CN1076221A - Form the method and apparatus of heat-treating atmosphere - Google Patents
Form the method and apparatus of heat-treating atmosphere Download PDFInfo
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- CN1076221A CN1076221A CN 93102479 CN93102479A CN1076221A CN 1076221 A CN1076221 A CN 1076221A CN 93102479 CN93102479 CN 93102479 CN 93102479 A CN93102479 A CN 93102479A CN 1076221 A CN1076221 A CN 1076221A
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Abstract
A kind of method and apparatus that forms heat-treating atmosphere, wherein with air by a kind of film separating system or pressure swing adsorption system to produce nitrogen-rich gas, in the presence of non-precious metal catalyst, preferably in improved reactor, with nitrogen-rich gas and appropriate hydrocarbon gas reaction, contain the heat-treating atmosphere of the high nitrogen-containing of a small amount of carbon monoxide and hydrogen with production.
Description
The application is the part continuation application of No. 07/848818 U.S. Patent application of submission on March 10th, 1992.
The present invention relates to form the method for heat-treating atmosphere.Handling air forms then and the rich nitrogen process gas flow of hydrocarbon gas blended.In the presence of non-precious metal catalyst, make the mixture through catalytic reaction of formation, form a kind of heat-treating atmosphere that contains advantage amount nitrogen and no more than trace carbonic acid gas and water vapor.
Under being higher than 650 ℃ of temperature, use heat-treating atmosphere in various furnaceman's skill processes of the operation and the atmosphere that needs protection.For example, by the heat absorption heat-treating atmosphere that the heat absorption producer of standard produces, containing approximately respectively is the nitrogen of 40 volume % and the carbon monoxide of hydrogen and about 20 volume %, and is at dew point, produces in about-10～+ 5 ℃ scope usually.Usually, wherein also there are amounts of carbon dioxide and water.
Another kind of heat-treating atmosphere obtains by the ammonia dissociation, and this atmosphere is used for annealing, sintering and brazing operation, generally contains about 75 volume % hydrogen and 25 volume % nitrogen.
Preferably use the higher heat-treating atmosphere of nitrogen content for neutral purposes, specific activity is less mutually because this atmosphere is with the atmosphere that contains quite high percentage ratio hydrogen and carbon monoxide.The heat-treating atmosphere of high nitrogen-containing utilizes fuel gas (as Sweet natural gas) and the method production with the oxygen composition reaction in the high-nitrogen hypoxia content gas.
A kind of such high nitrogen-containing heat-treating atmosphere utilizes liquid nitrogen as source nitrogen; Though the quite high-quality atmosphere of this method output, liquid expensive this method that makes is the glad employing of industrial institute.
Compare with liquid nitrogen base atmosphere, high nitrogen-containing heat release heat-treating atmosphere production cost is lower, but water content and carbon dioxide content height in the atmosphere that the heat release method is produced, thereby of poor quality.
Therefore, people wish to produce a kind of like this heat-treating atmosphere, nitrogen content height wherein, water vapor and carbon dioxide content for a small amount of or be lower than a small amount of, and with to adopt liquid method to compare production cost lower.In addition, people also wish in an equipment to form said heat-treating atmosphere, and compare this equipment price with standard heat absorption producer low and parts are few.
The present invention relates to a kind of method that forms the high nitrogen-containing heat-treating atmosphere, the nitrogen-rich gas that wherein will contain lower concentration oxygen and replacement or the unsubstituted hydrocarbon gas or its mixture mix.Make said mixture not form catalyzed reaction under the sooty condition basically, generation wherein contains the water vapor of the amount of preponderating nitrogen, small quantity of hydrogen and carbon monoxide and no more than trace and a kind of heat-treating atmosphere of carbonic acid gas.This heat treatment atmosphere, the content of activeconstituents reduces, and therefore has the certain operations advantage of the standard endothermic atmosphere that is better than containing a large amount hydrogen and carbon monoxide.Term used herein " high nitrogen-containing " refers to that nitrogen content is higher than some heat-treating atmospheres of 40 volume %.
According to the present invention, with the air raw material preferably, adopt preferential nitrogen membrane separation process or preferential nitrogen adsorption method in psa unit equipment, to obtain said nitrogen-rich gas.
Said high nitrogen-containing heat-treating atmosphere is produced in a kind of uniqueness, different with standard heat absorption producer reactor; This reactor does not contain reaction gas mixing-compression system, and the heat absorption producer of standard needs this system to guarantee the air that has suitable ratio of mixture and compression to enter between the air and the hydrocarbon gas.The mixture that forms in the standard thermo-negative reaction device is reacted in the presence of catalyzer.This improved reactor of the present invention does not adopt reactant gases mixing-compression system, because nitrogen-rich gas has been under the required pressure.And, can the preheating nitrogen-rich gas therefore should not do the pre-mixing of extra time to the said hydrocarbon gas and nitrogen-rich gas.
In a preferred embodiment of the present invention, said reactor comprises a kind of heat exchange system, in this system with product gas in heat recirculation so that heat said nitrogen-rich gas, just mix then with the said hydrocarbon gas.
Following accompanying drawing is used to illustrate embodiment of the present invention, rather than is used for limiting the present invention, and the present invention is limited by the claim as the application's partial content.
Fig. 1 is schematic illustration of one embodiment of the invention, and this method adopts membrane sepn air method to produce nitrogen-rich gas;
Fig. 2 is the synoptic diagram of a kind of specific reactor of the present invention;
Fig. 3 is the synoptic diagram of another embodiment of the present invention, and this scheme utilizes psa unit to produce nitrogen-rich gas;
Fig. 4 and scheme shown in Figure 3 similarly, comprising the synoptic diagram of a kind of feedback control system, another embodiment of the present invention;
Fig. 5 is the synoptic diagram of the present invention another concrete scheme similar to Fig. 3, wherein adopts a kind of heat exchange system that tolerance in the product gas is transferred to rich nitrogen unstripped gas;
Fig. 6 is shown in Fig. 2, uses a kind of heat exchange system transfer of heat in the product gas to be given the synoptic diagram of the reactor of rich nitrogen unstripped gas.
People's employing standard usually heat absorption producer, for example at＜power metallurgy equipment handbook〉(Samuel Bradbury compiles, the third edition) the heat absorption producer of introducing on the 119th page and the 124-126 page or leaf (by with reference to incorporating it into this paper) is produced the heat-treating atmosphere that wherein contains 20% carbon monoxide, 40% hydrogen, 40% nitrogen and trace amounts of methane, carbonic acid gas and water vapor approximately.
Said calibrated generator comprises shell, is generally steel garden cylindrical outer cover the major parts of system is covered on wherein; Wherein also have reactor tube assemblies hold catalyst bed and guarantee reaction mixture and catalyzer between produce fully contact.Said producer also comprises heating system, is used for improving and keeping the temperature of reaction mixture, and temperature controlling system is to guarantee the operating period temperature-stable.
The chilled product gas rapidly just in case react, stable when making product gas flow out said reactor tube assemblies.Usually for example cool off with watercooling jacket and heat exchanger.In addition, the heat absorption producer of standard needs reaction gas mixing-compression system, guarantees between the air and the hydrocarbon gas (as Sweet natural gas or propane flammable gas) suitable proportion and required top hole pressure is provided with it.
Said reaction gas mixing-compression system generally comprises a kind of air flowmeter assembly that has some valves and inlet filter.Said air flowmeter assembly monitoring and adjusting flow into the air in the said reactor tube assemblies, and remove the impurity in the said airflow.A kind of hydrocarbon gas flow meter assembly with some valves and pressure-regulator wherein also is housed, is used for monitoring and regulating the hydrocarbon stream that flows to said reactor tube assemblies.
In standard heat absorption producer, there is electric hybrid module to be used for the mixing air and the hydrocarbon gas; Be provided with a kind of mixture pump of just replacing in addition, guarantee that with it the air mixture that forms is under the constant pressure in said electric hybrid module.
According to one aspect of the present invention, saved some key parts-reaction gas mixing-compression system in the said reactor.The heat-treating atmosphere that this improved reactor is produced with in standard heat absorption producer, compare with the heat-treating atmosphere that hydrocarbon gas reaction method makes with air, contain higher nitrogen and lower carbon monoxide and hydrogen.
Improved reactor of the present invention, also save specially and comprise said said electric hybrid module of just replacing mixing pump, because the nitrogen-rich gas that obtains with pressure swing adsorption system has been under the sufficiently high pressure power that does not need further compression, thereby does not need to use said pump.
Referring now to Fig. 1 of a kind of concrete scheme of expression the present invention,, wherein produces heat-treating atmosphere, and use semi-permeable membranes separate raw materials airflow in the said system with a kind of system.The rich nitrogen process gas flow that forms is sent in the reactor, in a kind of as will be described improved heat absorption producer of example, make it to react with the hydrocarbon gas in the presence of non-precious metal catalyst in this reactor, significant quantity sooty heat-treating atmosphere mainly is made of and is not contained to output nitrogen.Reactor shown in Figure 1 is a kind of straight pass reactor, below will illustrate shown in Figure 2 be a kind of U-shaped reactor example, also can use the reactor of other type according to the present invention.
Air enters system 2 back via pipeline 8 and is compressed in compressor 10, film air-seperation system 4 of compressed air admission, for example 4200 serial air separation membrane systems that make of the Hao Sidun of Texas city Generon Systems.
Said film is made up of some bundle hollow fibers, promptly is made up of parallel some semi-permeable membraness that are assembled into a kind of central cores pipe.Hollow fiber bundle is put into shell form the air separation assembly.Air is divided into two kinds of air-flows, nitrogen-rich stream and oxygen enrichment and carbon dioxide gas stream.
When compressed air was led to the center of fiber of said membrane module one end, air contacted with film when being downward through said fiber holes.Oxygen, water vapor and other " fast gas " enter the outside of fiber by it.Oxygen-enriched stream flows through around the shell that fibrous bundle enters said separator system subsequently, discharges from here as bi-product gas.
When whole or small portion oxygen entered the hollow fiber outside by mould material, the most of the nitrogen that exists in the raw air was included among the hollow-fiber film.As a result, nitrogen component is told from raw air effectively and is discharged from film system 4 via pipeline 14, enters and reactor 6 conjointly among the catalyst bed 16.
The heat absorption producer of said reactor 6 advantageous embodiment, it is the standard heat absorption producer of removing the key part that has the reaction gas mixing-compression system of replacing mixing pump basically.
With reference to Fig. 2, the said improved heat absorption producer that adopts with preferred reactor 200 forms of the present invention is a U-shaped, and it comprises a bent neck container 202 that fills catalyzer 204, and this container 202 is enclosed in the shell 206, and heating system 208 is arranged in the shell 206.Can utilize hydrocarbon gas burning or electric installation (as electric heating system) 208 to press the traditional way heat supply.
Hydrocarbon stream by valve 211 and conduit 210 and through the nitrogen-rich stream of conduit 212 by separately under meter 214 and 216 controls, two kinds of gases are merged into mixed airflow after enter among the said reactor 200 by conduit 218.
After product gas was emitted from container 202 via conduit 220, by expander 222 coolings, and cooling gas was discharged from system via conduit 224.
According to the present invention, the mixing effect of the hydrocarbon gas and nitrogen-rich gas occurs in the reactor outside, and does not have reaction gas mixing-compression system.Therefore, the reactor 200 just displacement mixing pump that do not comprise electric hybrid module and illustrated in the past.
The preferred hydrocarbon gas that the present invention uses comprises Sweet natural gas, methane, ethane, propane and composition thereof.The hydrocarbon gas that replaces can use separately or mix use with the unsubstituted hydrocarbon gas.Sweet natural gas most preferably because its cost is quite low.In addition, also can add a small amount of other gas, for example hydrogen, carbon monoxide and water vapor in some applications.
These gases mix the back and feed and contain in the catalyst bed of non-precious metal catalyst under high pressure slightly, said catalyzer is selected from nickel oxide, nickel-base material and cobalt; Nickel oxide and nickel-base material are most preferred catalyzer.Because these materials are quite cheap and be easy to get.
The reaction of contained oxygen and the hydrocarbon gas (as Sweet natural gas or methane) in catalyst bed in the nitrogen-rich gas, carbon monoxide under the output dew point and hydrogen, said dew point can easily be adjusted in-50～+ 10 ℃ of scopes.Contain quite a large amount of hydrogen and little water steam and carbonic acid gas in the formed heat-treating atmosphere, will be used for annealing, soldering and so on any purposes of many thermal treatments in its feeding stove.
In a content of the present invention, said catalyst bed can be placed in the primary reformer, wherein the heat of Chan Shenging can be used for the heatable catalyst bed and make the reactant reaction that enters.
With reference to Fig. 1, nitrogen-rich gas enters in the catalyst bed 16 that is in the reactor 6 (as shown in Figure 1).From hydrocarbon gas source 20 hydrocarbon gas is sent into catalyst bed 16 via pipeline 22.Nitrogen-rich gas contacts with catalyst bed 16 with hydrocarbon gas mixing back and reacts in being higher than under 760 ℃ of temperature (being generally 980-1040 ℃) temperature.Mixed gas can directly be sent into it in stove after reacting in the presence of catalyzer.If said stove keeps clear of catalyst bed, then preferably this gas is cooled to rapidly be lower than under about 315 ℃ of temperature, this cooling step prevents that carbon monoxide from decomposing generation carbon and carbonic acid gas.A kind of heat-treating atmosphere that contains the amount of preponderating nitrogen and suitable small quantity of hydrogen and carbon monoxide is emitted from system 2 via pipeline 29.
A preferred embodiment of the present invention is to obtain oxygen rich gas by film system 4; Feeds forward via pipeline 26 to this gas of a major general part, make it to mix with the hydrocarbon gas via pipeline 28 20 acquisitions from hydrocarbon gas source, remaining oxygen rich gas emits from pipeline 85.Use the efficiency of combustion of this oxygen rich gas improvement from the hydrocarbon gas in source 20.The heat energy that is produced is used to heatable catalyst bed 16 and promotes to react between the nitrogen-rich gas and the hydrocarbon gas.
Leave in the nitrogen-rich gas of film system 4, nitrogen content preferably is at least 85 volume %, preferably is at least 97 volume %.Heat-treating atmosphere preferably contain be not more than 8(and be preferably 2-8) volume % hydrogen, 1-4 volume % carbon monoxide, carbonic acid gas, the unreacted hydrocarbon gas and water vapor that trace is following, and surplus nitrogen.
In another preferred version of the present invention, utilize to make air make nitrogen-rich gas by the method for psa unit.Referring to Fig. 3, a kind of psa unit 30 with two beds " A " and " B " is wherein disclosed.But, should expect that the present invention can be used in and has other structure, for example have on the more psa unit.
Air from the air source (not shown) is admitted to compressor 32 raising air pressures, at non-productive stage accumulation pressurized air and at the maximum load stage of bed output pressurized air.After pressurized air is admitted to storage tank 34, be sent to outlet 40 of leading to an A and the outlet 42 of leading to a B via pipeline 36 and 38.Each outlet 40,42 is controlled by valve 44,46 separately.When valve 44 was opened, pressurized air can reach an A, and valve 46 still cuts out, so that a B can be regenerated in the pressure relief stage of psa unit 30.
Pressurized air enters an A via valve of opening 44 and pipeline 48; At least the sorbing material that contains a kind of preferably adsorb oxygen and other waste gas among the bed A; Preferred sorbing material is selected from molecular sieve and silica gel.As a result, purified basically nitrogen is emitted from bed A, behind pipeline 50 and valve 52, enters in the nitrogen storage vessel 54 via all-product line 56.
In the process of bed A production nitrogen, a bed B is under the normal atmosphere.In case the nitrogen production cycle of bed A is finished, system just carries out Balance Treatment, and the pressure among the bed B is brought up under the intermediate pressure; Nitrogen product valve 52,58 is closed in utilization and compressed air inlet valve 44 and 46 is finished this operation.Therefore, the output of compressed-air actuated input and nitrogen product is supspended.
Finishing the pressure equilibrium method of operating is: with the pressurized air of a part from bed A top, feed the top of bed B through pipeline 60, valve 62, pipeline 64, pressure limiting hole 66 and pipeline 68.In addition, with the top of gas under pressure, feed the bottom of bed B via pipeline 48, valve 70, pipeline 72, pressure limiting hole 74 and pipeline 76 by bed A.
In case finish the pressure equilibrium operation, an A and B are under the similar pressure, bed A just regenerates by laxative remedy: remove bed A pressure, make it to be under the normal atmosphere, so that remove oxygen; Concrete Method Of Accomplishment is: close equilibrium valve 62,70, open the regeneration valve 78 of an A.The said waste gas of at least a portion is fed pipeline 80 from bed A bottom via pipeline 48, be fed forward through valve 78 again, deliver in the reactor 6 through pipeline 82 and valve 84.Remaining waste gas is emitted from pipeline 84 via pipeline 85.Bed A obtains regeneration as a result.
The further cleaning of bed A can be finished with laxative remedy, with purge gas (as purified nitrogen basically) from 86 beginnings of source nitrogen, through pipeline 88 and 90 and valve 92 after, send among the A by pipeline 50.When bed B did further to clean, rinsing gas was sent into by pipeline 68 through pipeline 88,90 and valve 94.After the flushing, sorbent material is prepared to adsorb waste gas in new nitrogen production cycle.
Because pressure is enhanced under the intermediate pressure among the bed B, so bed B prepares to accept pressurized air.Pressurized air provides by valve 46 and pipeline 76.In order to obtain rapidly the pressure of bed B to be brought up to enough pressurized air required under the working pressure, the pressurized air charging that is produced by compressor must be replenished with the pressurized air that is stored in the storage tank 34.
Bed B opens valve 58 product gas can 68 be entered in the product feed channel 56 by the road after in a single day loading, and enters thus in the storage vessel 54 again.Distribution piping 96 stretches out from said storage vessel 54, so that provide nitrogen-rich stream to reactor 6.Can selectivity have second flush pot, so that make the purity of nitrogen-rich gas stable.
Shut-off valve 58 and 46 after nitrogen production is finished among the bed B is ended the pressurized air charging.Open valve 62 and 70, the conducting equalizing line enters pressurized air from top and the bottom of bed B to bed A, so that improve wherein pressure to intermediate pressure.Remove the pressure of bed B then, its method is through pipeline 76,98, valve 100, pipeline 82 and valve 84, oxygen is sent among the reactor 6, with this method discharge oxygen-rich air.
After this, will send among the A through valve 44 and pipeline 48, pressure among the bed A is brought up under the required working pressure, so that the nitrogen production cycle of beginning bed A from the pressurized air of compressor 32 and storage vessel 34.
Again referring to Fig. 3, rich nitrogen product gas is sent among the reactor 6 via pipeline 96 and selectivity flush pot, merge with the hydrocarbon gas herein via pipeline 22 20 outputs from hydrocarbon gas source.This mixed gas reacts by the mode described in the concrete scheme of top Fig. 1 in the presence of catalyzer.
The oxygen rich gas that process pipeline 82 and valve 84 are discharged from psa unit can optionally with from the hydrocarbon gas of hydrocarbon source 20 via pipeline 28 outputs mix.The combustion heat that produces after the formed mixture ignition can be used for satisfying nitrogen-rich gas and the required heat of hydrocarbon gas reaction.
Enter oxygen level in the amount of hydrocarbon gas of catalyst bed and the nitrogen-rich gas, can be controlled so that more effectively promote reaction with feedback control system.
Referring to Fig. 4, wherein disclose out a kind of concrete scheme of the present invention, this scheme adopts as produces nitrogen-rich gas with regard to the described psa unit 30 of Fig. 3.This system is provided with a kind of feedback control unit 110; The pipeline that will contain heat-treating atmosphere is received by pipeline 112 specially and is measured carbonic acid gas, carbon monoxide, hydrogen and/or water-content in the product air-flow that leaves reactor 6 on the monitor 114.
The feedback control signal that is produced by monitor 114 is transferred to the control valve 118 that is located on the pipeline 22 through circuit 116, and the hydrocarbon gas is sent into forward in the reactor 6 by hydrocarbon gas source 20.Enter the amount of hydrocarbon gas in the reactor thereby controlled by the reactive gas that exists in the product air-flow (being carbon monoxide and/or hydrogen) content or impurity (carbonic acid gas and/or water vapor) amount.
Said feedback control system 110 also can be provided with the device of oxygen level in the control nitrogen-rich gas.Referring again to Fig. 4, can adopt said monitor 114 by traditional way with feedback control signal via circuit 120 send into the electronically controlled nitrogen-rich gas oxygen level and or the transformation absorption controller 122 used of flow among.
Thermo-efficiency of the present invention is improved with hydrocarbon feed gases blended method after can utilizing and catching in the product gas heat and it is given to rich nitrogen unstripped gas.
Referring to Fig. 5,, send in the heat exchanger 302 via pipeline 300 with the rich nitrogen unstripped gas of outside flush pot from psa unit 30.This outside nitrogen-rich gas is heated by the product gas of emitting via pipeline autoreactor 6.Temperature when product gas leaves reactor 6 is in 900～1040 ℃ of scopes usually.Send into the nitrogen-rich gas in the heat exchanger 302, be heated to be generally 700～1000 ℃ down after, deliver to the bottom of reactor 6 via pipeline 306 and mix with the hydrocarbon gas.
By the heat of nitrogen-rich gas carrier band, may be enough to make the mixture of the nitrogen-rich gas and the hydrocarbon gas before entering catalyst bed, to react.Enter this reaction before the catalyst bed and can cause forming the efficient of soot and this process of reduction.Therefore, preferably just before entering reactor, mix the nitrogen-rich gas and the hydrocarbon gas, so that the restriction mixture contacts the residence time before with catalyst bed.Residence time before mixture contacts with catalyst bed should be no more than several seconds.
Referring to Fig. 6, wherein illustrate a kind of preferred heat exchange system, in this system, entering in the reactor 200 just before and can react before just the heated nitrogen-rich gas and the hydrocarbon gas are mixed.Send into the speed of nitrogen-rich gas from the source of the gas (not shown) via pipeline 212, as the front in conjunction with Fig. 2 described with under meter 216 controls.Rate controlled nitrogen-rich gas is sent into heat exchanger 302 through pipeline 320, and nitrogen-rich gas absorbs heat there from the product gas that enters wherein via conduit 322 in heat exchanger.Heated nitrogen (generally being in 700～1000 ℃ of scopes) flows out via conduit 324 from heat exchanger 302.
From the outside hydrocarbon gas of source of the gas (not shown), flow in the under meter through valve 211 and conduit 210, regulate entering reactor 200 hydrocarbon gas flow velocity before.The hydrocarbon gas flows out under meter and enters the pipeline 326,328 mixes with heated nitrogen-rich gas in the junction in this pipe, passes through conduit 330 then just before inflow reactor 200.
The heat exchanger type of can be at just Fig. 5 and Fig. 6 using in the described and embodiments shown is actually unrestricted, and those skilled in the art select easily.About this introduction that comprises the heat exchanger of housing and tubulose or plate heat exchanger, be stated from people such as Warren L.McCabe work＜unit operation of chemical engineering (the third edition, McGraw Hill publication in 1976) on the 398-426 page or leaf of a book, incorporates it into this paper by reference.
Even a part of heat is removed the product gas in heat exchanger, said product gas generally also must be cooled off before in entering said stove.As shown in Figure 6, product gas (for example heat-treating atmosphere of forming by most of the nitrogen, a small amount of carbon monoxide and hydrogen and trace carbonic acid gas and water) generally in 900～1040 ℃ of temperature ranges under certain temperature via conduit 322 outflow reactors 200.Through heat exchanger 302 cooled product gas, generally in 400～700 ℃ of scopes under the temperature via conduit 332 outflow heat exchangers 302.
Said product gas flows through second heat exchanger or expander 334 subsequently, so that the product gas temperature is reduced under the envrionment temperature, sends into forward in the stove (not shown) via conduit 336.
Cross as noted earlier like that, by the heated nitrogen-rich gas and the hydrocarbon gas are mixed, so as with the residence time that reduces mixture before catalyst bed contact, sooty formation is minimized basically and reduces.
The quantity that soot forms also can be utilized and stop the method for hydrocarbon gas incomplete reaction to be controlled.Temperature and hydrocarbon gas content by the control mixture are finished this task.Temperature is lower than about 760 ℃ and can causes sooty to form, and therefore preferably makes temperature of reaction remain on about at least 760 ℃.And preferably also reduce ratio between the hydrocarbon gas and oxygen level.Say that in theory all the carbon that can get all can change into carbon monoxide.For example, produce the actually operating scope that heat-treating atmosphere uses and be: approximately be at least when carrying out under 760 ℃ of temperature when being reflected at, methane content is lower than 2.15mol/mol oxygen.
Embodiment 1
Adopt a kind of embodiment of the present invention (as depicted in figs. 1 and 2) to produce heat-treating atmosphere as follows.
The pressurized air of about 3600 standard cubic foots/hour (SCFH) is entered in one group of 4200 membrane separation apparatus of Generon Systems manufacturing.The nitrogen-rich gas of 2000 SCFH, wherein contain 93V% nitrogen (1860SCFH) and 7V% oxygen (140SCFH), flow out said film system 4, enter in the thermo-negative reaction device of making by Ohio Maumee surface combustion company limited 6 via pipeline 14, be filled with in the reactor 6 nickel-base catalyst (by J.L.Becker company provide 3/4 " cubes).
The Sweet natural gas of 280SCFH sent in the reactor 6 mix, simultaneously by catalyst bed 16 with nitrogen-rich gas.
The 1600SCFH waste gas that will contain 35% oxygen is discharged via pipeline 26 from said film system 4.Most of exhaust flow (910SCFH), is carried 690SCFH waste gas by pipeline 26 in atmosphere simultaneously via discharge of pipes, mixes with the 120SCFH Sweet natural gas of sending here through piping 28 from source of the gas 20.This gaseous mixture igniting back provides heat for reactor 6, so that carry out the catalyzed reaction between nitrogen-rich gas and the Sweet natural gas.
The condition that this reaction is carried out is: the residence time 3-6 second in 1040 ℃ of the temperature, catalyst bed.
Under about 2700SCFH speed, from reactor, emit heat-treating atmosphere via pipeline 29, this heat-treating atmosphere has following composition:
CO 280 SCFH (10.3V%)
H
2560 SCFH (20.7V%)
H
21860 SCFH (68.9V%)
CO
2Trace
H
2The O trace
Add up to 2700 SCFH
Embodiment 2
Adopt system shown in Figure 3, among pressure swing adsorption system 30, supply with 3800SCFH pressurized air, produce the nitrogen-rich gas that 2000SCFH wherein contains 1960SCFH nitrogen (98V%) and surplus oxygen.Make it and the reaction of 80SCFH Sweet natural gas, the heat-treating atmosphere of producing is 2200SCFH, and it is composed as follows:
H
2160 SCFH (7.3V%)
N
21960 SCFH (89.0V%)
CO
2Trace
H
2The O trace
Add up to 2200 SCFH
Discharge the 1800SCFH oxygen rich gas from pressure swing adsorption system 30, make wherein that the 630SCFH oxygen rich gas reacts to reactor 6 heat supplies with the 110SCFH Sweet natural gas, remaining oxygen rich gas enters in the atmosphere.
Embodiment 3
Adopt system shown in Figure 3, in pressure swing adsorption system 30, supply with the nitrogen-rich gas (98V% nitrogen and 2V% oxygen) under 40SCFH Sweet natural gas and the 1000 SCFH flow velocitys simultaneously.Temperature of reactor remains on about 980 ℃.Measured carbon monoxide in the product gas, carbonic acid gas, Sweet natural gas, hydrogen and oxygen level under the dew point and reached three hours, the results are shown among the table 1.
Table 1
| Time (branch) | Volume % CO | Volume % CO 2 | Volume % Sweet natural gas | Volume % H 2 | O 2ppm | Dew point (℃) |
| start | 3.54 | 0.62 | 0.00 | 5.5 | 4 | 23.5 |
| 30 | 4.00 | 0.31 | 0.00 | 6.5 | 5 | 11.0 |
| 60 | 4.00 | 0.00 | 0.00 | 7.0 | 6 | -37.0 |
| 90 | 3.20 | 0.00 | 0.00 | 6.5 | 6 | -37.0 |
| 120 | 3.32 | 0.00 | 0.00 | 6.5 | 5 | -42.0 |
| 135 | 3.38 | 0.00 | 0.00 | 6.5 | 5 | -42.0 |
| 150 | 3.38 | 0.00 | 0.00 | 6.5 | 5 | -45.0 |
| 165 | 3.40 | 0.00 | 0.00 | 7.0 | 5 | -45.0 |
| 180 | 3.40 | 0.00 | 0.00 | 7.5 | 5 | -46.0 |
Adopt Fig. 5 and system shown in Figure 6, in pressure swing adsorption system 30, supply with 3800 SCFH pressurized air, produce 2000 SCFH nitrogen-rich gas, wherein contain 1960 SCFH nitrogen (98V%) and surplus oxygen.320(sees Fig. 6 via pipeline) send into outside nitrogen-rich gas in the heat exchanger, temperature is enhanced 750 ℃ in heat exchanger.
Heated nitrogen-rich gas is carried by pipeline 324, and 328 mix with methane gas (80SCFH) in the junction.Blended gas is admitted among the reactor 200 that nickel catalyzator is housed through pipeline 330.Residence time less than before mixture contacts with catalyst bed 2 seconds.
Under 980 ℃ of temperature of reaction and nickel catalyzator in the presence of mixed gas generation catalyzed reaction.Through conduit 322 heat exchanger 302 conveying products gases, the carbonic acid gas and the water vapor that wherein contain 80 SCFH carbon monoxide, 160 SCFH hydrogen, 1960 SCFH nitrogen and trace, the temperature of this product gas are lowered to about 600 ℃ in heat exchanger 302.After product gas is cooled under the envrionment temperature, sent to the anneal of doing under the envrionment temperature for example in expander 334.
Provide the method for heat to reactor, can adopt: by heated nitrogen-rich gas heat supply, the hydrocarbon gas and as the by product of pressure swing adsorption system 30 and react heat supply, electricradiator 208 heat supplies shown in Figure 2 or the mode heat supply of its combination between the oxygen that obtains.Specifically, see Fig. 5 from pressure swing adsorption system 30(by pipeline 82) discharge after 170 SCFH contain the waste gas of 35% oxygen, and mix from the 30 SCFH methane gas that source of the gas transports through pipeline 28.In addition, the energy of 50000 Board of Trade Units (BTV)/hour (hr) is provided by heated nitrogen-rich gas by heat exchanger, and the energy of all the other 6 kilowatt-hours (KWH) is supplied with by electricradiator.
Though the present invention is with reference to the specific embodiment explanation, those skilled in the art can know that the present invention can be embodied among many other forms.
Claims (12)
1, a kind of method of making heat-treating atmosphere comprises:
A) remove contained most of oxygen in the raw air stream at least, produce nitrogen-rich gas and oxygen,
B) mix said nitrogen-rich gas and the replacement or the unsubstituted hydrocarbon gas, make first mixture,
C) said first mixture is reacted in the presence of non-precious metal catalyst, preparation contains the said heat-treating atmosphere of the amount of preponderating nitrogen and no more than trace carbonic acid gas and water vapor.
2, the process of claim 1 wherein that said step of removing most of oxygen at least comprises: make said raw air stream by a kind of film, and this film preferentially from said raw air stream with other gaseous constituent and nitrogen separation.
3, the method for claim 1, wherein said step of removing most of oxygen at least comprises makes said raw air stream by a kind of psa unit, said psa unit is equipped with contained oxygen and other gas in the said raw air stream of a kind of preferentially adsorbed, makes said nitrogen-rich gas.
4, the process of claim 1 wherein that said heat-treating atmosphere comprises the 1-4V% carbon monoxide, is not more than the carbonic acid gas and the water vapor of the hydrogen of 8V%, no more than trace, and surplus nitrogen.
5, the process of claim 1 wherein that the said hydrocarbon gas is selected from Sweet natural gas, methane, ethane, propane and composition thereof.
6, the process of claim 1 wherein that said non-precious metal catalyst is selected from nickel oxide, nickel-base material and cobalt.
7, the method for claim 1 also comprises:
A) mix the said oxygen and the said hydrocarbon gas and make second mixture,
B) make second mixture ignition burning produce heat and
C) give said catalyzer with heat delivery, so that promote the reaction that catalysis causes between first mix ingredients.
8, a kind of mixture with the hydrocarbon gas and nitrogen-rich gas prepares the heat-treating atmosphere device, comprising:
A) reactor assembly wherein is equipped with and said mixture is reacted use catalyst bed in the presence of non-precious metal catalyst,
B) said catalyst bed is heated to the temperature of reaction device,
C) remove said heat-treating atmosphere device from said reactor assembly, and
D) under the condition of said reactor assembly outside and reactionless gas mixing-compression system, the said hydrocarbon gas and said nitrogen-rich gas are mixed into the device that said mixture is used.
9, the device of claim 8 comprises also that wherein said mixture uses in order to form, the device of the device of control hydrocarbon gas flow and control nitrogen-rich gas flow.
10, the device of claim 9 wherein also comprises:
A) make the pressure swing adsorption system that said nitrogen-rich gas is used with air; And
B) said nitrogen-rich gas is transported to the device that said nitrogen-rich gas control device is used.
11, the device of claim 9 wherein also comprises:
A) with air make membrane separation unit that said nitrogen-rich gas uses and
B) said nitrogen-rich gas is transported to the device that said nitrogen-rich gas flow rate control device is used.
12, the device of claim 8 wherein also comprises:
A) with the heat of said heat-treating atmosphere heat heat exchanger that said nitrogen-rich gas uses and
B) mix the device that the heated nitrogen-rich gas and the hydrocarbon gas are used.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84881892A | 1992-03-10 | 1992-03-10 | |
| US848,818 | 1992-03-10 | ||
| US97102292A | 1992-11-02 | 1992-11-02 | |
| US971,022 | 1992-11-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1076221A true CN1076221A (en) | 1993-09-15 |
Family
ID=27126804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93102479 Pending CN1076221A (en) | 1992-03-10 | 1993-03-09 | Form the method and apparatus of heat-treating atmosphere |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH06212251A (en) |
| CN (1) | CN1076221A (en) |
| AU (1) | AU659719B2 (en) |
| CA (1) | CA2091209A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9304731A (en) * | 1992-11-17 | 1994-08-02 | Praxair Technology Inc | Process and system for the production of a protective atmosphere for kiln operations |
| US5320818A (en) * | 1992-12-22 | 1994-06-14 | Air Products And Chemicals, Inc. | Deoxygenation of non-cryogenically produced nitrogen with a hydrocarbon |
| US5968457A (en) * | 1994-06-06 | 1999-10-19 | Praxair Technology, Inc. | Apparatus for producing heat treatment atmospheres |
| US5441581A (en) | 1994-06-06 | 1995-08-15 | Praxair Technology, Inc. | Process and apparatus for producing heat treatment atmospheres |
| US6531105B1 (en) | 1996-02-29 | 2003-03-11 | L'air Liquide-Societe Anonyme A'directoire Et Conseil De Surveillance Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for removing carbon monoxide from a gas stream |
| EP2541176A3 (en) * | 2005-11-23 | 2014-09-24 | Surface Combustion, Inc. | Fluid delivery system for an atmospheric furnace used for treating one or more articles |
| JP5647802B2 (en) * | 2010-03-04 | 2015-01-07 | 大陽日酸株式会社 | Heat treatment atmosphere gas generation method |
| JP2019189942A (en) * | 2018-04-24 | 2019-10-31 | エア・ウォーター株式会社 | Annealing method of metal |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3644099A (en) * | 1969-09-15 | 1972-02-22 | Holcroft & Co | Gas atmosphere generating means for heat-treating furnaces |
| US4960579A (en) * | 1988-04-01 | 1990-10-02 | Union Carbide Corporation | Membrane process and system for nitrogen production |
-
1993
- 1993-03-08 AU AU34059/93A patent/AU659719B2/en not_active Ceased
- 1993-03-08 CA CA 2091209 patent/CA2091209A1/en not_active Abandoned
- 1993-03-09 CN CN 93102479 patent/CN1076221A/en active Pending
- 1993-03-10 JP JP5049582A patent/JPH06212251A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2091209A1 (en) | 1993-09-11 |
| AU659719B2 (en) | 1995-05-25 |
| JPH06212251A (en) | 1994-08-02 |
| AU3405993A (en) | 1993-09-16 |
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