CN105258152A - Composite firing process for natural gas and surplus hydrogen from HCL synthesis device - Google Patents
Composite firing process for natural gas and surplus hydrogen from HCL synthesis device Download PDFInfo
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- CN105258152A CN105258152A CN201510706302.5A CN201510706302A CN105258152A CN 105258152 A CN105258152 A CN 105258152A CN 201510706302 A CN201510706302 A CN 201510706302A CN 105258152 A CN105258152 A CN 105258152A
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Abstract
The invention relates to the technical field of recycling of surplus hydrogen of the chlorine-alkali industry and discloses a composite firing process for natural gas and surplus hydrogen from an HCL synthesis device. The surplus hydrogen from the HCL synthesis device is utilized and subjected to pressure regulation, dewatering and other treatment, then the surplus hydrogen and natural gas are mixed and burnt in a molten salt furnace, heat is provided for a salt melting reaction, and therefore the purposes of recycling hydrogen and reducing the use amount of the natural gas are achieved, and a strong guarantee is provided for improving the benefits, saving energy and reducing emission for enterprises.
Description
Technical field
The present invention relates to chlorine industry have more than needed hydrogen recycle technical field.
Background technology
For the recycling of hydrogen more than needed in chlorine industry, mainly produce other byproducts as raw material at present, example hydrochloric acid, PVC, hydrogen peroxide etc.This Application way needs chlor-alkali enterprises to arrange corresponding downstream production equipment, and due to the inflammable and explosive characteristic of hydrogen, and its transport, management cost are all very high.
Except the above-mentioned approach producing other byproducts as raw material, in addition can using hydrogen more than needed as fuel for chlorine industry course of reaction provides the energy.Because impure hydrogen easily detonation occurs in During Co-firing, so main hydrogen gas boiler carries out pure burning to hydrogen more than needed in industrial production.But hydrogen gas boiler is in the market mainly import equipment, and price is high.And the temperature provided is lower, only can be used for transpiring moisture, required heat can not be provided for molten salt react ion.
Existing molten salt react ion, required origin of heat is mainly the burning of natural gas.Combustion of natural gas not only needs to bear extra cost, and the carbon monoxide contained in emission and carbon dioxide have contaminative.
Although in energy field, hydrogen and natural gas mixed combustion become known technology, and are used widely in hybrid vehicle and fuel cell.But how this technology being applied to chlorine industry has more than needed among hydrogen utilization, still has many technical barriers.Specifically, first between the energy and chemical industry two fields, professional span is very large, the direction of institute's technical solution problem is also different, need in energy field in the scope of conditions permit, the temperature of multifuel combustion is improved as far as possible, larger power can be provided, and the temperature needed for molten salt react ion to be certain; Secondly the two hydrogen state participating in reacting is not identical, and in chlorine industry, hydrogen more than needed has specific force value and moisture.So, in sum, the mixed combustion technique of energy field can not be directly applied to molten salt react ion.
Summary of the invention
High for the cost existed in existing hydrogen treat, security is low and heat energy discharges low shortcoming, and existing molten salt react ion natural gas energy supply cost high with pollute high problem, the invention provides a kind of HCL synthesizer and to have more than needed hydrogen and natural gas multifuel combustion technique.
Realizing know-why of the present invention is: hydrogen treat pipeline more than needed in old HCL synthesizer and lava stove are simply transformed, both be communicated with, reduce the transport in hydrogen treat process, management cost by hydrogen treat device more than needed.And by the pressure regulation of this device, dewater, hydrogen more than needed is met condition that natural gas carries out multifuel combustion in solid potash device combustion furnace.When two gases during multifuel combustion, by both dynamic adjustments flow, make steadily to discharge the Constant Heat met needed for molten salt react ion in During Co-firing in combustion furnace.In addition, the method also reduces the use cost of natural gas and the pollution of emission.
The invention provides following technical scheme: provide a kind of HCL synthesizer to have more than needed hydrogen and natural gas multifuel combustion technique.Comprise the following steps:
(1) hydrogen is collected: collect the hydrogen more than needed in HCl synthesizer, its pressure limit is between 75 to 85kPa, and water content is less than 2%;
(2) hydrogen is processed: the hydrogen more than needed collected is reduced pressure, except water treatment, make its pressure be reduced between 5 to 15kPa, water content is reduced to less than 1.8%;
(3) drive separately: when the water content that the pressure of hydrogen more than needed is less than 5kPa or is greater than 15kPa or hydrogen more than needed is greater than 1.8%, be used alone natural gas in burner in lava stove as fuel of heat supply, the hydrogen more than needed that pressure, water content do not satisfy condition will by emptying;
(4) multifuel combustion is passed into: treating that 60% alkali of solid potash device in lava stove enters film supplying tube flow is 6.8 to 7.1m3/h, manifold trunk liquidus temperature is 390 to 410 DEG C, during product NaOH content >=98%, if now the pressure of hydrogen more than needed, water content meet step (2) conditional, hydrogen more than needed is passed in burner and carries out multifuel combustion;
(5) proportion adjustment: after hydrogen more than needed is passed into combustion furnace, the temperature in maintenance burner is between 410 to 450 DEG C, and in this process, hydrogen flowing quantity is 0 to 2020m3/h, and gas discharge is 50 to 660m3/h.
In the present invention, collected hydrogen is the hydrogen more than needed discharged in HCl synthesizer, therefore in collection process, reaction in original HCl synthesizer can not be affected to some extent, through practical operation, between pressure 75 to the 85kPa of hydrogen more than needed in HCl synthesizer, the hydrogen moisture more than needed discharged in HCl synthesizer is 2% through measuring and calculating.
The hydrogen collected due to pressure and moisture too high, do not meet the condition of burner of directly passing into, need to reduce pressure to it, except water treatment.Through actual measuring and calculating, Hydrogen Vapor Pressure scope is between 5 to 15kPa, and when moisture is below 1.8%, passing into burner and natural gas, to carry out the effect of multifuel combustion best.
Required heat is reacted because hydrogen in During Co-firing and combustion of natural gas provide in burner, therefore, the flow regulating hydrogen and natural gas is carried out using burner temperature as standard, so while processing hydrogen, burner first passes into separately natural gas as fuel, drives to make the temperature in burner reach 410 to 450 DEG C.Be 6.8 to 7.1m3/h when 60% alkali in solid potash device enters film supplying tube flow, manifold trunk liquidus temperature is 390 to 410 DEG C, during product NaOH content >=98%, molten salt react ion in solid potash device is in even running state, if now the pressure of hydrogen and water content satisfy condition, can pass into immediately in burner and carry out multifuel combustion with natural gas.
In During Co-firing, under the prerequisite that temperature is floated between 410 to 450 DEG C in guarantee burner, volume content according to hydrogen in burner carries out dynamic adjustments to the flow of natural gas, but for preventing hydrogen content from too much causing detonation, the flow of natural gas must be greater than 50m3/h.The present invention calculates after having carried out practical operation to combustion furnace, and gas discharge adjustable range is 50 to 660m3/h, and hydrogen flowing quantity adjustable range is 0 to 2020m3/h.
Further, the hydrogen collected first is carried out voltage stabilizing process by the present invention, reduced pressure treatment again, because the Hydrogen Vapor Pressure more than needed collected is constantly change, in order to prevent this change, threat is produced to follow up device, simultaneously for solid burner provides stable hydrogen source, therefore first voltage stabilizing is carried out to collected hydrogen, through practical operation, when stable-pressure device pressure limit is set between 50 to 70kPa, to not meet the hydrogen gas automatic blow down of pressure condition, the hydrogen meeting pressure condition carries out reduced pressure treatment, and its Pressure Drop is low to moderate 5 to 15kPa.
Further, the present invention dewaters respectively in spark arrester and displacement can, can be more complete by what dewater and carry out.
Further; the present invention adds nitrogen displacement step step (1) is front; with nonflammable nitrogen as air in protection gas displacement apparatus; prevent hydrogen and too much oxygen mix from producing danger; through practical operation, the oxygen content of gas in pipeline is controlled the safety that can ensure whole system below 2%.
Further, the gas oxygen Gas content of the gas vent of nitrogen replaceable equipment is detected when whether the oxygen content of gas reaches below 2% in signal piping of the present invention.When the oxygen content of detected gas is continuous reach below 2% for three times time, prove that in device, gas is in a safe condition, now can pass into hydrogen in burner.
Further, the present invention adds security control step, when the pressure of hydrogen, water content do not meet the condition entering and carry out in burner burning, when namely pressure is less than 5kPa or is greater than 15kPa, stop the input of hydrogen, increase gas discharge to keep in-furnace temperature.When hydrogen satisfies condition, then pass into qualified hydrogen in combustion furnace.This step makes the Flow-rate adjustment of natural gas and hydrogen more smooth on the one hand, more effectively controls the condition passing into hydrogen in combustion furnace on the other hand.
Further, the present invention adds nitrogen displacement step.Due to when hydrogen input is by termination, in hydrogen treat device, there is fire and explosive risks in residual a large amount of combustible hydrogen.Therefore this method for optimizing adds hydrogen exchange step, after hydrogen input is stopped, in device, input nitrogen, make remaining hydrogen emptying, eliminate safe hidden trouble with this.
In sum, owing to have employed technique scheme, the beneficial effect that the present invention reaches is:
(1) improving technique cost is simple, uses this technique only old equipment hydrogen treat device need be connected and can complete, reduces in hydrogen utilization process more than needed its transport, management cost.
(2) better make use of the hydrogen more than needed in HCl building-up process, its range of application has been extended in molten salt react ion.
(3) the 3rd replace portion of natural gas with clean hydrogen more than needed, reduce cost and the pollution of molten salt react ion.
Accompanying drawing explanation
Fig. 1 is process chart of the present invention.
Detailed description of the invention
In order to make object of the present invention, technical scheme, technique effect more clear, below in conjunction with specific embodiment, the present invention is further elaborated.Embodiment described herein, its effect only for illustration of and non-limiting.
Existing lava reaction process provides required heat, gas discharge 660m3/h, fused salt heating cost 332.64 yuan/ton for passing into separately combustion of natural gas for molten salt react ion, contains carbon monoxide 5.37%, carbon dioxide 5.19%, methane 3.26% in emission.
Multifuel combustion technique of the present invention is specific as follows:
Embodiment 1:
(1) hydrogen is collected: collect the hydrogen more than needed in HCl synthesizer, its force value is 85kPa, and water content is 2%;
(2) process hydrogen: to the first voltage stabilizing of the hydrogen more than needed collected to 70kPa, then be decompressed to 15KPa, carry out, except water treatment, making its water content be reduced to 1.8% simultaneously;
(3) drive separately: when the water content that the pressure of hydrogen more than needed is less than 5kPa or is greater than 15kPa or hydrogen more than needed is greater than 1.8%, burner passes into separately natural gas as fuel of heat supply, and the hydrogen more than needed that pressure, water content do not satisfy condition will by emptying;
(4) multifuel combustion is passed into: treating that 60% alkali of solid potash device in lava stove enters film supplying tube flow is 6.8m3/h, manifold trunk liquidus temperature is 390 DEG C, during product NaOH content >=98%, if now the pressure of hydrogen more than needed, water content meet step (2) conditional, hydrogen more than needed is passed in burner and carries out multifuel combustion;
(5) proportion adjustment: after hydrogen more than needed is passed into combustion furnace, the temperature in maintenance burner is between 410 DEG C, and in this process, hydrogen flowing quantity is 200m3/h, and gas discharge is 600m3/h;
Now fused salt heating cost 302.4 yuan/ton, containing carbon monoxide 4.65% in emission, carbon dioxide 5.35%.
Embodiment 2:
(1) hydrogen is collected: collect the hydrogen more than needed in HCl synthesizer, its force value is 85kPa, and water content is 2%;
(2) process hydrogen: to the first voltage stabilizing of the hydrogen more than needed collected to 68kPa, then be decompressed to 12KPa, carry out, except water treatment, making its water content be reduced to 1.8% simultaneously;
(3) drive separately: when the water content that the pressure of hydrogen more than needed is less than 5kPa or is greater than 15kPa or hydrogen more than needed is greater than 1.8%, burner passes into separately natural gas as fuel of heat supply, and the hydrogen more than needed that pressure, water content do not satisfy condition will by emptying;
(4) multifuel combustion is passed into: treating that 60% alkali of solid potash device in lava stove enters film supplying tube flow is 7m3/h, manifold trunk liquidus temperature is 400 DEG C, during product NaOH content >=98%, if now the pressure of hydrogen more than needed, water content meet step (2) conditional, hydrogen more than needed is passed in burner and carries out multifuel combustion;
(5) proportion adjustment: after hydrogen more than needed is passed into combustion furnace, the temperature in maintenance burner is between 410 DEG C, and in this process, hydrogen flowing quantity is 860m3/h, and gas discharge is 400m3/h;
Now fused salt heating cost 201.6 yuan/ton, containing carbon monoxide 3.76% in emission, carbon dioxide 4.97%.
Embodiment 3:
(1) hydrogen is collected: collect the hydrogen more than needed in HCl synthesizer, its force value is 80kPa, and water content is 2%;
(2) process hydrogen: to the first voltage stabilizing of the hydrogen more than needed collected to 65kPa, then be decompressed to 10KPa, carry out, except water treatment, making its water content be reduced to 1.8% simultaneously;
(3) drive separately: when the water content that the pressure of hydrogen more than needed is less than 5kPa or is greater than 15kPa or hydrogen more than needed is greater than 1.8%, burner passes into separately natural gas as fuel of heat supply, and the hydrogen more than needed that pressure, water content do not satisfy condition will by emptying;
(4) multifuel combustion is passed into: treating that 60% alkali of solid potash device in lava stove enters film supplying tube flow is 7.1m3/h, manifold trunk liquidus temperature is 410 DEG C, during product NaOH content >=98%, if now the pressure of hydrogen more than needed, water content meet step (2) conditional, hydrogen more than needed is passed in burner and carries out multifuel combustion;
(5) proportion adjustment: after hydrogen more than needed is passed into combustion furnace, the temperature in maintenance burner is between 450 DEG C, and in this process, hydrogen flowing quantity is 1200m3/h, and gas discharge is 300m3/h;
Now fused salt heating cost 151.2 yuan/ton, containing carbon monoxide 2.83% in emission, carbon dioxide 3.74%.
Embodiment 4:
(1) hydrogen is collected: collect the hydrogen more than needed in HCl synthesizer, its force value is 75kPa, and water content is 2%;
(2) process hydrogen: to the first voltage stabilizing of the hydrogen more than needed collected to 50kPa, then be decompressed to 5KPa, carry out, except water treatment, making its water content be reduced to 1.8% simultaneously;
(3) drive separately: when the water content that the pressure of hydrogen more than needed is less than 5kPa or is greater than 15kPa or hydrogen more than needed is greater than 1.8%, burner passes into separately natural gas as fuel of heat supply, and the hydrogen more than needed that pressure, water content do not satisfy condition will by emptying;
(4) multifuel combustion is passed into: treating that 60% alkali of solid potash device in lava stove enters film supplying tube flow is 7m3/h, manifold trunk liquidus temperature is 400 DEG C, during product NaOH content >=98%, if now the pressure of hydrogen more than needed, water content meet step (2) conditional, hydrogen more than needed is passed in burner and carries out multifuel combustion;
(5) proportion adjustment: after hydrogen more than needed is passed into combustion furnace, the temperature in maintenance burner is between 440 DEG C, and in this process, hydrogen flowing quantity is 2020m3/h, and gas discharge is 50m3/h;
Now fused salt heating cost 25.2 yuan/ton, containing carbon monoxide 1.34% in emission, carbon dioxide 1.88%.
In sum, HCL synthesizer of the present invention is adopted to have more than needed hydrogen and natural gas multifuel combustion technique, by to the dewatering of hydrogen more than needed in HCL synthesizer, reduced pressure treatment, and by controlling the flow passing into hydrogen and natural gas in burner, reduce fused salt heating cost, decrease the content of carbon monoxide in emission, carbon dioxide, thus reach the object reducing blowdown.
Claims (7)
1.HCL synthesizer is had more than needed hydrogen and natural gas multifuel combustion technique, it is characterized in that, comprises the following steps:
(1) hydrogen is collected: collect the hydrogen more than needed in HCl synthesizer, its pressure limit is between 75 to 85kPa, and water content is less than 2%;
(2) hydrogen is processed: the hydrogen more than needed collected is reduced pressure, except water treatment, make its pressure be reduced between 5 to 15kPa, water content is reduced to less than 1.8%;
(3) drive separately: when the water content that the pressure of hydrogen more than needed is less than 5kPa or is greater than 15kPa or hydrogen more than needed is greater than 1.8%, be used alone natural gas in burner in lava stove as fuel of heat supply, the hydrogen more than needed that pressure, water content do not satisfy condition will by emptying;
(4) multifuel combustion is passed into: treating that 60% alkali of solid potash device in lava stove enters film supplying tube flow is 6.8 to 7.1m3/h, manifold trunk liquidus temperature is 390 to 410 DEG C, during product NaOH content >=98%, if now the pressure of hydrogen more than needed, water content meet step (2) conditional, hydrogen more than needed is passed in burner and carries out multifuel combustion;
(5) proportion adjustment: after hydrogen more than needed is passed into combustion furnace, the temperature in maintenance burner is between 410 to 450 DEG C, and in this process, hydrogen flowing quantity is 0 to 2020m3/h, and gas discharge is 50 to 660m3/h.
2. HCL synthesizer according to claim 1 is had more than needed hydrogen and natural gas multifuel combustion technique, it is characterized in that: before process hydrogen, first with the air in nitrogen displacement hydrogen more than needed, when in hydrogen more than needed, oxygen volume content is less than 2%, start to process hydrogen.
3. HCL synthesizer according to claim 2 is had more than needed hydrogen and natural gas multifuel combustion technique, it is characterized in that: when nitrogen replaces the air in hydrogen more than needed, within every 5 minutes, the gas vent at nitrogen replaceable equipment samples, if when continuous 3 oxygen volume contents are all less than 2%, start to process hydrogen.
4. HCL synthesizer according to claim 1 is had more than needed hydrogen and natural gas multifuel combustion technique, it is characterized in that: the reduced pressure treatment in step (2), for first by the pressure voltage stabilizing to 50 of hydrogen to 70kPa, then be decompressed to 5 to 15kPa.
5. HCL synthesizer according to claim 1 is had more than needed hydrogen and natural gas multifuel combustion technique, it is characterized in that: in step (2) except water treatment, carry out in spark arrester and displacement can.
6. HCL synthesizer according to claim 1 is had more than needed hydrogen and natural gas multifuel combustion technique, it is characterized in that: when passing into the pressure of hydrogen more than needed of burner in step (5), water content is not when meeting the condition in step (2), stop the supply of hydrogen more than needed, increase the flow passing into natural gas in burner, temperature when going out fused salt heating furnace to keep fused salt in step (5), after the pressure of hydrogen more than needed, water content meet the condition in step (2), repeat step (4), (5).
7. HCL synthesizer according to claim 6 is had more than needed hydrogen and natural gas multifuel combustion technique, it is characterized in that: the confession stopping hydrogen more than needed is seasonable, passes into the air in nitrogen displacement hydrogen more than needed in hydrogen treat device more than needed.
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