CN105293434B - A kind of method that integrated form gaseous hydrocarbon heat exchange type steam conversion is combined production synthesis gas with non-catalytic partial oxidation - Google Patents
A kind of method that integrated form gaseous hydrocarbon heat exchange type steam conversion is combined production synthesis gas with non-catalytic partial oxidation Download PDFInfo
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- CN105293434B CN105293434B CN201510830913.0A CN201510830913A CN105293434B CN 105293434 B CN105293434 B CN 105293434B CN 201510830913 A CN201510830913 A CN 201510830913A CN 105293434 B CN105293434 B CN 105293434B
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Abstract
The present invention relates to the method that a kind of conversion of integrated form gaseous hydrocarbon heat exchange type steam is combined production synthesis gas with non-catalytic partial oxidation, use integrated form reburner, it is divided into upper and lower two parts, top is free cavity, it is gaseous hydrocarbon non-catalytic partial oxidation reaction zone, bottom is equipped with the shell and tube steam reforming reaction device of catalyst, and it is the high-temperature synthesis gas of non-catalytic partial oxidation reaction zone generation that pipe is outer.Gaseous hydrocarbon after preheating is matched and enters shell and tube steam reforming reaction device after mixing by a certain percentage with vapor, using the heat needed for the sensible heat supply steam reformation for managing outer high-temperature synthesis gas;The product of heat exchange type steam conversion reacts generation high-temperature synthesis gas after entering non-catalytic partial oxidation area through nozzle according to a certain percentage with oxygen, realize the further conversion of gaseous hydrocarbon;High-temperature synthesis gas by conduit after steam reforming reaction heat supply to leading to downstream heat reclamation device.This method has the advantages that device integration is high, floor space is small, energy consumption is low, the thermal efficiency is high, reduced investment.
Description
Technical field
The present invention relates to a kind of method that hydrocarbon-bearing material produces synthesis gas, and in particular to a kind of integrated form gaseous hydrocarbon heat exchange type
The method that steam conversion is combined production synthesis gas with non-catalytic partial oxidation.
Background technology
The gaseous hydrocarbons such as natural gas, shale gas, coal bed gas, casing-head gas, refinery gas, oven gas, pyrolysis gas are main with methane
Composition, is important basic energy resource and industrial chemicals.It is through synthesis gas (CO+H by gaseous hydrocarbons2), then synthesize through synthesis gas
The chemicals such as ammonia, methyl alcohol, oil product are the common methods that gaseous hydrocarbon is utilized.Between developing or having been carried out industrialized methane
Switching through has following several:Steam conversion, non-catalytic partial oxidation, self-heating recapitalization, catalyzing part oxidation and carbon dioxide weight
Whole etc., the main distinction of these process routes has reactor types, key reaction, the heat-supplying mode of methane conversion etc..At these
In reactor, the main reaction for occurring has steam reformation, CO 2 reformation, methane completely or partially to aoxidize and water coal
Gas transformationreation etc..
Industrialized gaseous hydrocarbon had been carried out in the world prepare synthesis gas route mainly there are three at present:One is that steam turns
Change, the technique is generally two sections of conversions, one section is Steam Reforming, after gaseous hydrocarbon and vapor mix in proportion, outside tube wall
Side is reacted by the tubular reactor of fuel gas buring heat supply, in second stage reactor (generally autothermal reforming reaction device), one section
The further conversion that gas completes methane with the oxygen reaction of supplement is converted, the technique is because that need to suppress one section of carbon distribution generation and raising
The conversion ratio of methane, steam/hydrocarbons ratio is (industrial general using 3~5) higher, and energy consumption is of a relatively high, and device area is big, and investment is high;
Two is non-catalytic partial oxidation, and the quantity of steam of process route addition is smaller, main using methane and water under high-temperature and high-pressure conditions
The reaction of steam and carbon dioxide completes the thorough conversion of gaseous hydrocarbon;Three is self-heating recapitalization, and the process route is by the non-of heat release
Catalyzing part oxidation is incorporated into single reactor with the steam conversion of heat absorption, compared to steam reformation, self-heating recapitalization steam/hydrocarbons ratio
Decrease, but still need to add a large amount of vapor and suppress carbon distribution generation.
Higher according to steam conversion second stage exit synthesis gas temperature, the sensible heat using second stage reactor exiting syngas replaces
Conventional external fuel gas buring provides reaction institute calorific requirement, i.e., second stage exit high-temperature synthesis gas are outside one section of tubular reactor and in pipe
Gas converting heat heat supply, this technique is converted for heat exchange type steam, and Typical Representative has LCA techniques.The process route is effectively utilized two
The heat of section outlet high-temperature synthesis gas, while reducing the ratio oxygen consumption of process route.
The heat exchange type steam conversion that existing factory uses is general using self-heating recapitalization as second stage reactor, but this heat exchange
Formula Steam Reforming Process still has the problems such as conventional vapor conversion reactor integrated level is low, occupation area of equipment is big.
Technically can also be realized using the second stage reactor that non-catalytic partial oxidation reburner is converted as heat exchange type steam,
And the process route has the advantage that:
(1) non-catalytic partial oxidation reburner is more thorough compared to methane conversion in self-heating recapitalization reburner exiting syngas
Bottom, the integral energy utilization ratio of technique is higher;
(2) non-catalytic partial oxidation reburner synthesis gas is higher than self-heating recapitalization conversion furnace temperature, can improve one section of tubulation
The operation temperature of formula reactor, is conducive to improving in methane steam reforming reaction speed, and then improve one section of Steam Reforming Methane
Conversion ratio, meanwhile, according to studies have found that improving steam conversion operation temperature is conducive to suppression carbon distribution generation, therefore on-catalytic
Partial oxidation reforming stove can reduce by one section of steam addition as second stage reactor, effectively reduce unit product and consumed than steam;
(3) self-heating recapitalization reburner longtime running can cause the catalyst activity to reduce, and need to interrupt after a period of time is run
Operation more catalyst changeout, non-catalytic partial oxidation reburner without using catalyst, using non-catalytic partial oxidation reburner as
The heat exchange type Steam Reforming Process of second stage reactor in the continuity that equipment is run also advantageously.
Therefore, the present invention proposes that a kind of integrated form gaseous hydrocarbon heat exchange type steam conversion is combined production with non-catalytic partial oxidation
The method of synthesis gas, the conversion of heat exchange type steam and non-catalytic partial oxidation are integrated in a reactor.Compared to traditional
The process routes, synthesis gas yield high with efficiency of utilization such as the conversion of non-catalytic partial oxidation, self-heating recapitalization and heat exchange type steam
It is high, device integration is high, floor space is small, reduced investment the features such as.
The content of the invention
In view of the above problems, a kind of integrated form gaseous hydrocarbon heat exchange type steam conversion of the purpose of the present invention and Non-catalytic partial oxygen
Change the method for combining production synthesis gas, the equipment that the method is used is integrated form reburner.Concrete technical scheme is as follows:
A kind of method that integrated form gaseous hydrocarbon heat exchange type steam conversion is combined production synthesis gas with non-catalytic partial oxidation, bag
Include following steps:
(1) gaseous hydrocarbon of purification is preheated to 100~600 DEG C, integrated form reburner is entered after then mixing with vapor
1;The proportioning of the water vapour and the gaseous hydrocarbon makes water carbon mol ratio reach 1.5~3.0:1;
(2) mixture that step 1 is obtained enters shell and tube steam reforming reaction area 3 by air-flow even distributor 2, and gaseous state occurs
Hydrocarbon steam reforming reaction, the sensible heat of the high-temperature synthesis gas that reaction institute's calorific requirement is generated by non-catalytic partial oxidation area 4 passes through tube wall
Heat exchange is provided;
The product of gaseous hydrocarbon steam reforming reaction through gas collector 5 collect after, with by oxygen heater 6 preheating after
Oxygen enters the further reaction generation high-temperature synthesis gas of non-catalytic partial oxidation area 4 through nozzle 7, realizes further turning for gaseous hydrocarbon
Change, the high-temperature synthesis gas convert the gap of shell and tube reactor by steam, after converting heat supply to one section of steam from tube wall, by
Conduit 8 leaves integrated form reburner into the heat reclaim unit in downstream.
The gaseous hydrocarbon is selected from natural gas, shale gas, casing-head gas, coal bed gas, refinery gas, oven gas, pyrolysis gas gaseous state and contains
One or more in hydrocarbon compound.
The oxidant is oxygen, air or oxygen-enriched air.
The material of the side towards the fire lining of the integrated form reburner 1 is refractory brick.
The synthesis gas for going out integrated form reburner 1 enters heat reclaim unit through conduit 8, and the heat reclaim unit can use water
Pipe boiler or multitubular boiler.
The operating pressure of the integrated form reburner 1 is 0.1~12MPa;The oxidant of the supplement of non-catalytic partial oxidation area 4
The synthesis gas temperature in Xu Shi non-catalytic partial oxidations area reaches 1000~1700 DEG C, to realize the thorough conversion of methane, while protecting
Demonstrate,prove the heat supply of shell and tube reactor;High temperature heat is into gas by after shell and tube reactor cooling, going out integrated form conversion furnace temperature
Spend is 650~800 DEG C.
The present invention proposes the conversion of integrated form gaseous hydrocarbon heat exchange type steam and production synthesis gas is combined with non-catalytic partial oxidation
Method, the advantage is that:Bottom is surveyed in methane conversion, and steam reforming reaction area steam consumption is low, and the integral energy of technique is using effect
Rate is high;Non-catalytic partial oxidation area uses non-catalytic partial oxidation gasification furnace, and device continuous operating time is long;Device integration
High, floor space is small, reduced investment.
Brief description of the drawings
Fig. 1 is the process flow diagram that embodiment 1 produces synthetic gas method.
Symbol description
1 integrated form reburner;2 even gas distribution devices;3 shell and tube steam reforming reaction areas;
4 non-catalytic partial oxidation reaction zones;5 gas collectors;6 oxygen heaters;
7 nozzles;8 conduits.
Specific embodiment
With reference to example, the present invention will be further described in detail, but is not limited to these examples, the technology in the field
Personnel can carry out nonessential modifications and adaptations according to the content of foregoing invention to the present invention.
Referring to the process flow diagram of Fig. 1, a kind of integrated form gaseous hydrocarbon heat exchange type steam is converted and Non-catalytic partial oxygen
Change the method for combining production synthesis gas, the capital equipment of the method is integrated form reburner.
Gaseous hydrocarbon after purifying, preheating enters integrated form reburner 1 after mixing by a certain percentage with vapor, first passes around
Air-flow even distributor 2 enters shell and tube steam reforming reaction area 3 and gaseous hydrocarbon steam reforming reaction occurs, and reaction institute's calorific requirement is urged by non-
The high-temperature synthesis gas for changing the generation of partial oxidation area 4 are provided by tube wall heat exchange, and the product of gaseous hydrocarbon steam reforming reaction enters gas
After body collector 5 is collected, one is entered into non-catalytic partial oxidation area 4 through nozzle 7 with by the oxygen after the preheating of oxygen heater 6
Step reaction generation high-temperature synthesis gas, high-temperature synthesis gas are left integrated form and are converted after converting heat supply to one section of steam by conduit 8
Stove is toward downstream heat reclaim unit.
Embodiment 1
Synthesis gas is converted into by natural gas using the technology of the present invention to certain factory's methanol from natural gas device, reburner pressure is
3.4MPaG, the composition of natural gas is listed in table 1, and flow is 58723Nm3/ h, steam rates are 108.5t/h (135062.9Nm3/
H), reburner is entered after the mixture of natural gas and vapor is preheating to 510 DEG C, oxygen purity is 99.6%, and flow is
28789.58Nm3/ h, from non-catalytic partial oxidation area, top jet nozzle enters reburner after being heated to 220 DEG C through oxygen heater.
The natural gas of table 1 constitutes (mol%)
2.108 | |
2.184 | |
94.947 | |
0.699 | |
0.062 | |
It is total | 100 |
Integrated form reburner exiting syngas parameter is listed in table 2, and main technique index is listed in table 3.
The integrated form reburner exiting syngas parameter of table 2
Integrated form converts outlet of still | |
Temperature DEG C | 710.00 |
Pressure MPaG | 3.30 |
Composition v% | |
38.58% | |
CO | 12.76% |
4.96% | |
0.421% | |
0.17% | |
43.10% |
The main technique index of table 3
Technic index | |
Integrated form reburner outlet syngas temperatures (DEG C) | 710.00 |
Integrated form reburner pressure (MPaG) | 3.30 |
90.23 | |
355 | |
174 | |
816 |
Embodiment 2
Certain factory's methanol from natural gas device is proposed to found a set of new equipment, and the technology of the present invention is made with existing use self-heating recapitalization
For every energy consumption index of traditional heat exchange type Steam Reforming Process of secondary reformer is analyzed in the lump.The composition row of natural gas
In table 4, flow is 64531Nm3/ h, oxygen purity is 99.6%, to realize comparing energy consumption, natural gas and water under identical conditions
The temperature of the entrance reburner of steam is 500 DEG C, and the temperature that oxygen enters reburner is 240 DEG C.
The natural gas of table 4 constitutes (mol%)
93.44 | |
2.43 | |
1.21 | |
0.65 | |
1.74 | |
0.53 | |
It is total | 100.00 |
Different process reburner exiting syngas parameter is listed in table 5, and main technique index is listed in table 6.
The reburner exiting syngas parameter of table 5
The main technique index of table 6
The present invention is described in detail above, its object is to allow the understanding for being familiar with this art to will appreciate that this
The content of invention is simultaneously carried out, and it is not intended to limit the scope of the present invention, all Spirit Essence institutes of the invention
The equivalent change or modification done, should all be included within the scope of the present invention.
Claims (5)
1. a kind of method that integrated form gaseous hydrocarbon heat exchange type steam conversion is combined production synthesis gas with non-catalytic partial oxidation, it is special
Levy and be, comprise the following steps:
1st, the gaseous hydrocarbon of purification is preheated to 100~600 DEG C, integrated form reburner is entered after then mixing with vapor(1);Institute
The proportioning for stating water vapour and the gaseous hydrocarbon makes water carbon mol ratio reach 1.5~3.0:1;
2nd, the mixture that step 1 is obtained passes through air-flow even distributor(2)Into shell and tube steam reforming reaction area(3), there is gaseous state
Hydrocarbon steam reforming reaction, reaction institute's calorific requirement is by non-catalytic partial oxidation area(4)The sensible heat of the high-temperature synthesis gas of generation is by pipe
Wall heat exchange is provided;
The product of gaseous hydrocarbon steam reforming reaction is through gas collector(5)After collection, and by oxygen heater(6)After preheating
Oxygen is through nozzle(7)Into non-catalytic partial oxidation area(4)Further reaction generates high-temperature synthesis gas;The high-temperature synthesis gas are led to
The gap that steam converts shell and tube reactor is crossed, after converting heat supply to one section of steam from tube wall, by conduit(8)Integrated form is left to turn
Change stove(1)Into the heat reclaim unit in downstream.
2. method according to claim 1, it is characterised in that the gaseous hydrocarbon be selected from natural gas, shale gas, casing-head gas,
Coal bed gas, refinery gas, oven gas, pyrolysis gas gaseous state are containing one or more in hydrocarbon compound.
3. method according to claim 1, it is characterised in that the integrated form reburner(1)Side towards the fire lining material
Material is refractory brick.
4. method according to claim 1, it is characterised in that go out integrated form reburner(1)Synthesis gas through conduit(8)Enter
Enter heat reclaim unit, the heat reclaim unit is water-tube boiler or multitubular boiler.
5. method according to claim 1, it is characterised in that the integrated form reburner(1)Operating pressure for 0.1~
12MPa;The non-catalytic partial oxidation area(4)The temperature of the high-temperature synthesis gas of middle generation is 1000~1700 DEG C;Through steaming
After vapour conversion shell and tube reactor cooling, synthesis gas goes out integrated form reburner(1)Temperature be 650~800 DEG C.
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