CN106946637B - A kind of device and technique of skid-mounted type lower carbon number hydrocarbons production methane - Google Patents
A kind of device and technique of skid-mounted type lower carbon number hydrocarbons production methane Download PDFInfo
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- CN106946637B CN106946637B CN201710176923.6A CN201710176923A CN106946637B CN 106946637 B CN106946637 B CN 106946637B CN 201710176923 A CN201710176923 A CN 201710176923A CN 106946637 B CN106946637 B CN 106946637B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0405—Apparatus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/10—Process efficiency
Abstract
The present invention provides the device and technique of a kind of skid-mounted type lower carbon number hydrocarbons production methane.The device that the skid-mounted type lower carbon number hydrocarbons produces methane includes the first feed pump, the second feed pump, fine de-sulfur reactor, heating furnace, hydrocarbon-water conversion reactor, depth methanator, gas-liquid separator and membrane separator.The device of skid-mounted type lower carbon number hydrocarbons production methane provided by the invention has the characteristics that raw material is easily stored, device volume is small, conveniently moving, is easy to modularization, is suitble to skid design, easily designed manufacture and commercial applications；The present invention has high production efficiency using the technique that the device carries out lower carbon number hydrocarbons production methane simultaneously, methane conversion is high, up to 97% or more, product calorific value is high, it can produce on demand, it is flexible and convenient to use, it is suitable for distributed energy and peak regulation, not only can be complementary with biofermentation methane, but also to can be used for being not easy to pipe defeated but need place using clean energy resource.
Description
Technical field
The invention belongs to methane production technology fields, and in particular to a kind of device and work of skid-mounted type lower carbon number hydrocarbons production methane
Skill.
Background technique
Chinese haze is serious, and natural gas is an important solutions for the anti-haze of coal.But Natural Gas In China pipe network lacks, in nothing
In the case where pipe network, natural gas supply and peaking problem are badly in need of solving, especially outlying cities and towns.
Methane is the clean energy and good industrial chemicals, is all widely used in the energy and chemical field.2015
Natural gas consumption based on year China methane be up to 197,300,000,000 sides, and lasting for years keeps steady-state growth, based on methane
Clean fuel demand it is big.
There are many production method and approach of methane, and the production of industrial methane mainly has: (1) being based on nature long-term evolution
The natural resources such as natural gas, shale gas, the associated gas that the conventional fossil fuel of formation is formed, usual scale is big, investment is high,
It needs using pipeline, inconvenient storage and transportation；(2) natural gas from coal is based on extensive coal gasification and methanation mass production methane
Based on substitute natural gas.Since coal gasification and environmental protection investments are high, while in order to reduce cost, scale is typically up to billions of
In side/year, storage and transportation is equally inconvenient, and relies on pipeline；(3) bioanalysis such as ferments, and scale is generally little, but due to adopting
With bio-fermentation process, produce gas velocity degree and efficiency be not usually high, the place for needing to occupy is very big, and raw material compiling costs compared with
Height, product gas are inconvenient to use.Large-scale methane turns to main natural gas production and using pipeline is all limited to, simultaneously also
By the huge bring peak regulation challenge of Summer and winter gas consumption difference.The production of bioanalysis methane is then collected by raw material, produces gas effect
The limitation of rate, place occupancy, actionradius etc..
Only for methane production, the sustained, stable growth and China recently as clean energy resource demand are extensive
The development of natural gas from coal industrialization, many enterprises and the relevant preparing methane by synthetic gas production technology skill of research and development unit application
Art: application No. is 201080040515.4 patent applications to disclose a kind of method for producing methane, containing carbon monoxide and hydrogen
Unstripped gas generates the product gas comprising methane in the internal water cooling methanator containing nickel methenyl catalyst；Application No. is
200810226891.7 patent application discloses a kind of off-gas or coal based synthetic gas using from methanol, takes heat cold using interior
The technique that pipe heat exchange type reactor passes through depth methanation catalyst synthesizing methane；Application No. is 201310226488.5 patent Shens
It please disclose a kind of method by carbonaceous material production methane coproduction liquid fuel, the thick synthesis obtained after carbonaceous material is gasified
It is mixed after gas purification with water and generates gas and product liquid, isolated methane on a catalyst；Application No. is
201310226609.6 patent application disclose a kind of producing firedamp by syngas coproduction low-carbon alcohols by carbonaceous material gasification
Method, isolated methane；A kind of gasified by carbonaceous material is disclosed application No. is 201310226488.5 patent application to close
At the method for gas production methane coproduction liquid fuel；One kind is disclosed application No. is 200910074977.7 patent application to be based on
The methane production technique of oven gas utilizes carbon monoxide in purified oven gas and carbon dioxide and hydrogen methanation reaction system
Methane.
In addition, there are also the methods much based on biofermentation methane: application No. is the patent Shens of 201380024947.X
A kind of process for solid state fermentation and its bioreactor and solid carrier please be disclose for methane production；Application No. is
200910195302.8 patent application disclose it is a kind of use sludge anaerobic fermenting and producing methane；Application No. is
201310572573.7 patent application discloses a kind of side using house refuse and domestic animal fowl hybrid anaerobic fermentation production methane
Method.
The above method is mainly based upon synthesis gas or biofermentation and directly produces or co-production of methane.It needs to have enough
Big scale is produced, main to be rich in carbon monoxide and hydrogen using the synthesis gas of carbonaceous raw material gasification or oven gas of pyrolysis etc.
The mixed gas of gas is raw material, it is therefore necessary to while considering seasonal effect bring peaking problem；Detested based on biomass
Aerobe fermentation, needs to consider to produce radius and very big place occupies, and production efficiency is lower, and application range is limited.
Summary of the invention
In order to solve to produce the problems such as methane is at high cost, production efficiency is low, peak regulation in the prior art, the purpose of the present invention exists
In providing the device and technique of a kind of skid-mounted type lower carbon number hydrocarbons production methane, the device have raw material is easily stored, device volume is small,
The features such as conveniently moving, while technique of the invention has high production efficiency, methane conversion is high, and it is flexible and convenient to use, it is suitble to
As distributed energy, or complementary with other methane production techniques, for the cities and towns without pipeline gas, or with life
Object fermentation complementation solves the problems, such as cities and towns energy of dispersion etc..
The purpose of the present invention is achieved by the following technical programs:
The present invention provides a kind of device of skid-mounted type lower carbon number hydrocarbons production methane, which produces the device of methane
Including the first feed pump, the second feed pump, fine de-sulfur reactor, heating furnace, hydrocarbon-water conversion reactor, depth methanation reaction
Device, gas-liquid separator and membrane separator；
First feed pump is connected with the fine de-sulfur reactor, the fine de-sulfur reactor and the heating furnace phase
Connection, second feed pump are connected with the heating furnace, the heating furnace, the hydrocarbon-water conversion reactor, the depth
Methanator and the gas-liquid separator are sequentially connected logical, the gas outlet end of the gas-liquid separator and the UF membrane
Device is connected, and the methane outlet end of the membrane separator generates methane, the offgas outlet end of the membrane separator and the heating
Furnace is connected.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the device of skid-mounted type lower carbon number hydrocarbons production methane
It further include First Heat Exchanger and the second heat exchanger, the hydrocarbon-water conversion reactor outlet end is connected with the First Heat Exchanger
Logical, the First Heat Exchanger is connected with the depth methanator, the depth methanator and described second
Heat exchanger is connected, and second heat exchanger is connected with the gas-liquid separator.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the device of skid-mounted type lower carbon number hydrocarbons production methane
It further include methane storing tank, the methane outlet end of the membrane separator is connected with the methane storing tank.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the fine de-sulfur inside reactor is provided with de-
Sulphur agent bed is mounted with Cu/ molecular sieve desulfurizer on the desulfurizing agent bed, and the trade mark of the Cu/ molecular sieve desulfurizer is SQ-
108。
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the hydrocarbon-water conversion reactor is internally provided with
Reforming catalyst bed, the reforming catalyst bed are mounted with unreduced Ni/Al2O3Catalyst, this is unreduced
Ni/Al2O3Catalyst can also be prepared by commercially available purchase by laboratory.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the unreduced Ni/Al2O3In catalyst
The content of nickel oxide is more than or equal to 60%, remaining is aluminium oxide.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the unreduced Ni/Al2O3Catalyst is
It is prepared by following preparation method:
Nickel nitrate, aluminum nitrate are weighed, sesbania powder is added and desalted water is configured to mixed solution A；It is added into mixed solution A
Urea stirs to dissolve, and is subsequently placed in the reflux unit with heating, heats while stirring, and urea is made slowly to decompose and incite somebody to action
Nickel ion and aluminium ion are precipitated as uniform mixture B；Sufficiently after precipitating, stop heating, after solution is cooling, using sheet frame pressure
Filter filters pressing is simultaneously washed with water precipitating and obtains filter cake；Filter cake is dried to obtain Ni/Al2O3Catalyst precarsor；To after drying
Ni/Al2O3Catalyst precarsor in graphite powder and sesbania powder is added, squeezed, be granulated, then beaten sheetmolding and be particle and rise
Temperature roasting, Temperature fall obtain unreduced Ni/Al2O3Catalyst.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the unreduced Ni/Al2O3Catalyst is
It is prepared by following preparation method:
Nickel nitrate, aluminum nitrate are weighed by Ni:Al atomic ratio 1:1 batching metering, and nickel nitrate and aluminum nitrate gross mass is added
2% sesbania powder and desalted water is configured to the mixed solution A 1 that concentration of metal ions is 1-2mol/L；
Urea is added into mixed solution A 1, the urea amount of addition is measured by molal quantity are as follows: n (CO (NH2)2)=1.2 × [n
(Ni)+1.5n (Al)], it stirs to dissolve, is subsequently placed in the reflux unit with heating, is heated to 100 DEG C while stirring, and
It is kept for 24 hours, decomposes urea slowly and nickel ion and aluminium ion are precipitated as uniform mixture B1；
Sufficiently after precipitating, stop heating, after solution is cooling, using plate and frame filter press filters pressing and with the bodies such as mixture B1
Long-pending deionized water washing precipitating obtains filter cake three times；
Filter cake is put into baking oven, 80 DEG C is warming up to from room temperature with the speed of 1 DEG C/min, drying is kept in circulating air
12 hours, obtain Ni/Al2O3Catalyst precarsor；
To the Ni/Al after drying2O3Catalyst precarsor in the graphite powder of its quality 1% and 2% sesbania powder is added, into
Row is squeezed, is granulated, and then beating sheetmolding is 6 × 6mm cylindrical particle, is then warming up to 650 DEG C with the speed of 5 DEG C/min, is protected
Hold temperature calcination 12 hours, Temperature fall obtains unreduced Ni/Al2O3Catalyst.
When carrying out catalysis reaction, by unreduced Ni/Al2O3Catalyst is loaded on reforming catalyst bed, is passed through
Conventional method is reduced into Ni/Al2O3Catalyst.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that setting inside the depth methanator
There is methanation catalyst bed, the methanation catalyst bed is mounted with unreduced Ni/La2O3/Al2O3Catalyst, should
Unreduced Ni/La2O3/Al2O3Catalyst can also be prepared by commercially available purchase by laboratory.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the unreduced Ni/La2O3/Al2O3It urges
The content of nickel oxide is more than or equal to 50% in agent, and the content of lanthana is 3%, remaining is aluminium oxide.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the unreduced Ni/La2O3/Al2O3It urges
Agent is prepared by following preparation method:
It is roasted by raw material of boehmite, Temperature fall obtains the aluminium oxide of high temperature preparation；Using nickel nitrate and
Lanthanum nitrate is configured to solution, is precipitated using ammonium carbonate, and heating heating is carried out after filtering, and then Temperature fall obtains the oxidation of nickel lanthanum
Object；The aluminium oxide of high temperature preparation and nickel lanthanum-oxides are mixed to get mixture C, graphite powder and sesbania powder is then added, and put
Enter ball milling in ball mill, after being sufficiently mixed, beating sheetmolding is particle；Molding particle is roasted, then Temperature fall, is obtained
To unreduced Ni/La2O3/Al2O3Catalyst.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the unreduced Ni/La2O3/Al2O3It urges
Agent is prepared by following preparation method:
Using boehmite as raw material, 950 DEG C are warming up to the speed of 5 DEG C/min and is roasted 6 hours, Temperature fall obtains height
The aluminium oxide of temperature preparation；
Use nickel nitrate and lanthanum nitrate according to Ni:La atomic ratio 36:1 for the solution for being configured to 2mol/L, using ammonium carbonate
Precipitating is warming up to 350 DEG C after filtering with the speed of 5 DEG C/min, is kept for 6 hours, then Temperature fall obtains nickel lanthanum-oxides；
By high temperature preparation aluminium oxide and nickel lanthanum-oxides 50:50 in mass ratio be mixed to get mixture C 1, then according to
1% graphite powder and 2% sesbania powder is added in the quality of mixture C 1, is put into ball milling 2 hours in ball mill, after being sufficiently mixed,
Beating sheetmolding is 6 × 6mm cylindrical particle；
Molding cylindrical particle ball is warming up to 550 DEG C with the speed of 5 DEG C/min, is kept for temperature calcination 12 hours, so
Temperature fall afterwards obtains unreduced Ni/La2O3/Al2O3Catalyst.
When carrying out catalysis reaction, by unreduced Ni/La2O3/Al2O3Catalyst is loaded into methanation catalyst bed
Ni/La is reduced on layer by conventional method2O3/Al2O3Catalyst.
In the device of above-mentioned skid-mounted type lower carbon number hydrocarbons production methane, it is preferable that the film used in the membrane separator is polyamides
Imines hollow-fibre membrane.
The present invention also provides a kind of techniques of lower carbon number hydrocarbons production methane, use above-mentioned skid-mounted type lower carbon number hydrocarbons production methane
Device carries out, comprising the following steps:
Lower carbon number hydrocarbons is delivered on the desulfurizing agent bed of fine de-sulfur inside reactor by the first feed pump and is carried out by step 1
Desulfurization process makes total sulfur content be less than 1ppm；
Step 2, the lower carbon number hydrocarbons after desulfurization process, which mixes to be delivered to together with the water conveyed via the second feed pump, to be added
Hot stove carries out heating heating, and the mixture after heating is delivered on the reforming catalyst bed in hydrocarbon-water conversion reactor
Catalysis reaction is carried out, reaction carries out under adiabatic conditions, obtains the synthesis containing methane, carbon monoxide, carbon dioxide and hydrogen
Gas；
Step 3, the methanation being delivered in depth methanator after synthesis gas is cooled down via First Heat Exchanger are urged
Catalysis reaction is carried out on agent bed, and the carbon monoxide in synthesis gas, carbon dioxide and hydrogen catalytic is further made to be converted into first
Alkane obtains the gaseous mixture of methane and tail gas；
Step 4 is delivered in gas-liquid separator after gaseous mixture cools down via the second heat exchanger and is carried out dehydrating；
Step 5 is delivered in membrane separator by dewatered gaseous mixture and is further separated out methane gas and tail gas,
Methane gas is delivered in methane storing tank, and tail gas is delivered to burning recycling heat in heating furnace.
In the technique of above-mentioned lower carbon number hydrocarbons production methane, it is preferable that the temperature of catalysis reaction in the hydrocarbon-water conversion reactor
It is 350-550 DEG C, pressure is normal pressure to 6MPa, carbon space velocity 300-3000h-1, steam/hydrocarbons ratio is (1-4): 1.
In the technique of above-mentioned lower carbon number hydrocarbons production methane, it is preferable that the temperature of catalysis reaction in the depth methanator
Degree is 240-650 DEG C, and pressure is normal pressure to 6MPa, carbon space velocity 1000-3000h-1, steam/hydrocarbons ratio is (1-4): 1.
In the technique of above-mentioned lower carbon number hydrocarbons production methane, it is preferable that after the First Heat Exchanger cooling processing, the temperature of synthesis gas
Degree is 250-300 DEG C.
In the technique of above-mentioned lower carbon number hydrocarbons production methane, it is preferable that the lower carbon number hydrocarbons is C4-C10Lightweight saturated hydrocarbons；More
Preferably, the lower carbon number hydrocarbons may include casing-head gas, liquefied petroleum gas and the medium one or more combinations of naphtha.This hair
Low-carbon hydrocarbon raw material used by bright is lightweight lower carbon number hydrocarbons, these raw materials are easy to liquefy and storage and transportation, has very high energy density,
It is small in size, it is convenient for skid.
In the technique of above-mentioned lower carbon number hydrocarbons production methane, lower carbon number hydrocarbons desulfurization of raw material purified treatment is to adopt to pump up into Cu/
In molecular sieve desulfurizer bed, directly sulfur compounds adsorption therein is removed, thus raw material is purified, in purified raw material
To the harmful sulfide total sulfur content of following process control in 1ppm hereinafter, thereby guarantee that subsequent transformation process can smoothly into
Row.
In the technique of above-mentioned lower carbon number hydrocarbons production methane, the mixture after heating is delivered to hydrocarbon-water conversion reactor (dress
It is filled with unreduced Ni/Al2O3The insulation fix bed reactor of catalyst) catalysis reaction is carried out, the temperature of reaction is 350-
550 DEG C, pressure is normal pressure to 6MPa, carbon space velocity 300-3000h-1, lower carbon number hydrocarbons occur on the catalyst be shown in the following table 1
Column complex reaction.Here, lower carbon number hydrocarbons is completely converted into CH4, CO2, the one carbon atom compounds such as CO and H2.Usually these reactions are because of heat release
The temperature that will lead to exit gas greater than heat absorption rises, CH in product gas4Content may be up to 50%, concrete content and raw material and work
Skill condition is closely related.
Table 1
In the technique of above-mentioned lower carbon number hydrocarbons production methane, via the synthesis gas that hydrocarbon-water conversion reactor generates usually contain compared with
More CO2、H2With a small amount of CO.In general, the temperature of the logistics is also higher, because adiabatic temperature rise is usually up to 500 DEG C or more.For
This, which needs to cool to about 300 DEG C or so by the second heat exchanger, and being delivered to depth methanator, (filling is efficient
CO2Methanation and the unreduced Ni/La of CO methanation2O3/Al2O3The fixed bed reactors of catalyst), by part CO2, it is several
Whole CO and H2It is converted into CH4, obtain and contain CH4Based on, a small amount of CO2With trace amounts of CO and H2Methanation gaseous mixture.Using low-carbon
Lightweight saturated hydrocarbons, CH4Mass yield can achieve 85% or more.
In the technique of above-mentioned lower carbon number hydrocarbons production methane, in membrane separator, using Polyimide Hollow Fiber, preferred
In the case of, it is purified using two-stage UF membrane, CH can be obtained4Content is up to 97% product gas, CH4The rate of recovery reaches 95%
More than.Tail gas after separation is used as combustion furnace fuel and heats raw material, high concentration CH4Product gas enters buffer reservoir and makes for user
With.
The device of skid-mounted type lower carbon number hydrocarbons production methane provided by the invention is with raw material is easily stored, device volume is small, moves
The features such as facilitating is moved, modularization is easy to, is suitble to skid design, easily designed manufacture and commercial applications；The present invention uses simultaneously
The technique that the device carries out lower carbon number hydrocarbons production methane has high production efficiency, and methane conversion is high, and up to 97% or more, product heat
Value is high, can produce on demand, flexible and convenient to use, is suitable for distributed energy and peak regulation, both can be mutual with biofermentation methane
It mends, and it is defeated but need place using clean energy resource to can be used for being not easy to pipe.
Detailed description of the invention
Fig. 1 is the schematic device that 1 skid-mounted type lower carbon number hydrocarbons of the embodiment of the present invention produces methane；
Accompanying drawings symbol description:
1 first feed pump, 2 second feed pumps, 3 fine de-sulfur reactors, 4 heating furnaces, 5 hydrocarbon-water conversion reactor, 6 first
Heat exchanger, 7 depth methanators, 8 second heat exchangers, 9 gas-liquid separators, 10 membrane separators, 11 methane storing tanks.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
The present embodiment provides a kind of devices of skid-mounted type lower carbon number hydrocarbons production methane, as shown in Figure 1, the skid-mounted type lower carbon number hydrocarbons is raw
The device of methane phase includes the first feed pump 1, the second feed pump 2, fine de-sulfur reactor 3, heating furnace 4, hydrocarbon-water conversion reactor
5, First Heat Exchanger 6, depth methanator 7, the second heat exchanger 8, gas-liquid separator 9, membrane separator 10 and methane storing
Tank 11；
First feed pump 1 is connected with fine de-sulfur reactor 3, and fine de-sulfur reactor 3 is connected with heating furnace 4, second into
Material pump 2 is connected with heating furnace 4, and heating furnace 4 is connected with hydrocarbon-water conversion reactor 5, and hydrocarbon-water conversion reactor 5 is changed with first
Hot device 6 is connected, and First Heat Exchanger 6 is connected with depth methanator 7, depth methanator 7 and the second heat exchange
Device 8 is connected, and the second heat exchanger 8 is connected with gas-liquid separator 9, the gas outlet end and membrane separator 10 of gas-liquid separator 9
Be connected, the methane outlet end of membrane separator 10 is connected with methane storing tank 11, the offgas outlet end of membrane separator 10 with plus
Hot stove 4 is connected.
Fine de-sulfur reactor 3 is internally provided with desulfurizing agent bed, is mounted with Cu/ molecular sieve sweetneing on the desulfurizing agent bed
Agent, the trade mark of the Cu/ molecular sieve desulfurizer are SQ-108；Hydrocarbon-water conversion reactor 5 is internally provided with reforming catalyst bed,
The reforming catalyst bed is mounted with unreduced Ni/Al2O3Catalyst, the unreduced Ni/Al2O3In catalyst
The content of nickel oxide is more than or equal to 60%, remaining is aluminium oxide；Depth methanator 7 is internally provided with methanation catalyst
Bed, the methanation catalyst bed are mounted with unreduced Ni/La2O3/Al2O3Catalyst, the unreduced Ni/
La2O3/Al2O3The content of nickel oxide is more than or equal to 50% in catalyst, and the content of lanthana is 3%, remaining is aluminium oxide；Film
The film used in separator 10 is Polyimide Hollow Fiber.
In the present embodiment, unreduced Ni/Al2O3Catalyst the preparation method comprises the following steps:
Nickel nitrate, aluminum nitrate are weighed by Ni:Al atomic ratio 1:1 batching metering, and nickel nitrate and aluminum nitrate gross mass is added
2% sesbania powder and water is configured to the mixed solution A that concentration of metal ions is 1-2mol/L；
Urea is added into mixed solution, the urea amount of addition is measured by molal quantity are as follows: n (CO (NH2)2)=1.2 × [n
(Ni)+1.5n (Al)], it stirs to dissolve, is subsequently placed in the reflux unit with heating, is heated to 100 DEG C while stirring, and
It is kept for 24 hours, decomposes urea slowly and nickel ion and aluminium ion are precipitated as uniform mixture B；
Sufficiently after precipitating, stop heating, after solution is cooling, using plate and frame filter press filters pressing and with the bodies such as mixture B
Long-pending deionized water washing precipitating obtains filter cake three times；
Filter cake is put into baking oven, 80 DEG C is warming up to from room temperature by the speed of 1 DEG C/min, drying is kept in circulating air
12 hours, obtain Ni/Al2O3Catalyst precarsor；
By the Ni/Al after drying2O3Catalyst precarsor in the graphite powder of its quality 1% and 2% sesbania powder is added, into
Row is squeezed, is granulated, and then beating sheetmolding is 6 × 6mm cylindrical particle, is then warming up to 650 DEG C according to the speed of 5 DEG C/min,
It is kept for temperature calcination 12 hours, Temperature fall, so that unreduced Ni/Al be prepared2O3Catalyst.It, will when being catalyzed
It is loaded on reforming catalyst bed and is reduced into Ni/Al by conventional method2O3Catalyst.
In the present embodiment, unreduced Ni/La2O3/Al2O3Catalyst the preparation method comprises the following steps:
Using boehmite as raw material, 950 DEG C are warming up to by the speed of 5 DEG C/min and is roasted 6 hours, Temperature fall obtains height
The aluminium oxide of temperature preparation；
Use nickel nitrate and lanthanum nitrate according to Ni:La atomic ratio 36:1 for the solution for being configured to 2mol/L, using ammonium carbonate
Precipitating is warming up to 350 DEG C after filtering with the speed of 5 DEG C/min, is kept for 6 hours, then Temperature fall obtains nickel lanthanum-oxides；
The aluminium oxide of high temperature preparation and nickel lanthanum-oxides 50:50 in mass ratio are mixed to get mixed liquor C, then according to mixed
1% graphite powder and 2% sesbania powder is added in the quality for closing liquid C, is put into ball milling 2 hours in ball mill, after being sufficiently mixed, beats piece
It is shaped to 6 × 6mm cylindrical particle；
Molding cylindrical particle ball is warming up to 550 DEG C with the speed of 5 DEG C/min, is kept for temperature calcination 12 hours, so
Temperature fall afterwards obtains unreduced Ni/La2O3/Al2O3Catalyst.When being catalyzed, it is loaded into methanation catalyst
It is reduced into Ni/La by conventional method on agent bed2O3/Al2O3Catalyst.
Embodiment 2
The present embodiment provides a kind of techniques of lower carbon number hydrocarbons production methane, use the skid-mounted type low-carbon provided in embodiment 1
The device that hydrocarbon produces methane carries out, and lower carbon number hydrocarbons is liquefied petroleum gas in the present embodiment, the technique the following steps are included:
Liquefied petroleum gas is delivered to fine de-sulfur reaction according to 820kg/h mass flow by the first feed pump 1 by step 1
Carry out desulfurization process on desulfurizing agent bed inside device 3, after desulfurization process, in liquefied petroleum gas total sulfur content by
55.9ppm dropping to 0.8ppm；
Step 2, the liquefied petroleum gas after desulfurization process mix defeated together with the water conveyed via the second feed pump 2
It send to heating furnace 4 and carries out heating heating, the feed rate of water is 1000kg/h, and the feed pressure for controlling mixture is 1MPa, is risen
Catalysis reaction is carried out on the reforming catalyst bed that the mixture that temperature is heated to 370 DEG C is delivered in hydrocarbon-water conversion reactor 5,
Reaction carries out under adiabatic conditions, CH in dry gas ingredient in obtained synthesis gas469.1%, CO219%, CO 0.6%, H2
11.3%, more vapor is also contained in the synthesis gas, synthesis gas temperature is 455 DEG C；
Synthesis gas is cooled to after 250 DEG C via First Heat Exchanger 6 and is delivered in depth methanator 7 by step 3
Methanation catalyst bed on carry out catalysis reaction, further urge the carbon monoxide in synthesis gas, carbon dioxide and hydrogen
Change is converted into methane, obtains the gaseous mixture of methane and tail gas, CH in middle outlet dry gas ingredient478.5%, CO218.8%,
CO 0.2%, H22.4%, water content 36.7%, temperature is 320 DEG C；
Step 4 is delivered in gas-liquid separator 9 after gaseous mixture cools down via the second heat exchanger 8 and is carried out dehydrating,
Dehydrating amount is 600kg/h；
Step 5 is delivered in membrane separator 10 by dewatered gaseous mixture and is further separated out about 950Nm3The first of/h
The tail gas of alkane gas and surplus, methane gas are delivered in methane storing tank, and tail gas is delivered to burning recycling heat in heating furnace.
Embodiment 3
The present embodiment provides a kind of techniques of lower carbon number hydrocarbons production methane, use the skid-mounted type low-carbon provided in embodiment 1
The device that hydrocarbon produces methane carries out, and lower carbon number hydrocarbons is casing-head gas in the present embodiment, the technique the following steps are included:
Certain casing-head gas is delivered to fine de-sulfur reaction according to 1000kg/h mass flow by the first feed pump 1 by step 1
Desulfurization process is carried out on desulfurizing agent bed inside device 3, after desulfurization process, total sulfur content is dropped to by 30ppm in casing-head gas
0.7ppm；
Step 2, the casing-head gas after desulfurization process is mixed with the water conveyed via the second feed pump 2 to be delivered to together
Heating furnace 4 carries out heating heating, and the feed rate of water is 2000kg/h, and the feed pressure for controlling mixture is 3MPa, and heating adds
Catalysis reaction is carried out on the reforming catalyst bed that the mixture of heat to 350 DEG C is delivered in hydrocarbon-water conversion reactor 5, is reacted
It carries out under adiabatic conditions, CH in dry gas ingredient in obtained synthesis gas471.4%, CO220.3%, CO 0.2%, H2
8.1%, more vapor is also contained in the synthesis gas, synthesis gas temperature is 430 DEG C；
Synthesis gas is cooled to after 300 DEG C via First Heat Exchanger 6 and is delivered in depth methanator 7 by step 3
Methanation catalyst bed on carry out catalysis reaction, further urge the carbon monoxide in synthesis gas, carbon dioxide and hydrogen
Change is converted into methane, obtains the gaseous mixture of methane and tail gas, CH in middle outlet dry gas ingredient477.4%, CO220.1%,
CO 0.02%, H22.4%, water content 53.7%, temperature is 330 DEG C；
Step 4 is delivered in gas-liquid separator 9 after gaseous mixture cools down via the second heat exchanger 8 and is carried out dehydrating,
Dehydrating amount is 1400kg/h；
Step 5 is delivered in membrane separator 10 by dewatered gaseous mixture and is further separated out about 1170Nm3/ h's
The tail gas of methane gas and surplus, methane gas are delivered in methane storing tank, and tail gas is delivered to burning recycling heat in heating furnace
Amount.
Embodiment 4
The present embodiment provides a kind of techniques of lower carbon number hydrocarbons production methane, use the skid-mounted type low-carbon provided in embodiment 1
The device that hydrocarbon produces methane carries out, and lower carbon number hydrocarbons is naphtha in the present embodiment, the technique the following steps are included:
It is anti-by the first feed pump 1 to be delivered to fine de-sulfur according to 1200kg/h mass flow by step 1 for liquefied petroleum gas
It answers and carries out desulfurization process on the desulfurizing agent bed inside device 3, after desulfurization process, total sulfur content is dropped by 70ppm in naphtha
To 0.9ppm；
Step 2, the naphtha after desulfurization process is mixed with the water conveyed via the second feed pump 2 to be delivered to together
Heating furnace 4 carries out heating heating, and the feed rate of water is 2000kg/h, and the feed pressure for controlling mixture is 5MPa, and heating adds
Catalysis reaction is carried out on the reforming catalyst bed that the mixture of heat to 360 DEG C is delivered in hydrocarbon-water conversion reactor 5, is reacted
It carries out under adiabatic conditions, CH in dry gas ingredient in obtained synthesis gas471.8%, CO221.9%, CO 0.2%, H2
6.1%, more vapor is also contained in the synthesis gas, synthesis gas temperature is 440 DEG C；
Synthesis gas is cooled to after 280 DEG C via First Heat Exchanger 6 and is delivered in depth methanator 7 by step 3
Methanation catalyst bed on carry out catalysis reaction, further urge the carbon monoxide in synthesis gas, carbon dioxide and hydrogen
Change is converted into methane, obtains the gaseous mixture of methane and tail gas, CH in middle outlet dry gas ingredient477%, CO221.9%, CO
0.01%, H21.1%, water content 49.7%, temperature is 310 DEG C；
Step 4 is delivered in gas-liquid separator 9 after gaseous mixture cools down via the second heat exchanger 8 and is carried out dehydrating,
Dehydrating amount is 1300kg/h；
Step 5 is delivered in membrane separator 10 by dewatered gaseous mixture and is further separated out about 1250Nm3/ h's
Methane gas and tail gas, methane gas are delivered in methane storing tank, and tail gas is delivered to burning recycling heat in heating furnace.
In conclusion the device of skid-mounted type lower carbon number hydrocarbons provided by the invention production methane has, raw material is easily stored, device
The features such as small in size, conveniently moving, it is easy to modularization, is suitble to skid design, easily designed manufacture and commercial applications；Simultaneously originally
Invention has high production efficiency using the technique that the device carries out lower carbon number hydrocarbons production methane, and methane conversion is high, up to 97% with
On, product calorific value is high, can produce on demand, and it is flexible and convenient to use, it is suitable for distributed energy and peak regulation, it both can be with biofermentation
Methane processed is complementary, and it is defeated but need place using clean energy resource to can be used for being not easy to pipe.
Claims (11)
1. a kind of device of skid-mounted type lower carbon number hydrocarbons production methane, it is characterised in that: the device of skid-mounted type lower carbon number hydrocarbons production methane
Including the first feed pump, the second feed pump, fine de-sulfur reactor, heating furnace, hydrocarbon-water conversion reactor, depth methanation reaction
Device, gas-liquid separator and membrane separator；
First feed pump is connected with the fine de-sulfur reactor, and the fine de-sulfur reactor is connected with the heating furnace
Logical, second feed pump is connected with the heating furnace, the heating furnace, the hydrocarbon-water conversion reactor, the depth first
Alkylation reactors and the gas-liquid separator are sequentially connected logical, the gas outlet end of the gas-liquid separator and the membrane separator
It is connected, the methane outlet end of the membrane separator generates methane, the offgas outlet end of the membrane separator and the heating furnace
It is connected；
The device of the skid-mounted type lower carbon number hydrocarbons production methane further includes First Heat Exchanger and the second heat exchanger, the hydrocarbon-water conversion
The outlet end of reactor is connected with the First Heat Exchanger, and the First Heat Exchanger is connected with the depth methanator
Logical, the depth methanator is connected with second heat exchanger, second heat exchanger and the gas-liquid separator
It is connected；
The device of skid-mounted type lower carbon number hydrocarbons production methane further includes methane storing tank, the methane outlet end of the membrane separator with
The methane storing tank is connected；
Wherein, the fine de-sulfur inside reactor is provided with desulfurizing agent bed, is mounted with Cu/ molecular sieve on the desulfurizing agent bed
Desulfurizing agent；
The hydrocarbon-water conversion reactor is internally provided with reforming catalyst bed, the reforming catalyst bed be mounted with without
The Ni/Al of reduction2O3Catalyst；
The unreduced Ni/Al2O3Catalyst is prepared by following preparation method:
Nickel nitrate, aluminum nitrate are weighed, sesbania powder is added and desalted water is configured to mixed solution A；Urine is added into mixed solution A
Element stirs to dissolve, and is subsequently placed in the reflux unit with heating, heats while stirring, decomposes urea slowly and by nickel
Ion and aluminium ion are precipitated as uniform mixture B；Sufficiently after precipitating, stop heating, after solution is cooling, using plate compression
Machine filters pressing is simultaneously washed with water precipitating and obtains filter cake；Filter cake is dried to obtain Ni/Al2O3Catalyst precarsor；To the Ni/ after drying
Al2O3Catalyst precarsor in graphite powder and sesbania powder is added, squeezed, be granulated, then beating sheetmolding is particle and the roasting that heats up
It burns, Temperature fall obtains unreduced Ni/Al2O3Catalyst；
The depth methanator is internally provided with methanation catalyst bed, and the methanation catalyst bed is mounted with
Unreduced Ni/La2O3/Al2O3Catalyst；
The unreduced Ni/La2O3/Al2O3Catalyst is prepared by following preparation method:
It is roasted by raw material of boehmite, Temperature fall obtains the aluminium oxide of high temperature preparation；Using nickel nitrate and nitric acid
Lanthanum is configured to solution, is precipitated using ammonium carbonate, and heating heating is carried out after filtering, and then Temperature fall obtains nickel lanthanum-oxides；It will
The aluminium oxide and nickel lanthanum-oxides of high temperature preparation are mixed to get mixture C, graphite powder and sesbania powder are then added, and be put into ball milling
Ball milling in machine, after being sufficiently mixed, beating sheetmolding is particle；Molding particle ball is roasted, then Temperature fall, obtains not
Ni/La through restoring2O3/Al2O3Catalyst.
2. the device of skid-mounted type lower carbon number hydrocarbons production methane according to claim 1, it is characterised in that: described unreduced
Ni/Al2O3The content of nickel oxide is more than or equal to 60% in catalyst, remaining is aluminium oxide.
3. the device of skid-mounted type lower carbon number hydrocarbons production methane according to claim 1, it is characterised in that: described unreduced
Ni/Al2O3Catalyst is prepared by following preparation method:
Nickel nitrate, aluminum nitrate are weighed by Ni:Al atomic ratio 1:1 batching metering, and nickel nitrate and aluminum nitrate gross mass 2% is added
Sesbania powder and desalted water are hybridly prepared into the mixed solution A 1 that concentration of metal ions is 1-2mol/L；
Urea is added into mixed solution A 1, the urea amount of addition is measured by molal quantity are as follows: n (CO (NH2)2)=1.2 × [n (Ni)
+ 1.5n (Al)], it stirs to dissolve, is subsequently placed in the reflux unit with heating, is heated to 100 DEG C while stirring, and keep
It 24 hours, decomposes urea slowly and nickel ion and aluminium ion is precipitated as uniform mixture B1；
Sufficiently after precipitating, stop heating, it is isometric using plate and frame filter press filters pressing and with mixture B1 after solution is cooling
Deionized water washing precipitating obtains filter cake three times；
Filter cake is put into baking oven, is warming up to 80 DEG C from room temperature with the speed of 1 DEG C/min, keeps drying 12 small in circulating air
When, obtain Ni/Al2O3Catalyst precarsor；
To the Ni/Al after drying2O3Catalyst precarsor in the graphite powder of its quality 1% and 2% sesbania powder is added, squeezed
Pressure is granulated, and then beating sheetmolding is 6 × 6mm cylindrical particle, is then warming up to 650 DEG C with the speed of 5 DEG C/min, keeps temperature
Degree roasting 12 hours, Temperature fall obtains unreduced Ni/Al2O3Catalyst.
4. the device of skid-mounted type lower carbon number hydrocarbons production methane according to claim 1, it is characterised in that: described unreduced
Ni/La2O3/Al2O3The content of nickel oxide is more than or equal to 50% in catalyst, and the content of lanthana is 3%, remaining is aluminium oxide.
5. the device of skid-mounted type lower carbon number hydrocarbons production methane according to claim 1, it is characterised in that: described unreduced
Ni/La2O3/Al2O3Catalyst is prepared by following preparation method:
Using boehmite as raw material, 950 DEG C are warming up to the speed of 5 DEG C/min and is roasted 6 hours, Temperature fall obtains high temperature system
Standby aluminium oxide；
Nickel nitrate and lanthanum nitrate is used, for the solution for being configured to 2mol/L, to precipitate using ammonium carbonate according to Ni:La atomic ratio 36:1,
350 DEG C are warming up to the speed of 5 DEG C/min after filtering, is kept for 6 hours, then Temperature fall obtains nickel lanthanum-oxides；
The aluminium oxide of high temperature preparation and nickel lanthanum-oxides 50:50 in mass ratio are mixed to get mixture C 1, then according to mixing
1% graphite powder and 2% sesbania powder is added in the quality of object C1, is put into ball milling 2 hours in ball mill, after being sufficiently mixed, beats piece
It is shaped to 6 × 6mm cylindrical particle；
Molding cylindrical particle is warming up to 550 DEG C with the speed of 5 DEG C/min, is kept for temperature calcination 12 hours, it is then natural
Cooling, obtains unreduced Ni/La2O3/Al2O3Catalyst.
6. the device of skid-mounted type lower carbon number hydrocarbons production methane according to claim 1, it is characterised in that: in the membrane separator
The film used is Polyimide Hollow Fiber.
7. a kind of technique of lower carbon number hydrocarbons production methane uses any one of claim 1-6 skid-mounted type lower carbon number hydrocarbons production first
The device of alkane carries out, comprising the following steps:
Lower carbon number hydrocarbons is delivered on the desulfurizing agent bed of fine de-sulfur inside reactor by the first feed pump and carries out desulfurization by step 1
Processing makes total sulfur content be less than 1ppm；
Step 2, the lower carbon number hydrocarbons after desulfurization process is mixed with the water conveyed via the second feed pump is delivered to heating furnace together
Heating heating is carried out, is carried out on the reforming catalyst bed that the mixture after heating is delivered in hydrocarbon-water conversion reactor
Catalysis reaction, reaction carry out under adiabatic conditions, obtain the synthesis gas containing methane, carbon monoxide, carbon dioxide and hydrogen；
Step 3, the methanation catalyst being delivered to after synthesis gas is cooled down via First Heat Exchanger in depth methanator
Catalysis reaction is carried out on bed, so that the carbon monoxide in synthesis gas, carbon dioxide and hydrogen catalytic is converted into methane, is obtained
To the gaseous mixture of methane and tail gas；
Step 4 is delivered in gas-liquid separator after gaseous mixture cools down via the second heat exchanger and is carried out dehydrating；
Step 5 is delivered in membrane separator by dewatered gaseous mixture and is further separated out methane gas and tail gas, methane
Gas is delivered in methane storing tank, and tail gas is delivered to burning recycling heat in heating furnace.
8. the technique of lower carbon number hydrocarbons production methane according to claim 7, it is characterised in that: the hydrocarbon-water conversion reactor
The temperature of interior catalysis reaction is 350-550 DEG C, and pressure is normal pressure to 6MPa, carbon space velocity 300-3000h-1, steam/hydrocarbons ratio is (1-
4):1。
9. the technique of lower carbon number hydrocarbons production methane according to claim 7, it is characterised in that: the depth methanator
The temperature of interior catalysis reaction is 240-650 DEG C, and pressure is normal pressure to 6MPa, carbon space velocity 1000-3000h-1, steam/hydrocarbons ratio is (1-
4):1。
10. the technique of lower carbon number hydrocarbons production methane according to claim 7, it is characterised in that: the First Heat Exchanger cooling
After processing, the temperature of synthesis gas is 250-300 DEG C.
11. the technique of lower carbon number hydrocarbons production methane according to claim 7, it is characterised in that: the lower carbon number hydrocarbons is C4-C10's
Lightweight saturated hydrocarbons.
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| JPH0613720B2 (en) * | 1985-12-27 | 1994-02-23 | 日揮株式会社 | Method for producing methane gas |
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|---|---|---|---|---|
| US4280820A (en) * | 1977-07-11 | 1981-07-28 | British Gas Corporation | Steam reforming process |
| CN1034530A (en) * | 1987-12-17 | 1989-08-09 | 大阪瓦斯株式会社 | The process for steam-reforming of hydro carbons |
| CN1301666A (en) * | 1999-12-29 | 2001-07-04 | 中国石化集团齐鲁石油化工公司 | Steam preconversion catalyst for hydrocarbon |
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