CN105347302A - Method for producing synthesis gas by converting natural gas - Google Patents

Method for producing synthesis gas by converting natural gas Download PDF

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CN105347302A
CN105347302A CN201510542065.3A CN201510542065A CN105347302A CN 105347302 A CN105347302 A CN 105347302A CN 201510542065 A CN201510542065 A CN 201510542065A CN 105347302 A CN105347302 A CN 105347302A
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gas
gas mixture
natural gas
water vapour
sweet natural
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CN105347302B (en
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张绍延
骆瑞平
张红才
李桂萍
刘飞
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Hubei Chemical Fertilizer Branch Co Of China Petroleum & Chemical Corp
China Petroleum and Chemical Corp
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Hubei Chemical Fertilizer Branch Co Of China Petroleum & Chemical Corp
China Petroleum and Chemical Corp
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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Abstract

The invention discloses a method for producing synthesis gas by converting natural gas. The method comprises the following steps: 1) mixing natural gas and first water vapor to form first mixed gas; 2) feeding the first mixed gas into a one-stage converter and reacting to generate one-stage converted gas; 3) mixing the one-stage converted gas and the natural gas and then reacting in a two-stage converter to generate two-stage converted gas; and 4) recycling heat of the two-stage converted gas by using a recycling device for reproducing water vapor. The content of nitrogen in the synthesis gas produced by the method is reduced, and the content of carbon monoxide is increased. Because the hydrogen-carbon ratio is qualified, the synthesis gas is particularly suitable to serve as feed gas for producing ethylene glycol.

Description

A kind of conversion of natural gas produces the method for synthetic gas
Technical field
The present invention relates to the production method of synthetic gas, be specifically related to a kind of method that conversion of natural gas produces synthetic gas.
Background technology
Sweet natural gas (NaturalGas) combustible gas that to be the extinct plants and animal that is imbedded in underground formed through effects such as the high temperature and high pressures of 1 years, be that a kind of colorless and odorless is nontoxic, calorific value is high, flameholding, clean environmental protection high-grade energy.Its main component of Sweet natural gas is methane, and calorific value is 8500 kilocalories/rice, is a kind of gaseous state fossil oil primarily of methane composition.It is mainly present in oil field and natural-gas field, also has a small amount of for coal seam.Sweet natural gas is also known as green energy resource, and the quantity discharged of its sulfurous gas, dust is close to zero, and the quantity discharged of carbonic acid gas is also very low, does not almost pollute.In addition Sweet natural gas is clean, easy to use, of many uses, and therefore the exploitation of Sweet natural gas are the important directions of world energy sources development, and world's natural gas energy resource epoch come up to us.
At present, the various novel process of gas chemical industry's utilization and the exploitation of course of industrialization become the hot fields of research.Gas chemical industry is strengthened status in the industrial production just gradually.The chemical utilization of Sweet natural gas, can be divided into two approach: one is direct translation method, as Catalyst for Oxidative Coupling of Methane, and Selective Oxidation methyl alcohol and formaldehyde; Another is indirect reformer, and be first namely synthetic gas by conversion of natural gas, synthetic gas is as important industrial chemicals, industrially of many uses, can be used for a series of important chemical productss such as synthetic liquid fuel, methyl alcohol and chemical fertilizer.
Synthetic gas is for main ingredient is for a kind of unstripped gas of chemosynthesis with hydrogen, carbon monoxide.Transformed as coal, oil, Sweet natural gas and coke-oven gas, refinery gas etc. by carbon containing mineral matter and obtain.By the different sources of synthetic gas, composition and purposes, they also can be described as coal gas, syngas for synthetic ammonia, methyl methanol syngas (see methyl alcohol) etc.The raw material range of synthetic gas is extremely wide, and production method is a lot of, and purposes differs, and composition (volume %) has very big difference.
Before World War II, synthetic gas is mainly raw material production with coal; After the war, main hydrogeneous higher liquid hydrocarbon (refining of petroleum cut) or the hydrocarbon gas (Sweet natural gas) of adopting makes raw material.Since the seventies, coal gasification process comes into one's own again, and new technology and various new large-scale plant occur in succession, shows the proportion produced coal in raw material of synthetic gas and will likely increase from now on.But still main is at present raw material production synthetic gas with Sweet natural gas, comprises natural gas steam reforming and gas by partial oxidation of natural method.
Natural gas steam reforming is take Sweet natural gas as raw material, reacts producing synthesis gas with water vapour.1915, A. meter Ta Si and C. Shi Naide steam and the Sweet natural gas based on methane, reaction obtained hydrogen on nickel catalysts.Nineteen twenty-eight, first USS oil company devises a small steam converter and produces hydrogen.World War II, starts to produce syngas for synthetic ammonia by this method.But, now this technique due to ratio of carbon-hydrogen higher and be difficult to meet the requirement of synthesizing methanol, liquid fuel and dme product, and energy consumption is comparatively large, facility investment is large, and Sweet natural gas expends also large, is therefore difficult to realize large-scale industrial application.
For this consideration, the present inventor conducts in-depth research, and object is the problem that solution association area prior art comes out, and produces synthetic gas method desirable to provide a kind of environmental protection, energy-conservation and safe conversion of natural gas.
Summary of the invention
The present inventor is found by lot of experiments and creative work, in synthetic gas preparation process, natural gas via two sections transforms and waste heat recovery, not only fully, reasonably can utilize the water vapour needed for waste-heat of different sites, to reach the object of waste heat recovery, but also effectively can reduce the energy consumption of equipment, save energy, alleviate the load of device.
Therefore, the object of this invention is to provide a kind of method that conversion of natural gas produces synthetic gas, it comprises the steps:
1) Sweet natural gas forms the first gas mixture after mixing with the first water vapour;
2) generation one section of reforming gas is reacted by the first gas mixture feeding one-stage converter;
3) one section of reforming gas reacts after mixing with Sweet natural gas and generates two process transform gas in secondary reformer;
4) heat of two process transform gas is reclaimed for regenerative ratio water vapor by retrieving arrangement.
In the method for the invention, the effect of one-stage converter is by unstripped gas and the first water vapor generation conversion reaction.The reaction occurred in one-stage converter may have: CH 4+ H 2o=CO+3H 2; CH 4+ 2H 2o=CO 2+ 3H 2; CO+H 2o=CO 2+ H 2.
In the method for the invention, described one-stage converter have high temperature resistant, volume is little, improve catalyst activity, be beneficial to conversion reaction feature, can improve catalyst activity, be conducive to conversion reaction carrying out fruit.
According to a specific embodiment of the present invention, in one-stage converter, temperature of reaction can be 500 ~ 530 DEG C, and pressure can be 2.8 ~ 3.2MPa; Preferable temperature can be 510 ~ 520 DEG C, and pressure is 2.9 ~ 3.0MPa.The technical problem that methane is less than 10% at primary reformer outlet content can be solved thus further.
In the method for the invention, the effect of secondary reformer is transformed further by the methane in primary reformer gas.The reaction occurred in secondary reformer may have: 2H 2+ O 2=2H 2o; CH 4+ H 2o=CO+3H 2; CH 4+ 2H 2o=CO 2+ 3H 2.
In the method for the invention, described secondary reformer has does not need outside heat supply, in reaction in furnace heat release, make conversion reaction self-heating carry out feature, brings fixed bed adiabatic formula reaction technology effect.
According to a specific embodiment of the present invention, the temperature of reaction in described secondary reformer can be 1100 ~ 1400 DEG C, and pressure can be about 2.5 ~ 3.5MPa; Preferable temperature can be 1200 ~ 1350 DEG C, and pressure can be 3.0 ~ 3.5MPa.Effectively can control the conversion reaction of methane in secondary reformer thus.
According to a specific embodiment of the present invention, described first gas mixture and the second gas mixture are sent in one-stage converter simultaneously and are reacted; Wherein, described second gas mixture comprises the second water vapour, carbon dioxide and oxygen.
According to a specific embodiment of the present invention, the volume ratio of the second water vapour, carbonic acid gas and oxygen in described second gas mixture is 1:(0.5 ~ 0.9): (1.2 ~ 1.8), preferred 1:(0.7 ~ 0.8): (1.4 ~ 1.6), more preferably 1:(0.72 ~ 0.78): (1.45 ~ 1.55), most preferably 1:0.75:1.5.
Method of the present invention substitutes former air conventional in prior art and/or purity oxygen by the second gas mixture formed after oxygen, carbonic acid gas, water vapour three proportionally being mixed in one section of conversion process, regulate ratio of carbon-hydrogen, not only significantly reduce the content of nitrogen in synthetic gas, but also further increase the content of carbon monoxide, produced synthetic gas is particularly suitable for as producing the unstripped gas of ethylene glycol.
According to a specific embodiment of the present invention, the preparation process of described second gas mixture is as follows: first carbonic acid gas is carried out heat exchange process, then it is mixed with the second water vapour to obtain the 3rd gas mixture, finally obtain described second gas mixture by after the 3rd gas mixture and oxygen mix.
According to a specific embodiment of the present invention, in described 3rd gas mixture, the mol ratio of carbonic acid gas and the second water vapour is 1:(1 ~ 5), preferred 1:(2 ~ 4), more preferably 1:(2.5 ~ 3.5) and, most preferably 1:3.
In the method for the invention, carbonic acid gas can carry out heat exchange with the second steam in an interchanger, and then mix in a mixing tank with the second steam, ratio of carbon-hydrogen adjustment is carried out by instrument chained approach, the pure oxygen that the 3rd gas mixture that ratio of carbon-hydrogen is qualified divides with next arrogant sky after a metre filter impurity mixes in a mixing tank, and the preheating section that the second gas mixture that mixed carbonic acid gas, the second water vapour and oxygen are formed is sent to primary reformer reacts.
Method of the present invention needs the strict ratio of carbon-hydrogen controlled in the 3rd gas mixture, can reduce the growing amount of methane in one-stage converter thus, improves the content of carbon monoxide.
The second gas mixture that method oxygen of the present invention, carbonic acid gas and water vapour three are mixed to get according to a certain percentage and the first gas mixture react simultaneously in one-stage converter, the temperature of reaction of synthetic gas in secondary reformer can be reduced, reduce the heat needed for technique, reduce N is set simultaneously 2tripping device, economy system is invested.
According to a specific embodiment of the present invention, in described first gas mixture, the volume ratio of the first water vapour and Sweet natural gas is (1 ~ 5): 1, preferably (1.2 ~ 3.5): 1.
In the method for the invention, Sweet natural gas can enter hydrocracking device and desulfurizer first successively, removes the hydrogen sulfide in Sweet natural gas and organosulfur.Sweet natural gas after desulfurization forms the first gas mixture after allocating the first water vapor into.Why will limit the ratio of Sweet natural gas in the first gas mixture and the first water vapour, reason is that Sweet natural gas and water vapour react and generates carbon monoxide and hydrogen.When the ratio of the first water vapour and Sweet natural gas is 1 ~ 5:1, preferably during 1.2 ~ 3.5:1, can realize peak optimization reaction in one-stage converter, the activity of catalyzer can reach the highest effect.
According to a specific embodiment of the present invention, calculate according to volume percent, described one section of reforming gas comprises: the carbon monoxide of 4.5 ~ 5.5%, the hydrogen of 25 ~ 30%, the methane of 6.5 ~ 7.0% and the carbonic acid gas of 15 ~ 17%.
According to a specific embodiment of the present invention, the hydrogen in described two process transform gas and the mol ratio of carbon monoxide are (0.5 ~ 3): 1, preferably (2 ~ 2.5): 1, more preferably (2.1 ~ 2.3): 1, and most preferably 2.2:1.
According to a specific embodiment of the present invention, the temperature of described first gas mixture is 400 ~ 600 DEG C, pressure is 2.0 ~ 6.0MPa; Preferable temperature 500 ~ 550 DEG C, pressure is 3.0 ~ 4.0MPa.
According to a specific embodiment of the present invention, the temperature of described second water vapour can be 250 ~ 300 DEG C, and pressure can be 3.0 ~ 4.0MPa; Preferable temperature can be 260 ~ 280 DEG C, and pressure can be 3.4 ~ 3.8MPa.Can reduce the content of nitrogen in synthetic gas thus, improve the content of carbon monoxide, explained hereafter flow process is stablized.
According to a preferred embodiment of the present invention, carry out heat exchange from secondary reformer two process transform gas out further by retrieving arrangement, reclaim heat, for the preheating of Sweet natural gas or water vapour,
According to a preferred embodiment of the present invention, described retrieving arrangement comprises 2 waste heat boilers.In the method for the invention, waste heat boiler is connected with an interchanger.
In the method for the invention, the two process transform gas after heat exchange can carry out decarburization purifying treatment after being separated lime set by separator.The method of described decarburization purifying treatment can be physical absorption process, such as low-temp methanol washing method, polyglycol dimethyl ether process (Selexd method) or propylene carbonate ester process (Flour method) etc.; Also can be chemical absorption process, such as these luxuriant and rich with fragrance youngster (Benfild) method, composite catalyzing method or Padil method etc.Wherein, this luxuriant and rich with fragrance youngster (Benfild) method is particularly preferred.
In the method for the invention, the two process transform gas after purification can export after water cooler heat exchange cooling through methanation furnace and enter separator and be separated.The process condensate separated is delivered to stripping tower and is carried out air lift.Two process transform pneumatic transmission after separation is to molecular sieve Temp .-changing adsorption (TSA), after the component reaching pressure-variable adsorption (PSA) entrance synthetic gas after absorption and quality requirements, this synthetic gas can be directly used in the PSA separation circuit in follow-up ethylene glycol production technique.Wherein, it is to have hazardous substance to remove in process condensate that the process condensate separated delivers to the object that stripping tower carries out air lift, realizes process condensate recycling; The object of molecular sieve Temp .-changing adsorption (TSA) removes the water vapour in two process transform gas, meets the requirement of pressure-variable adsorption (PSA) separation circuit in ethylene glycol production process.
The synthetic gas utilizing method of the present invention to produce reduces the content of nitrogen in synthetic gas, improves the content of carbon monoxide.Owing to having qualified hydrogen-carbon ratio, be therefore particularly suitable as the unstripped gas producing ethylene glycol.Compared with prior art, beneficial effect of the present invention has: efficient, continuous, mass-producing Reforming Natural gas; Two process transform gas is particularly suitable for the unstripped gas as producing ethylene glycol; Simple to operate, process optimization; Less energy-consumption, has good economic benefit and social benefit; Pollution-free, zero release, really realizes cleaner production.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is done and introduce simply, obviously, accompanying drawing in brief description is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 represents a kind of preferred embodiment schematic diagram realizing the inventive method.
Fig. 2 represents another the preferred embodiment schematic diagram realizing the inventive method.
Fig. 3 represents another the preferred embodiment schematic diagram realizing the inventive method.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.
Embodiment 1
As shown in Figure 1, the Sweet natural gas from battery limit (BL) enters hydrocracking device 1 and zinc oxide desulfurization groove 2 successively, to remove hydrogen sulfide in Sweet natural gas and organic sulfide.Sweet natural gas after desulfurization is with the first water vapor mixing, and to form 530 DEG C, first gas mixture of 3.8MPa, and the volume ratio of the first water vapour and Sweet natural gas is 3.5:1.By the mixed constraint of the convection zone of one-stage converter 3, first gas mixture is heated to about 505 DEG C, then in the boiler tube entering one-stage converter 3, (boiler tube divides nine rows, often arrange 42), hydrocarbon steam conversion is carried out, to generate one section of reforming gas under the effect of nickel-base catalyst.Hydrocarbon steam conversion reaction is thermo-negative reaction, and one section of conversion reaction institute heat requirement is supplied by the radiation section top burner of one-stage converter.The temperature of described one section of reforming gas is 810 DEG C.Calculate according to volume percent, one section of reforming gas contains CO:5.0%, H 2: 26.5%, CH 4: 6.85%, CO 2: 16.0%.Stack gas after one-stage converter 3 radiation section combustion heat supplying about 1060 DEG C, carries out heat recuperation by the coil pipe of convection zone, is used for preheating mixing raw material gas, process air, superheated vapour, Sweet natural gas, oiler feed and periodic off-gases.Flue gas by after coil pipe, then enters primary reformer combustion air pre-heater, the combustion air of heating primary reformer burner.After recovery heat, effluent gas temperature reduces to 145 DEG C, is extracted out discharged to air by induced draft fan.
From one Sweet natural gas out of the natural gas main branch after desulfurization with one section of reforming gas from one-stage converter 3 after one-stage converter effuser 4 mixes, deliver to secondary reformer 5, and reaction is continued in secondary reformer 5, to generate the two process transform gas that the mol ratio of hydrogen and carbon monoxide is 2:1, its temperature is 1020 DEG C, pressure is 3.0MPa, and the content of methane is less than 0.3%.
First waste heat boiler 6 (double-jacket tube formula) shell side is entered from secondary reformer 5 two process transform gas out.Synthetic gas temperature after heat exchange is 371 DEG C.Waste heat boiler produces the saturated high pressure steam of 10.4MPa (G), and the two process transform gas after interchanger 7 heat exchange enters this luxuriant and rich with fragrance youngster's decarbonization system 9 and purifies after being separated lime set by reforming gas separator 8.Two process transform gas after purification enters separator 11 and is separated after methanation furnace outlet water cooler 10 heat exchange cooling.The process condensate separated is delivered to stripping tower and is carried out air lift, two process transform pneumatic transmission after separation carries out Temp .-changing adsorption (TSA) to molecular sieve 12, after adsorbing the component and quality requirements reaching pressure-variable adsorption (PSA) entrance synthetic gas, just synthetic gas can be directly used in the PSA separation circuit in follow-up ethylene glycol production technique.
Embodiment 2
Sweet natural gas from battery limit (BL) enters hydrocracking device 1 and zinc oxide desulfurization groove 2 successively, to remove hydrogen sulfide in Sweet natural gas and organic sulfide.Sweet natural gas after desulfurization allocates the first water vapor into, with formation temperature be 550 DEG C, pressure first gas mixture that is 4.0MPa, wherein the volume ratio of the first water vapour and Sweet natural gas is 2:1.
From carbon dioxide compressor outlet carbonic acid gas in interchanger 13, carry out heat exchange with middle pressure steam after, the second gas mixture is formed, to make the volume ratio of the second water vapour, carbonic acid gas and oxygen in the second gas mixture for 1:0.7:1.4 after the pure oxygen (25 DEG C, 4.6MPa) that itself and the second water vapor and next arrogant sky divide mixes in mixing tank 14.
Being reacted by the preheating section that second gas mixture and the first gas mixture deliver to one-stage converter 3 simultaneously, is 830 DEG C to generate temperature, and pressure is one section of reforming gas of 3.01MPa, and it contains CO:4.9%, H 2: 26%, CH 4: 6.9%, CO 2: 15.26%.
From one Sweet natural gas out of the natural gas main branch after desulfurization with one section of reforming gas from one-stage converter 3 after one-stage converter effuser 4 mixes, deliver to secondary reformer 5, and reaction is continued in secondary reformer 5, to generate the two process transform gas that the mol ratio of hydrogen and carbon monoxide is 2.2:1, its temperature is 1017 DEG C, and pressure is 2.9MPa, and the content of methane is less than 0.3%, the content of carbon monoxide is up to 13.69%, and the content of nitrogen is lower than 0.152%.
The two process transform gas flowed out from secondary reformer carries out heat exchange to reclaim heat by waste heat boiler 6, interchanger 7, and enters this luxuriant and rich with fragrance youngster's decarbonization system 9 after being separated lime set by reforming gas separator 8 and purify.Two process transform gas after purification enters separator 11 and is separated after methanation furnace outlet water cooler 10 heat exchange cooling.The process condensate separated is delivered to stripping tower and is carried out air lift, two process transform pneumatic transmission after separation is to molecular sieve 12 Temp .-changing adsorption (TSA), after adsorbing the component and quality requirements reaching pressure-variable adsorption (PSA) entrance synthetic gas, just synthetic gas can be directly used in the PSA separation circuit in follow-up ethylene glycol production technique.
Embodiment 3
Sweet natural gas from battery limit (BL) enters hydrocracking device 1 and zinc oxide desulfurization groove 2 successively, to remove hydrogen sulfide in Sweet natural gas and organic sulfide.Sweet natural gas after desulfurization allocates the first gas mixture that the first water vapor formation temperature is 510 DEG C, pressure is 3.5MPa into, and wherein the volume ratio of the first water vapour and Sweet natural gas is 2:1.
After carrying out heat exchange with middle pressure steam from the carbonic acid gas of carbon dioxide compressor outlet in interchanger 13, its and the second water vapor mix and afterwards form the 3rd gas mixture in mixing tank 15.The temperature of described second water vapor is 273 DEG C, pressure is 3.5MPa.Regulate ratio of carbon-hydrogen, make the mol ratio of carbonic acid gas and the second water vapour in the 3rd gas mixture be 1:3.The second gas mixture is formed, to make the volume ratio of the second water vapour, carbonic acid gas and oxygen in the second gas mixture for 1:0.75:1.5 after the pure oxygen (25 DEG C, 4.6MPa) that the 3rd gas mixture that ratio of carbon-hydrogen is qualified divides with next arrogant sky after strainer 16 impurity screening mixes in mixing tank 14.
Reacted by the preheating section that second gas mixture and the first gas mixture deliver to one-stage converter 3 simultaneously, generating temperature is 822 DEG C, and pressure is one section of reforming gas of 2.95MPa, and it contains CO:5.1%, H2:28.9%, CH4:6.82%, CO2:15.66%.
From one Sweet natural gas out of the natural gas main branch after desulfurization with one section of reforming gas from one-stage converter after one-stage converter effuser 4 mixes, deliver to secondary reformer 5, and reaction is continued in secondary reformer, the mol ratio generating hydrogen and carbon monoxide is the two process transform gas of 2.2:1, its temperature is 1017 DEG C, and pressure is 2.9MPa, and the content of methane is less than 0.3%, the content of carbon monoxide is up to 13.69%, and the content of nitrogen is lower than 0.152%.
The two process transform gas flowed out from secondary reformer 5 carries out heat exchange to reclaim heat by waste heat boiler 6, interchanger 7, and enters benzene Fei Er decarbonization system 9 after being separated lime set by reforming gas separator 8 and purify.Two process transform gas after purification enters separator 11 and is separated after methanation furnace outlet water cooler 10 heat exchange cooling.The process condensate separated is delivered to stripping tower and is carried out air lift, two process transform pneumatic transmission after separation carries out Temp .-changing adsorption (TSA) to molecular sieve 12, after adsorbing the component and quality requirements reaching pressure-variable adsorption (PSA) entrance synthetic gas, just synthetic gas can be directly used in the PSA separation circuit in follow-up ethylene glycol production technique.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.

Claims (10)

1. conversion of natural gas produces a method for synthetic gas, and it comprises the steps:
1) Sweet natural gas forms the first gas mixture after mixing with the first water vapour;
2) generation one section of reforming gas is reacted by the first gas mixture feeding one-stage converter;
3) one section of reforming gas reacts after mixing with Sweet natural gas and generates two process transform gas in secondary reformer;
4) heat of two process transform gas is reclaimed for regenerative ratio water vapor by retrieving arrangement.
2. method according to claim 1, is characterized in that, described first gas mixture and the second gas mixture are sent in one-stage converter simultaneously and reacted; Wherein, described second gas mixture comprises the second water vapour, carbon dioxide and oxygen.
3. method according to claim 1 and 2, it is characterized in that, the volume ratio of the second water vapour, carbonic acid gas and oxygen in described second gas mixture is 1:(0.5 ~ 0.9): (1.2 ~ 1.8), preferred 1:(0.7 ~ 0.8): (1.4 ~ 1.6), more preferably 1:(0.72 ~ 0.78): (1.45 ~ 1.55), most preferably 1:0.75:1.5.
4. according to the method in claim 2 or 3, it is characterized in that, the preparation process of described second gas mixture is as follows: first carbonic acid gas is carried out heat exchange process, then it is mixed with the second water vapour to obtain the 3rd gas mixture, finally obtain described second gas mixture by after the 3rd gas mixture and oxygen mix.
5. method according to claim 4, it is characterized in that, in described 3rd gas mixture, the mol ratio of carbonic acid gas and the second water vapour is 1:(1 ~ 5), preferred 1:(2 ~ 4), more preferably 1:(2.5 ~ 3.5), most preferably 1:3.
6. according to the method in Claims 1 to 5 described in any one, it is characterized in that, in described first gas mixture, the volume ratio of the first water vapour and Sweet natural gas is (1 ~ 5): 1, preferably (1.2 ~ 3.5): 1.
7. according to the method in claim 1 ~ 6 described in any one, it is characterized in that, calculate according to volume percent, described one section of reforming gas comprises: the carbon monoxide of 4.5 ~ 5.5%, the hydrogen of 25 ~ 30%, the methane of 6.5 ~ 7.0% and the carbonic acid gas of 15 ~ 17%.
8. according to the method in claim 1 ~ 7 described in any one, it is characterized in that, the hydrogen in described two process transform gas and the mol ratio of carbon monoxide are (0.5 ~ 3): 1, preferably (2 ~ 2.5): 1, more preferably (2.1 ~ 2.3): 1, most preferably 2.2:1.
9. according to the method in claim 1 ~ 8 described in any one, it is characterized in that, the temperature of described first gas mixture is 400 ~ 600 DEG C, pressure is 2.0 ~ 6.0MPa; Preferable temperature is 500 ~ 550 DEG C, and pressure is 3.0 ~ 4.0MPa.
10. according to the method in claim 1 ~ 9 described in any one, it is characterized in that, described retrieving arrangement comprises 2 waste heat boilers.
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CN1660733A (en) * 2004-02-25 2005-08-31 庞玉学 Technique method for preparing synthesis gas of methyl by using transformation of hydrocarbons and water vapour
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