CN101531347B - Method for recycling and synthesizing nitrogen and hydrogen in off-gases of ammonia and device thereof - Google Patents
Method for recycling and synthesizing nitrogen and hydrogen in off-gases of ammonia and device thereof Download PDFInfo
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Abstract
The invention relates to a method for recycling and synthesizing nitrogen and hydrogen in off-gases of ammonia. The method comprises the following steps: off-gases of synthetic ammonia discharged from a gas outlet of an ammonia recycling tower of a synthetic ammonia device are led to a hydration reactor so as to be in contact with the reflux of hydrate working fluid at the top of the hydration reactor; methane and argon contained in the off-gases of ammonia generate hydration reaction with water in the hydrate working fluid to form a hydrate, and the nitrogen and the hydrogen in the off-gases of ammonia are concentrated to obtain concentrated gases; the concentrated gases return to a synthetic ammonia reaction unit for further utilization while the hydrate is led to a hydrate resolver for resolving. The invention also relates to a device for realizing the method. The method and the device can recycle about 80 percent or more of hydrogen and nitrogen in the off-gases of synthetic ammonia, reduce the burden of a hydrogen production unit, increase the output of the device and reduce energy consumption and emission of off-gases.
Description
Technical field
The present invention relates to a kind of method and device that reclaims nitrogen and hydrogen in the synthetic ammonia relief gas, specifically, the present invention relates to a kind of nitrogen and the method for hydrogen and device that is used to realize this method in exitting of speeding that utilizes ammonia recovery tower cat head that hydrate reclaims synthetic ammonia installation.
Background technology
In the ammonia synthesis process, hydrogen and nitrogen are the raw materials of synthetic ammonia, nitrogen replenishes from air, hydrogen then transforms by Sweet natural gas or coal and obtains, raw hydrogen and nitrogen enter ammonia synthesis reaction unit (reactors for synthesis of ammonia) by synthesic gas compressor and react the production ammonia, because the restriction of separation accuracy, in syngas for synthetic ammonia, can contain a certain amount of methane and argon gas inevitably, these components are inert component in synthetic ammonia process, along with continuous accumulation, the concentration of methane and argon gas constantly increases, and after running up to a certain degree, will influence normally carrying out of ammonia synthesis reaction, so a part of gas release must be come out, with the concentration of methane and argon gas in the reduction syngas for synthetic ammonia, this part discharges gas, and the ammonia that arrives synthetic ammonia installation reclaims the unit and (is generally the ammonia stripping tower, or title ammonia recovery tower), through washing, behind the recovery ammonia wherein, put into fuel gas system or hydrogen recovery system as speeding.Because in the synthetic ammonia relief gas except that containing a certain amount of methane and argon gas, a large amount of still hydrogen and nitrogen, certainly also has a certain amount of ammonia, the release of these gases can cause certain loss, if can reclaim this part hydrogen and nitrogen, then can improve the throughput of device or alleviate the unitary load of hydrogen manufacturing.
The pressure of synthetic ammonia installation is generally very high, and the synthetic ammonia relief gas top hole pressure that ammonia reclaims cat head is generally 5MPa～10MPa.And present can be used for carried in the method for dense hydrogen, and sophisticated pressure swing adsorption general requirement working pressure is low, thereby it is dense not to be suitable for carrying of hydrogen in the synthetic ammonia relief gas; Though the technology of another kind of separating gas mixture---membrane separation technique is fit to separate high pressure gas, but because hydrogen must see through film, so the hydrogen pressure of the high density that obtains is too low, need could to circulate after a large amount of superchargings reactors for synthesis of ammonia, energy consumption is very high not to be suitable for actual industrial production yet.CN1272618A discloses a kind of generation hydrate or its precursor utilized the Hydrogen Separation in the hydrogeneous gas mixture has been put forward dense method, CN1970697A discloses a kind of method of utilizing hydrate to carry dense recycle hydrogen in hydrocracking process, and the pressure of dense hydrogen is carried in suitable high top pressure operation of these methods and not obvious reduction.But be not used for reclaiming the report of synthetic ammonia relief gas nitrogen and hydrogen at present about hydrate.
Summary of the invention
Main purpose of the present invention is to provide a kind of method that reclaims nitrogen and hydrogen in the synthetic ammonia relief gas, carry dense with nitrogen and hydrogen during synthetic ammonia is speeded to exit, make the resulting dense gas of carrying of high concentration hydrogen and nitrogen that contains remain on high pressure conditions and return synthesis ammonia system, thereby reduce the energy expenditure of compression.
Another object of the present invention is to provide a kind of device that is used for realizing the method for synthetic ammonia relief gas nitrogen of described recovery and hydrogen.
Technology of the present invention mainly is on the basis of existing ammonia synthesis process, introduce a hydration separation unit, this hydration separation unit comprises that mainly hydration reactor and hydrate dissolve device (or claim decomposition of hydrate device), make nitrogen and hydrogen in speeding to exit obtain carrying dense by making methane contained in the synthetic ammonia relief gas and argon gas generate hydrate, contain carrying dense gas and can keeping the elevated pressures state to return the ammonia synthesis reaction unit of the nitrogen of high density and hydrogen, reach the nitrogen that reclaims in the synthetic ammonia relief gas and the purpose of hydrogen.
On the one hand, the invention provides a kind of method that reclaims nitrogen and hydrogen in the synthetic ammonia relief gas, this method mainly comprises step:
To introduce hydration reactor from the synthetic ammonia relief gas (mainly being the mixed gas of hydrogen, nitrogen, methane, argon gas and ammonia) that synthetic ammonia installation ammonia recovery tower pneumatic outlet is discharged, with hydrate working fluid (or claiming the hydrate Generation Liquid) counter current contact from the hydration reactor top, make the water generation hydration reaction in methane contained in speeding to exit and argon gas and the hydrate working fluid form hydrate, nitrogen in speeding simultaneously to exit and hydrogen are carried the dense dense gas that obtains carrying;
To carry dense gas and return the ammonia synthesis reaction unit and be used, and dissolve device and dissolve and hydrate is introduced hydrate.
Utilize above-mentioned by making the method for synthesizing methane contained in the ammonia relief gas and argon gas generation hydrate make nitrogen and hydrogen in speeding to exit obtain carrying dense, the resulting pressure of carrying dense gaseous mixture that contains high concentration hydrogen and nitrogen can't significantly be reduced, can be through returning the ammonia synthesis reaction unit after suitable the boosting, thus the consumption of compression work reduced greatly.
According to specific embodiments of the present invention, in the nitrogen in the synthetic ammonia relief gas of recovery of the present invention and the method for hydrogen, the hydrate working fluid that is suitable for is an aqueous phase solution.This aqueous phase solution does not contain oily substance, for example kerosene, diesel oil or other hydrocarbons etc.
In the nitrogen in the synthetic ammonia relief gas of recovery of the present invention and the method for hydrogen, owing to contain a certain amount of ammonia inevitably in the described synthetic ammonia relief gas, consider that ammonia is in the solubleness of aqueous phase and the influence that the hydration reaction condition is produced, hydrate working fluid in the described hydration reactor is preferably the ammoniated aqueous solution, and wherein the mole fraction of ammonia is preferably 0.005～0.08.In the method for the invention, can also add thermodynamics promotor tetrahydrofuran (THF) (THF) in described hydrate working fluid, the mass concentration of tetrahydrofuran (THF) in the hydrate working fluid is preferably 10%～30%.
According to specific embodiments of the present invention, the flow of exitting of speeding that enters described hydration reactor can also can be a portion gas for all gas of discharging from ammonia recovery tower cat head.The working pressure of described hydration reactor is that the pressure of synthetic ammonia installation ammonia recovery tower overhead gas outlet (is generally that 5MPa～10MPa), service temperature is 4～15 ℃.Wherein, the cold that needs in the hydro-combination process can be provided by refrigeration system, is preferably provided by the synthetic ammonia installation ammonia refrigeration system.According to preferred specific embodiments of the present invention, the amount of introducing the hydrate working fluid of hydration reactor is 1: 80～1: 130 with the volume ratio of amount under standard state of speeding to exit.Among the present invention, the formed solid hydrate of hydration reaction is to exist with the slurries form that mixes with unreacted hydrate working fluid in hydration reactor, and the mixture with this solid hydrate and liquid phase water compound working fluid among the present invention is called " hydrate slurry "; Be discharged from hydration reactor after this hydrate slurry and enter hydrate and dissolve device and dissolve.In hydration reactor, after contained methane and the water generation hydration reaction in argon gas and the hydrate working fluid are removed in the synthetic ammonia relief gas, nitrogen in the gas phase and hydrogen obtain carrying dense, and the nitrogen that contains higher concentration that among the present invention this is obtained and the mixed gas of hydrogen are called " carrying dense gas ".In the method for the present invention, resultingly carry the composition requirement that dense gas can reach syngas for synthetic ammonia, can return a section or two sections inlets of the synthesic gas compressor (feed gas compressor) in the ammonia synthesis process; Also can with the described synthesic gas compressor that enters again after dense gas dewaters through mole sieve drier earlier in the synthetic ammonia installation of carrying, be used as required and return the ammonia synthesis reaction unit.
According to specific embodiments of the present invention, described hydrate is transported to hydrate with the form of hydrate slurry from hydration reactor to be dissolved device and dissolves.Among the present invention, the working pressure that hydrate is dissolved device is 0.2～2MPa, and service temperature is 8～23 ℃.Described hydrate is dissolved in hydrate is dissolved device and is formed gas stream and liquid stream, gas stream mainly is the mixed gas that comprises methane and argon gas, this gas stream can be dissolved device from hydrate and draws, and further sends into follow-up methane refining plant or directly sends to fuel gas system; And liquid stream (hydrate working fluid) can be dissolved device by the drawing-off water compound and return hydration reactor after liquid circulating pump boost and recycles.
On the other hand; It is a kind of for realizing described recovery synthetic ammonia speed the to exit device of method of nitrogen and hydrogen that the present invention also provides; Namely; The invention provides a kind of hydrate reclaim synthetic ammonia speed to exit in the device of nitrogen and hydrogen; This device mainly comprises a hydration separative element; This hydration separative element is arranged between the overhead gas outlet and synthesic gas compressor entrance of ammonia recovery tower of synthetic ammonia installation during application; This hydration separative element comprises that hydration reactor and hydrate dissolve device; Wherein
The bottom of described hydration reactor (bottom) is provided with speed venting inlet and hydrate slurry outlet, and top (top) is provided with hydrate working fluid inlet and carries dense pneumatic outlet;
The described inlet of speeding to exit is connected with the overhead gas outlet of the ammonia recovery tower of synthetic ammonia installation, in order to introducing this hydration reactor from the synthetic ammonia relief gas that synthetic ammonia installation ammonia recovery tower pneumatic outlet is discharged, with the hydrate working fluid counter current contact of introducing from the hydration reactor top, make the water generation hydration reaction in methane contained in speeding to exit and argon gas and the hydrate working fluid form hydrate, nitrogen in speeding simultaneously to exit and hydrogen are carried the dense dense gas that obtains carrying, and described hydrate is to exist with hydrate working fluid blended slurries form;
The described synthesic gas compressor inlet of carrying in dense pneumatic outlet and the synthetic ammonia installation is connected, and returns the ammonia synthesis reaction unit after dense gas boosts through synthesic gas compressor and is used in order to carrying;
Described hydrate is dissolved device and is provided with the hydrate slurry inlet, this hydrate slurry inlet is connected with the hydrate slurry outlet of hydration reactor, dissolves device and dissolves formation and contain the mixed gas logistics of methane and argon gas and the liquid stream that contains the hydrate working fluid in order to the hydrate slurry in the hydration reactor is introduced hydrate; And this 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 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 hydration reactor after liquid circulating pump boosts and recycle in order to hydrate is dissolved liquid stream drawing-off water compound in the device.And hydrate is dissolved the pneumatic outlet that the device top is provided with and can be linked to each other with methane refining plant or fuel gas system, dissolves device and sends into methane refining plant or fuel gas system in order to hydrate is dissolved gas stream drawing-off water compound in the device.
According to specific embodiments of the present invention, on the pipeline between the inlet of speeding to exit of the outlet of the overhead gas of described ammonia recovery tower and hydration reactor, also can be provided with first interchanger, be gone into the hydration reactor by heat exchange to temperature of reaction (4～15 ℃) is laggard in order to will pass through this first interchanger from the synthetic ammonia relief gas that ammonia reclaims cat head.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, in order to hydrate slurry is drawn the back earlier by first interchanger and the described preliminary heat-shift of synthetic ammonia relief gas from ammonia recovery cat head from hydration reactor, be further heated laggardly to go into hydrate and dissolve device by second interchanger again.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.
In addition, also can further be provided with mole sieve drier as required carrying on the pipeline between dense pneumatic outlet and the synthesic gas compressor inlet of described hydration reactor top, enter synthesic gas compressor in order to carrying again after dense gas dewaters through this mole sieve drier earlier, be used and return the ammonia synthesis reaction unit.
Among the present invention, the ammonia synthesis process of being mentioned is the common process in this field, mainly be to be synthesis material with hydrogen and nitrogen, produce ammonia by entering the ammonia synthesis reaction unit process behind the synthesic gas compressor, after the unitary portion gas of ammonia synthesis reaction is released, arrive the ammonia recovery tower, behind washing and recycling ammonia wherein, exit from the overhead gas outlet discharge of ammonia recovery tower as speeding, wherein equipment therefor equipment such as synthesic gas compressor, the ammonia synthesis reaction unit, ammonia recovery tower etc. also is the conventional equipment in this field, no longer concrete ammonia synthesis process is given unnecessary details among the present invention.Technology of the present invention mainly is to introduce a hydration separation unit between the overhead gas outlet of the ammonia recovery tower of synthetic ammonia installation and synthesic gas compressor inlet, equipment in this hydration separation unit hydration reactor and hydrate as described dissolved device, interchanger, recycle pump and optionally set valve, pipeline, strapping table etc. and all can be adopted conventional equipment in this field, and for example described hydration reactor and hydrate are dissolved normally tower reactor of device.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, also be provided with and be used to remove the spiral coil cooling tube that reaction generates heat, the bottom of hydration reactor is the sieve plate district, is provided with the multilayer sieve plate.Hydration reaction is mainly finished at spraying area, and the cold that needs in the hydro-combination process can be provided by the synthetic ammonia installation ammonia refrigeration system, 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 (abbreviation hydrate slurry) of hydrate solids that spraying area forms and hydrate working fluid contact with up gas, mass transfer, hydrogen and the nitrogen carried secretly in the slurries are extracted, improve the rate of recovery of hydrogen and nitrogen.According to preferred specific embodiments of the present invention, in the used hydration reactor of the present invention, described hydrate slurry outlet is arranged on the bottom side of hydration reactor, and be provided with porous filter plate near the bottom in this hydrate slurry exit in hydration reactor, 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, helps controlling the internal circulating load of hydrate working fluid.
In a word, the present invention is applied to Hydrate Technology in the ammonia synthesis process, be used for reclaiming the nitrogen and the hydrogen of synthetic ammonia relief gas, and at the characteristic of ammonia synthesis process and synthetic ammonia relief gas, research provides a kind of nitrogen that reclaims in the synthetic ammonia relief gas and the concrete processing method and device of hydrogen of being exclusively used in, accomplished that simultaneously technical process is the shortest, equipment is the compactest.In the technology of the present invention, adopt ammoniated aqueous phase solution as the hydrate working fluid, and rational technical process and operational condition have been designed, realized that serialization reclaims nitrogen in the synthetic ammonia relief gas and hydrogen (in the prior art when practical application generates the method divided gas flow of hydrate, all be to adopt the mixed emulsion of water and oil phase, with the continuity that guarantees to produce in the practical application) as the hydrate working fluid.Experimental results show that, utilize method and apparatus of the present invention, can reclaim in the synthetic ammonia relief gas about 80% or more hydrogen and nitrogen, after speed methane in exitting and the argon gas that enters hydrate reactor formed hydrate and be removed, the two mole fraction sum of hydrogen and nitrogen can reach more than 0.93; And, utilize technology of the present invention, can make the mixture of resulting nitrogen that contains high density and hydrogen remain on high pressure conditions and return the ammonia synthesis reaction unit, thereby reduce the consumption of compression work greatly, reduce the unitary hydrogen manufacturing load of gas making, improve the throughput of device, reduce the discharging of speeding to exit, increase economic efficiency.
Description of drawings
The nitrogen that Fig. 1 synthesizes in the ammonia relief gas for demonstration hydrate of the present invention reclaims and the device and the process flow diagram of hydrogen;
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 synthesic gas compressors, 5 second interchanger, 6 liquid circulating pumps
The venting inlet 12 hydrate slurries outlet of speeding of 7 the 3rd interchanger 11
13 hydrate working fluids inlet 14 is carried dense pneumatic outlet 15 nozzles
16 spiral coil cooling tubes, 17 sieve plates, 18 screen plates
19 hydrate working fluids export 21 hydrate slurries, 22 pneumatic outlets that enter the mouth
23 liquid exits, the 10 hydrate slurry hydraulic control valves 20 bleed flow control valve of speeding
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 1, the device that utilizes hydrate to reclaim nitrogen in the synthetic ammonia relief gas and hydrogen of the present invention mainly is (specifically being between the overhead gas outlet of the ammonia recovery tower of synthetic ammonia installation and synthesic gas compressor inlet) introducing one hydration separation unit in existing ammonia synthesis process, this hydration separation unit comprises that mainly hydration reactor 1 and hydrate dissolve device 2, the bottom of described hydration reactor 1 is provided with speed venting inlet 11 and hydrate slurry outlet 12, and the top is provided with hydrate working fluid inlet 13 and carries dense pneumatic outlet 14; The described inlet 11 of speeding to exit is connected with the overhead gas outlet (not shown) of the ammonia recovery tower of synthetic ammonia installation, and the pipeline of the overhead gas of the ammonia recovery tower of speed to exit inlet 11 and synthetic ammonia installation between exporting is provided with first interchanger 3; Describedly carry one section of synthesic gas compressor 4 in dense pneumatic outlet 14 and the synthetic ammonia installation or two sections inlets and be connected; Described hydrate is dissolved device 2 and is provided with hydrate slurry inlet 21, this hydrate slurry inlet 21 is connected with the hydrate slurry outlet 12 of hydration reactor 1, and hydrate is dissolved the pipeline that the hydrate slurry of the hydrate slurry inlet 21 of device 2 and hydration reactor 1 exports between 12 and is provided with first interchanger 3 and second interchanger 5; And this hydrate is dissolved device 2 tops and is provided with pneumatic outlet 22, the bottom is provided with liquid exit 23, liquid exit 23 is connected with the hydrate working fluid inlet 13 of hydration reactor 1, and the pipeline that this hydrate is dissolved between the hydrate working fluid inlet 13 of the liquid exit 23 of device 2 and hydration reactor 1 is provided with a liquid circulating pump 6, and is provided with the 3rd interchanger 7.In this device, flowrate control valve such as hydrate slurry hydraulic control valve 10, the bleed flow control valve 20 of speeding, hydrate working fluid valve 30 etc. can be set as required also.
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, also be provided with and be used to remove the spiral coil cooling tube 16 that reaction generates heat, the bottom of hydration reactor 1 is the sieve plate district, is provided with multilayer sieve plate 17.
When utilizing device shown in Figure 1 and technical process to reclaim nitrogen in the synthetic ammonia relief gas and hydrogen, the all or part of venting of speeding of discharging from synthetic ammonia installation ammonia recovery tower pneumatic outlet (mainly comprises hydrogen, nitrogen, methane, argon gas and ammonia) carry out heat exchange through interchanger 3 and hydrate slurry, after being pre-chilled to 4～15 ℃, enter hydration reactor 1 from the venting inlet 11 of speeding of hydration reactor 1 bottom (bottom), and from bottom to up by hydration reactor 1, the hydrate working fluid counter current contact of this venting of speeding under with entering from the hydrate working fluid at hydration reactor 1 top (top) inlet 13 through nozzle 15 sprays, methane and the water generation hydration reaction in argon gas and the hydrate working fluid contained in speeding to exit form hydrate, and nitrogen in speeding simultaneously to exit and hydrogen are carried the dense dense gas that obtains carrying.The working pressure of hydration reactor 1 is from the pressure of the synthetic ammonia relief gas of ammonia recovery tower, is generally 5MPa～10MPa, and service temperature is 4～15 ℃.Used hydrate working fluid is that (this ammonia can painstakingly add in raw water compound working fluid the aqueous phase solution that contains the ammonia of mole fraction 0.005～0.08, but the ammonia in exitting by speeding in actual process dissolves in the water working fluid, and processing condition according to the present invention reach balance), and can further be added with the tetrahydrofuran (THF) (THF) of mass concentration 10%～30%, but can not add oily substances such as kerosene, diesel oil or other water-insoluble hydrocarbons, can the catalyzer in the ammonia synthesis process not exerted an influence to guarantee technology of the present invention.Among the present invention, from hydration reactor 1 top spray and under the hydrate working fluid preferably be controlled at 1: 80～1: 130 with the volume ratio of introducing from hydration reactor 1 bottom of speeding to exit (standard state be in scope V/V).The heat that hydration reaction produced is removed by hydration reactor 1 built-in spiral coil cooling tube 16, and the cryogen in the coil pipe can adopt the liquefied ammonia refrigeration system.The hydrate solids that hydration reactor 1 inherent spraying area forms and the mixed serum (abbreviation hydrate slurry) of unreacted liquid are advanced into the sieve plate district of bottom down in hydration reactor 1, contact with up gas, mass transfer, hydrogen and the nitrogen carried secretly in the slurries are extracted, improve the rate of recovery of hydrogen and nitrogen.
Carrying of obtaining in the hydration reactor 1 contained higher concentration in the dense gas hydrogen and nitrogen (hydrogen and nitrogen the two mole fraction sum can reach more than 0.93), return one section or two sections inlets of the synthesic gas compressor 4 of synthetic ammonia installation, enter the ammonia synthesis reaction unit then.The mole sieve drier (not shown) can also be set before synthesic gas compressor, carry dense gas and draw to enter again after dewatering through this mole sieve drier earlier in the back from hydration reactor 1 and return the ammonia synthesis reaction unit after synthesic gas compressor 4 suitably boosts and be used.
Hydrate slurry in the hydration reactor 1 leaves hydration reactor 1 from the hydrate slurry outlet 12 of hydration reactor 1 bottom (bottom), elder generation carries out heat exchange by first interchanger 3 and the venting of speeding from the raw material of ammonia recovery cat head and is tentatively heated, and as required by behind second interchanger 5 (adopt termite heat exchange) 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 0.2MPa～2MPa, 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 dissolved the pneumatic outlet 22 at the top of device 2 and is discharged for mainly comprising the mixed gas of methane and argon gas from hydrate, can send to fuel gas system; After the liquid exit 23 that liquid stream is dissolved device 2 bottoms from hydrate is drawn through after the liquid circulating pump 6 suitable superchargings, after reducing temperature by the 3rd interchanger 7 (liquefied ammonia refrigeration) again, the hydrate working fluid inlet 13 that returns hydration reactor 1 top recycles, and can replenish an amount of hydrate working fluid according to the production loss needs.
The nitrogen in the synthetic ammonia relief gas of method recovery of above-mentioned utilization generation hydrate and the technology of hydrogen have technical process weak point, facility compact, make full use of the characteristics of the energy.
In addition, see also shown in Fig. 3 A and Fig. 3 B, in the structure of the hydration reactor 1 among the present invention, described hydrate slurry outlet 12 can also be arranged on the bottom side of hydration reactor, and below near this hydrate slurry outlet 12, be provided with a porous filter plate 18, the shadow area of screen plate 18 on the hydration reactor horizontal plane accounts for 60%～75% of sectional area in the hydration reactor, the relative uniform distribution of a plurality of perforates that is provided with on the screen plate, each perforate aperture is about 3～8mm, and each perforate total area is about 10% of screen plate area; Screen plate shown in the figure is to about 5～15 ° of settings of tilting of hydrate slurry Way out, so that the concentration that exports the hydrate in the 12 effusive hydrate slurries by hydrate slurry is improved.Also be provided with hydrate working fluid outlet 19 in this hydration reactor 1 bottom, the hydrate working fluid that the hydrate working fluid (containing a spot of hydrate) that is filled into screen plate 18 belows can directly return (or cool to 4～15 ℃ after return through suitable heat exchange) hydration reactor 1 top from this hydrate working fluid outlet 19 13 recycles that enter the mouth, thus more help controlling the internal circulating load of hydrate working fluid.
Adopt technical process shown in Figure 1 and device (wherein hydration reactor 1 adopts spraying shown in Figure 2 and sieve plate unitized construction, and is provided with the screen plate 18 shown in Fig. 3 A and Fig. 3 B), reclaim nitrogen and hydrogen in the synthetic ammonia relief gas.Wherein, enter consisting of of the unitary unstripped gas of hydration separation (being equivalent to the venting of speeding): H from the discharge of ammonia stripping cat head
2(65.23mol%)+CH
4(8.96mol%)+N
2(23.36mol%)+Ar (2.43%)+NH
3(0.013%).The service temperature of hydration reactor 1 is 10 ℃, and working pressure is 8.00MPa.The hydrate working fluid is the ammoniated aqueous solution, and wherein the mole fraction of ammonia is 2.093% (0.002093), and to contain mass concentration be 20% tetrahydrofuran (THF).From hydration reactor 1 top spray and under hydrate working fluid and the volume ratio of introducing from hydration reactor 1 bottom of speeding to exit be that (standard state, V/V), gas residence time in reactor was 19 minutes in 1: 80.After reaction was finished, the gas composition of hydration reactor 1 inner equilibrium gas phase was: H
2(79.42mol%)+CH
4(1.98mol%)+N
2(17.46mol%)+Ar (1.13%)+NH
3(0.008%), consisting of of the gas after corresponding hydrate is dissolved hydrates in the device 2 and dissolved: H
2(22.27mol%)+CH
4(29.20mol%)+N
2(41.70mol%)+Ar (6.83%)+NH
3(0.011%).Show the processing method of utilizing present embodiment, 87.30% of hydrogen in exitting from speeding and nitrogen can be returned.
Present embodiment adopts and embodiment 1 same process and device, and the composition of unstripped gas (synthetic ammonia relief gas) is also identical with embodiment 1.In the present embodiment, the service temperature of hydration reactor 1 is 8 ℃, and working pressure is 6.00MPa.The mass concentration of tetrahydrofuran (THF) is 20% in the hydrate working fluid, and the mole fraction of ammonia is 2.093%.From hydration reactor 1 top spray and under hydrate working fluid and the volume ratio of introducing from hydration reactor 1 bottom of speeding to exit be that (standard state, V/V), gas residence time in hydration reactor was 25 minutes in 1: 100.After hydration reaction was finished, the gas composition of balance gas phase was: H
2(75.78mol%)+CH
4(3.09mol%)+N
2(19.56mol%)+Ar (1.57%)+NH
3(0.009%), consisting of of the gas after corresponding hydrate is dissolved: H
2(27.40mol%)+CH
4(29.07mol%)+N
2(36.98mol%)+Ar (6.55%)+NH
3(0.0105%).Show the processing method of utilizing present embodiment, 79.26% of hydrogen in exitting from speeding and nitrogen can be returned.
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 (15)
1. method that reclaims nitrogen and hydrogen in the synthetic ammonia relief gas, wherein utilize a kind of device that is used for realizing the method for synthetic ammonia relief gas nitrogen of this recovery and hydrogen, this device mainly comprises a hydration separation unit, this hydration separation unit is between the overhead gas outlet that is used to be arranged on the ammonia recovery tower of synthetic ammonia installation enters the mouth with synthesic gas compressor, and this hydration separation unit comprises that hydration reactor and hydrate dissolve device, wherein
The bottom of described hydration reactor is provided with speed venting inlet and hydrate slurry outlet, and the top is provided with hydrate working fluid inlet and carries dense pneumatic outlet;
The described inlet of speeding to exit is connected with the overhead gas outlet of the ammonia recovery tower of synthetic ammonia installation, in order to introducing this hydration reactor from the synthetic ammonia relief gas that synthetic ammonia installation ammonia recovery tower pneumatic outlet is discharged, with the hydrate working fluid counter current contact of introducing from the hydration reactor top, make the water generation hydration reaction in methane contained in speeding to exit and argon gas and the hydrate working fluid form hydrate, nitrogen in speeding simultaneously to exit and hydrogen are carried the dense dense gas that obtains carrying, and described hydrate is to exist with hydrate working fluid blended slurries form;
The described synthesic gas compressor inlet of carrying in dense pneumatic outlet and the synthetic ammonia installation is connected, and returns the ammonia synthesis reaction unit after dense gas boosts through synthesic gas compressor and is used in order to carrying;
Described hydrate is dissolved device and is provided with the hydrate slurry inlet, this hydrate slurry inlet is connected with the hydrate slurry outlet of hydration reactor, dissolves device and dissolves formation and contain the mixed gas logistics of methane and argon gas and the liquid stream that contains the hydrate working fluid in order to the hydrate slurry in the hydration reactor is introduced hydrate; And this 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 method comprises step:
To introduce hydration reactor from the synthetic ammonia relief gas that synthetic ammonia installation ammonia recovery tower pneumatic outlet is discharged, with hydrate working fluid counter current contact from the hydration reactor top, make the water generation hydration reaction in methane contained in speeding to exit and argon gas and the hydrate working fluid form hydrate, nitrogen in speeding simultaneously to exit and hydrogen are carried the dense dense gas that obtains carrying;
To carry dense gas and return the ammonia synthesis reaction unit and be used, and dissolve device and dissolve and hydrate is introduced hydrate.
2. method according to claim 1, wherein, described hydrate working fluid is an aqueous phase solution.
3. method according to claim 2 wherein, contains the ammonia of mole fraction 0.005～0.08 in the described hydrate working fluid.
4. according to claim 2 or 3 described methods, wherein, contain the tetrahydrofuran (THF) of mass concentration 10%～30% in the described hydrate working fluid.
5. method according to claim 1, wherein, described hydrate is dissolved in hydrate is dissolved device and is formed gas stream and liquid stream, and the liquid stream of formation is dissolved device by the drawing-off water compound and return hydration reactor after liquid circulating pump is boosted and recycles.
6. method according to claim 1, wherein, the working pressure of described hydration reactor is the pressure of synthetic ammonia installation ammonia recovery tower pneumatic outlet, service temperature is 4～15 ℃; The working pressure that described hydrate is dissolved device is 0.2～2MPa, and service temperature is 8～23 ℃.
7. method according to claim 1 wherein, enters all gas or the portion gas of flow for discharging from ammonia recovery tower cat head of exitting of speeding of described hydration reactor; The cold that needs in the hydro-combination process is provided by the synthetic ammonia installation ammonia refrigeration system.
8. method according to claim 1, wherein, the amount of introducing the hydrate working fluid of hydration reactor is 1: 80～1: 130 with the volume ratio of amount under standard state of speeding to exit.
9. device that is used for realizing the method for synthetic ammonia relief gas nitrogen of the described recovery of claim 1 and hydrogen, it is characterized in that: this device mainly comprises a hydration separation unit, this hydration separation unit is between the overhead gas outlet that is used to be arranged on the ammonia recovery tower of synthetic ammonia installation enters the mouth with synthesic gas compressor, and this hydration separation unit comprises that hydration reactor and hydrate dissolve device, wherein
The bottom of described hydration reactor is provided with speed venting inlet and hydrate slurry outlet, and the top is provided with hydrate working fluid inlet and carries dense pneumatic outlet;
The described inlet of speeding to exit is connected with the overhead gas outlet of the ammonia recovery tower of synthetic ammonia installation, in order to introducing this hydration reactor from the synthetic ammonia relief gas that synthetic ammonia installation ammonia recovery tower pneumatic outlet is discharged, with the hydrate working fluid counter current contact of introducing from the hydration reactor top, make the water generation hydration reaction in methane contained in speeding to exit and argon gas and the hydrate working fluid form hydrate, nitrogen in speeding simultaneously to exit and hydrogen are carried the dense dense gas that obtains carrying, and described hydrate is to exist with hydrate working fluid blended slurries form;
The described synthesic gas compressor inlet of carrying in dense pneumatic outlet and the synthetic ammonia installation is connected, and returns the ammonia synthesis reaction unit after dense gas boosts through synthesic gas compressor and is used in order to carrying;
Described hydrate is dissolved device and is provided with the hydrate slurry inlet, this hydrate slurry inlet is connected with the hydrate slurry outlet of hydration reactor, dissolves device and dissolves formation and contain the mixed gas logistics of methane and argon gas and the liquid stream that contains the hydrate working fluid in order to the hydrate slurry in the hydration reactor is introduced hydrate; And this 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.
10. device according to claim 9, wherein, the liquid exit that described hydrate is dissolved the setting of device bottom is 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 hydration reactor after liquid circulating pump boosts and recycle in order to hydrate is dissolved liquid stream drawing-off water compound in the device.
11. device according to claim 10, wherein,
The outlet of the overhead gas of described ammonia recovery tower is provided with first interchanger with the pipeline of speeding to exit between the inlet of hydration reactor, is gone into the hydration reactor in order to will pass through this first interchanger from the synthetic ammonia relief gas that ammonia reclaims cat head by heat exchange to 4～15 are ℃ laggard;
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, in order to hydrate slurry is drawn the back earlier by first interchanger and the described preliminary heat-shift of synthetic ammonia relief gas from ammonia recovery cat head from hydration reactor, be further heated laggardly to go into hydrate and dissolve device by second interchanger again;
Pipeline between the liquid exit that described hydrate is dissolved device bottom enters the mouth with the hydrate working fluid of hydration reactor is provided with the 3rd interchanger, 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.
12. device according to claim 9, wherein, described hydration reactor adopts spraying and sieve plate unitized construction, the top of described hydration reactor is spraying area, spraying area is provided with and is used to spray the nozzle of hydrate working fluid and is used to remove the spiral coil cooling tube that reaction generates heat, and the bottom of hydration reactor is provided with the multilayer sieve plate.
13. according to claim 9 or 12 described devices, wherein, the outlet of the hydrate slurry of described hydration reactor 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.
14. according to the described device of claim 13, wherein, described screen plate tilts to the hydrate slurry outlet, 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.
15. according to the described device of claim 14, wherein, the perforate total area on the described screen plate accounts for 5%～20% of screen plate area.
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| CN101850209B (en) * | 2010-06-08 | 2012-08-22 | 中煤能源黑龙江煤化工有限公司 | Vent gas treatment method and treatment device |
| CN104709877B (en) * | 2013-12-13 | 2017-08-04 | 中国石油天然气股份有限公司 | One kind reclaims nitrogen and hydrogen device and method in synthesis ammonia relief gas |
| CN103864098B (en) * | 2014-03-24 | 2016-06-08 | 河南心连心化肥有限公司 | Ammonia tank periodic off-gases ammonia absorption plant and absorption technique thereof |
| US20190291048A1 (en) * | 2016-05-20 | 2019-09-26 | Khalifa University of Science and Technology | Bulk separation of undesired components from gas mixtures |
| CN107349773B (en) * | 2017-08-10 | 2020-11-24 | 中国石油大学(北京) | Low temperature hydration separation method and system |
| CN107563545A (en) * | 2017-08-17 | 2018-01-09 | 上海大学 | Fine chemistry industry ecological Industrial Area industrial chain construction method using natural gas as raw material |
| CN108623651A (en) * | 2018-06-19 | 2018-10-09 | 南京肽业生物科技有限公司 | Efficient Peptide systhesis device |
| CN112473336A (en) * | 2020-11-25 | 2021-03-12 | 兰州理工大学 | Hydrate method for recovering and storing CO in flue gas2Method (2) |
| CN112499647A (en) * | 2020-12-23 | 2021-03-16 | 宁波四明化工有限公司 | Hydrogen recovery process |
| CN115027288B (en) * | 2022-03-15 | 2024-04-26 | 福州大学 | On-vehicle ammonia hydrogen fuel cell based heat, electricity and cold triple supply system |
| CN114414705B (en) * | 2022-03-29 | 2022-07-01 | 南京霍普斯科技有限公司 | Gas chromatography detection system and method for constant nitrogen and hydrogen in synthetic ammonia |
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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 |
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