 | 23.3558 |
| Gas phase is formed | 92.9832 | 4.8369 | 2.1799 |
Example 3: operational condition: 20.0MPa, 10.0 ℃
| Mol percentage ratio | H 2 | CH 4 |
| Feed composition | 50.48 | 49.52 |
| The immobilization composition of venting one's spleen | 16.9 | 83.1 |
| Gas phase is formed | 98.70 | 1.30 |
Example 4: operational condition: 0.5MPa ,-5.0 ℃
| Mol percentage ratio | H 2 | CH 4 | C 3H 8 |
| Feed composition | 20.0 | 40.1 | 39.9 |
| The immobilization composition of venting one's spleen | 1.3 | 47.4 | 51.3 |
| Gas phase is formed | 82.3 | 15.1 | 2.6 |
Example 5: operational condition: 0.1MPa-20.0 ℃
| Mol percentage ratio | H 2 | CH 4 | C 3H 8 |
| Feed composition | 50.7 | 30.8 | 18.5 |
| The immobilization composition of venting one's spleen | 0.9 | 60.3 | 38.8 |
| Gas phase is formed | 93.1 | 5.7 | 1.2 |
The basic procedure of many equilibrium stages: adopt a plurality of equilibrium stages, gas phase among the single-stage A (charging equilibrium stage) is entered next equilibrium stage B (working pressure is higher or service temperature is lower) as charging, immobilization is vented one's spleen and is returned in the A equilibrium stage among the equilibrium stage B, reclaim light constituent, the operation of repetition equilibrium stage is satisfied product requirement up to gas phase.So just can utilize many equilibrium stages that the weight component is all had better selectivity.And among the equilibrium stage A immobilization to separate gas be byproduct (containing small quantity of hydrogen).
Present method can adopt different technical process to realize: hydrator can adopt fully mixing or multiple reactor such as tower, can adopt several different methods such as step-down or heating to dissolving the pond.
The dense hydrogen that is respectively applied in the splitting gas that produces in hydrogen in the hydrogeneous coal-seam gas, the hydrogen in the hydrogeneous refinery gas, the hydrogen in the hydrogenation technique circulation gas, the cracking of ethylene production process is separated, carried to the method that utilize to generate hydrate or its precursor.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00100279 CN1111708C (en) | 2000-01-13 | 2000-01-13 | Method for extracting concentrated hydrogen gas by utilizing separation of aqua compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00100279 CN1111708C (en) | 2000-01-13 | 2000-01-13 | Method for extracting concentrated hydrogen gas by utilizing separation of aqua compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1272618A CN1272618A (en) | 2000-11-08 |
| CN1111708C true CN1111708C (en) | 2003-06-18 |
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|---|---|---|---|
| CN 00100279 Expired - Fee Related CN1111708C (en) | 2000-01-13 | 2000-01-13 | Method for extracting concentrated hydrogen gas by utilizing separation of aqua compound |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530719B (en) * | 2008-03-13 | 2011-11-30 | 中国石油大学(北京) | Method and device for low-pressure processing of coal bed gas |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387691C (en) * | 2005-02-03 | 2008-05-14 | 石油大学(北京) | Method of forming hydrate |
| CN101096908B (en) * | 2006-06-27 | 2011-08-31 | 上海标氢气体技术有限公司 | Two stage low pressure method for coal bed gas producing natural gas |
| CN109847555B (en) * | 2019-02-01 | 2021-07-27 | 常州大学 | A device and method for recovering various gases in catalytic dry gas based on hydrate method |
| CN113117503B (en) * | 2019-12-31 | 2023-04-07 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy-saving hydrate method |
-
2000
- 2000-01-13 CN CN 00100279 patent/CN1111708C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530719B (en) * | 2008-03-13 | 2011-11-30 | 中国石油大学(北京) | Method and device for low-pressure processing of coal bed gas |
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| Publication number | Publication date |
|---|---|
| CN1272618A (en) | 2000-11-08 |
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