CN101580229A - Method and reaction vessel for reforming and preparing synthetic gas - Google Patents
Method and reaction vessel for reforming and preparing synthetic gas Download PDFInfo
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- CN101580229A CN101580229A CNA200810094580XA CN200810094580A CN101580229A CN 101580229 A CN101580229 A CN 101580229A CN A200810094580X A CNA200810094580X A CN A200810094580XA CN 200810094580 A CN200810094580 A CN 200810094580A CN 101580229 A CN101580229 A CN 101580229A
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Abstract
The invention relates to a method for reforming and preparing synthetic gas, which comprises the following steps: mixing feed gas, oxygen and steam; heating mixture gas to 1250 DEG C-1400 DEG C under the pressure condition of 0.1 MPa-2 MPa; then cooling the mixture gas to 650 DEG C-850 DEG C; and collecting the gas part. A reaction vessel for realizing the method comprises a metal shell. The top of the reaction vessel is provided with a unit combustion nozzle, and the unit combustion nozzle is communicated with an oxygen inlet, a steam inlet and a feed gas inlet by a premixing chamber; the upper section inside the reaction vessel is provided with a refractory lining so as to form a conversion reaction section; the outer surface of the reaction vessel, which corresponds to the conversion reaction section is sleeved with a surface water-cooled jacket; a metal lining is arranged inside the lower section, and a cooling coil is arranged between the metal lining and the metal shell of the reaction vessel so as to form a sulfur conversion section; a chilling combustion nozzle is arranged between the conversion reaction section and the sulfur conversion section; and the bottom of the reaction vessel is provided with a synthetic gas outlet.
Description
Technical field
The present invention relates to a kind of preparation method of synthetic gas.
The invention still further relates to the reactor of realizing aforesaid method.
Background technology
Be rich in CH
4The Sweet natural gas of gas, coal-seam gas, coke-oven gas are main gas phase resources.When it is used to produce the liquid energy Chemicals, must be transformed.Method for transformation can be divided into following a few class: catalytic steam conversion, catalyzing part oxidation and non-catalytic partial oxidation method.
1) catalytic steam transforms
The catalytic steam conversion method is meant and passes through CH under catalyst action such as nickel, rhodium
4-H
2The O reforming reaction transforms CH
4Become CO and H
2Technology.Its principal reaction is as (1-4) formula.
CH
4+H
2O＝CO+3H
2 ΔH298＝206.4kJ/mol (1)
CH
4+2H
2O＝CO
2+4H
2 ΔH298＝165.4kJ/mol (2)
CH
4+CO
2＝2CO+2H
2 ΔH298＝247.4kJ/mol (3)
CO+H
2O＝CO
2+H
2 ΔH298＝-41.0kJ/mol (4)
Its main drawback is raw material consumption height, energy consumption height, production intensity is low, catalyst life is short, poisoning of catalyst occurs easily and phenomenons such as carbon deposit appear in warm.
2) non-catalytic partial oxidation method
The conversion of coke-oven gas non-catalytic partial oxidation is the CH under the general thermodynamic control condition
4Conversion reaction improves reaction with temperature of reaction and quickens.For example, it to steam/hydrocarbons ratio 2 steam methane gas mixture, reacted 6 hours down at 700 ℃ and 750 ℃, remaining methane content is respectively 86% and 72% in the dried reforming gas, transformation efficiency only reaches 3～8% of equilibrium conversion, heated 2 hours down when temperature rises to 950 ℃ and 1050 ℃, methane conversion reaches 68% and 86% of equilibrium conversion.When the non-catalytic partial oxidation service temperature reaches 1300～1500 ℃, CH
4Could transform fast, process just has the industrialization meaning.
On-catalytic transforms following characteristics: (1) unstripped gas requires loose, and coke(oven)gas does not need deep desulfuration to purify catalyst-free poisoning problem; (2) Pintsch process all alkane, alkene and aromatic compound all cracking change into C and H
2(3) there is carbon black to generate in the product gas, needs deficiencies such as purification system.
The reforming reaction speed and the temperature correlation of methane.Under the condition that catalyzer such as nickel, rhodium exist, theory thinks that methane conversion finishes at 950 ℃～1050 ℃, and the industrial application meaning is arranged in the time of 1150 ℃～1250 ℃.Under the condition of non-catalytic, conversion of methane needs more than 1300 ℃ the value of industrial application is arranged.No matter be that catalyzed conversion or on-catalytic transform, reasonable Arrangement reacting field temperature, set up rational temperature of reaction field, be the core of finishing methane conversion and improving thermo-efficiency.If improve temperature of reaction simply, can cause oxygen consumption increase, thermo-efficiency to reduce and because the problems such as industrial application cost increase that material cause produces.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing synthetic gas by reforming.
Another purpose of the present invention is to provide a kind of reactor that is used to realize aforesaid method.
For achieving the above object, the method of preparing synthetic gas by reforming provided by the invention, be to be unstripped gas with in the coke-oven gas, coal-seam gas and the Sweet natural gas that are rich in methane gas one or more, adopting the partial oxidation process preparation under the on-catalytic condition is the synthetic gas of main component with hydrogen, carbon monoxide.
Being rich in the methane gas conversion and producing synthetic gas, is existing H
2, again CH arranged
4Under the condition, methane is converted into CO and H by reforming reaction
2Process.CH
4-H
2O, CH
4-CO
2Reforming reaction has two kinds of channels, and promptly (1) transforms under (1150～960 ℃) condition in temperature under Ni catalyst series condition.(2) conversion under the condition of not using catalyzer realizes CH when promptly being (more than 1300 ℃) in temperature
4Reform and transform.The present invention is according to the conversion of methane feature, propose a kind of simple in structure, do not use catalyzer, investment is low, energy consumption is low, the method for stable operation and reactor.
Concrete operation method of the present invention is, with unstripped gas, oxygen and after water vapor mixes, is heated to 1250-1400 ℃ under 0.1MPa～2Mpa pressure condition, makes unstripped gas transform the generation synthetic gas, by being cooled to 650-850 ℃, collects the gas part.
In the aforesaid method, how many proportional ranges of comparatively ideal raw material, oxygen and water vapor is.
The reactor that is used to realize aforesaid method provided by the invention is that a metal shell constitutes, and the top of this reactor is equipped with the unit burner, and this unit burner is communicated with oxygen inlet, water vapour import and raw material gas inlet by a premixer; Unit burner between centers is 2～10 times of unit burner diameter, and whole burner is formed in the burner unit of arrayed thus;
The epimere of reactor inboard is provided with refractory lining, constitutes the conversion reaction section, and reactor outside surface that should the conversion reaction section is arranged with surperficial water jacket; The hypomere inboard is provided with metal inner lining, is provided with spiral coil cooling tube between the metal shell of this metal inner lining and reactor, constitutes the sulphur conversion zone; Between conversion reaction section and sulphur conversion zone, be provided with the Quench burner;
Reactor bottom is provided with syngas outlet.
Described reactor, wherein, the length-to-diameter ratio of conversion reaction section is 0.5～5.
Described reactor wherein, is provided with insulating lining between the refractory lining of conversion reaction section and the metal shell.
Described reactor, wherein, the unit burner is made up of array unit burner, and each unit burner is equidistant trilateral, quincunx or hexagon distribution.
Described reactor, wherein, burner inside is provided with anti-tempering structure.
Described reactor, wherein, the unit burner is connected to flame monitoring system and temperature monitoring system.
The present invention has following advantage:
(1) do not use any catalyzer, do not produce the poisoning of catalyst phenomenon.
(2) device is simple, no inner member burning phenomenon.
(3) unstripped gas does not need preheating, the thermo-efficiency height, and the oxygen consumption is low.The inside reactor medial temperature is lower than various conversion reaction devices.
(4) the two reactor structure can effectively suppress bad side reaction generation, improves the available gas component content in the product gas.
(5) the unstripped gas requirement is loose, does not produce in the warm because the equipment failure that the tar carbonization causes.
(6) in conversion process, finish in the unstripped gas sulphur simultaneously to the conversion that is easy to remove form.
(7) the overall craft flow process is simple, has saved devices such as preheating oven, saturex, and facility investment is few, stable.
Description of drawings
Fig. 1 is a structure of reactor synoptic diagram of the present invention.
Embodiment
Below be detailed description of the invention, the present invention do not imposed any restrictions.Need to prove that the known technology that the present invention relates to is not partly done in detail, and does not mark in the accompanying drawings yet, as: the tempering restraining device that is provided with on the combustion control system of control burner and the burner etc., all known technology of Cai Yonging.In addition, as previously mentioned, unstripped gas of the present invention can be one or more in coke-oven gas, coal-seam gas and the Sweet natural gas, for ease of narration, is that unstripped gas describes with the coke-oven gas.Those skilled in the art can understand and adopt other unstripped gas also can finish the present invention according to the description of present embodiment.
Reaction of the present invention is carried out under 0.1MPa～2Mpa pressure condition, unstripped gas with
Rationally Flow velocity(how many concrete flow velocitys is) enters inside reactor.Water vapor and oxygen enter reactor simultaneously (specifically what to be) on a small quantity.
Reactor of the present invention, be to constitute cylindrical space by metal shell 1, the top of this reactor is equipped with unit burner 2, and this unit burner 2 is communicated with oxygen inlet 4, water vapour import 5 and raw material gas inlet 6 by a premixer 3, and the oxygen, water vapour and the unstripped gas that enter in the reactor are mixed.Unit burner between centers is 2～10 times of unit burner diameter, and the unit burner is made up of array unit burner, and each unit burner can be to be equidistant trilateral, quincunx, hexagon distribution.Burner inside is provided with anti-tempering structure (known technology); The unit burner is by flame monitoring system and temperature monitoring system (known technology).
The epimere of reactor inboard is provided with the refractory lining of being made by refractory materials 7, constitutes the conversion reaction section, and the length-to-diameter ratio of conversion reaction section is 0.5～5.The mixed gas of the oxygen that the unit burner sprays into, water vapour and unstripped gas is heated to 1250-1400 ℃ in this conversion reaction section, finishes methane conversion, unstripped gas is transformed generate synthetic gas.For avoiding high temperature to the damage of reactor shell and the invert point of maintenance conversion reaction section; be provided with insulating lining 8 between the refractory lining of conversion reaction section and the metal shell; reactor outside surface in corresponding conversion reaction section is arranged with surperficial water jacket 9, by cold water reactor shell is carried out cooling protection.
In the conversion reaction section, oxidizing reaction and reduction reaction take place simultaneously, finish conversion of methane fast.
Because reactive system of the present invention has 0.1MPa～2Mpa pressure, unstripped gas is finished methane conversion in the conversion reaction section after, enters the sulphur conversion zone of reactor hypomere.Suppress adverse effect at the sulphur conversion zone by Quench and take place, and guarantee the intact conversion that helps removing composition to one-tenth of sulphur of various forms.At sulphur conversion zone internal temperature is that sulphur conversion zone temperature is 650 ℃～850 ℃.
The concrete structure of sulphur conversion zone is that the inboard of hypomere is provided with metal inner lining 10, is provided with spiral coil cooling tube 11 between the metal shell of this metal inner lining 10 and reactor.Between conversion reaction section and sulphur conversion zone, be provided with Quench burner 12, by spraying water coolant, the high-temperature synthesis gas that the conversion reaction section is generated is cooled to 650-850 ℃, and synthetic gas enters by the syngas outlet 13 that is located at reactor bottom and collects heat reclamation device (known technology).Synthetic gas through heat reclamation device is 350 ℃～500 ℃, this synthetic gas can be carried out entering refrigerating unit after the heat exchange by interchanger (known technology) and unstripped gas.
Table 1 is the coke-oven gas of this example employing and the major ingredient content in the synthetic gas
| Composition | CH 4 | CO | C 2H 4 | C 2H 6 | H 2 | Effective constituent |
| Unstripped gas | 17.16 | 7.48 | 1.70 | 0.38 | 65.49 | 72.97 |
| Product gas | 1.95 | 24.32 | 0.97 | 0.00 | 67.66 | 90.97 |
From above description as can be seen, innovative point of the present invention is:
1) the new technology principle that a kind of partial oxidation on-catalytic transforms has been proposed.Promptly make up low diffusion, array distribution plug-flow field under the differential speeds condition.Constitute a kind of oxidation, transform the one field with three kinds of reaction raw materials.This reacting field presents and the visibly different species distribution of other reacting fields, hydromeehanics and chemical feature.Effectively reduce raw material consumption, the generation of inhibited reaction by product, improve thermo-efficiency by the state in the control flow field.Realized the methane high conversion under hypoxemia consumption, low water vapor consumption, the harmonic(-)mean temperature of reaction condition.
2) the present invention proposes a kind of non-catalytic partial oxidation burner.This burner makes (1) inside reactor form unique flow of matter field, forms the stratiform reaction zone that is array distribution.Make methane participate in partial oxidation reaction, form the large interface reaction of the assisted reaction material of primitive reaction material and interpolation.Make full use of the diffusion characteristic of reactive group, in the zonule, finish conversion reaction.(2) inside reactor does not have tangible oxidation panel and reduction section is cut apart.Oxidation and reduction reaction are finished in stratiform reaction zone inter-sync in one.(3) the low-temperature working condition of formation burner.Specific feed distribution is in burner to be lower than 900 ℃ working order, to have improved the working life of burner, reduced the material requirement of burner, has improved the whole operation stability of device.(4) on inside reactor and the burner matrix FCS is set, improves the control and the supervision level of system, improve system stability.
3) reactor of the present invention is a two section reactor, and the significantly not axial high-temperature zone, top of its conversion reaction section can not occur owing to the high deficiency that burns out burner and reactor head of head temperature.Simultaneously because the use of little length-to-diameter ratio parameter is shortened the reactor monolith high-temperature area.The back segment of reactor is the sulphur conversion zone of controllable temperature, and assurance sulphur transforms to finish and suppress unfavorable side reaction and takes place.
4) burner of the present invention is equipped with the reactor of combustion control system.This Controlling System can be operated under controlled condition by assurance device, finds that in time the plant failure state avoids serious accident to take place.
5) the present invention is provided with the tempering restraining device on burner.In the device operating process, suppress tempering phenomenon to greatest extent and take place, guarantee equipment safety operation.
6) having concentrated with reaction conversion system and non-preheating is the conversion process of one.
Claims (9)
1, the method for synthetic gas is produced in a kind of reformation, and unstripped gas, oxygen are mixed with water vapor, is heated to 1250-1400 ℃ under 0.1MPa～2Mpa pressure condition, is cooled to 650-850 ℃ afterwards, collects the gas part;
Described unstripped gas is one or more in coke-oven gas, coal-seam gas and the Sweet natural gas.
2, the method for claim 1, wherein how many proportional ranges of unstripped gas, oxygen and water vapor is.
3, a kind of reactor that is used to realize the described method of claim 1 is that a metal shell constitutes, and the top of this reactor is equipped with the unit burner, and this unit burner is communicated with oxygen inlet, water vapour import and raw material gas inlet by a premixer; Unit burner between centers is 2～10 times of unit burner diameter, and whole burner is formed in the burner unit of arrayed thus;
The epimere of reactor inboard is provided with refractory lining, constitutes the conversion reaction section, and reactor outside surface that should the conversion reaction section is arranged with surperficial water jacket; The hypomere inboard is provided with metal inner lining, is provided with spiral coil cooling tube between the metal shell of this metal inner lining and reactor, constitutes the sulphur conversion zone; Between conversion reaction section and sulphur conversion zone, be provided with the Quench burner;
Reactor bottom is provided with syngas outlet.
4, reactor as claimed in claim 3, wherein, the length-to-diameter ratio of conversion reaction section is 0.5～5.
5, reactor as claimed in claim 3 wherein, is provided with insulating lining between the refractory lining of conversion reaction section and the metal shell.
6, reactor as claimed in claim 3, wherein, the unit burner is made up of array unit burner, and each unit burner is equidistant trilateral, quincunx or hexagon distribution.
7, as claim 3 or 6 described reactors, wherein, burner inside is provided with anti-tempering structure.
8, reactor as claimed in claim 3, wherein, the unit burner is connected to flame monitoring system and temperature monitoring system.
9, reactor as claimed in claim 3, wherein, inside reactor is a cylindrical space.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810094580XA CN101580229A (en) | 2008-05-15 | 2008-05-15 | Method and reaction vessel for reforming and preparing synthetic gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200810094580XA CN101580229A (en) | 2008-05-15 | 2008-05-15 | Method and reaction vessel for reforming and preparing synthetic gas |
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| CN101580229A true CN101580229A (en) | 2009-11-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113927A (en) * | 2013-03-15 | 2013-05-22 | 金川集团股份有限公司 | Method of improving utilization rate of heat in desulfurizing process of raw gas |
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- 2008-05-15 CN CNA200810094580XA patent/CN101580229A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113927A (en) * | 2013-03-15 | 2013-05-22 | 金川集团股份有限公司 | Method of improving utilization rate of heat in desulfurizing process of raw gas |
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Open date: 20091118 |