CN107774095B - Full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas - Google Patents
Full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas Download PDFInfo
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Abstract
The invention discloses a full temperature range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas, which comprises a light hydrocarbon steam concentration process and a temperature swing adsorption fine-removal process; the adsorption pressure of the light hydrocarbon water vapor concentration process is 0.5-7.0 MPa, the operation temperature is 50-150 ℃, desorption is carried out under normal pressure and evacuation, unadsorbed natural gas, methane and the like are discharged from the top of the adsorption tower to be used as intermediate gas for removing most of water and light hydrocarbon, then the intermediate gas enters a temperature swing adsorption fine-removal process, the water and hydrocarbon dew point released from the top of the tower are reduced to be 30-50 ℃ of the minimum environmental temperature, one part of the natural gas is used as regeneration gas to regenerate the temperature swing adsorption fine-removal process, and then, the regeneration gas and the raw gas are mixed and returned to the light hydrocarbon water vapor concentration process to further recover the natural gas, or the flushing gas used as the water vapor light hydrocarbon concentration process and the desorption gas are pressurized and then processed to recover C2 +. The yield of methane is 90-95% or more, and the yield of C2+ is more than 90%.
Description
Technical Field
The invention relates to the field of purification of natural gas dehydration and dealkylation, in particular to a full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas.
Background
Natural gas is a high-quality, economic and clean energy and chemical raw material, mainly takes methane as a main raw material, and also comprises alkane components such as ethane, propane and butane and a small amount of non-hydrocarbon gas components such as nitrogen, carbon dioxide and water vapor. The natural gas is processed or purified for transportation or use, wherein natural gas dehydration and hydrocarbon removal are the two most important processes for purifying the natural gas, namely dew point control and/or alkane recovery.
Natural gas dehydration and de-hydrocarbon are two very important independent units in natural gas purification. Generally, the natural gas is dehydrated before the natural gas is dehydrated, and the hydrocarbon is removed or recovered after the natural gas is dehydrated. The natural gas dehydration method includes an absorption method, an adsorption method, a low temperature method (temperature drop method), a membrane separation method, a gas stripping method, a distillation method, and the like, and among them, the absorption method, the low temperature method, and the adsorption method are most common. The main purpose of natural gas dehydration is to reduce the water dew point (dew point drop). The main methods for removing hydrocarbons from natural gas include adsorption and absorption methods, wherein the main method for recovering hydrocarbon components from natural gas, also called natural gas condensate recovery, is a condensation separation method, i.e., a low temperature method, in addition to the adsorption and absorption methods. For natural gas purification, the purpose of hydrocarbon removal is mainly to reduce the dew point (dew point drop) of hydrocarbons and avoid adverse effects such as gas-liquid separation and blockage during transportation or use.
The low temperature method, also called condensation separation method, is to cool natural gas to a certain low temperature below the dew point of hydrocarbon to obtain a part of liquid hydrocarbon (natural gas condensate or condensate) rich in heavier hydrocarbons, and separate the liquid hydrocarbon from the gas at the low temperature, in order to prevent the natural gas from forming hydrate due to the separation of condensed water in the cooling process, a hydrate inhibitor can be added before cooling, so that the natural gas is removed (deoiled and dehydrated) in a low temperature separator together with the liquid hydrocarbon after the separation of condensed water and inhibitor aqueous solution in the cooling process, thereby achieving the purpose of controlling the dew point of water and hydrocarbon of the natural gas. The refrigeration method includes three methods of expansion refrigeration (including throttling refrigeration and turbine expander refrigeration), refrigerant refrigeration and combined refrigeration. The low-temperature method is mature and simple, and is suitable for gas field well heads, gas gathering stations or treatment plants to control the dew points of water and hydrocarbon. The defects comprise that firstly, the dehydration and hydrocarbon removal depth is not enough, and the feed gas, especially the high-pressure condensate gas contains a considerable amount of components such as ethane, propane or butane and the like due to the fact that the temperature of a low-temperature separator is not low enough (only minus 20 ℃ to minus 10 ℃), under the condition, most of ethane, propane and the like with higher added values are not recovered and directly sent to downstream users, the economic benefit of a natural gas treatment plant is reduced, meanwhile, the produced natural gas is classified into two types, and the dew points of water and hydrocarbon are less than the lowest environmental temperature of 5 ℃; second, the energy consumption is relatively high and the cryogenic process still requires some refrigeration, including throttling or expander refrigeration. If the refrigerant is used for refrigeration, more refrigerant is needed to be consumed. At the same time, the pressure needs to be increased. If the raw material gas is high-pressure condensate gas, redundant pressure at a well head can be utilized, but components such as ethane and propane with higher content in the raw material cannot be recovered under the low-temperature condition, and the dew point of the hydrocarbon is not greatly reduced. In recent years, a supersonic separator is a trend to replace a low-temperature separator, but is only suitable for the working conditions that raw gas contains more heavy hydrocarbon components, such as dehydration and hydrocarbon recovery of natural gas condensate (NGL), Natural Gas Oil (NGO), stable light hydrocarbon and the like, and cannot meet the requirements of deep dehydration and hydrocarbon removal of natural gas; third, a reverse condensation phenomenon occurs in the hydrocarbon removal.
The dehydration by the absorption method is to make the hydrophilic solvent and the natural gas in countercurrent contact to dissolve the water vapor in the natural gas, thereby realizing the purpose of dehydration. Commonly used hydrophilic absorbents include glycols (ethylene glycol polymers), calcium chloride, etc., of which triethylene glycol (TEG) is the most common among the glycol process, including DRIZO (azeotropic), clearol + and COLDFINGER processes, as well as steam stripping, vacuum, PROGLY, ecotemp processes, etc. The absorption method has the advantages of mature and reliable operation, simple flow, low cost and higher depth of dehydration dew point, but the increase of the circulation amount and the loss amount of the absorbent caused by the co-absorption phenomenon is not suitable for the dehydration of natural gas with more acid components, heavy hydrocarbon components and liquid or solid impurities, and the simultaneous hydrocarbon removal can not be realized, particularly, the absorbent TEG can dissolve hydrogen sulfide (H2S) in the natural gas to corrode equipment, pipelines and the like. In addition, in order to increase the lean glycol concentration and to improve the absorption efficiency, more facilities must be added, the investment is increased accordingly, and the process becomes complicated.
The adsorption method is specially referred to as Temperature Swing Adsorption (TSA), and deep dehydration and dealkylation of natural gas are carried out by adopting the TSA, so that the adsorption method is mature and convenient. The TSA method is characterized in that a certain or some adsorbents are adopted, strong adsorbate water and heavy hydrocarbon components in natural gas are respectively adsorbed by utilizing the principle that low temperature is favorable for adsorption and high temperature is favorable for desorption, deep dehydration and dealkylation are realized, and the adsorbents are regenerated through a heat carrier at the temperature of 150-250 ℃. However, firstly, the adsorbent molecular sieve used for dehydration can adsorb both water and heavy hydrocarbon, and because the molecular sieve in dehydration has large adsorption capacity, the heat load required for regeneration is larger, and the dealkylation does not need larger heat load, therefore, dehydration and dealkylation must be separated, and dehydration and dealkylation are carried out first, and then dealkylation is carried out, and the temperature and pressure of two adsorption and desorption cyclic operations are not the same, so that the investment is increased, and the process is complicated; secondly, for a natural gas raw material which is high in pressure and contains more light hydrocarbon components such as ethane, propane and the like, dehydration and dealkylation are not economical, high-pressure energy carried by the raw gas is not utilized, TSA (TSA) purification efficiency of the light hydrocarbon components such as ethane, propane and the like is low, and the natural gas raw material cannot be effectively recovered; thirdly, the temperature stress borne by the adsorbent is increased due to frequent temperature change period, so that the service life of the adsorbent is greatly influenced; fourth, the contradiction between adsorption and regeneration is very prominent, the easier the adsorption, the more difficult the desorption, and the time required for heating for regeneration, the difficulty in forming a cycle operation with adsorption. Therefore, deep adsorption is required to achieve the aim of deep dehydration and hydrocarbon removal, but desorption is quite difficult, which in turn causes incomplete regeneration of the adsorbent, easy penetration of the adsorbent and influence on the quality of dehydration and hydrocarbon removal; fifth, TSA regeneration requires a large thermal load, increases energy consumption, particularly for large-flow natural gas treatment, has an excessive thermal load, and requires a heat carrier to be selected, so that even if no chemical or physical reaction occurs with natural gas, the subsequent heat carrier can be easily separated from water and hydrocarbon components to be recycled, or the heat carrier (regeneration gas) can also adopt a part of raw material gas or product gas, but the product gas yield is affected; sixthly, the natural gas is subjected to hydrocarbon removal, particularly the removal of light hydrocarbons such as ethane and propane, and because the relative adsorption separation coefficient between methane and ethane and between ethane and propane is relatively small, the traditional adsorption methods such as TSA and Pressure Swing Adsorption (PSA) are difficult to adopt; seventh, before the natural gas is subjected to dealkylation, deep dehydration must be performed, otherwise, water is very easily adsorbed in the process of dealkylation circulation, and the separation of methane and light hydrocarbon components such as ethane and propane is further influenced.
Other methods for dehydrating and dealkylating or recovering hydrocarbons include coupling triethylene glycol solvent absorption dehydration with TSA method dealkylation, coupling TSA dehydration drying with membrane separation to recover light hydrocarbons, coupling TSA dehydration drying with cold oil absorption to recover light hydrocarbons and the like, some methods can achieve deep dehydration and dealkylation, even the recovery rate of light hydrocarbons is very high, but each method is different due to different working conditions of raw gas and different purification requirements, dehydration and dealkylation still need to be respectively arranged, the investment cost is high, and the flow is complex.
The invention provides a solution for solving the technical problem of the existing natural gas dehydration and dealkylation purification.
Disclosure of Invention
The invention provides a Full-Temperature-Range Pressure Swing Adsorption purification method for simultaneously dehydrating and dealkylating natural gas, wherein Full-Temperature-Range Pressure Swing Adsorption (FTrPSA) is a method which is based on Pressure Swing Adsorption and coupled with various separation technologies, and a method for separating and purifying various gases (including natural gas purification) by adopting the cyclic operation of easy matching and balancing of Adsorption and desorption of medium-high Temperature Pressure Swing Adsorption (PSA) by utilizing the differences of Adsorption separation coefficients and physicochemical properties of different material components under different pressures and temperatures; among them, in the conventional PSA cycle operation, adsorption is generally performed at normal temperature, and the lower the temperature and the higher the pressure, the more favorable the adsorption. However, the easier the adsorption, the more difficult the desorption, and under the working condition of low content of strong adsorbate in the separation or purification system, the more difficult the desorption or incomplete regeneration caused by instantaneous adsorption or co-adsorption in the traditional PSA cycle, for example, C2+ light hydrocarbon in natural gas can be well adsorbed but difficult to desorb at normal or low temperature, even the bed layer can be damaged; in the FTrPSA process, the inventor firstly proposes PSA of natural gas in a medium-high temperature range and coupling with other various separation technologies, thoroughly solves the technical bottleneck or low efficiency and the like that natural gas is easy to adsorb and difficult to desorb with C2+ light hydrocarbon components in PSA circulating operation at normal temperature and low temperature, for example, by utilizing the difference of adsorption and desorption mechanisms of the medium-low boiling point components (methane, a small amount of hydrogen and nitrogen) and the high boiling point components (water and C2 +) on different adsorbents at the temperature of 60-150 ℃ and the pressure of 0.5-6.0 MPa, different process designs are adopted, the composite beds comprise a parallel-series combination mode of multi-tower adsorption and multi-tower regeneration and different adsorbents, and the composite beds are coupled with other separation methods (temperature swing adsorption, condensation and the like) to reduce the load or difficulty of desorption regeneration in the PSA circulating process and enable the load or difficulty to be easily matched with the adsorption step, the contradiction that the adsorption is easy to desorb is overcome, and the effects of saving energy, reducing consumption, prolonging the service life of an adsorption bed layer and the like are realized; the FTrPSA method adopted by the invention utilizes the different physical characteristics of various components of natural gas as raw material gas under the conditions of generally high temperature and pressure, such as different adsorption and desorption mechanisms on different adsorbents, firstly adopts water and a C2+ concentration process which mainly comprise medium-high temperature PSA steps, and divides the raw material gas into intermediate gas consisting of components such as methane, nitrogen and the like, hydrocarbon-rich gas and water gas (light hydrocarbon-rich water gas for short), so that most of water and C2+ which are easy to be adsorbed at medium-high temperature are adsorbed, and methane is basically not adsorbed at medium-high temperature, so that the separation of the intermediate gas consisting of the most of water, the C2+ component and the methane, a small amount of nitrogen, the hydrogen and the like is easily realized. Most of the adsorbed water and C2+ components are desorbed under normal pressure or evacuation through the special pressure equalizing and reverse releasing steps in the PSA circulating process at medium and high temperature, so that the adsorption and desorption processes of the water and C2+ components are easy to match and balance, the water and C2+ are concentrated to obtain 'light hydrocarbon-rich water gas' for recycling, the load and energy consumption of the subsequent steps are reduced, the method is easy to match and combine with other subsequent separation processes, such as pressurization cooling, oil absorption, oil desorption and Temperature Swing Adsorption (TSA), the dehydration and dealkylation or C2+ recovery from natural gas are realized, and the problems of separate treatment, long flow path, high energy consumption, multiple limits on effective components and temperature and pressure ranges of raw gas, low product recovery rate and purity, large investment, unstable operation and the like of the existing process in the conventional natural gas dehydration and dealkylation purification are solved, particularly in the conventional PSA method, the heavy hydrocarbon component can not be well desorbed, and the adsorbent in the tower is inactivated due to long-term accumulation, so that the service life of the adsorbent is short; the conventional TSA method also results in a short adsorbent life because the temperature is periodically changed. Similarly, in the case of the recovered C2+, the absorption liquid used in oil absorption is also consumed more due to a large processing load, and the processing cost and energy consumption of the low-temperature condensation separation method are also high.
In order to solve the technical problems, the invention adopts the following technical scheme:
a full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas comprises the following steps:
(1) light hydrocarbon water-gas concentration process: natural gas with the temperature of 50-150 ℃ and the pressure of 0.5-7.0 MPa is pretreated to remove acid components, and then directly enters a light hydrocarbon water vapor concentration process through an air inlet pipeline, a multi-tower series or parallel process is adopted, adsorption is carried out under the conditions that the operation temperature is 50-150 ℃ and the operation pressure is 0.5-7.0 MPa, a plurality of adsorption towers are alternately and circularly operated, the raw material gas is ensured to continuously enter, 1 or more adsorption towers are in an adsorption state, the rest adsorption towers are in a regeneration state, in the adsorption towers, intermediate gas consisting of methane, a small amount of nitrogen, hydrogen and the like is discharged from the top of the tower through a bed layer, and then enters the next process, and a temperature swing adsorption fine-removal process is carried out; most of water in the natural gas and the carbon dioxide and the alkane (C2 +) components are adsorbed, desorption gas rich in light hydrocarbon and water, which is called light hydrocarbon-rich water gas for short, is obtained after desorption, and is pressurized for further treatment and recovery or is sent out of a boundary area for treatment.
(2) Temperature swing adsorption fine-removing process: the intermediate gas from the light hydrocarbon water gas concentration process is cooled or
Keeping the temperature to 50-60 ℃ and the pressure to 0.5-7.0 MPa, entering a system consisting of 2 adsorption towers for Temperature Swing Adsorption (TSA) to ensure that intermediate gas continuously enters, wherein 1 adsorption tower is in an adsorption state, the other adsorption tower is in a regeneration state, discharging natural gas which is deeply dehydrated and dealkylated from the top of the tower through a bed layer in the adsorption towers, wherein the water and hydrocarbon dew point of the natural gas meets the condition that the temperature is 30-50 ℃ lower than the lowest environmental temperature, most of the natural gas is output as a natural gas product, one part of the natural gas is subjected to heat exchange to 120-150 ℃ and serves as regeneration gas, enters the adsorption towers which are completely adsorbed for regeneration, and the regeneration gas and the natural gas are mixed and returned to a light hydrocarbon water-gas concentration.
Further, the natural gas is pretreated to remove acidic components, and the method comprises an alcohol amine method, a low-temperature methanol washing (Rectisol), a polyethylene glycol dimethyl ether washing (Selexol), a sulfone amine method (Sulinol), a direct oxidation method, an adsorption method, a membrane separation method and other conventional methods for removing acidic components.
Furthermore, a plurality of adsorption towers in the light hydrocarbon water gas concentration process are alternately and circularly operated, and the system belongs to a Pressure Swing Adsorption (PSA) system and consists of N adsorption towers, wherein N is a natural number more than 1; wherein 1-N-1 adsorption towers are in adsorption state, and the rest adsorption towers are in regeneration state.
Furthermore, the filling material in the PSA adsorption tower is one or more of activated carbon, silica gel, activated alumina and molecular sieve.
Furthermore, the light hydrocarbon aqueous vapor in the light hydrocarbon aqueous vapor concentration process is further processed by pressurization, and comprises low-temperature cooling condensation or condensation and cold oil absorption, condensed water is separated, C2+ components are recovered, non-condensable gas is mixed with the natural gas raw material after heat exchange to enter the light hydrocarbon aqueous vapor concentration process, and the natural gas is further dehydrated and dealkylated to recover the natural gas. Or the noncondensable gas is used as the regeneration gas of the temperature swing adsorption fine-removing process after heat exchange, and the temperature swing adsorption tower is regenerated.
Furthermore, the intermediate gas in the temperature swing adsorption fine-removal process enters a system consisting of 2N +1 adsorption towers for temperature swing adsorption, wherein N adsorption towers are used for adsorption, N adsorption towers are used for regeneration, 1 adsorption tower is used as a standby tower, and N is a natural number greater than 1.
Further, the packing material in the TSA tower is one or more of activated carbon, silica gel, activated alumina and molecular sieve.
Furthermore, the intermediate gas in the light hydrocarbon water gas concentration process exchanges heat with a part of the natural gas product which is used as the regeneration gas in the temperature swing adsorption fine desorption process.
Furthermore, the water and hydrocarbon dew points of the intermediate gas in the light hydrocarbon water-gas concentration process are lower than the lowest environmental temperature by 5 ℃, and the intermediate gas can be directly used as a natural gas product with the dew point not greatly reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention couples the traditional independent natural gas dehydration and dealkylation units into a system for the first time to realize simultaneous dehydration and dealkylation, which not only can meet the qualified dew point drop requirement, but also can recover most of light hydrocarbon components with higher economic value, such as ethane, propane, butane and the like;
(2) the invention solves the problems of long flow, high energy consumption, insufficient dehydration and dealkylation depth, difficult recovery of hydrocarbons and the like in the traditional natural gas dehydration and dealkylation method;
(3) for natural gas raw materials which are high in pressure and contain more light hydrocarbon components such as ethane, propane and the like, the traditional method for simultaneously dehydrating and dealkylating is not economical, high-pressure energy carried by the raw gas is not utilized, TSA (TSA) purification efficiency of the light hydrocarbon components such as ethane, propane and the like is low, and the TSA can not be effectively recovered, so that the problem can be effectively solved;
(4) the invention is suitable for various natural gas sources, is suitable for selection of different pretreatment processes, adapts to different working conditions and fluctuation of the raw material gas, and improves the stability and safety of the whole natural gas purification process;
(5) the invention solves the problem that the service life of the adsorbent is shortened due to the increase of the temperature stress born by the TSA adsorbent caused by frequent temperature change period; meanwhile, the problem that the traditional PSA can not be effectively applied due to low adsorbate partial pressure in the natural gas purification process is solved;
(6) the invention effectively solves the outstanding contradiction between adsorption and regeneration in the traditional natural gas TSA purification, dehydration and dealkylation process, namely the easier the adsorption, the more difficult the desorption, the time required for regeneration and heating and the difficulty in forming cycle operation with the adsorption; the invention couples PSA and TSA, realizes relative deep adsorption on the premise of fully achieving the goal of deep dehydration and dealkylation, simultaneously makes desorption relatively easy, and completely regenerates the adsorbent, thereby preventing the adsorbent from being penetrated to influence the quality of dehydration and dealkylation;
(7) the traditional TSA regeneration needs a larger heat load, the energy consumption is increased, and especially for the treatment of large-flow natural gas, the heat load is too large, so that the use of the TSA is limited. The invention adopts the light hydrocarbon water gas PSA concentration process to concentrate most of water and C2+ components in the natural gas, and the natural gas subjected to initial concentration, dehydration and dealkylation can meet the quality requirement of initial dew point drop (less than 5 ℃ of the lowest environmental temperature), and can be directly used. If further deep dehydration is needed, the natural gas is subjected to TSA fine dehydration, the depth of natural gas dehydration and dealkylation can reach that the dew point drop is 30-50 ℃ lower than the lowest environmental temperature, the TSA regeneration load is smaller at the moment, in addition, a part of natural gas products are taken out to be used as the regeneration gas of a heat carrier, the regeneration gas after regeneration is returned to the light hydrocarbon water-gas concentration process, the natural gas products are further recovered, and the yield is higher;
(8) the relative separation and adsorption separation coefficient of each component in natural gas is small, for example, between methane and ethane and between ethane and propane, the traditional adsorption methods such as TSA and PSA are difficult to adopt. The invention makes full use of the energy and physical properties of the raw material gas, and selectively realizes the balance of adsorption and desorption and the cyclic operation to achieve organic unification.
The regeneration of the light hydrocarbon water vapor concentration process is desorbed at medium temperature by adopting a normal pressure or vacuum pumping mode, a heat source and regenerated gas are not needed, compared with the traditional TSA which needs high-temperature steam or hot regenerated gas as the heat source, the invention saves a large amount of heat energy and regenerated gas, and simultaneously, the regenerated gas of the TSA fine-removal process is subjected to heat exchange with intermediate gas generated in the light hydrocarbon water vapor concentration process and then returns to the feed gas, thereby further realizing the purposes of energy saving and consumption reduction.
Drawings
FIG. 1 is a schematic flow chart of the present invention and a schematic flow chart of example 1;
FIG. 2 is a schematic flow chart of example 2;
FIG. 3 is a schematic flow chart of example 3;
FIG. 4 is a schematic flow chart of example 6.
Detailed Description
In order to make those skilled in the art better understand the present invention, the technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention.
Example 1
As shown in figure 1, a full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas comprises the following steps:
(1) light hydrocarbon water-gas concentration process: natural gas at a temperature of 50 to 80 ℃ and a pressure of 5.0 to 7.0MPa,
after the pretreatment to remove the acidic components, the components are 92.18% (volume ratio, the same below), 3.33% ethane, 1.48% propane, 0.79% butane, 0.25% pentane and C6 +0.05 percent, the dew point of water is 5-20 ℃, and the total sulfur is less than or equal to 30mg/m3，CO2Less than or equal to 10ppmv and 0.73 percent of nitrogen directly enter a light hydrocarbon water gas concentration procedure through an air inlet pipeline, a 10-tower series-parallel Pressure Swing Adsorption (PSA) process is adopted, adsorption is carried out under the conditions that the operating temperature is 50-80 ℃ and the operating pressure is 5.0-7.0 MPa, 3-tower adsorption and 7-tower regeneration are carried out, cyclic operation is carried out, the continuous entering of feed gas is ensured, and the treatment scale is larger than 5-10 ten thousand square/hour of natural gas. In the adsorption tower, middle gas consisting of methane and a small amount of nitrogen is discharged from the top of the tower through a bed layer and enters the next procedure, namely a temperature swing adsorption fine desorption procedure; most of water in natural gas is reacted with alkane (C) of two or more carbon atoms2 +) The components are adsorbed and desorbed to obtain desorption gas rich in light hydrocarbon and water, which is called light hydrocarbon-rich water gas for short, and the desorption gas is pressurized and further treated for recovery.
In the working procedure, the natural gas raw material with temperature and pressure after the acid components are removed directly enters the working procedure without cooling and pressurizing, thereby saving energy consumption and equipment investment. Active alumina, silica gel, active carbon and molecular sieve adsorbent are filled in a PSA adsorption tower, water and C2+ hydrocarbon components are adsorbed by adsorbate, methane and a small amount of nitrogen are non-adsorption phases and are taken as intermediate gas to permeate a bed layer to be discharged from the top of the tower, water and C2+ are taken as control components in the process, and the dew point of the flowing intermediate gas is controlled within the range of 5 ℃ lower than the lowest ambient temperature. The temperature of the working procedure is in a middle temperature range of 50-80 ℃, the adsorption pressure is 5.0-7.0 MPa, natural gas raw materials directly enter without cooling or pressurizing, so that the energy consumption is reduced, the adsorption phase desorption is ensured to be thorough, the service life of the adsorbent is prolonged to more than 10 years, the adsorbate light hydrocarbon water gas is concentrated to more than 15-30% in the desorption gas, and the C2+ component accounts for most of the total weight of the adsorbent. The traditional PSA method has the advantages that heavy hydrocarbon components cannot be well desorbed, and the adsorbent in the tower is inactivated due to long-term accumulation, so that the service life of the adsorbent is usually less than 2-3 years, the traditional TSA method has the advantages that the service life of the adsorbent is usually less than 3 years due to the periodic alternation of temperature, so that the adsorbent cannot be well desorbed, and the service life of the adsorbent is easily shortened due to the periodic alternation of temperature.
(2) Temperature swing adsorption fine-removing process: the temperature of intermediate gas from a light hydrocarbon water gas concentration process is maintained to be 50-80 ℃, the pressure is 5.0-7.0 MPa, the intermediate gas enters a system consisting of 3 adsorption towers to be subjected to Temperature Swing Adsorption (TSA) to ensure that the intermediate gas continuously enters, 1 adsorption tower is in an adsorption state, 1 adsorption tower is in a regeneration state, and 1 adsorption tower is taken as a standby tower to ensure that the intermediate gas continuously flows in and adapts to the condition fluctuation of the flow, the composition and the like. And (3) discharging the deeply dehydrated and dealkylated natural gas from the top of the tower through the bed layer, wherein the dew point of water and hydrocarbon meets the condition that the dew point is 30-50 ℃ lower than the lowest environmental temperature, most of the natural gas is output as a natural gas product, one part of the natural gas is subjected to heat exchange to 120-130 ℃ and is used as regeneration gas, the regeneration gas enters an adsorption tower after adsorption for regeneration, the regeneration gas and the natural gas feed gas are mixed and return to a light hydrocarbon water gas concentration process for further dehydration and.
The intermediate gas from the light hydrocarbon water gas concentration process directly enters the process for Temperature Swing Adsorption (TSA) cycle operation without heat exchange with a part of natural gas products as regeneration gas. Because the temperature of the intermediate gas is not high, the adsorption is relatively facilitated, and the regeneration is relatively easy, the temperature of the regenerated gas in the embodiment is 120-130 ℃, and the heat load is relatively reduced. The natural gas product flowing out from the TSA tower top meets the dew point drop requirement of deep dehydration and dealkylation, and the purity of methane can reach more than 99% (v/v). And (3) regenerating a part of natural gas products as regenerated gas to the TSA adsorption tower, cooling to 50-80 ℃, mixing with the raw material gas, and further recovering the natural gas, so that the yield of the methane is up to more than 90-95%.
Example 2
As shown in figure 2, the full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas is further optimized on the basis of the full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas in example 1, the natural gas is pretreated to remove acid components, and high-pressure crude natural gas from a wellhead is subjected to acid gas component removal by adopting a high-pressure alcohol amine method (MDEA: methyldiethanolamine) so that the total sulfur in the clean natural gas is less than or equal to 30mg/m3、CO2Less than or equal to 10ppmv as the feed gas for the natural gas entering this example.
Example 3
As shown in fig. 3, the method is further optimized based on the full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas in embodiment 1, wherein light hydrocarbon steam in the light hydrocarbon steam concentration step is pressurized to 5.0 to 7.0MPa, and then sent to a drying system to further remove the concentrated moisture, and then sent to a cold oil absorption method to recover C2+, an absorbent is C4 (a mixture of n-butane and isobutane), the temperature is 50 to 80 ℃, non-condensable gas mainly containing methane escapes from the top of the absorption tower, or the condensed gas is directly used as regeneration gas in the temperature swing adsorption refining step after being heated, so that the use of natural gas as regeneration gas is reduced, and the product yield of natural gas can reach more than 95%; or mixing the natural gas with the natural gas raw material, performing a light hydrocarbon water-gas concentration process, further dehydrating and dealkylating the natural gas, and recovering the natural gas, wherein the yield of the methane is as high as 90-95% and above; desorbing the C2+ -enriched absorption liquid (rich oil liquid) by a desorption tower, allowing C2+ components to escape from the top of the desorption tower, ensuring that the yield of C2+ is up to over 90 percent, obtaining an absorbent C4 (lean oil liquid) at the bottom of the desorption tower, and pressurizing for recycling. Furthermore, in the operation of the desorption tower, different pressure reduction working procedures are adopted, so that ethane, propane, butane and heavy hydrocarbon components escape from the top of the desorption tower in sequence, and are respectively recovered. The embodiment comprises a process of recovering light hydrocarbon water gas, is suitable for the condition that C2+ hydrocarbon components need to be recovered, realizes C2+ recovery treatment through drying and cold oil absorption, is convenient for increasing the value of byproducts, and improves the economic benefit.
Example 4
The full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas is further optimized on the basis of the full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas in the embodiments 1 and 3, the pretreated natural gas raw material gas in the light hydrocarbon water gas concentration process is at the temperature of 90-120 ℃ and the pressure of 3.0-4.0 MPa, the rest working conditions are unchanged, the pretreated natural gas raw material gas directly enters the light hydrocarbon water gas concentration process for dehydrating and dealkylating, the outflow intermediate gas is cooled to 50-60 ℃ through heat exchange, the pressure is kept at 3.0-4.0 MPa, the natural gas product enters the temperature swing adsorption fine-dealkylation process, and the natural gas product flows out of the tower top, so. Heating a part of natural gas product gas to 130-140 ℃, and regenerating the natural gas product gas as regeneration gas of a temperature swing adsorption fine-removing process. The regenerated gas is mixed with natural gas raw material gas through heat exchange, and enters a light hydrocarbon water gas concentration process again to further recover the natural gas, the yield of methane reaches 90-95% and above, the light hydrocarbon water gas flowing out in the light hydrocarbon water gas concentration process is sent to a drying and C4 cold oil absorption recovery C2+ processing unit to recover C2+, and the recovery rate of C2+ exceeds 90%.
Example 5
The method is further optimized on the basis of the full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas in the embodiment 1, the pretreated natural gas feed gas in the light hydrocarbon water gas concentration process is at the temperature of 130-150 ℃ and the pressure of 0.5-1.0 MPa, and the rest working conditions are unchanged, and the pretreated natural gas feed gas directly enters the light hydrocarbon water gas concentration process for dehydrating and dealkylating. In the PSA separation system in the process, 10 towers are connected in series and in parallel, 3 towers are used for adsorption, and 7 towers are used for desorption, wherein the desorption regeneration mode adopts the mode that the regeneration gas from the temperature swing adsorption fine desorption process is flushed and vacuumized at the same temperature and pressure, and the formed light hydrocarbon water gas is pressurized and then sent out of a boundary area for treatment. And the temperature of the effluent intermediate gas is reduced to 50-80 ℃ through heat exchange, the pressure is kept at 0.5-1.0 MPa, the intermediate gas enters a temperature swing adsorption fine desorption process, and a natural gas product flows out from the top of the tower, so that the depth requirement that the dew point of water and hydrocarbon is reduced to be 30-50 ℃ below the lowest environmental temperature is met. Heating a part of natural gas product gas to 140-150 ℃, and regenerating the natural gas product gas as regeneration gas in a temperature swing adsorption fine-removal process. The regenerated gas is directly used as desorption flushing gas in the light hydrocarbon water vapor concentration process without heat exchange, and is taken as light hydrocarbon water vapor to be discharged out of a boundary area for processing together with the pumped air. The yield of methane reaches 90 percent or more.
Example 6
As shown in fig. 4, the method is further optimized based on the full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas in embodiment 1, and the water and hydrocarbon dew points of the intermediate gas in the light hydrocarbon water gas concentration process can meet the requirement that the temperature is lower than the minimum ambient temperature by 5 ℃, and can be directly used as a natural gas product with a low dew point.
It should be apparent that the above-described embodiments are only some, but not all, of the embodiments of the present invention. All other embodiments and structural changes that can be made by those skilled in the art without inventive effort based on the embodiments described in the present invention or based on the teaching of the present invention, all technical solutions that are the same or similar to the present invention, are within the scope of the present invention.
Claims (8)
1. A full temperature range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas is characterized by comprising the following steps:
(1) light hydrocarbon water-gas concentration process: natural gas with the temperature of 50-150 ℃ and the pressure of 0.5-7.0 MPa is pretreated to remove acid components, and then directly enters a light hydrocarbon water vapor concentration process through an air inlet pipeline, a multi-tower series or parallel Pressure Swing Adsorption (PSA) process is adopted, adsorption is carried out under the conditions that the operation temperature is 50-150 ℃ and the operation pressure is 0.5-7.0 MPa, a plurality of PSA adsorption towers alternately and circularly operate to ensure that raw gas continuously enters, 1 or more PSA adsorption towers are in an adsorption state, the rest adsorption towers are in a regeneration state, in the PSA adsorption towers, intermediate gas mainly composed of methane, a small amount of nitrogen and hydrogen is discharged from the top of the tower through a bed layer, and the intermediate gas enters the next process and a temperature swing adsorption fine-removal process; most of water in the natural gas is adsorbed with the alkane components above carbon and carbon two, desorption gas rich in light hydrocarbon and water is obtained after desorption, the desorption gas is called light hydrocarbon-rich water gas for short, and the light hydrocarbon-rich water gas is pressurized for further treatment and recovery or is sent out of a boundary area for treatment;
(2) a temperature swing adsorption fine-removing process; the method comprises the steps that intermediate gas from a light hydrocarbon water vapor concentration process enters a system consisting of 2 adsorption towers to be subjected to Temperature Swing Adsorption (TSA) after being cooled or maintained to 50-60 ℃ and the pressure is 0.5-7.0 MPa, the intermediate gas is enabled to continuously enter, 1 adsorption tower is in an adsorption state, the other adsorption tower is in a regeneration state, natural gas which is subjected to deep dehydration and dealkylation is discharged from the top of the tower through a bed layer in the adsorption towers, the dew point of water and hydrocarbon meets the condition that the dew point is 30-50 ℃ lower than the lowest environmental temperature, most of the natural gas is output as a natural gas product, one part of the natural gas is subjected to heat exchange to 120-150 ℃ to serve as regeneration gas, the regeneration gas enters the adsorption towers which are subjected to adsorption to regeneration, the regeneration gas and the natural gas.
2. The full-temperature-range pressure swing adsorption purification method for simultaneous dehydration and dealkylation of natural gas according to claim 1, wherein the natural gas is pretreated to remove acidic components, and the method comprises an alcohol amine method, a low-temperature methanol wash (Rectisol), a dimethyl ether glycol wash (Selexol) method, a sulfone amine method, a direct oxidation method, an adsorption method, a membrane separation method and other conventional methods for removing acidic components.
3. The full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas as claimed in claim 1, wherein a plurality of adsorption towers in the light hydrocarbon water gas concentration process are alternately operated in a circulating manner, belong to a Pressure Swing Adsorption (PSA) system and consist of N adsorption towers, and N is a natural number greater than 1; wherein 1-N-1 adsorption towers are in adsorption state, and the rest adsorption towers are in regeneration state.
4. The full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas according to claim 1, wherein the packing material in the PSA adsorption tower is one or more of activated carbon, silica gel, activated alumina and molecular sieve.
5. The full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas as claimed in claim 1, wherein the light hydrocarbon steam in the light hydrocarbon steam concentration step is further treated by pressurization, and comprises low-temperature cooling condensation or condensation and cold oil absorption, condensed water is separated, carbon dioxide and alkane components above are recovered, non-condensable gas is subjected to heat exchange and then is mixed with the natural gas raw material to enter the light hydrocarbon steam concentration step, and the natural gas is further dehydrated and dealkylated to recover the natural gas; or the noncondensable gas is used as the regeneration gas of the temperature swing adsorption fine-removing process after heat exchange, and the temperature swing adsorption tower is regenerated.
6. The full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas according to claim 1, characterized in that the intermediate gas in the temperature swing adsorption fine-removal process enters a system consisting of 2N +1 adsorption towers for temperature swing adsorption, wherein N adsorption towers are used for adsorption, N adsorption towers are used for regeneration, 1 adsorption tower is used as a spare tower, and N is a natural number more than 1.
7. The full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas as claimed in claim 1, wherein the packing material in the TSA tower is one or more of activated carbon, silica gel, activated alumina and molecular sieve.
8. The full-temperature-range pressure swing adsorption purification method for simultaneously dehydrating and dealkylating natural gas as claimed in claim 1, wherein the intermediate gas in the light hydrocarbon water gas concentration process exchanges heat with a natural gas product which is a part of the regeneration gas in the temperature swing adsorption fine-removal process.
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