CN100515925C - Process for preparing CO, synthetic gas and methanol by steam heat-exchanging type conversion of hydrocarbons - Google Patents
Process for preparing CO, synthetic gas and methanol by steam heat-exchanging type conversion of hydrocarbons Download PDFInfo
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- CN100515925C CN100515925C CNB2005100802785A CN200510080278A CN100515925C CN 100515925 C CN100515925 C CN 100515925C CN B2005100802785 A CNB2005100802785 A CN B2005100802785A CN 200510080278 A CN200510080278 A CN 200510080278A CN 100515925 C CN100515925 C CN 100515925C
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 43
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000007789 gas Substances 0.000 claims abstract description 179
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 238000002407 reforming Methods 0.000 claims description 36
- 238000002485 combustion reaction Methods 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000629 steam reforming Methods 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000002737 fuel gas Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003345 natural gas Substances 0.000 abstract description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000015111 chews Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to a method of thermal hydrocarbon steam conversion to produce CO, synthetic gas and methanol. An outer heater first converter and a heat-exchanger type first converter cooperate to complete first steam conversion reaction. Second converter is fed with reformed gas from the two first converters, pure oxygen and hydrocarbons such as gas of CO2 and natural gas to complete oxidation reaction and deep conversion reaction of CH4. After high-heat second reformed gas from second converter heating logistics to act chemical reaction in heat-exchanger type first converter tube, the reformed gas enters into CO separating arrangement to separate part of CO when it is cooled down in heat recovery equipment. The residue gas is used as synthetic gas to produce methanol. The invention is adapted to not only new methanol-acetate associated enterprises but also technical innovation of old methanol factory to add new product of acetate.
Description
Technical field
The present invention relates to a kind of hydrocarbon vapours heat exchange type and transform the method for preparing CO and synthetic gas and methyl alcohol.
Background technology
Adopting hydrocarbon gas is the feedstock production ammonia-synthesizing material gas, industrialized the earliest technological process is the normal pressure partial oxidation, development along with the metallurgical technology technology, the processing and fabricating of high temperature alloy conversion tube (as HK-40, HP-Nb) has obtained solution, and hydrocarbon gas steam under pressure conversion process has just replaced the 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 single series synthetic ammonia maximum-norm is 1700MTPD in the world today, and single series methyl alcohol maximum-norm is more than the 2540MTPD.Tradition synthesis gas preparation technology, no matter be the normal pressure partial oxidation process, the continuous conversion process that perhaps pressurizes 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 has to solve by a part of hydrocarbons that burns.
The core of energy-saving technique is exactly to reduce the consumption of burning with hydrocarbons as far as possible, thereby realizes the autothermal balance or the half autothermal balance of conversion process process.
For autothermal balance or the half autothermal balance that realizes conversion process, just set about developing heat exchange type abroad since the eighties in last century and transform gas-making 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-exchanged reformer replaces traditional external-heat one-stage converter, and with the portion C H of one-stage converter
4The steam reforming load is shifted to secondary reformer, in secondary reformer, add excess air, to keep the autothermal balance of 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 ammonia synthesis reaction to H in the unstripped gas
2/ N
2Requirement, be provided with the PSA device, removing the excess nitrogen of the system that brings into excess air, 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 two sections conversion process of string oxygen-rich air behind the heat exchange type one-stage converter, thereby has both reached system's autothermal equilibrated purpose, does not have H again
2The loss problem just need be provided with cover PSA air separation (or empty branch) device in addition.
In last century end, I.C.I has succeeded in developing the LCM technology that is used to produce methyl methanol syngas on LCA technology basis, promptly uses to add pure oxygen to replace excess air in secondary reformer.Meanwhile, also succeed in developing the heat exchange type oxygen-rich air at home in succession and transformed the system ammonia-synthesizing material gas, heat-exchanging type parallel conversion and heat exchange type are connected to transform and are prepared ammonia synthesis gas technology, and the methyl alcohol synthetic raw gas are made in two sections conversions of heat exchange type pure oxygen and the methyl alcohol synthetic raw gas is made in two sections conversions of heat-exchanging type parallel conversion string pure oxygen.
But all exist natural gas source not to be fully used in the above technology, methanol production and carbonylation of methanol acetic acid production can not be united and carry out, need a large amount of combustion fuel gas and can not fundamentally solve hydrogen and the unbalanced problem of carbon in the synthetic gas.
Summary of the invention
Main purpose of the present invention is to make full use of natural gas source, methanol production and carbonylation of methanol acetic acid production can be united and carry out, use to realize resources circulation, reduce fuel gas consumption, energy-saving and cost-reducing, minimizing is invested and the reduction of erection time, and has fundamentally been solved hydrogen and the unbalanced problem of carbon in the synthetic gas.
In order to achieve the above object, the invention provides a kind of hydrocarbon vapours heat exchange type and transform the method for preparing CO and synthetic gas.The unstripped gas that contains hydrocarbons that present method adopts is Sweet natural gas, liquefied petroleum gas (LPG) or coal mine gas, and its technological process is as follows:
After the unstripped gas of A, hydrocarbon-containifirst material and water vapor mix, enter an external-heat one-stage converter and a heat exchange type one-stage converter respectively, one section steam reforming reaction of hydrocarbons is carried out in described external-heat one-stage converter and the parallel operation of described heat exchange type one-stage converter, hydrocarbon steam conversion reaction institute heat requirement is from the heat energy of two sections reforming gas of high temperature of secondary reformer generation in the described heat exchange type one-stage converter, and this heat obtains by the indirect heat exchange between two sections reforming gas of high temperature and the described heat exchange type one-stage converter inner reaction tube thing; Described external-heat one-stage converter is chewed combustion fuel gas by burning, for the hydrocarbon steam conversion reaction provides heat; Enter described secondary reformer after one section reforming gas that described external-heat one-stage converter and described heat exchange type one-stage converter generate mixes and carry out partial oxidation reaction and CH
4Degree of depth conversion reaction; Simultaneously in described secondary reformer, add CO
2Gas is in order to regulate the H of the two sections reforming gas of high temperature that generate
2/ C ratio, the described CO that in secondary reformer, adds
2The mole number of gas be enter described heat exchange type one-stage converter and external-heat one-stage converter unstripped gas total carbon mole number 0～25%; Described CO
2Be from the combustion product gases of described external-heat one-stage converter, to reclaim.Described combustion product gases is reclaiming CO
2Before, the CO that also is provided with the convection zone of described external-heat one-stage converter
2Preheat coil, hydro carbons gas/steam preheating coil pipe, hydro carbons gas preheat coil, oxygen preheat coil pipe and the heat exchange of combustion air preheat coil enter stack gas after self temperature reduces and reclaim CO
2Device;
B, the two sections reforming gas of high temperature that export from described secondary reformer offer described heat exchange type one-stage converter with heat, enter the CO tripping device again after heat recovery equipment reduces temperature, cutting out partial CO, and the tail gas behind the separation of C O is as synthetic gas.
Above-mentioned preparation method's concrete processing condition are: the pressure that enters the gas mixture of interior unstripped gas of described external-heat one-stage converter and described heat exchange type primary reformer tubes and water vapor in the steps A is 0.2～4MPa, and temperature is 400～600 ℃; One section reforming gas temperature of the outlet of described heat exchange type one-stage converter is 500～750 ℃, CH
4Butt mol ratio therein is 12～26%; One section reforming gas temperature of the outlet of described external-heat primary reformer tubes is 700～800 ℃, CH
4Butt mol ratio therein is 3～12%; Two sections reforming gas temperature of the high temperature of the outlet of described secondary reformer are 800～1070 ℃.
H in the synthetic gas that above-mentioned preparation method obtains
2, CO and CO
2Gas composition can meet the following conditions, and is used for the low pressure methanol synthesis technique:
In the formula: f-ratio,
H
2The molar flow of-hydrogen, kmol/h,
CO
2The molar flow of-carbonic acid gas, kmol/h,
The molar flow of CO-carbon monoxide, kmol/h.
The CO that above-mentioned preparation method prepares can be used as the methanol carbonyl synthesized acetic acid unstripped gas, and the synthetic gas of acquisition can be used as the methyl alcohol synthetic raw gas.
The present invention also provides a kind of method of utilizing synthesis gas preparation methyl alcohol, the H that the off-gas that produces in the described synthesis gas preparation methanol process obtains through separation
2, rich CO
2Gas and tail gas turn back in the synthesis gas preparation process, realize resource circulation utilization.The technological process of this method is as follows:
A, with the off-gas that produces in the unstripped gas of hydrocarbon-containifirst material and water vapor and the described methyl alcohol building-up process through separating the H that obtains
2After the mixing, enter an external-heat one-stage converter and a heat exchange type one-stage converter respectively, one section steam reforming reaction of hydrocarbons is carried out in described external-heat one-stage converter and the parallel operation of described heat exchange type one-stage converter, hydrocarbon steam conversion reaction institute heat requirement is from the heat energy of two sections reforming gas of high temperature of secondary reformer generation in the described heat exchange type one-stage converter, and this heat obtains by the indirect heat exchange between two sections reforming gas of high temperature and the described heat exchange type one-stage converter inner reaction tube thing; Described external-heat one-stage converter is chewed combustion fuel gas by burning, for hydrocarbon steam conversion reaction provides heat, wherein part of fuel gas from described off-gas through separating H
2With rich CO
2Remaining tail gas behind the gas; Enter described secondary reformer after one section reforming gas that described external-heat one-stage converter and described heat exchange type one-stage converter generate mixes and carry out partial oxidation reaction and CH
4Degree of depth conversion reaction; In described secondary reformer, add the rich CO that described off-gas obtains through separation simultaneously
2Gas is in order to regulate the H of the two sections reforming gas of high temperature that generate
2/ C ratio, the described CO that in secondary reformer, adds
2The mole number of gas be enter described heat exchange type one-stage converter and external-heat one-stage converter unstripped gas total carbon mole number 0～25%; Described CO
2Be from the combustion product gases of described external-heat one-stage converter, to reclaim.Described combustion product gases is reclaiming CO
2Before, the CO that also is provided with the convection zone of described external-heat one-stage converter
2Preheat coil, hydro carbons gas/steam preheating coil pipe, hydro carbons gas preheat coil, oxygen preheat coil pipe and the heat exchange of combustion air preheat coil enter stack gas after self temperature reduces and reclaim CO
2Device;
B, the two sections reforming gas of high temperature that export from described secondary reformer offer described heat exchange type one-stage converter with heat, enter the CO tripping device again after heat recovery equipment reduces temperature, cutting out partial CO, and the tail gas behind the separation of C O is as synthetic gas.
This preparation method is adoptable to be used for that the device (or method) of separation of C O comprises that PSA separates adsorption unit from cooled second stage exit gas, and Deep Cooling Method separation of C O, or complexed absorption separation of C O recommend to use PSA to separate adsorption unit.
In the inventive method in heat exchange type one-stage converter and the external-heat primary reformer tubes hydrocarbons steam reforming reaction such as methane be:
In secondary reformer, owing to added pure oxygen, CO to secondary reformer
2Hydrocarbons such as gas and Sweet natural gas, so its steam reforming reaction is:
The synthetic gas that is obtained among this preparation method can be used for the unstripped gas of methyl alcohol and acetic acid process for combination producing process, also can produce methyl alcohol separately, and providing purity to other user simultaneously is high-purity CO product gas more than 99.8%.The present invention has following characteristics:
1. the present invention is better than traditional external-heat steam reforming technology, it can utilize the high level heat of secondary reformer exit gas to add the interior reactant of heat exchange type primary reformer tubes, and provide essential heat for its steam reforming reaction, the fuel natural gas consumption and the smoke discharge amount of external-heat converter have been significantly reduced, certainly also reduced the thermosteresis that causes with fume emission, thereby greatly reduce the norm quota of consumption of hydrocarbon gas, realized half autothermal balance of hydrocarbon steam conversion reaction process substantially.
2. the CO in the recycling flue gas
2With methanol synthetic discharged gas delayed in H
2, CO
2Deng, realized the resources circulation use.
3. this technology is with portion C H
4Steam reforming is transferred to secondary reformer from one-stage converter, and secondary reformer is a thermo-efficiency near 100% adiabatic reactor, therefore has very high thermo-efficiency.
4. can realize methyl alcohol and acetic acid combination producing.
5. owing to the content of all gases that adds in secondary reformer can be regulated, and two sections reforming gas of part can mix as synthetic gas by tail gas direct without the CO tripping device and behind the separation of C O, so just can regulate the ratio of hydrogen and carbon in the synthetic gas of acquisition, thoroughly solve hydrogen and the unbalanced problem of carbon in the synthetic gas.
Reaction temperature and, risk is little, and is reliable.
Description of drawings
Fig. 1 prepares the system and the process flow sheet of CO and synthetic gas and methyl alcohol for this preparation method.
Embodiment
Referring to Fig. 1, the unstripped gas of hydrocarbon-containifirst material through manage 1 (or with from pipeline 3 by the methanol synthetic discharged gas delayed H that obtains that separates
2After the mixing) the unstripped gas preheat coil that enters in the convection zone of external-heat one-stage converter 9 is preheated to 250～430 ℃, enters hydrodesulphurisatioreactors reactors 6 through pipeline 5 then, to remove the deleterious sulphur of follow-up operation, catalyzer is housed in the reactor.The qualified gas of desulfurization is flowed out by pipeline 7 and (vapor pressure is 0.2～4.5MPa) with technological process vapor mixing from pipeline 23, be process feed gas, enter external-heat one-stage converter convection zone, Sweet natural gas/steam preheating coil pipe makes temperature rise to 400～600 ℃, enter respectively in the conversion tube of external-heat one-stage converter 9 and heat exchange type one-stage converter 10 through pipeline 8, catalyzer all is housed in these conversion tubes.In heat exchange type one-stage converter 10, by means of the heat that the high-temperature technology gas that comes from secondary reformer 14 between conversion tube is provided, make hydrocarbons and water vapor generation chemical reaction, and generate CO and H
2, in external-heat one-stage converter 9, the raw material hydrocarbon in the conversion tube still goes up the burning that is provided with by means of furnace roof (furnace wall) and chews, and the combustion heat of a certain amount of fuel gas by pipeline 25 that burns is kept itself and the required heat of steam reforming reaction.After two one- stage converters 9 and 10 conversion reaction separately proceeded to a certain degree, one section reforming gas temperature of the outlet of described heat exchange type one-stage converter 10 was 500～750 ℃, CH
4Butt mol ratio therein is 12～26%; One section reforming gas temperature of the outlet of described external-heat primary reformer tubes 9 is 700～800 ℃, CH
4Butt mol ratio therein is 3～12%; Two one-stage converters 9 and one section reforming gas of 10 are flowed out by outlet pipe 11 and enter secondary reformer 14 by pipeline 13 after pipeline 12 converge, and catalyzer is housed in the secondary reformer.Technology uses oxygen after pipeline 2 and a little vapor mixing from pipeline 23, enter the convection zone of external-heat converter 9, be preheated to 250～350 ℃, enter secondary reformer through pipeline 15, with from one section reforming gas of pipeline 13 after fierce turbulence mixes, at first in the combustion reactions of furnace roof generation hydrogen and oxygen, for continue after the conversion reaction of the methane degree of depth essential heat is provided.The CO that from flue gas, reclaims
2Through pipeline 4 with mix from the small amount of steam of pipeline 23 after, after external-heat transforms 9 convection zone and is preheated to 300～450 ℃, through pipeline 27 with enter secondary reformer again after one section reforming gas of pipeline 13 mixes.Enter the burner of secondary reformer without unstripped gas after a part of desulfurization of one-stage converter through pipeline 22, carry out turbulence with one section reforming gas and technology with oxygen simultaneously and mix, and carry out partial oxidation reaction in on-catalytic conversion reaction space.When two sections conversion reactions proceed to a certain degree, be that temperature out is when reaching 800～1070 ℃, two sections reforming gas enter between the pipe of heat exchange type one-stage converter 10 through pipeline 16, high-order technology waste heat is passed to the interior reactant of pipe, self temperature is reduced to 500～750 ℃, enter reforming gas waste-heat boiler 24 through pipeline 17, reclaim used heat with the byproduct steam form, go out to give up the pot reforming gas be chilled to about 40 ℃ through BFW preheater 28 and water cooler 29, enter PSA transformation adsorption separation device 21 through pipeline 20, the CO pneumatic transmission of separating is made the carbonyl synthesis acetic acid unstripped gas, and the tail gas behind the separation of C O is because of being rich in a large amount of H
2, CO, CO
2Deng active principle, as synthetic gas, as the methyl alcohol synthetic raw gas.
Flue gas is reclaiming CO
2Before, the CO that also is provided with the convection zone of external-heat one-stage converter 9
2Preheat coil, hydro carbons gas/steam preheating coil pipe, hydro carbons gas preheat coil, oxygen preheat coil pipe and the heat exchange of combustion air preheat coil enter stack gas after self temperature reduces and reclaim CO
2Device.
The synthetic gas that obtains separates the H that obtains from the off-gas that produces in the process of synthesizing methanol
2, rich CO
2The resources circulation use has been realized at the pipeline 3 that gas and tail gas are got back to respectively again, pipeline 4 and pipeline 25 (tail gas is as fuel gas) position.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that, still can to the present invention make amendment and or be equal to replacement, and do not break away from the spirit and scope of the present invention.
Claims (4)
1, a kind of hydrocarbon vapours heat exchange type transforms the method for preparing CO and synthetic gas, it is characterized in that:
After the unstripped gas of A, hydrocarbon-containifirst material and water vapor mix, enter an external-heat one-stage converter and a heat exchange type one-stage converter respectively, one section steam reforming reaction of hydrocarbons is carried out in described external-heat one-stage converter and the parallel operation of described heat exchange type one-stage converter, hydrocarbon steam conversion reaction institute heat requirement is from the heat energy of two sections reforming gas of high temperature of secondary reformer generation in the described heat exchange type one-stage converter, and this heat obtains by the indirect heat exchange between two sections reforming gas of high temperature and the described heat exchange type one-stage converter inner reaction tube thing; Described external-heat one-stage converter is chewed combustion fuel gas by burning, for the hydrocarbon steam conversion reaction provides heat; Enter described secondary reformer after one section reforming gas that described external-heat one-stage converter and described heat exchange type one-stage converter generate mixes and carry out partial oxidation reaction and CH
4Degree of depth conversion reaction; Simultaneously in described secondary reformer, add CO
2Gas is in order to regulate the H of the two sections reforming gas of high temperature that generate
2/ C ratio, the described CO that in secondary reformer, adds
2The mole number of gas be enter described heat exchange type one-stage converter and external-heat one-stage converter unstripped gas total carbon mole number 0～25%; Described CO
2Gas is to reclaim from the combustion product gases of described external-heat one-stage converter, and described combustion product gases is reclaiming CO
2Before, the CO that is provided with the convection zone of described external-heat one-stage converter
2Preheat coil, hydro carbons gas/steam preheating coil pipe, hydro carbons gas preheat coil, oxygen preheat coil pipe and the heat exchange of combustion air preheat coil enter stack gas after self temperature reduces and reclaim CO
2Device;
B, the two sections reforming gas of high temperature that export from described secondary reformer offer described heat exchange type one-stage converter with heat, enter the CO tripping device again after heat recovery equipment reduces temperature, cutting out partial CO, and the tail gas behind the separation of C O is as synthetic gas.
2, hydrocarbon vapours heat exchange type according to claim 1 transforms the method for preparing CO and synthetic gas, the pressure that it is characterized in that entering in the steps A gas mixture of unstripped gas in described external-heat one-stage converter and the described heat exchange type primary reformer tubes and water vapor is 0.2～4MPa, and temperature is 400～600 ℃; One section reforming gas temperature of described heat exchange type one-stage converter outlet is 500～750 ℃, CH
4Butt mol ratio therein is 12～26%; One section reforming gas temperature of the outlet of described external-heat primary reformer tubes is 700～800 ℃, CH
4Butt mol ratio therein is 3～12%; Two sections reforming gas temperature of the high temperature of the outlet of described secondary reformer are 800～1070 ℃.
3, hydrocarbon vapours heat exchange type according to claim 1 and 2 transforms the method for preparing CO and synthetic gas, it is characterized in that the H in the described synthetic gas
2, CO and CO
2Gas composition meets the following conditions, and is used for the low pressure methanol synthesis technique:
In the formula: f-ratio,
H
2The molar flow of-hydrogen, kmol/h,
CO
2The molar flow of-carbonic acid gas, kmol/h,
The molar flow of CO-carbon monoxide, kmol/h.
4, a kind of method of utilizing synthesis gas preparation methyl alcohol, the H that the off-gas that it is characterized in that producing in the synthesis gas preparation methanol process obtains through separation
2, rich CO
2Gas and tail gas turn back in the synthesis gas preparation process, realize resource circulation utilization;
The preparation method of described synthetic gas is as follows:
A, with the off-gas that produces in the unstripped gas of hydrocarbon-containifirst material and water vapor and the described methyl alcohol building-up process through separating the H that obtains
2After the mixing, enter an external-heat one-stage converter and a heat exchange type one-stage converter respectively, one section steam reforming reaction of hydrocarbons is carried out in described external-heat one-stage converter and the parallel operation of described heat exchange type one-stage converter, hydrocarbon steam conversion reaction institute heat requirement is from the heat energy of two sections reforming gas of high temperature of secondary reformer generation in the described heat exchange type one-stage converter, and this heat obtains by the indirect heat exchange between two sections reforming gas of high temperature and the described heat exchange type one-stage converter inner reaction tube thing; Described external-heat one-stage converter is chewed combustion fuel gas by burning, for hydrocarbon steam conversion reaction provides heat, wherein part of fuel gas from described off-gas through separating H
2With rich CO
2Remaining tail gas behind the gas; Enter described secondary reformer after one section reforming gas that described external-heat one-stage converter and described heat exchange type one-stage converter generate mixes and carry out partial oxidation reaction and CH
4Degree of depth conversion reaction; In described secondary reformer, add the rich CO that described off-gas obtains through separation simultaneously
2Gas is in order to regulate the H of the two sections reforming gas of high temperature that generate
2/ C ratio, the described CO that in secondary reformer, adds
2The mole number of gas be enter described heat exchange type one-stage converter and external-heat one-stage converter unstripped gas total carbon mole number 0～25%; Described CO
2Gas is to reclaim from the combustion product gases of described external-heat one-stage converter, and described combustion product gases is reclaiming CO
2Before, the CO that is provided with the convection zone of described external-heat one-stage converter
2Preheat coil, hydro carbons gas/steam preheating coil pipe, hydro carbons gas preheat coil, oxygen preheat coil pipe and the heat exchange of combustion air preheat coil enter stack gas after self temperature reduces and reclaim CO
2Device;
B, the two sections reforming gas of high temperature that export from described secondary reformer offer described heat exchange type one-stage converter with heat, enter the CO tripping device again after heat recovery equipment reduces temperature, cutting out partial CO, and the tail gas behind the separation of C O is as synthetic gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100802785A CN100515925C (en) | 2005-06-28 | 2005-06-28 | Process for preparing CO, synthetic gas and methanol by steam heat-exchanging type conversion of hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100802785A CN100515925C (en) | 2005-06-28 | 2005-06-28 | Process for preparing CO, synthetic gas and methanol by steam heat-exchanging type conversion of hydrocarbons |
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|---|---|
| CN1702036A CN1702036A (en) | 2005-11-30 |
| CN100515925C true CN100515925C (en) | 2009-07-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2709688T3 (en) * | 2016-04-22 | 2019-04-17 | Air Liquide | Procedure and installation for the production of synthesis gas by steam catalytic reforming of a hydrocarbon-containing feed gas |
| CN107285277B (en) * | 2017-07-21 | 2020-09-29 | 成都市通用工程技术有限责任公司 | Device and method for preparing synthesis gas by hydrocarbon steam conversion |
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| CN1702036A (en) | 2005-11-30 |
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Assignee: Chengdu General Engineering Technology Co., Ltd. Assignor: Pang Yuxue Contract record no.: 2011510000126 Denomination of invention: Process for preparing CO and synthetic gas and methanol by steam heat-exchanging type conversion of hydrocarbons Granted publication date: 20090722 License type: Exclusive License Open date: 20051130 Record date: 20110810 |
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Effective date of registration: 20161221 Address after: 610041 Sichuan, Chengdu, Wuhou District, wash Bridge Street, No. 29 Patentee after: Chengdu General Engineering Technology Co., Ltd. Address before: 610041 Sichuan Province, Chengdu Wuhou Temple street, No. 30 Chengdu general engineering Technology Development Company Patentee before: Pang Yuxue |