CN101531337A - Method and device for low-pressure processing of coal coking gas - Google Patents
Method and device for low-pressure processing of coal coking gas Download PDFInfo
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- CN101531337A CN101531337A CN200810101851A CN200810101851A CN101531337A CN 101531337 A CN101531337 A CN 101531337A CN 200810101851 A CN200810101851 A CN 200810101851A CN 200810101851 A CN200810101851 A CN 200810101851A CN 101531337 A CN101531337 A CN 101531337A
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Abstract
The invention relates to a method for low-pressure processing of coal coking gas, comprising the steps of: introducing the coking gas into a hydration reactor so as to be in counter-current contact with hydrate working liquid coming from the top of a hydration reactor, leading methane contained in the coking gas and water in the hydrate working liquid to generate the hydration reaction to form a hydrate, meanwhile, hydrogen in the coking gas is concentrated to obtain the hydrogen with high concentration; wherein the operation pressure of the hydration reactor is 0.20-1.00MPa (absolute pressure), and the operation temperature is 3-15 DEG C. The formed hydrate can be further introduced into a hydrate decomposition device for decomposition, thereby releasing methane gas with high concentration. The invention simultaneously relates to a device for realizing the method for low-pressure processing of the coal coking gas. The application of the technology can separate out the coking gas under lower pressure and obtain the hydrogen with high concentration and the methane with high concentration, thereby reducing the energy consumption and the operation difficulty of the process and increasing the economic benefits.
Description
Technical field
The present invention relates to a kind of method and device of handling coal coking gas, specifically, the present invention relates to a kind of hydrate that under the low pressure condition, utilizes coal coking gas is carried out the method for separating treatment with the hydrogen of the methane that obtains high density respectively and high density, and the device that is used to realize this method.
Background technology
In the carbonization of coal process, all be attended by emitting of gas, be called coking gas, the main component of these coking gases is methane and hydrogen, also contains some a spot of CO in addition
2And N
2The total amount of China's coking gas surpasses 20 x 10 according to estimates
8m
3/ year, utilize these coking gases rationally and effectively, all significant for environment protection and raising economic benefit of enterprises.
At present can take low temperature separation process, membrane separation technique, also can take the isolating method of high pressure water compound the separation of coking gas.These methods all need than higher working pressure, a kind of method of utilizing hydrate separating and concentrating hydrogen is disclosed as CN1272618A, the pressure that methane generates hydrate when wherein having put down in writing 1 ℃ is up to 30 normal atmosphere, and along with the rising of temperature, the generation pressure of hydrate also increases.Yet, the pressure of the coal coking gas of discharging from coking furnace in the actual industrial is very low, be generally normal pressure or near normal pressure, separate coal coking gas if utilize above-mentioned low temperature separation process, membrane sepn or high pressure water compound isolation technique, need earlier coking gas to be brought up to needed condition of high voltage, energy consumption is bigger.
Therefore, the method for seeking separation coal coking gas under the low pressure condition is necessary, for the energy consumption that reduces sepn process, improves economic benefit of enterprises, with significant.
Summary of the invention
Main purpose of the present invention is to provide a kind of method of low-pressure processing of coal coking gas, to realize the separation of coking gas under the lower pressure condition, reduces the energy consumption of process and the operation easier of process.
Another object of the present invention is to provide a kind of method of low-pressure processing of coal coking gas, under the lower pressure condition, coking gas is separated,, obtain the hydrogen of high density simultaneously to reclaim the methane in the coking gas.
Another object of the present invention is to provide a kind of device that is used to realize the method for described low-pressure processing of coal coking gas.
According to the method for low-pressure processing of coal coking gas provided by the present invention, specifically be a kind of isolating method of utilizing the method that generates hydrate under the low pressure condition, to realize coking gas.It is generally acknowledged in the prior art that hydrate forms under certain temperature and certain condition of high voltage, methane generates the pressure of hydrate up to 30 normal atmosphere during as put down in writing among the CN1272618A 1 ℃.And the inventor finds under lower pressure, when the coking gas that contains methane contacts with the hydrate working fluid that contains tetrahydrofuran (THF) (THF), when forming hydrate, the methane in the coking gas will enter in the hydrate and be pulled away, thereby can realize separating of other component in methane and the coking gas.On this basis, the invention provides a kind of method of low-pressure processing of coal coking gas, the method comprising the steps of:
Coking gas is introduced hydration reactor, with hydrate working fluid counter current contact from the hydration reactor top, make the water generation hydration reaction in methane contained in the coking gas and the hydrate working fluid form hydrate, the hydrogen in the coking gas is carried the dense dense gas (high concentration hydrogen) that obtains carrying simultaneously; Wherein, the working pressure of described hydration reactor is 0.20～1.00MPa (pressure is absolute pressure described in the present invention), and service temperature is 3～15 ℃.
According to specific embodiments of the present invention, the method of processing coal coking gas of the present invention also can comprise step: the hydrate introducing hydrate that forms in the hydration reactor is dissolved device dissolve, form gas stream and liquid stream, and the liquid stream drawing-off water compound that forms is dissolved device after liquid circulating pump boosts, return the hydration reactor recycle.More particularly, the working pressure that described hydrate is dissolved device is 0.1～0.25MPa, and service temperature is 8～23 ℃.
According to specific embodiments of the present invention, the volume fraction of methane is 0.10～0.60 in the coking gas of described introducing hydration reactor.Preferably, before entering hydration reactor, described coking gas is compressed to pressure 0.2～1.0MPa earlier, and enters after cooling to 3～15 ℃ in the hydration reactor again, contacts with the hydrate working fluid hydration reaction takes place.
Utilization of the present invention generates hydrate and separates in the method for coal coking gas under the low pressure condition, described hydrate working fluid preferably oil-phase solution is that 1:1～5:1 mixes the mixed emulsion that obtains with aqueous phase solution according to volume ratio.Adding oil-phase solution be in the hydrate working fluid in order to guarantee that water in the hydrate working fluid generates noncondensingly behind the hydrate becomes big solid piece, in order to avoid the occluding device pipeline, the steady and continuous that helps process is carried out, and satisfies the needs of large-scale industrial application.Among the present invention, the saturation pressure when described oil-phase solution is preferably condensation point and is lower than-20 ℃ and 30 ℃ is lower than the oily substances such as kerosene, diesel oil or silicone oil of 0.05MPa; Described water is for containing the aqueous solution of tetrahydrofuran (THF) (THF), and the mass concentration of THF preferred 10%～30% in this aqueous phase solution.
According to more preferred of the present invention, preferably also contain tensio-active agent and/or kinetics promotor in the described hydrate working fluid.Wherein, described tensio-active agent is in order to make aqueous phase solution and oil-phase solution in the hydrate working fluid form emulsion (emulsion) better, the preferred tensio-active agent that uses comprises the serial emulsifying agent of this dish (Span) among the present invention, for example can comprise sorbitan mono-laurate (Span-20), anhydrous sorbitol monopalmitate (Span-40), sorbitan monostearate (Span-60), anhydrous sorbitol tristearate (Span-65), sorbitan monooleate (Span-80), sorbitan sesquioleate (Span-83), in the Witconol AL 69-66 (Span-85) etc. one or more, more preferably Span-20, Span-40, among Span-60 and the Span-80 one or more; Amount with the aqueous phase solution in the hydrate working fluid is a benchmark, and the mole fraction of tensio-active agent is preferably 0.5%～3%.Described kinetics promotor is in order to improve the speed that hydro-combination process carries out, and preferred kinetics promotor of using comprises Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt and/or sodium lauryl sulphate etc. among the present invention; Amount with the aqueous phase solution in the hydrate working fluid is a benchmark, and the content of kinetics promotor is preferably 300ppm～1500ppm.
Among the present invention, the volume ratio of amount under standard state of amount and coking gas of introducing the hydrate working fluid of hydration reactor is preferably 1:1～1:50, and (conversion is a standard state, V/V).
The method according to this invention, in hydration reactor, in the coking gas contained methane form hydrate with water generation hydration reaction in the hydrate working fluid and the mixed emulsion that enters profit mutually after, the concentration of the hydrogen in the gas phase will be improved, the volume fraction of hydrogen can be up to more than 0.93 in this high concentration hydrogen gas phase, this can be contained the dense gas of carrying of high concentration hydrogen and discharge, for steel-making or coal-to-oil industry provide hydrogen source from the hydration reactor top.
The hydrate that forms in the hydration reactor is to exist with unreacted hydrate working fluid blended slurries form, among the present invention this hydrate and unreacted hydrate working fluid blended slurries are called " hydrate slurry ", being introduced into hydrate after this hydrate slurry dissolves device and dissolves, discharge methane, and be divided into gas stream that comprises high density methane and the liquid stream that comprises the hydrate working fluid.The volume fraction of methane can be dissolved the device top with this gas stream that comprises the methane of high density from hydrate and draw up to more than 0.92 in the gas stream, can send to fuel gas system or sells as product through processed compressed; And liquid stream (hydrate working fluid) can be dissolved device and return the hydration reactor recycle after liquid circulating pump boosts by the drawing-off water compound.
On the other hand, the present invention also provides a kind of device that is used to realize the method for described processing coal coking gas, and this device mainly comprises a hydration reactor.This hydration reactor can adopt the conventional hydration reactor in this field, normally tower reactor.According to preferred specific embodiments of the present invention, described hydration reactor can adopt spraying and sieve plate unitized construction, the top of hydration reactor is spraying area, spraying area is provided with the nozzle that is used to spray the hydrate working fluid, the bottom of hydration reactor is the sieve plate district, be provided with the multilayer sieve plate, and be provided with the spiral coil cooling tube that is used to remove reaction generation heat in the hydration reactor.The bottom of this hydration reactor (bottom) is provided with coking gas inlet and hydrate slurry outlet, and top (top) is provided with hydrate working fluid inlet and carries dense pneumatic outlet.Hydration reaction is mainly finished at spraying area, and also there is partial reaction in the sieve plate district, and the heat that reaction is produced is removed by built-in described spiral coil cooling tube.The function in the sieve plate district of hydration reactor bottom mainly be allow the mixed serum of hydrate solids that spraying area forms and unreacted hydrate working fluid contact with up gas, mass transfer, the hydrogen of carrying secretly in the slurries is extracted, minimizing is entrained into the amount that hydrate is dissolved the hydrogen of device by hydrate slurry, thereby improves the concentration that hydrate is dissolved methane in the device gas stream.According to preferred specific embodiments of the present invention, in the used hydration reactor of the present invention, described hydrate slurry outlet can be arranged on the bottom side of hydration reactor, and the bottom near this hydrate slurry exit is provided with porous filter plate in hydration reactor; Preferably, the shadow area of screen plate on the hydration reactor horizontal plane accounts for 60%～75% of sectional area in the hydration reactor; This screen plate preferably is obliquely installed to the hydrate slurry Way out, and the angle of screen plate and horizontal plane is 5～15 °; The a plurality of perforates that are provided with on the screen plate are relative uniform distribution on screen plate preferably, and each perforate aperture is about 3～8mm; Each perforate total area is about 5%～20% of screen plate area.The setting of this porous filter plate can make to flow into hydrate by hydration reactor and dissolve the concentration of the hydrate in the hydrate slurry of device and be improved to a certain extent, reduces the internal circulating load of dissolving the hydrate working fluid of device by hydrate.
According to specific embodiments of the present invention, the device that is used to realize the method for described processing coal coking gas of the present invention comprises that also monohydrate dissolves device, described hydrate is dissolved device and is provided with the hydrate slurry inlet, this hydrate slurry inlet exports with the hydrate slurry of hydration reactor and is connected, and is used for that hydrate is drawn and introduced to hydrate slurry from hydration reactor and dissolves in the device and dissolve; And hydrate is dissolved the device top and is provided with the pneumatic outlet that is used to draw gas stream, and the bottom is provided with the liquid exit that is used to draw liquid stream.According to preferred specific embodiments of the present invention, the liquid exit that described hydrate is dissolved the setting of device bottom can be connected with the hydrate working fluid inlet of hydration reactor, and the pipeline that this hydrate is dissolved between the hydrate working fluid inlet of the liquid exit of device and hydration reactor is provided with a liquid circulating pump, dissolves device and return the hydration reactor recycle after liquid circulating pump boosts in order to the liquid stream drawing-off water compound of hydrate being dissolved in the device.
According to specific embodiments of the present invention, pipeline between the hydrate slurry inlet that the hydrate slurry outlet of described hydration reactor and hydrate are dissolved device is provided with first interchanger and second interchanger, described first interchanger is used to make heat-shift between the hydrate slurry that the feed coal coking gas draws before entering hydration reactor and from the hydration reactor bottom, described second interchanger is used for further heating through the hydrate slurry of first interchanger.Also be provided with the 3rd interchanger on the pipeline between the liquid exit of dissolving device bottom at described hydrate enters the mouth with the hydrate working fluid of hydration reactor, again by the 3rd interchanger cooling, return hydration reactor then after boosting through described liquid circulating pump in order to the liquid stream after will dissolving as the recycle of hydrate working fluid.
Used equipment hydrate is as described dissolved device, interchanger, recycle pump and set connecting pipeline (pipeline) in the device of the present invention, optionally set valve and strapping table etc. all can adopt the conventional equipment in this field, the setting of concrete parts such as sieve plate, nozzle and spiral coil cooling tube also is easy to grasp and implement for a person skilled in the art after reading the present invention in the described hydration reactor, and the present invention no longer gives unnecessary details the concrete structure of these equipment.
In sum, the device that the invention provides a kind of method of low-pressure processing of coal coking gas and be used to realize this method, the present invention breaks through the water past compound and generates the restriction that must under high pressure carry out, can lower pressure (0.20～1.00MPa) with temperature (3～15 ℃) condition that is fit under make methane in the coal coking gas generate hydrate to realize to the separating of coking gas, thereby the energy consumption of the process of reduction and the operation easier of process; Use technology of the present invention, can reclaim about methane more than 70% in the coking gas, obtain the hydrogen of high density simultaneously, the volume fraction of hydrogen is higher than 0.93 in the resulting high concentration hydrogen, and the volume fraction of methane is higher than 0.92 in the high density methane gas, the hydrogen that utilizes the resulting high density of technology of the present invention and methane can satisfy the needs of different chemical processes respectively, increase economic benefit of enterprises.
Description of drawings
Fig. 1 is the process flow diagram of the method for demonstration low-pressure processing of coal coking gas of the present invention;
Fig. 2 is the synoptic diagram of the structure of the hydration reactor in the demonstration device of the present invention;
Fig. 3 A and Fig. 3 B are the synoptic diagram that is provided with of the screen plate in the hydration reactor in the demonstration device of the present invention, and wherein, Fig. 3 A is the vertical view of the structure of demonstration screen plate, and Fig. 3 B is for showing the side-view of the set-up mode of screen plate in hydration reactor.
Major label description in figure:
1 hydration reactor, 2 hydrates are dissolved device 3 first interchanger
4 second interchanger, 5 liquid circulating pumps 6 the 3rd interchanger
11 coking gases, 12 hydrate slurries that enter the mouth export 13 hydrate working fluids inlets
14 carry dense pneumatic outlet 15 nozzles 16 sieve plates
The outlet of 17 spiral coil cooling tubes, 18 screen plates, 19 hydrate working fluids
21 hydrate slurries, 22 pneumatic outlets, 23 liquid exits that enter the mouth
10 hydrate slurry hydraulic control valves, 20 flow of feed gas control valves, 30 hydrate working fluid valves
Embodiment
Below by preferred exemplary embodiment and conjunction with figs. apparatus and method of the present invention and beneficial effect thereof are described in further detail.
See also shown in Figure 1ly, the invention provides the technology that a kind of utilization generates hydrate under the low pressure condition method is separated coal coking gas, wherein used appliance arrangement comprises that mainly hydration reactor 1 and hydrate dissolve device 2.The bottom of described hydration reactor 1 (bottom) is provided with coking gas inlet 11 and hydrate slurry outlet 12, and top (top) is provided with hydrate working fluid inlet 13 and carries dense pneumatic outlet 14; Described hydrate is dissolved device 2 and is provided with hydrate slurry inlet 21, and this hydrate slurry inlet 21 is connected with the hydrate slurry outlet 12 of hydration reactor 1; And hydrate is dissolved device 2 tops and is provided with the pneumatic outlet 22 that is used to draw gas stream, and the bottom is provided with the liquid exit 23 that is used to draw liquid stream, and this liquid exit 23 is connected with the hydrate working fluid inlet 13 of hydration reactor 1; And, the connecting pipeline that the outlet 12 of the hydrate slurry of described hydration reactor 1 and hydrate are dissolved between the hydrate slurry inlet 21 of device 2 is provided with first interchanger 3 and second interchanger 4, and described hydrate is dissolved the connecting pipeline that the hydrate working fluid of the liquid exit 23 of device 2 bottoms and hydration reactor 1 enters the mouth between 13 and is provided with liquid circulating pump 5 and the 3rd interchanger 6.In addition, flowrate control valve such as hydrate slurry hydraulic control valve 10, flow of feed gas control valve 20, hydrate working fluid valve 30 etc. also can be set as required.
Concrete structure about the hydration reactor among the present invention 1 can be referring to shown in Figure 2, adopt spraying and sieve plate unitized construction, the top of hydration reactor 1 is spraying area, spraying area is provided with the nozzle 15 that is used to spray the hydrate working fluid, the bottom of hydration reactor 1 is the sieve plate district, be provided with multilayer sieve plate 16, and also be provided with the spiral coil cooling tube 17 that is used to remove reaction generation heat in this hydration reactor 1.
When utilizing the present invention's technical process shown in Figure 1 to handle coal coking gas, (mainly comprise hydrogen and methane, the volume fraction of methane is about 0.1～0.6, also has the CO of minute quantity for the low pressure coking gas that will discharge from coking furnace
2And N
2, N wherein
2To almost not influence of technology of the present invention, can ignore), after the compression of compressor (not shown), regulate flow by flow of feed gas control valve 20, then through first interchanger 3, with from the hydration reactor 1 bottom hydrate slurry outlet 12 hydrate slurry heat-shifts of drawing, after being lowered temperature to 3～15 ℃, enter hydration reactor 1 from coking gas inlet 11, and from bottom to up by hydration reactor 1, this coking gas is hydrate working fluid counter current contact down with entering from the hydrate working fluid at hydration reactor 1 top inlet 13 through nozzle 15 sprays, contained methane and the formation of the water generation hydration reaction in hydrate working fluid hydrate in the coking gas.The working pressure of hydration reactor 1 is lower pressure 0.20MPa～1.00MPa, and service temperature is 3～15 ℃.Used hydrate working fluid is that oil-phase solution is that 1:1～5:1 mixes the mixed emulsion that obtains with aqueous phase solution according to volume ratio, wherein, described oil-phase solution is the oily substances such as kerosene, diesel oil or silicone oil that the saturation pressure of condensation point when being lower than-20 ℃ and 30 ℃ is lower than 0.05MPa, and described aqueous phase solution is the aqueous solution that contains tetrahydrofuran (THF) mass concentration 10%～30%; In order to promote the mixing of oil phase and water, tensio-active agent such as Span-20, Span-40, Span-60 or Span-80 etc. have also been added in the hydrate working fluid; In order to improve the speed that hydro-combination process carries out, also added kinetics promotor in the hydrate working fluid, simultaneously as Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt or sodium lauryl sulphate etc.Among the present invention, from hydration reactor 1 top spray and under the volume ratio of hydrate working fluid and the coking gas of introducing from hydration reactor 1 bottom preferably be controlled at 1:1～1:50 (standard state, V/V) in the scope, this hydrate working fluid can suitably be adjusted according to the concentration height of methane in gaseous tension size and the raw material coking gas with the flow rate ratio of unstripped gas, generally speaking, gaseous tension is high more, and the amount of round-robin hydrate working fluid is just more little; Otherwise gaseous tension is low more, and the amount of round-robin hydrate working fluid is just big more; The concentration of methane is higher in the raw material coking gas, and the amount of round-robin hydrate working fluid can suitably increase; The concentration of methane is lower in the raw material coking gas, and the amount of round-robin hydrate working fluid can suitably reduce.The heat that hydration reaction produced is removed by hydration reactor 1 built-in spiral coil cooling tube 17, and the refrigeration agent in the coil pipe can adopt liquefied ammonia etc.The hydrate solids that forms at spraying area in the hydration reactor 1 and the mixed serum of unreacted working fluid are advanced into the sieve plate district (one of effect of sieve plate 16 is the back-mixing that reduces gas) of bottom down in hydration reactor 1, contact with up gas, mass transfer, the hydrogen of carrying secretly in the slurries is extracted, improve the rate of recovery of hydrogen.
In the hydration reactor 1, after methane in the coking gas contacts with the hydrate working fluid and generates hydrate and be removed, and make hydrogen in the gas phase obtain carrying dense (mole fraction of carrying methane in the high concentration hydrogen after dense can be reduced to below 0.07), high concentration hydrogen is carried dense pneumatic outlet 14 and is discharged from hydration reactor 1 top, can provide hydrogen source for steel-making or coal-to-oil industry.
Hydrate slurry in the hydration reactor 1 leaves hydration reactor 1 from the hydrate slurry outlet 12 of hydration reactor 1 bottom, elder generation carries out heat exchange by first interchanger 3 with the raw material coking gas and is tentatively heated, and as required by behind second interchanger 4 (the heat exchange agent can be adopted termite such as heating steam etc.) heat exchange to 8～23 ℃, the hydrate slurry inlet 21 of dissolving device 2 from hydrate enters hydrate and dissolves device 2; The working pressure that hydrate is dissolved device is 0.1MPa～0.25MPa, and service temperature is 8～23 ℃; Described hydrate slurry is dissolved to dissolve in the device 2 at hydrate and is divided into gas and two bursts of logistics of liquid; Gas stream is the gas of high density methane, dissolves the pneumatic outlet 22 at the top of device 2 from hydrate and discharges, and can send to fuel gas system or process processed compressed, sells as product; After boosting through liquid circulating pump 5 after the liquid exit 23 that liquid stream is dissolved device 2 bottoms from hydrate is drawn, after reducing temperature by the 3rd interchanger 6 (refrigeration agent can adopt liquefied ammonia etc.) again, the hydrate working fluid that returns hydration reactor 1 top 13 recycles that enter the mouth, and can replenish an amount of hydrate working fluid according to the production loss needs.
By the separation of above-mentioned technology realization coking gas, can obtain the hydrogen and the methane of high density simultaneously, satisfy the needs of different chemical processes respectively, increase economic benefit of enterprises, and technical process is short, facility compact.
Adopt technical process shown in Figure 1 (wherein hydration reactor 1 adopts structure shown in Figure 2, and screen plate is not set), the simulation coking gas is separated, with hydrogen and the methane that obtains high density respectively.Wherein, enter the consisting of of unstripped gas (being equivalent to coking gas) of hydration reactor 1: H
2(50.21mol%)+CH
4(49.79mol%); Hydration reactor 1 service temperature is 3.0 ℃, and working pressure is 0.20MPa; The hydrate working fluid is that oil-phase solution is that 4:1 mixes the emulsion that obtains with aqueous phase solution according to volume ratio, oil-phase solution is commercially available-No. 20 diesel oil, aqueous phase solution is the aqueous solution (wherein the mole fraction of THF is 0.06) that contains tetrahydrofuran (THF), and contain the Span-60 of mole fraction 0.0128 in this aqueous phase solution, and contain the Sodium dodecylbenzene sulfonate of 500ppm; The amount of the hydrate working fluid of introducing hydration reactor 1 and the volume ratio of amount under standard state of coking gas are that (standard state, V/V), gas residence time in reactor is about 12 minutes to 1:5.Among this embodiment, after coking gas handles to simulation, the high concentration hydrogen that obtains consist of H
2(93.23mol%)+CH
4(6.77mol%); The mole of methane consists of 92.80% in the high density methane, and all the other are H
2Utilize the technology of this embodiment, have 72% methane to be removed in the unstripped gas.
Adopt technical process shown in Figure 1 (wherein hydration reactor 1 adopts structure shown in Figure 2, and screen plate is not set), the simulation coking gas is separated, with hydrogen and the methane that obtains high density respectively.Wherein, enter the consisting of of unstripped gas (being equivalent to coking gas) of hydration reactor 1: H
2(59.16mol%)+CH
4(40.84mol%); Hydration reactor 1 service temperature is 3.5 ℃, and working pressure is 0.96MPa; The hydrate working fluid is that oil-phase solution and aqueous phase solution are 4:1 according to volume ratio, wherein, oil-phase solution is commercially available-No. 20 diesel oil, aqueous phase solution is the aqueous solution (wherein the mole fraction of THF is 0.06) that contains tetrahydrofuran (THF), and contain the Span-60 of mole fraction 0.0128 in this aqueous phase solution, and contain the Sodium dodecylbenzene sulfonate of 500ppm; The amount of the hydrate working fluid of introducing hydration reactor 1 and the volume ratio of amount under standard state of coking gas are that (standard state, V/V), gas residence time in reactor is about 28 minutes to 1:30.Among this embodiment, after coking gas handles to simulation, the high concentration hydrogen that obtains consist of H
2(95.11mol%)+CH
4(4.89mol%); The mole of methane consists of 93.22mol% in the high density methane, and all the other are H
2Utilize the technology of this embodiment, have 89% methane to be removed in the unstripped gas.
Adopt technical process shown in Figure 1 (wherein hydration reactor 1 adopts structure shown in Figure 2, and screen plate is not set), the simulation coking gas is separated, with hydrogen and the methane that obtains high density respectively.Wherein, enter the consisting of of unstripped gas (being equivalent to coking gas) of hydration reactor 1: H
2(58.07mol%)+CH
4(39.22mol%)+CO
2(2.71mol%); Hydration reactor 1 service temperature is 3.8 ℃, and working pressure is 0.90MPa; The hydrate working fluid is that oil-phase solution is that 4:1 mixes the emulsion that obtains with aqueous phase solution according to volume ratio, wherein, oil-phase solution is commercially available-No. 20 diesel oil, aqueous phase solution is the aqueous solution (wherein the mole fraction of THF is 0.06) that contains tetrahydrofuran THF, and contain the Span-60 of mole fraction 0.0128 in this aqueous phase solution, and contain the Sodium dodecylbenzene sulfonate of 500ppm; The amount of the hydrate working fluid of introducing hydration reactor 1 and the volume ratio of amount under standard state of coking gas are that (standard state, V/V), gas residence time in reactor is about 30 minutes to 1:27.Among this embodiment, after coking gas handles to simulation, the high concentration hydrogen that obtains consist of H
2(94.82mol%)+CH
4(4.73mol%)+CO
2(0.45mol%); The mole of methane consists of 92.15mol%, CO in the high density methane
2Be 3.67mol%, all the other are H
2Utilize the technology of this embodiment, have 87.5% methane to be removed in the unstripped gas.
Though above-mentioned invention has been described in conjunction with preferred exemplary; those skilled in the art can make recombinant, modification or the variation of various equivalences to each technical characterictic of the present invention in the scope of connotation of the present invention, these recombinants, modifications and variations ought to fall into the scope that the present invention should protect.
Claims (10)
1. the method for a low-pressure processing of coal coking gas, the method comprising the steps of:
Coking gas is introduced hydration reactor, with hydrate working fluid counter current contact from the hydration reactor top, make the water generation hydration reaction in methane contained in the coking gas and the hydrate working fluid form hydrate, the hydrogen in the coking gas is put forward the dense high concentration hydrogen that obtains simultaneously; Wherein, the working pressure of described hydration reactor is 0.20～1.00MPa, and service temperature is 3～15 ℃.
2. method according to claim 1, this method also comprises step:
The hydrate introducing hydrate that forms in the hydration reactor is dissolved device dissolve, form gas stream and liquid stream, and the liquid stream drawing-off water compound that forms is dissolved device after liquid circulating pump boosts, return the hydration reactor recycle.
3. method according to claim 2, wherein, the working pressure that described hydrate is dissolved device is 0.1～0.25MPa, service temperature is 8～23 ℃.
4. method according to claim 1, wherein, the volume fraction of methane is 0.10～0.60 in the coking gas of described introducing hydration reactor.
5. method according to claim 1, wherein, the amount of the hydrate working fluid of introducing hydration reactor and the volume ratio of amount under standard state of coking gas are 1:1～1:50.
6. method according to claim 1, wherein, described hydrate working fluid is that oil-phase solution is that 1:1～5:1 mixes the mixed emulsion that obtains with aqueous phase solution according to volume ratio; Preferably, described oil-phase solution is kerosene, diesel oil or the silicone oil that the saturation pressure of condensation point when being lower than-20 ℃ and 30 ℃ is lower than 0.05MPa; Described aqueous phase solution is the aqueous solution that contains tetrahydrofuran (THF) mass concentration 10%～30%.
7, method according to claim 6 wherein, also contains tensio-active agent and/or kinetics promotor in the described hydrate working fluid; Amount with the aqueous phase solution in the hydrate working fluid is a benchmark, and the mole fraction of described tensio-active agent is 0.5%～3%, and this tensio-active agent comprises that this coils serial emulsifying agent; The content of described kinetics promotor is 300ppm～1500ppm, and this kinetics promotor comprises one or more in Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt and the sodium lauryl sulphate.
8. device that is used to realize the method for the described low-pressure processing of coal coking gas of claim 1, this device mainly comprises a hydration reactor, this hydration reactor adopts spraying and sieve plate unitized construction, the top of hydration reactor is spraying area, spraying area is provided with the nozzle that is used to spray the hydrate working fluid, the bottom of hydration reactor is provided with the multilayer sieve plate, and is provided with the spiral coil cooling tube that is used to remove reaction generation heat in the hydration reactor; The bottom of this hydration reactor is provided with coking gas inlet and hydrate slurry outlet, and the top is provided with hydrate working fluid inlet and carries dense pneumatic outlet; Described hydrate slurry outlet is arranged on the bottom side of hydration reactor, and the bottom near this hydrate slurry exit is provided with porous filter plate in hydration reactor; Preferably, this screen plate tilts to the hydrate slurry outlet, and the angle of screen plate and horizontal plane is 5～15 °; The shadow area of this screen plate on the hydration reactor horizontal plane accounts for 60%～75% of sectional area in the hydration reactor; Each perforate aperture is 3～8mm on the screen plate; More preferably, the perforate total area on this screen plate accounts for 5%～20% of screen plate area.
9. device according to claim 8, this device comprise that also monohydrate dissolves device, and described hydrate is dissolved device and is provided with the hydrate slurry inlet, and this hydrate slurry inlet exports with the hydrate slurry of hydration reactor and is connected; And hydrate is dissolved the device top and is provided with the pneumatic outlet that is used to draw gas stream, and the bottom is provided with the liquid exit that is used to draw liquid stream; Described hydrate is dissolved the liquid exit that device bottom is provided with and is connected with the hydrate working fluid inlet of hydration reactor, and the pipeline of this hydrate hydrate working fluid of dissolving the liquid exit of device and hydration reactor between entering the mouth is provided with a liquid circulating pump.
10. device according to claim 9, wherein, pipeline between the hydrate slurry inlet that the hydrate slurry outlet of described hydration reactor and hydrate are dissolved device is provided with first interchanger and second interchanger, described first interchanger is used to make heat-shift between the hydrate slurry that the feed coal coking gas draws before entering hydration reactor and from the hydration reactor bottom, described second interchanger is used for further heating through the hydrate slurry of first interchanger; Also be provided with the 3rd interchanger on the pipeline between the liquid exit of dissolving device bottom at described hydrate enters the mouth with the hydrate working fluid of hydration reactor, again by the 3rd interchanger cooling, return hydration reactor then after boosting through described liquid circulating pump in order to the liquid stream after will dissolving as the recycle of hydrate working fluid.
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| CN200810101851XA CN101531337B (en) | 2008-03-13 | 2008-03-13 | Method and device for low-pressure processing of coal coking gas |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101943321A (en) * | 2010-08-19 | 2011-01-12 | 中国石油大学(北京) | Method and device for delivering marsh gas |
| WO2019024403A1 (en) * | 2017-07-31 | 2019-02-07 | 中国科学院广州能源研究所 | Apparatus and method for continuously separating gas with hydrate method |
| CN109420419A (en) * | 2017-08-20 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of decomposition of hydrate device, mixed gas separation system and separation method |
| CN113117504A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy recovery type hydrate method |
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| CN1537666A (en) * | 2003-04-14 | 2004-10-20 | 石油大学(北京) | Reactor for separating gas mixture by hydrate method |
| CN100475933C (en) * | 2004-06-11 | 2009-04-08 | 中国石油天然气股份有限公司 | Combined process for separating and recovering hydrogen, ethylene and ethane from refinery dry gas or separating ethylene cracking gas |
| CN100387691C (en) * | 2005-02-03 | 2008-05-14 | 石油大学(北京) | Method for generating aqua compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101943321A (en) * | 2010-08-19 | 2011-01-12 | 中国石油大学(北京) | Method and device for delivering marsh gas |
| WO2019024403A1 (en) * | 2017-07-31 | 2019-02-07 | 中国科学院广州能源研究所 | Apparatus and method for continuously separating gas with hydrate method |
| CN109420419A (en) * | 2017-08-20 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of decomposition of hydrate device, mixed gas separation system and separation method |
| CN113117504A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy recovery type hydrate method |
| CN113117503A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy-saving hydrate method |
| CN113117504B (en) * | 2019-12-31 | 2023-03-28 | 中国石油化工股份有限公司 | System and method for separating mixed gas by energy recovery type hydrate method |
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