CN1390776A - Serial transfer process for hydrocarbon vapour - Google Patents
Serial transfer process for hydrocarbon vapour Download PDFInfo
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- CN1390776A CN1390776A CN 02124262 CN02124262A CN1390776A CN 1390776 A CN1390776 A CN 1390776A CN 02124262 CN02124262 CN 02124262 CN 02124262 A CN02124262 A CN 02124262A CN 1390776 A CN1390776 A CN 1390776A
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Abstract
A serial hydrocarbon vapour converting process for preparing synthetic ammonia and methanol from natural gas features that a heat exchange type convertor is serially connected with an externally heated convertor to perform the conversion reaction of hydrocarbon vapour. Its advantages are less energy consumption, low investment and simple operation and equipment.
Description
The present invention is a kind of hydrocarbon steam conversion new energy-saving process, is applicable to that hydrocarbon steam conversion produces the technological process of synthetic gas.
Adopting hydrocarbon gas is the feedstock production ammonia-synthesizing material gas, industrialized the earliest technological process is a normal pressure partial oxidation method, development along with the metallurgical technology technology, the high temperature alloy conversion tube is (as HK-40, HP-Nb) processing and fabricating has obtained solution, and hydrocarbon gas steam under pressure conversion process has just replaced normal pressure partial oxidation technology.Up to now, transfer pressure is brought up to 3.0～4.3MPa from normal pressure, and industrial scale also maximizes day by day, and monophyly synthetic ammonia maximum-norm is 1700MTPD in the world today, and monophyly methyl alcohol maximum-norm is more than the 2540MTPD.The beginning of the sixties, China still can not produce the high temperature alloy conversion tube, in order to satisfy the demand of China's agricultural development to chemical fertilizer, had developed intermittently conversion process of C.C.R.Traditional technology, no matter be intermittently conversion process of normal pressure partial oxidation method, the continuous conversion process of pressurization or C.C.R., all be high-temperature technology gas directly to be imported waste heat boiler produce high-parameters steam, and the required heat of hydrocarbon gas steam reforming have to be situated between certainly by a part of hydrocarbons of burning.
The core of these energy-saving techniques is exactly to reduce the consumption of burning with hydrocarbons as far as possible, thereby realize the autothermal thermal equilibrium of conversion process process or half autothermal thermal equilibrium (the former is as LCA technology and one section conversion of heat exchange type, two sections conversion process of oxygen-rich air, the latter such as class hydrocarbon steam heat-exchanging type parallel conversion technology and this technology etc.).
For autothermal thermal equilibrium or the half autothermal thermal equilibrium that realizes conversion process, just set about developing heat exchange type abroad since the eighties and transform the gas making novel process.Realizing industrialized the earliest is the LCA technology of Britain I.C.I company, and its industrial scale is 300～450MTPD.This process using heat exchange type one-stage converter replaces traditional external-heat converter, and with the part CH of one-stage converter
4The steam reforming load is shifted to secondary reformer, in secondary reformer, add excess air to keep the autothermal thermal equilibrium of this system, be used to simultaneously carry out heat exchange outside the heat exchange type primary reformer tubes and between the inner reaction tube thing, so that the required heat of hydrocarbons steam reforming reaction in the pipe to be provided from the high-temperature technology gas of secondary reformer.In order to satisfy synthetic ammonia to H in the unstripped gas
2/ N
2Requirement, be provided with the PSA device, to remove the excessive N of the system that brings into excess air
2, also remove CO simultaneously
2Gas.LCA technology is removing excessive N
2Process in caused certain amount of H
2Loss, in order to overcome this shortcoming, lattice sieve De-Nol nitrogen synthesis of Byelorussia adopts the technology of two sections conversions of heat exchange type one-stage converter string oxygen-rich air, thereby has both reached system's autothermal thermal equilibrium purpose, does not have H again
2The loss problem just also needs to be provided with a cover PSA air separation plant.
Existing equipment, pipeline and auxiliary facility that purpose of the present invention mainly is to make full use of synthesis ammonia plant carry out energy saving technical reconstruction, propose a kind of hydrocarbon steam conversion energy-saving technique, be applicable to that hydrocarbon steam conversion produces the technological process of synthetic gas and reach energy-saving and cost-reducing and the double effects that reduces investment, reduction of erection time.
Hydrocarbon steam conversion tandem process of the present invention is with after raw material hydrocarbon and the process steam mixing preheating, at first enter the heat exchange type one-stage converter, flow between pipe by high-temperature technology gas from secondary reformer, carry out indirect heat exchange with the inner reaction tube thing, so that the required heat of hydrocarbon steam conversion in the pipe to be provided, after the hydrocarbon steam conversion reaction proceeds to a certain degree, enter again in traditional external-heat converter (converter in the middle of being called for short) and further carry out CH
4Steam reforming reaction, and then enter and carry out CH in the secondary reformer
4Degree of depth conversion reaction.Promptly adopt a heat exchange type one-stage converter and an external-heat one-stage converter serial operation, finish one section conversion reaction of hydrocarbon vapours jointly, we are with this technology called after hydrocarbon vapours heat exchange type series connection conversion process.
Serial transfer process for hydrocarbon vapour of the present invention is characterized in that:
(1) adopt a heat exchange type one-stage converter and a traditional external-heat one-stage converter serial operation, raw material hydrocarbon and process steam are introduced into and enter external-heat one-stage converter continuation conversion after heat exchange type one-stage converter joint transforms, and enter secondary reformer again and carry out CH
4Degree of depth conversion reaction.
(2) the interior hydrocarbon steam conversion institute of heat exchange type one-stage converter heat requirement is from the high level heat of the high-temperature technology gas of secondary reformer, it obtains by the indirect heat exchange between high-temperature technology gas and the heat exchange type one-stage converter inner reaction tube thing, and traditional external-heat one-stage converter is still chewed combustion fuel gas by burning, for one section steam reforming of hydro carbons provides heat.
(3) secondary reformer outlet high-temperature technology gas at first offers heat the heat exchange type one-stage converter, and then utilize all the other heats to come preheating material Sweet natural gas/process steam gas mixture, self temperature enters reforming gas waste-heat boiler after reducing, continue after go into CO middle temperature transformation stove, just follow original technical process later on.
For serial transfer process for hydrocarbon vapour of the present invention, the processing condition of its concrete operations are: the pressure that enters unstripped gas in the heat exchange type primary reformer tubes is: 0.2～4Mpa, and temperature is 400～600 ℃, Outlet Gas Temperature is 500～750 ℃, CH
4Volume content is 8～24%, and Outlet Gas Temperature is 500～700 ℃ between pipe; Gas outlet temperature is 700～800 ℃ in one section middle reformer tube of external-heat, CH
4Volume content is 9～12%, and the secondary reformer Outlet Gas Temperature is 800～1050 ℃.
For serial transfer process for hydrocarbon vapour of the present invention, in the convection zone of one section middle converter of external-heat, also be provided with one group of oiler feed and give hot coil, behind the used heat of oiler feed from pipeline, enter reforming gas through giving hot coil recovery flue gas---conversion gas waste heat boiler; The useless pot of reforming gas waste-heat boiler and conversion gas institute producing steam enters the native system steam manifold after carbonated drink is separated.
The present invention is described in detail below in conjunction with accompanying drawing.
Accompanying drawing one is a hydrocarbon vapours heat exchange type series conversion technology schema.
To the part nomenclature in the accompanying drawing:
13-heat exchange type one-stage converter; Converter in the middle of the 19-
The 18-secondary reformer; 11-process feed gas/reforming gas interchanger;
The present invention imports compressor 2 with the raw material hydrocarbon gas through pipeline 1, boost to behind 1～3.5MPa with the hydrogen (fine gas after the methanation) that returns and mix from pipeline 3, unstripped gas in the middle of pipeline 4 enters in converter 19 convection zones gives hot coil 5, be preheated to 250～430 ℃, enter hydrodesulphurisatioreactors reactors 7 to remove through pipeline 6, catalyzer is housed in the reactor the deleterious sulphur of follow-up operation.The qualified gas of desulfurization is flowed out by pipeline 8 and with (pressure is 1.3～3.9MPa) to mix from the water vapor of pipeline 9, be process feed gas, enter process feed gas/reforming gas interchanger 11 through pipeline 10, make temperature rise to 400～600 ℃, enter each conversion tube 14 of heat exchange type one-stage converter 13 through pipeline 12, catalyzer is housed in the pipe.Export the heat that high-temperature technology gas is provided by means of secondary reformer between pipe, keep the carrying out of hydrocarbon steam conversion reaction, after reaction proceeds to a certain degree, be that temperature out is when being 500～750 ℃, each conversion tube 16 of converter 19 radiation sections in the middle of pipeline 15 enters is equipped with catalyzer in the pipe again.Chew the burning liberated heat by means of the external fuel gas of pipe (mixture of Sweet natural gas and off-gas) through burning, keep CH from fuelgas pipeline 50
4The carrying out of conversion reaction, when late 700～800 ℃ of temperature out, gas enters secondary reformer 18 through pipeline 17, and catalyzer is housed in the secondary reformer.Process air is after pipeline 20 enters compressor 21 and boosts to 1～2MPa, with mix from a small amount of water vapor of pipeline 23, give hot coil 25 in the middle of pipeline 24 enters in converter 19 convection zones, be preheated to 400～750 ℃, enter secondary reformer 18 through pipeline 26, mix with one section reforming gas, H takes place at secondary reformer 18 burners from pipeline 17
2With O
2Combustion reactions, be CH in the stove
4The degree of depth transforms provides essential thermal source.After reaction proceeds to a certain degree, be that temperature out is when being 800～1050 ℃, the gas that goes out secondary reformer enters between the pipe of heat exchange type one-stage converter 13 through pipeline 27, the air-flow of reaction will be participated in the high potential heat transferred pipe, when temperature is reduced to 500～700 ℃, enter process feed gas/reforming gas interchanger 11 through pipeline 28, heat is passed to process feed gas again after pipeline 29 enters reforming gas waste-heat boiler 30, further reclaim the technology waste heat of reforming gas in the byproduct steam mode, when temperature is reduced to 320～400 ℃, enter middle temperature transformation stove 32, in the middle temperature transformation stove catalyzer is housed through pipeline 31.In middle change stove, carry out water gas shift reaction, when CO content is reduced to 1～3.5% (V
Do) time, enter the useless pot 34 of conversion gas through pipeline 33, become the waste heat of gas in reclaiming with the byproduct steam form, temperature is reduced to 180～280 ℃ after pipeline 35 enters the feedwater preheater 36 further heats that reclaim, enter low temperature shift converter 38 through pipeline 37 again, catalyzer is housed in the low temperature shift converter.In stove, carry out water-gas depth conversion reaction near equilibrium concentration, outlet remainder CO content is reduced to about 0.3%, enter feedwater preheater 40 through pipeline 39 and enter water cooler 42 through pipeline 41 again with the waste heat that reclaims low changing air, through being cooled to about 40 ℃, enter follow-up operation through pipeline 43, follow original technical process later on.
In the convection zone of middle converter 19, also be provided with one group of oiler feed and give hot coil 46, after coil pipe 46 reclaims the used heat of flue gases, enter reforming gas by pipeline 47 from the oiler feed of pipeline 45---conversion gas waste heat boiler.34 producing steams of reforming gas waste-heat boiler 30 and the useless pot of conversion gas enter native system steam manifold 44 by pipeline 48, to keep the balance of steam of synthesis ammonia plant after carbonated drink is separated.
Design of the present invention mainly is at being that the energy saving technical reconstruction of medium and small ammonia factory of raw material and technology upgrading are regenerated and proposed with the hydrocarbon gas, also is applicable to the Sweet natural gas to be the synthesis ammonia plant of the various scales of raw material certainly.Its principal feature is as follows:
1. the low the present invention of energy consumption is better than traditional external-heat steam reforming technology, it can utilize the high level heat of secondary reformer outlet process gas to add the interior reactant of heat exchange type primary reformer tubes, for its hydrocarbon steam conversion provides essential thermal source, the fuel gas consumption and the smoke discharge amount of traditional external-heat one-stage converter (middle converter) have been significantly reduced, thereby reduced the thermosteresis that fume emission caused, improve envrionment conditions, thereby greatly reduced the norm quota of consumption of hydrocarbon gas.
The present invention compares with heat exchange type oxygen-rich steam conversion process, and it does not need oxygen, compares with LCA technology, and it does not need to remove excessive N
2, the former air separation plant and the latter's PSA tripping device all will consume a large amount of electric power.Therefore, if adopt the present invention that the existing medium and small ammonia factory of C.C.R gas-making process or traditional direct conversion process that adopts is carried out energy saving technical reconstruction, its comprehensive energy consumption (gas consumption+power consumption) is minimum.
2. technological operation and start-stop car are easy
The present invention compares with hydrocarbon vapours heat-exchanging type parallel conversion process, though one section transforms resistance drop more greatly, the conversion tube material will consume a bit more, but in serial flow, heat-exchanged reformer can be regarded as and gives converter, converter was checked in the middle of there was external-heat the back, and because of power technological operation and control are easy, system's start-stop car is also easier.
3. reduced investment, the construction period is short
When adopting the present invention that the middle-size and small-size ammonia factory of existing C.C.R gas-making process is carried out energy saving technical reconstruction, as long as transfer pressure is selected suitably, only need newly-built gas making gas head, therefrom warm shift conversion step rises, equipment, pipeline, electrical instrument and other auxiliary facility of each operation all can intactly be used later on.
When adopting the present invention that the synthetic ammonia installation of existing traditional open steam conversion process is transformed, only need before former external-heat one-stage converter, to set up a placed in-line heat exchange type one-stage converter, transform again and enlarge secondary reformer throughput, can reach the Increasing Production and Energy Saving purpose, original external-heat one-stage converter, reforming gas waste-heat boiler etc. also can directly utilize.
Heat-exchanged reformer is lower owing to pipe surface temperature, the operational conditions gentleness, and the external-heat one-stage converter of the more traditional steam reforming technology of material requires low.
Compare with heat exchange type oxygen-rich steam conversion process, it does not need to be provided with expensive PSA system oxygen-enriching device or air separation facility; Compare with LCA technology, it does not need setting to remove excessive N
2The PSA tripping device; Compare with above-mentioned two kinds of Auto-thermal reforming process, its secondary reformer does not add oxygen enrichment or excess air, and thermal load is little, the reaction conditions gentleness, the same with the secondary reformer of traditional technology, equipment material, structure, refractory materials and catalyzer there are not special requirement.
4. risk is little, stable and reliable operation
Converter and secondary reformer combination in the middle of of the present invention, be the direct conversion process flow process of traditional hydrocarbon vapours, therefore, even if the heat exchange type one-stage converter is out of order, unstripped gas can be walked around the heat exchange type one-stage converter by being close to the road, converter in the middle of directly entering, and make this technological process keep normal operation.
The present invention has also overcome the PSA system oxygen enrichment of heat exchange type oxygen-rich steam conversion process and LCA technology or has taken off N
2The risk brought of device fluctuation of service, and the easy overtemperature of the secondary reformer disadvantage that usually causes catalyst aging, inactivation and secondary reformer, heat exchange type one-stage converter to burn out, thereby move more stable, reliable.
In sum, the present invention is one and is suitable for the technology that small and medium ammonia synthesis plant is applied, is specially adapted to original C.C.R technology. the energy saving technical reconstruction of the synthesis ammonia plant of gas making.After adopting the present invention to undergo technological transformation, synthetic ammonia per ton can save energy 1.2～17.6 * 10
6Ki can save gasification system investment for trnasforming urban land 10～30%.
The present invention can be used for hydrocarbon gas synthesizing methanol and system H
2Production process and the energy saving technical reconstruction of gasification system.
Embodiment
60kgmol/h, pressure be the natural gas via pipe of 0.5MPa become 1 enter compressor 2 be forced into 1.1Mpa enter via pipeline 4 in the middle of converter 19 convection zone inner coil pipes 5 be preheated to 410 ℃, enter hydrodesulphurisatioreactors reactors 7 by pipeline 6 then, (total sulfur＜1PPM) is by pipeline 8 and 3400Kg/h vapor mixing from pipeline 9 for gas after the desulfurization, and to regulate steam/hydrocarbons ratio be 2.7 to be process feed gas, enter reforming gas/process feed gas interchanger 11 through pipeline 10, in being heated to conversion tube 14 pipes that enter heat exchange type one-stage converter 13 after 500 ℃ by pipeline 12, the gas temperature that goes out heat exchange type one-stage converter 13 is 680 ℃, CH
4Content is reduced to 30% (butt), in conversion tube 16 pipes of converter 19 radiation sections, manages outer fuel natural gas and off-gas (the being about 30gmol/h) combustion heat supplying that is provided by pipeline 50 in the middle of pipeline 15 enters, and the gas temperature that goes out conversion tube 16 is 760 ℃, CH
4Content 10% (butt) enters secondary reformer 18 through pipeline 17.From the about 100Kgmol/h of the air of pipeline 20, after being compressed to 1.05Mpa, air compressor machine 21 allocates small amount of steam into by pipeline 23, in middle converter 19 convection zone inner coil pipes 25, be preheated to 510 ℃, enter secondary reformer 18 and mix through pipeline 26 with one section reforming gas from pipeline 17, secondary reformer 18 Outlet Gas Temperatures are 960 ℃, CH
4Content 0.5% (butt), flow are 7500Kg/h, feed between the pipe of heat exchange type one-stage converter 13 through pipeline 27, and hydro carbons carries out the needed heat of conversion reaction in the conversion tube 14 to provide.The about 600 ℃ gas of temperature is introduced interchanger 11 through pipeline 28 after the heat release, gas is passed to unstripped gas by pipeline 10 with heat, introduce reforming gas waste-heat boilers 30 through further cooled gas by pipeline 29 and further reduce temperature to 355 ℃, enter middle temperature transformation stove 32 (middle change stove is factory's existing equipment) through pipeline 31 then, in middle change stove, carry out the transformationreation of carbon monoxide and water vapor, make its outlet remainder CO content reach 3.5% (butt), the middle gas that becomes enters the useless pot 34 of conversion gas to reclaim heat through pipeline 33, again after feedwater preheater 36 further is cooled to 190 ℃, enter low temperature shift converter 38 (the low stove that becomes is factory's existing equipment) again, the transformationreation of carbon monoxide and water vapor further takes place in low change stove, after making its outlet remainder CO content drop to 0.3% (butt), be cooled to 40 ℃ through feedwater preheater 40 and water cooler 42 successively, enter follow-up carbonation process.
Claims (3)
1. serial transfer process for hydrocarbon vapour is characterized in that:
(1) adopt a heat exchange type one-stage converter and a traditional external-heat one-stage converter serial operation, raw material hydrocarbon and process steam are introduced into and enter external-heat one-stage converter continuation conversion after heat exchange type one-stage converter joint transforms, and enter secondary reformer again and carry out CH
4Degree of depth conversion reaction;
(2) the interior hydrocarbon steam conversion institute of heat exchange type one-stage converter heat requirement is from the high level heat of the high-temperature technology gas of secondary reformer, it obtains by the indirect heat exchange between high-temperature technology gas and the heat exchange type one-stage converter inner reaction tube thing, and traditional external-heat one-stage converter is still chewed combustion fuel gas by burning, for one section steam reforming of hydro carbons provides heat;
(3) secondary reformer outlet high-temperature technology gas at first offers heat the heat exchange type one-stage converter, and then utilize all the other heats to come preheating material Sweet natural gas/process steam gas mixture, self temperature enters reforming gas waste-heat boiler after reducing, continue after go into CO middle temperature transformation stove, just follow original technical process later on.
2. according to the described technology of claim 1, it is characterized in that the pressure that enters unstripped gas in the heat exchange type primary reformer tubes is: 0.2～4Mpa, temperature is 400～600 ℃, Outlet Gas Temperature is 500～750 ℃, CH
4Volume content is 8～24%, and Outlet Gas Temperature is 500～700 ℃ between pipe; Gas outlet temperature is 700～800 ℃ in one section middle reformer tube of external-heat, CH
4Volume content is 9～12%, and the secondary reformer Outlet Gas Temperature is 800～1050 ℃.
3. according to claim 1 or 2 described technologies, it is characterized in that also being provided with one group of oiler feed in the convection zone of one section middle converter of external-heat gives hot coil, behind the used heat of oiler feed from pipeline, enter reforming gas through giving hot coil recovery flue gas---conversion gas waste heat boiler; The useless pot of reforming gas waste-heat boiler and conversion gas institute producing steam enters the native system steam manifold after carbonated drink is separated.
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| CN 02124262 CN1390776A (en) | 2002-07-12 | 2002-07-12 | Serial transfer process for hydrocarbon vapour |
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| CN 02124262 CN1390776A (en) | 2002-07-12 | 2002-07-12 | Serial transfer process for hydrocarbon vapour |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427384C (en) * | 2005-06-28 | 2008-10-22 | 庞玉学 | Process for preparing CO and synthetic gas and methanol by steam conversion of hydrocarbons |
| CN105565269A (en) * | 2016-02-04 | 2016-05-11 | 河南心连心化肥有限公司 | Device and method for making shifted gas for synthesis of ammonia synthesis poly-generation methanol |
-
2002
- 2002-07-12 CN CN 02124262 patent/CN1390776A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427384C (en) * | 2005-06-28 | 2008-10-22 | 庞玉学 | Process for preparing CO and synthetic gas and methanol by steam conversion of hydrocarbons |
| CN105565269A (en) * | 2016-02-04 | 2016-05-11 | 河南心连心化肥有限公司 | Device and method for making shifted gas for synthesis of ammonia synthesis poly-generation methanol |
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