CN109971521B - Method for concentrating and separating methane in low-concentration coal bed gas - Google Patents
Method for concentrating and separating methane in low-concentration coal bed gas Download PDFInfo
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- CN109971521B CN109971521B CN201910270800.8A CN201910270800A CN109971521B CN 109971521 B CN109971521 B CN 109971521B CN 201910270800 A CN201910270800 A CN 201910270800A CN 109971521 B CN109971521 B CN 109971521B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
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Abstract
The invention discloses a method for concentrating and separating methane in low-concentration coal bed gas. It comprises the following steps: carrying out at least one treatment on the low-concentration coal bed gas to realize concentration and separation of methane in the low-concentration coal bed gas; the treatment is compression treatment, purification treatment and pressure swing adsorption concentration treatment in sequence. The method is simple and quick in separation time, and can concentrate the methane in the low-concentration coal bed gas from 10-30% to more than 92% in volume percentage.
Description
Technical Field
The invention relates to a method for concentrating and separating methane in low-concentration coal bed gas, and belongs to the field of gas separation.
Background
The low-concentration coal bed gas refers to coal bed gas with methane concentration lower than 30%. According to the regulation of national coal mine safety regulations, when the coal bed gas is utilized, the concentration of methane is not lower than 30%. For this portion of the coal bed gas, current practice is to use domestic fuel or direct discharge near the coal mine. In 2005, low-concentration coal bed gas power generation technology has been developed and widely popularized and applied throughout the country, but the power generation technology has low resource utilization rate due to high requirements on oxygen-containing coal bed gas transportation technology and difficulty in grid connection with a power grid. Along with the continuous improvement of the requirement on environmental protection in China, the demand of natural gas as clean energy is gradually increased, and the utilization rate of low-concentration coal bed gas can be effectively improved by preparing Compressed Natural Gas (CNG) and Liquefied Natural Gas (LNG) from low-concentration coal bed gas through rapid pressure swing adsorption, concentration and separation. The pressure swing adsorption method is used as a main method for concentrating and separating the low-concentration coal bed gas, and has the characteristics of simple process, low energy consumption and small investment
At present, Compressed Natural Gas (CNG) and Liquefied Natural Gas (LNG) prepared by low-concentration coal-bed gas pressure swing adsorption concentration separation are mostly controlled to have single-tower adsorption time of more than 120s, a multi-stage pressure swing adsorption separation mode is adopted, and a low-concentration coal-bed gas pressure swing adsorption concentration separation process with single-tower adsorption time of less than 120s has not been reported successfully.
Disclosure of Invention
The invention aims to provide a method for concentrating and separating methane in low-concentration coal bed gas, which is simple and quick in separation time, and can concentrate the methane in the low-concentration coal bed gas from 10-30% to more than 92% in percentage by volume.
The invention provides a method for concentrating and separating methane in low-concentration coal bed gas, which comprises the following steps: carrying out at least one treatment on the low-concentration coal bed gas to realize concentration and separation of methane in the low-concentration coal bed gas;
the treatment is compression treatment, purification treatment and pressure swing adsorption concentration treatment in sequence.
In the method, the volume percentage of methane in the low-concentration coal bed gas can be 10-30%, specifically 10-15%, 10-20%, 15-20%, 14.79% or 19.77%.
In the above method, the number of treatments is 1 to 5, preferably 2.
In the method, the pressure of the low-concentration coal bed gas after compression treatment can be 0.1-0.5 MPa, and specifically can be 0.15MPa, 0.17MPa, 0.2MPa or 0.3 MPa.
In the above method, the purification treatment comprises the following steps: and carrying out dust removal, water removal and oil removal on the low-concentration coal bed gas subjected to the compression treatment at one time.
In the method, the dust removal, the water removal and the oil removal are respectively treated by a cyclone demister, a dissolved salt type dehydration device and an activated carbon tank which are connected in sequence.
In the method, the bulk specific gravity of the activated carbon filled in the activated carbon tank can be 400-500 g/L, and specifically can be 500 g/L.
In the method, the adsorbent adopted in the pressure swing adsorption concentration treatment is a BM-3 type carbon molecular sieve;
the temperature of the pressure swing adsorption concentration treatment can be 5-35 ℃, specifically 25 ℃, the time can be 60-120 s, specifically 90s, the pressure can be increased to 0.1-0.5 MPa at the pressure increasing rate of 0.001-0.1 MPa/s, and specifically 0.01MPa/s to 0.17 MPa;
the pressure swing adsorption concentration treatment is carried out in a conventional six-tower vacuum adsorption tower.
In the above method, the BM-3 type carbon molecular sieve has a separation coefficient aCH4/N2Can be 4.0, the bulk specific gravity can be 600-650 g/L, and can be purchased from coal science and technology researchGraduate institute, Inc.
In the method, when the treatment is more than one time, the waste gas discharged after the pressure swing adsorption concentration treatment in the second and later treatments is returned to the low-concentration coal bed gas to supplement the raw materials, so that the product recovery rate is improved.
The invention has the following advantages:
the method comprises the steps of compressing and purifying low-concentration coal bed gas serving as a raw material, separating and concentrating methane in the coal bed gas by adopting a pressure swing adsorption method, then performing secondary compression and purification on the gas subjected to primary pressure swing adsorption concentration, and performing secondary pressure swing adsorption concentration on the compressed and purified coal bed gas, so that the concentration of the methane in the coal bed gas is increased to more than 92% from 10-30% in the raw material gas. The concentration and separation method only selects one carbon molecular sieve (BM-3 type carbon molecular sieve) to achieve the concentration of CH4And the purpose of deoxidation, the pressure swing concentration time of the invention is shortened, the concentration and separation efficiency is obviously improved, and the invention has important significance and application value in the aspect of industrial popularization of coal bed gas.
Drawings
Fig. 1 is a process flow chart of the method for concentrating and separating methane from low-concentration coal-bed gas according to the invention, and the process flow charts of concentrating and separating methane from low-concentration coal-bed gas in examples 1 and 2.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The apparatuses or devices described in the following examples are conventional apparatuses or devices unless otherwise specified.
The contents described in the following examples are all volume percentages unless otherwise specified.
Wherein, the content of the measured methane is measured by an infrared analysis method, and the recovery rate of the methane (the amount of pure methane in the product obtained after pressure swing adsorption, concentration and separation accounts for the amount of pure methane in the concentrated feed gas) is calculated according to the following formula:
methane recovery rate (amount of methane recovered/amount of methane in raw gas) × 100%
The carbon molecular sieve BM-3 used in the following examples was purchased from coal research institute, Inc., and the physical and chemical parameters of the BM-3 type carbon molecular sieve were as follows: the diameter (mm) of the adsorbent is 2.5-3.2, the granularity (mesh) of the adsorbent is 4-12, the compressive strength (N/particle) of the adsorbent is not less than 100, the stacking weight (g/cc) of the adsorbent is 0.6-0.65, and the separation coefficient is not less than 4.
Example 1 for CH4Quickly concentrating and separating low-concentration coal bed gas with the content of 10-15%
The process flow of the rapid concentration and separation in this embodiment is shown in fig. 1, where 1 is a low-concentration coal-bed gas of a raw material gas, 2 is a compression step, 3 is a purification step, 4 is a first pressure swing adsorption concentration step, 5 is a first pressure swing adsorption concentration exhaust gas, 6 is a compression step, 7 is a purification step, 8 is a second pressure swing adsorption concentration step, 9 is a second pressure swing adsorption concentration return gas, and 10 is a final product gas.
The specific process is as follows:
1) compressing the low-concentration coal bed gas serving as the raw material gas to obtain compressed coal bed gas, wherein the pressure of the compressed coal bed gas is 0.15 MPa;
wherein, the names and volume percentage contents of the components of the feed gas are respectively as follows: CH (CH)4：14.79％、O2：17.89％、N2: 67.32 percent and the pressure of the raw material gas is 3-5 kPa;
2) dedusting the compressed coal bed gas obtained in the step 1) by a filter, removing water by a cyclone demister, and finally removing oil by an activated carbon tank to obtain purified coal bed gas; wherein the bulk specific gravity of the activated carbon in the activated carbon tank is 500 g/L;
3) performing first-stage pressure swing adsorption concentration separation on the purified coal bed gas obtained in the step 2) to obtain concentrated coal bed gas, and simultaneously performing evacuation treatment on first-stage pressure swing adsorption concentrated tail gas;
4) compressing the concentrated coal bed gas obtained in the step 3) to obtain compressed coal bed gas, wherein the pressure of the coal bed gas is 0.17 MPa;
the names and volume percentages of all components of the coal bed gas after the first-stage pressure swing adsorption concentration are respectively as follows: CH (CH)4：39.16％、O2：12.77％、N2：48.07％；
5) Removing water from the compressed coal bed gas obtained in the step 4) by using a cyclone demister, and finally removing oil by using an activated carbon tank to obtain purified coal bed gas; wherein the bulk specific gravity of the activated carbon in the activated carbon tank is 500 g/L;
6) and (3) carrying out second-stage pressure swing adsorption concentration separation on the purified coal bed gas obtained in the step 5) to obtain product gas, and mixing the second-stage pressure swing adsorption concentrated tail gas serving as return gas with fresh raw material gas.
In the example, the two-stage pressure swing adsorption tower is a six-tower vacuum adsorption tower, the inner diameter of the adsorption tower is 542mm, the carbon molecular sieve used as the adsorbent in the first-stage pressure swing adsorption concentration is BM-3, the adsorption temperature is 25 ℃, the adsorption time is 90s, and the adsorption pressure is 0.15 MPa. The carbon molecular sieve used in the second-stage pressure swing adsorption concentration treatment is BM-3, the adsorption temperature is 25 ℃, the adsorption time is 90s, and the adsorption pressure is 0.17 MPa.
In the step, the tail gas generated by the first-stage pressure swing adsorption concentration is discharged, and the tail gas generated by the second-stage pressure swing adsorption concentration is returned to the raw material gas to be continuously concentrated and separated according to the steps 2) to 6).
The method comprises the following steps of (1) measuring the methane content in the product gas by using an infrared analysis method, wherein the names and volume percentages of all components are respectively as follows: CH (CH)4：93.06％、O2：0.82％、N2: 3.12% and the methane recovery was 91.23%.
Example 2 for CH4Quickly concentrating and separating low-concentration coal bed gas with the content of 15-20%
The process flow of the rapid concentration and separation in this embodiment is shown in fig. 1, where 1 is low-concentration coal bed gas of raw gas, 2 is a compression step, 3 is a purification step, 4 is a first pressure swing adsorption concentration step, 5 is a first pressure swing adsorption concentration exhaust gas, 6 is a compression step, 7 is a purification step, 8 is a second pressure swing adsorption concentration step, 9 is a second pressure swing adsorption concentration return gas, and 10 is a final product gas.
The specific process is as follows:
1) compressing the low-concentration coal bed gas 1 serving as a raw material gas to obtain compressed coal bed gas, wherein the pressure of the compressed coal bed gas is 0.15 MPa;
wherein, the names and volume percentage contents of the components of the feed gas are respectively as follows: CH (CH)4：19.77％、O2：16.84％、N2: 63.39 percent and the pressure of the raw material gas is 3-5 kPa;
2) dedusting the compressed coal bed gas obtained in the step 1) by a filter, removing water by a cyclone demister, and finally removing oil by an activated carbon tank to obtain purified coal bed gas; wherein the bulk specific gravity of the activated carbon in the activated carbon tank is 500 g/L;
3) carrying out first-stage pressure swing adsorption concentration separation on the purified coal bed gas obtained in the step 2) to obtain concentrated coal bed gas, and simultaneously carrying out evacuation treatment on the first-stage pressure swing adsorption concentrated tail gas.
4) Compressing the concentrated coal bed gas obtained in the step 3) to obtain compressed coal bed gas, wherein the pressure of the coal bed gas is 0.17 MPa;
the names and volume percentages of all components of the coal bed gas after the first-stage pressure swing adsorption concentration are respectively as follows: CH (CH)4：54.70％、O2：9.51％、N2：35.79％；
5) Removing water from the compressed coal bed gas obtained in the step 4) by using a cyclone demister, and finally removing oil by using an activated carbon tank to obtain purified coal bed gas; wherein the bulk specific gravity of the activated carbon in the activated carbon tank is 500 g/L;
6) and (3) carrying out second-stage pressure swing adsorption concentration separation on the purified coal bed gas obtained in the step 5) to obtain product gas, and mixing the second-stage pressure swing adsorption concentrated tail gas serving as return gas with fresh raw material gas.
In the example, the two-stage pressure swing adsorption tower is a six-tower vacuum adsorption tower, the inner diameter of the adsorption tower is 542mm, the carbon molecular sieve used as the adsorbent in the first-stage pressure swing adsorption concentration is BM-3, the adsorption temperature is 25 ℃, the adsorption time is 90s, and the adsorption pressure is 0.15 MPa. The carbon molecular sieve used in the second-stage pressure swing adsorption concentration treatment is BM-3, the adsorption temperature is 25 ℃, the adsorption time is 90s, and the adsorption pressure is 0.17 MPa.
In the step, the tail gas generated by the first-stage pressure swing adsorption concentration is discharged, and the tail gas generated by the second-stage pressure swing adsorption concentration is returned to the raw material gas to be continuously concentrated and separated according to the steps 2) to 6).
The method comprises the following steps of (1) measuring the methane content in the product gas by using an infrared analysis method, wherein the names and volume percentages of all components are respectively as follows: CH (CH)4：96.02％、O2：0.8％、N2: 3.2% and the methane recovery was 90.83%.
Comparative example (c),
The specific process is as follows:
1) compressing low-concentration coal bed gas with the methane concentration of 20.10 percent as raw material gas to obtain compressed coal bed gas, wherein the pressure of the compressed coal bed gas is 0.6 MPa;
wherein, the names and volume percentage contents of the components of the feed gas are respectively as follows: CH (CH)4：20.10％、O2：16.84％、N2: 63.06 percent and the pressure of the raw material gas is 3-5 kPa;
2) dedusting and dewatering the compressed coal bed gas obtained in the step 1) through a filter, and finally removing oil through an activated carbon tank to obtain purified coal bed gas; wherein the bulk specific gravity of the activated carbon in the activated carbon tank is 500 g/L;
3) performing first-stage pressure swing adsorption concentration separation on the purified coal bed gas obtained in the step 2) to obtain concentrated coal bed gas, and simultaneously performing evacuation treatment on first-stage pressure swing adsorption concentrated tail gas;
4) compressing the concentrated coal bed gas obtained in the step 3) to obtain compressed coal bed gas, wherein the pressure of the coal bed gas is 0.5 MPa;
the names and volume percentages of all components of the coal bed gas after the first-stage pressure swing adsorption concentration are respectively as follows: CH (CH)4：55.70％、O2：8.51％、N2：35.79％；
5) Dewatering the compressed coal bed gas obtained in the step 4) through a filter, and finally removing oil through an activated carbon tank to obtain purified coal bed gas; wherein the bulk specific gravity of the activated carbon in the activated carbon tank is 500 g/L;
6) and (3) carrying out second-stage pressure swing adsorption concentration separation on the purified coal bed gas obtained in the step 5) to obtain product gas, and simultaneously carrying out second-stage pressure swing adsorption concentration tail gas evacuation treatment.
In the comparative example, the two-stage pressure swing adsorption tower used was a six-tower vacuum adsorption tower, the inner diameter of the adsorption tower was 542mm, the carbon molecular sieve used as the adsorbent in the first-stage pressure swing adsorption concentration was BM-3, the adsorption temperature was 25 ℃, the adsorption time was 210s, and the adsorption pressure was 0.6 MPa. The carbon molecular sieve used in the second-stage pressure swing adsorption concentration treatment is BM-3, the adsorption temperature is 25 ℃, the adsorption time is 270s, and the adsorption pressure is 0.5 MPa.
In the step, the tail gas generated by the first-stage pressure swing adsorption concentration is exhausted, and the tail gas generated by the second-stage pressure swing adsorption concentration is exhausted.
The method comprises the following steps of (1) measuring the methane content in the product gas by using an infrared analysis method, wherein the names and volume percentages of all components are respectively as follows: CH (CH)4：96.32％、O2：0.5％、N2: 3.2% and the methane recovery was 64.31%.
Claims (1)
1. A method for concentrating and separating methane in low-concentration coal bed gas comprises the following steps: carrying out the following treatment on the low-concentration coal bed gas for 2 times to realize the concentration and separation of methane in the low-concentration coal bed gas;
the treatment is compression treatment, purification treatment and pressure swing adsorption concentration treatment in sequence;
the volume percentage of methane in the low-concentration coal bed gas is 10-30%;
the pressure of the low-concentration coal bed gas after compression treatment is 0.1-0.5 MPa;
the purification treatment comprises the following steps: sequentially carrying out dust removal, water removal and oil removal on the low-concentration coal bed gas subjected to the compression treatment;
the dust removal, the water removal and the oil removal are respectively treated by a cyclone demister, a dissolved salt type dehydration device and an activated carbon tank which are connected in sequence;
the bulk specific gravity of the activated carbon filled in the activated carbon tank is 400-500 g/L;
the adsorbent adopted in the pressure swing adsorption concentration treatment is a BM-3 type carbon molecular sieve;
the temperature of the pressure swing adsorption concentration treatment is 5-35 ℃, the time is 90s, and the pressure is increased to 0.1-0.5 MPa at the pressure increasing rate of 0.001-0.01 MPa/s;
the pressure swing adsorption concentration treatment is carried out in a conventional six-tower vacuum adsorption tower;
separation coefficient of the BM-3 type carbon molecular sieve
4.0, and the bulk density is 600-650 g/L;
and when the treatment is secondary, returning the waste gas discharged after the pressure swing adsorption concentration treatment in the treatment to the low-concentration coal bed gas to supplement raw materials.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101921642B (en) * | 2010-08-18 | 2013-01-16 | 煤炭科学研究总院 | Method for deoxidizing coal bed gas and separating methane by concentration |
| CN104449924A (en) * | 2014-11-27 | 2015-03-25 | 煤炭科学技术研究院有限公司 | Concentration separation method for methane in low-concentration coal-bed gas |
| CN104479781A (en) * | 2014-11-27 | 2015-04-01 | 煤炭科学技术研究院有限公司 | Method for concentrating and separating methane from gas within explosive limit |
| CN104436993A (en) * | 2014-11-27 | 2015-03-25 | 煤炭科学技术研究院有限公司 | Concentration separation method for methane in low-concentration gas |
| CN105749699B (en) * | 2016-03-31 | 2020-04-21 | 四川天采科技有限责任公司 | Full-temperature-range pressure swing adsorption gas separation, purification and purification method |
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| US3751878A (en) * | 1972-10-20 | 1973-08-14 | Union Carbide Corp | Bulk separation of carbon dioxide from natural gas |
| JPS60114338A (en) * | 1983-11-03 | 1985-06-20 | カルゴン カーボン コーポレーシヨン | Carbons and carbon molecular sieves as mercury adsorbent |
| CN1406660A (en) * | 2001-09-05 | 2003-04-02 | 日本酸素株式会社 | Nitrogen production and its device |
| CN102728179A (en) * | 2012-07-17 | 2012-10-17 | 北京信诺海博石化科技发展有限公司 | Pressure-variable adsorption process for concentrating methane from low-concentration coal mine gas |
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