CN105312056B - Catalyst based on natural minerals and the gasification process using the catalyst - Google Patents
Catalyst based on natural minerals and the gasification process using the catalyst Download PDFInfo
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- CN105312056B CN105312056B CN201510363883.7A CN201510363883A CN105312056B CN 105312056 B CN105312056 B CN 105312056B CN 201510363883 A CN201510363883 A CN 201510363883A CN 105312056 B CN105312056 B CN 105312056B
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- natural minerals
- gasification
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 238000002309 gasification Methods 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000011707 mineral Substances 0.000 title claims abstract description 62
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 60
- 230000008569 process Effects 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims description 86
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- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 44
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 43
- 239000010457 zeolite Substances 0.000 claims description 43
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- 239000000470 constituent Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
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- 239000002243 precursor Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
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- 239000006028 limestone Substances 0.000 description 3
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Classifications
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Abstract
It is basic carrying active ingredients with the gasifying catalyst with specific composition range and the gasification process by the way that the catalyst is applied to fluidized bed gasification reactor to not only improve gasification reactivity but also can be easily separated and recycle catalyst that embodiment of the present invention, which is provided with natural minerals,.
Description
Technical field
The present invention relates to the catalyst based on natural minerals and utilize the gasification process of the catalyst.More specifically
Say, the present invention relates to natural minerals be basic carrying active ingredients with specific composition range gasifying catalyst and utilization
The fluidized bed gasification method of the catalyst.
Background technique
Recently, with the exhaustion of petroleum resources, demand efficiently uses the production high added value chemistry such as coal, particularly rudimentary carbon
The method of product, for this purpose, typically gasification process is attracted attention.
In general, gasification process refers to, in supply gasifying agent (for example, oxygen, steam, carbon dioxide or their mixture)
Under the conditions of, react the carbonaceous such as coal, biomass (carbonaceous) raw material, to be converted to principal component by hydrogen and carbon monoxide
The series of process of the synthetic gas of composition.At this point, so-called term " synthetic gas " typically refers to, generated by gasification reaction
Contain CO and H2As the mixed gas of principal component, CH can be further included4And/or CO2。
Gasification process technique extension is the technology for producing the raw material and fuel of multiple compounds, and application range gradually expands
To the multiple product including power generation can be produced.Such as it is known that it can use the synthesis gas of the principal product as gasification process
Hydrogen in body is applied to hydrogen gas generation, ammonia manufacture, oil refining process etc., and synthetic gas can be used and be used as by following reaction equations 1
The raw material of Fischer-Tropsch (Fischer-Tropsch) reaction of expression, to manufacture diesel oil, jet fuel, lube base oil, naphtha
Deng furthermore it is possible to obtain acetic acid, alkene, dimethyl ester, aldehydes, combustion using the methanol manufactured according to reaction equation 2 by synthetic gas
The high added values chemical substance such as material and additive.About this, in the case where Fischer-tropsch process and methanol synthesizing process, CO：H2's
Ratio is preferably from about 1：2 or so.
[reaction equation 1]
nCO+2nH2→CnH2n+nH2O
[reaction equation 2]
CO+2H2→CH3OH
However, in the case where the synthetic gas generated by gasification reaction, usual CO：H2Ratio be not achieved 1:2,
Therefore to gasification reaction product further progress water gas shift reaction (Water-Gas Shift reaction) or further
Supply hydrogen and by CO:H2Ratio be adjusted to 1:2.
On the other hand, there are a large amount of points in global extensive area as the coal of the representative base feed of gasification process
Cloth, therefore attract attention again as the currently fuels sources of widely used petroleum exhaustion can be replaced.In addition, recently by
The base oil component of various fuel and platform chemicals can also be provided by a variety for the treatment of process to the biomass attracted attention, this
Also it is applied as the raw material of gasification reaction.
Recently, implement the gasification process using catalyst gasification mode, typically such as under type：By alkali metal (K2CO3、
Na2CO3And Li2CO3) series alkali metal salt attachment (load) in coal, be then passed through and the preprocessing process such as dry and put into gasification
In device (U.S. Patent No. 4,318,712, U.S. Patent Publication No. the 2007/0000177th etc.).But above-mentioned catalysis
Agent gasification process due to alkali metal salt eutectic dot characteristics and need to be operated in low temperature, for example at 700 DEG C or so, its with
On at a temperature of due to ash content (ash) agglomerate and be difficult to be operated continuously.
In addition, the price of catalyst is relatively high, it is therefore necessary to recycle catalyst.But in order to recycle to be segregated with ash
The alkali metal salt of poly- state discharge, needing to be implemented multiple subsequent techniques, (hot water extracts (hot-water extraction), stone
Ash digestion (lime digestion) etc.) (U.S. Patent No. 7,922,782 etc.).
In this way, previous catalyst gasification process due to using alkali metal salt etc. as catalyst component due to existing and ash
The poly- tendency of fractional condensation, therefore carry out operating aspect under high-temperature gasification reaction condition and there is limitation.This, which becomes limitation, improves gasification
The factor of performance.
On the other hand, due in addition to H in gasification reaction product2With also contain CO except CO2, therefore from environmental protection side
Face considers, preferably inhibits discharge CO as far as possible2Gasification process.About this, although can by make the carbon in base feed at
Divide and carries out CO2Gasification reaction and be converted into H2The CO in synthetic gas be discharged is reduced with the methods of CO2, but CO2Gasification
Reaction usually causes positive reaction at a high temperature of 1200 DEG C or more, it is therefore desirable to improve gasification reaction temperature.However, institute as above
It states, in the case where using alkali metal salt as catalyst, needs to carry out gasification reaction at low temperature, therefore reducing CO2Row
There is limitation in terms of output.
Summary of the invention
One embodiment of the invention can not only provide the limitation for overcoming conventional art and also can at high temperature
The technique for showing excellent gasification reactivity, and the technology that can be easily separated and recycle catalyst is provided.Additionally
Offer is able to suppress from gasification process and CO is discharged2Technology.
According to first scheme, a kind of gasifying catalyst is provided, is to contain 15~25 weights on the basis of catalyst weight
Measure the MgO of %, the Fe of 25~35 weight %2O3And 10~20 weight % K2The gasification reaction catalyst of O, selected from by day
On at least one of the group of right zeolite, olivine (olivine) and dolomite (dolomite) the composition particle of natural minerals
Load MgO, Fe2O3And K2At least one of O is formed.
According to alternative plan, a kind of manufacturing method of gasifying catalyst is provided comprising：There is provided selected from by natural zeolite,
The step of natural minerals original stone of at least one of the group of olivine and dolomite composition；The natural minerals original stone is crushed
And the step of natural minerals particle is provided；And according to containing 15~25 weight % on the basis of the catalyst weight MgO,
The Fe of 25~35 weight %2O3And 10~20 weight % K2The mode of O makes selected from by MgO, Fe2O3And K2In the group of O composition
At least one active constituent is carried on the step on natural minerals particle.
According to third program, a kind of catalyst gasification process is provided comprising following steps：It is as with catalyst weight
Benchmark contains the Fe of the MgO of 15~25 weight %, 25~35 weight %2O3And 10~20 weight % K2The gasification reaction of O is catalyzed
Agent is born using on the particle selected from least one of the group being made of natural zeolite, olivine and dolomite natural minerals
Carry MgO, Fe2O3And K2Catalyst made of at least one of O is as bed material or at least part of quicksand, in fluidized bed gas
Changing makes carbonaceous base feed gasify in reactor.
One embodiment of the invention provide gasifying catalyst based on natural minerals further supplement activity at
Point with specific composition, may be implemented replace high price alkali metal salt catalyst and improve gasification reactivity technique (in particular,
High-temperature gasification technique).In turn, it in the case where being applied to fluidized-bed gasifier, has the following advantages that：It can be to replace bed material
The mode application of (or quicksand) can be easy the ash separation for generating it from gasification reaction and carry out recycling or sharp again
With.
Therefore, extensive commercialization will be expected from now on.
Detailed description of the invention
Fig. 1 diagrammatically shows and is pre-processed in one embodiment in order to make natural minerals can be used as catalyst
Illustrative steps；
Fig. 2 is the artwork for diagrammatically showing the fluidized bed gasifying process according to exemplary implementation scheme；
Fig. 3 a is the CO shown by using the catalyst manufactured respectively according to Examples 1 to 3 and comparative example 12Gas
Change CO conversion reaction speed (r obtained from reaction experimentCO) figure, Fig. 3 b is to show using respectively according to embodiment 1
~3 and comparative example 1 manufacture catalyst CO2By CO when gasification reaction is tested2Influx maintains persistently to supply while constant level
The CO measured with time going by the case where giving2The figure of discharge rate；
Fig. 4 a~Fig. 4 d will have been used respectively according to the CO of the methane of the catalyst of Examples 1 to 3 manufacture2Modified-reaction
Experimental result (CO2、CO、H2And CH4Composition variation) figure that is compared with ASPEN analog result；
Fig. 5 is the D of the partial size of the ash content and catalyst that are discharged after the gasification reaction shown according to embodiment 650Point
The figure of cloth characteristic；
Fig. 6 diagrammatically shows the mixing of the ash content and catalyst that are discharged after the gasification reaction according to embodiment 6
Object recycles the illustrative steps of catalyst according to density and the difference of partial size, magnetic force；And
Fig. 7 is to show the gas sent as an envoy to and carried out according to the catalyst i.e. MNZ04 catalyst that embodiment 4 manufactures according to embodiment 7
After changing reaction, using Particle Size Analyzer, the grain size analysis that the MNZ04 catalyst and ash content by means of magnetic separation are measured
As a result figure.
Specific embodiment
The present invention may be implemented by following explanations.It should be appreciated that following explanations is for describing the present invention excellent
Embodiment is selected, the present invention is not necessarily limited to this.Furthermore it should be appreciated that attached drawing is to be used to help understand the present invention, the present invention
It is not limited to this.
In this specification, " gasification (gasification) " refers to as broad sense in gasifying agent (air, oxygen, steam, dioxy
Change carbon or their mixture) in the presence of by the thermochemical study technique of the altered chemical structure of carbonaceous material, as narrow
Justice is the technique for instigating carbonaceous material to be converted mainly into synthetic gas.
" fluidized-bed gasifier " can refer to the reaction gas due to flowing up and solidify bed (bed material) with suspended state
Flow and mix and cause the reactor of gasification reaction, be generally divided into bubbling fluidized bed (bubbling fluidized bed) and
The gasifier of recirculating fluidized bed (circulating fluidized bed) type.
Gasification reaction catalyst according to an embodiment can be make active constituent (alkali metal, alkaline-earth metal and/or
Transition metal) load or the particle shape that is attached on natural minerals (for example, natural zeolite, dolomite and/or olivine) particle
The catalyst of state.
According to specific embodiment, the type and load capacity of the adjustable active constituent being carried in natural minerals make
Obtain (in particular about 18~23 weight %, more specifically about 20~22 that above-mentioned gasifying catalyst contains about 15~25 weight %
Weight %) MgO, 25~35 weight % (in particular about 26~34 weight %, more specifically about 27~31 weight %) Fe2O3、
And 10~20 weight % (in particular about 11~18 weight %, more specifically about 12~15 weight %) K2O。
It can be with according to following anti-according to the gasification reaction executed in the presence of the gasifying catalyst of the embodiment above
Answer the reaction of formula 3~8.
[reaction equation 3]
C+1/2O2→ CO (partial oxidation of carbon)
[reaction equation 4]
C+H2O→CO+H2(aqueous vapor of carbon is reacted)
[reaction equation 5]
C+CO2→ 2CO (carbon dioxide gasification of carbon reacts)
[reaction equation 6]
H2+CO2→CO+H2O (inverse water gas shift reaction)
[reaction equation 7]
CH4+H2O→CO+3H2(the steam modified-reaction of methane)
[reaction equation 8]
CH4+CO2→2CO+2H2(the carbon dioxide modified-reaction of methane)
Active constituent (MgO, Fe in catalyst based on by by natural minerals2O3And K2O it) is adjusted to respectively specific
In the case where content range, (it can be generated by the decomposition by macromolecule hydro carbons by the volatile ingredient contained in coal
CmHnDeng constituting) cracking and make the steam and/or CO of carbon2Gasification reaction is (that is, O2It is blown into H2O and/or CO2Gasification reaction)
Activity increase and the yield of synthetic gas can be increased.
In this way, residence time of the reactant in gasifier, therefore energy can be shortened when improving gasification reactivity
Enough reduce the size (dimension) of the riser (riser) in fluidized-bed gasifier and reduces equipment investment expense.Especially
It is, it, can be in high temperature compared with the case where using alkali metal salt catalyst due to based on the high natural minerals of fusing point
Lower realization gasification process.
In turn, though with for inducing common CO2(about 1200 DEG C or more) of reaction temperature of gasification reaction are compared to more
Low temperature region (or even about 850~950 DEG C), above-mentioned catalyst can also ensure that good CO2Gasification reactivity, furthermore
The CO of improvement methane can also be passed through2Modified reactivity reduces CO2Discharge rate.
On the other hand, according to specific embodiment, above-mentioned catalyst not only plays the effect for increasing gasification reactivity, and
And it can replace the bed material (bed material) or quicksand for playing the role of the heat transmission medium of existing fluidized bed gasification reactor
At least part, it might even be possible to instead of whole.That is, above-mentioned catalyst for example can replace the bed in fluidized bed gasification reactor
Expect at least about 50% (weight basis) in (quicksand), specifically at least about 70%, more specifically at least about 80%, it might even be possible to
Instead of 100%.According to exemplary implementation scheme, above-mentioned catalyst can have the size (d for being able to carry out solid circulation50), example
The size of such as from about 100~240 μm (in particular about 120~180 μm, more specifically about 130~150 μm) ranges, with can
It is enough to make bed material.
The advantages of above-mentioned catalyst, also resides in：Due to the natural minerals for using fusing point high, do not given birth to gasification reaction
At ash content ingredient agglomerate, and due to have for example, about 2~3.5 (in particular about 2.1~3, more specifically about 2.2~
2.8) high specific gravity of range, therefore can be easy in the rear end of gasification reactor from ash separation.Further, since can be used as flowing
The partial size of the catalyst of the bed material or quicksand of fluidized bed reactor is bigger than ash content, therefore further increases separative efficiency.
In addition to this, in an exemplary embodiment, the hardness (Mohs' hardness) of above-mentioned catalyst is although depend on conduct
The natural minerals of supporter, but for example, about 2~7 (in particular about 3~6, more specifically about 3.5~5.5, especially specifically
Ground is about 4~5) in the case where, being used as bed material (or quicksand), there is no problems.
Natural minerals
Natural zeolite
Natural zeolite is as the hydrous alumino silicates class mineral for containing a small amount of common cationic, in crystal structure (Si, Al)
O2Tetrahedral institute is aerobic public by another tetrahedron institute and dimensionally connects, and is formed about in crystalHole, in this way
The size in hole depend on the oxygen ring-shaped of the entrance formation of 4~12 oxygen with Si or Al ining conjunction in hole and the oxygen intervened
Number.Such characteristic is had any different with the clay etc. with layered crystal structure.So far, it is known that the type of natural zeolite has
About 46 seed types, they have architectural characteristic and chemical composition different from each other.Typically it is divided into clinoptilolite
(clinoptilolite), analcime (analcime), chabasie (chabazite), modenite (mordenite), hair boiling
Stone (erionite), faujasite (faujasite), heulandite (heulandite), phillipsite (phillipsite),
Ferrierite (ferrierite) etc..
For structure, natural zeolite has the crystal lattice indicated by the following general formula 1.
[general formula 1]
Mx/n[(AlO2)x(SiO2)y].wH2(wherein, n refers to the valence of cationic M to O, and x and y refer to the AlO in structure cell4
And SiO4The sum of tetrahedron (tetrahedra), w refer to moisture contained in zeolite).
In the general formula, x, y and the w about representative natural zeolite are as described in Table 1.
【Table 1】
| Zeolite | M | x | y | w |
| Chabasie | Ca | 4 | 8 | 13 |
| Modenite | Na | 8 | 40 | 24 |
| Erionite | Ca, Mg, Na2 or K2 | 9 | 27 | 27 |
| Faujasite | Ca, Mg, Na2 or K2 | 59 | 133 | 235 |
| Clinoptilolite | Na2 | 6 | 30 | 24 |
According to exemplary implementation scheme, can be used cation constituent (in particular alkali metal, more specifically Na and/
Or K) content (oxide benchmark) be, for example, at least about 5 weight %, be specifically at least about 7 weight %, more specifically about 7
The natural zeolite of~15 weight %.
According to specific embodiment, the Si/Al molar ratio of natural zeolite such as can be at least about 5, in particular at least
About 6, it more specifically can be about 5~6.5 range.In this way, being the natural boiling of certain level or more using Si/Al molar ratio
It is big for heat/acidic environment patience in the case where stone, therefore high-temperature gasification catalyst can be suitable as.As having in this way
The example of the natural zeolite of relatively high Si/Al molar ratio can enumerate clinoptilolite (clinoptilolite), modenite
(mordenite) and ferrierite (ferrierite), but the present invention is not necessarily limited to this.
According to exemplary implementation scheme, natural zeolite show about 2~6 (in particular about 3~5, more specifically about 4~
5) hardness (Mohs' hardness) of range, about 2~2.8 (in particular about 2.2~2.7, more specifically about 2.4~2.6) specific gravity,
And the fusing point (IDT) of at least about 1130 DEG C (in particular about 1135~1180 DEG C, more specifically about 1140~1170 DEG C).
Dolomite
" dolomite " is understood that as by chemical formula CaMg (CO3)2The natural minerals of composition or rock comprising it.According to
Situation, a part of Mg is by Fe2+Replace and forms Ca (Mg, Fe) (CO3)2Solid solution, for example, dolomite can be shown about
The hardness (Mohs' hardness) of 3~4 (in particular about 3.1~3.5, more specifically about 3.2~3.4), about 2.5~3.5 are (specifically
Be about 3~3.4, more specifically about 3.2~3.3) specific gravity (Fe of range2+More instead of the substitution amount of Mg, specific gravity also more increases),
And the fusing point (IDT) of about 1400~1480 DEG C (in particular about 1410~1470 DEG C, more specifically about 1420~1450 DEG C).
But dolomite does not exist in nature with oxide form, therefore in the case where wanting to be used as catalyst, such as
It is described afterwards, it is preferably calcined (calcination) processing and is converted to oxide form.
Olivine
Olivine can refer to fayalite (Fe2SiO4) and forsterite (Mg2SiO4) single formed solid solution mine
The group of object.Olivine belongs to typical mafic and Ultrabasic igneous rock mineral, belongs to orthorhombic system (orthorhombic), generally
It is produced with the bulk of grain structure or round particle.Workable olivine shows for example, about 6~7 (tools in the present embodiment
Be to body about 6~6.8, more specifically about 6.2~6.6) hardness (Mohs' hardness) of range, about 3.2~3.5 are (in particular about
3.25~3.4, more specifically about 3.3~3.35) specific gravity and about 1130~1170 DEG C (in particular about 1135~1160
DEG C, more specifically about 1140~1150 DEG C) fusing point (IDT).
Fig. 1 diagrammatically show in one embodiment in order to make natural minerals (in particular zeolite and olivine) use
Make catalyst and carries out pretreated illustrative steps.
As shown, can use known pulverizing tool in natural minerals original stone field, such as ball mill, paddle type mill powder
Broken machine, rod-toothed crusher (roller crasher), jaw crusher (Jaw crasher) etc., at least 1 time, specifically through 2 times
It is crushed.As shown, natural minerals can be ground into about 1 in the 1st pulverising step through 2 stage size reduction
~5mm (in particular about 2~3mm) and about 100~240 μm (in particular about 120 can be ground into the 2nd pulverising step
~180 μm) size.
Later, according to the type of zeolite and characteristic, in blocking (reduction) oxygen (air) or supply (oxidation) oxygen (air)
While, the pressure of about 0.5~5 atmospheric pressure (in particular normal pressure) and about 300~400 DEG C (in particular about 340~
360 DEG C) at a temperature of be heat-treated, so that it is guaranteed that supporter.It is sorted (or classification) and obtains to have and be suitable for being catalyzed
The particle of the size (for example, about 120~180 μm) of agent.At this point, natural minerals particle can use common sieve (sieve) or
Screening plant (for example, wire mesh screen etc.) is sorted (or classification).
Heat treatment process is to improve catalyst activity to be pyrolyzed crystal structure possessed by natural minerals, increases day
The specific surface area of right mineral particle and execute.At this point, after heat treatment, for the specific surface area of natural minerals particle, such as
It is at least about 50~90m in the case where zeolite2/ g (in particular about 60~80m2/ g, more specifically about 65~70m2/ g)
Range.It in addition, heat treatment time is not particularly limited, but substantially can be at least about 2 hours, in particular about 1.5~3 is small
When, more specifically about 2~2.5 hours.On the other hand, in the case where dolomite, due in nature in the form of carbonate
In the presence of, therefore preferably on one side for oxygen supply (air), on one side for example at about 800~1200 DEG C (in particular about 900~1000 DEG C)
Temperature under the conditions of be heat-treated (calcining).
According to optional embodiment, as described later, be intended to obtain from olivine the activity that is carried on natural minerals at
In the case where point, it can be ground into 1~5mm (in particular 2~3mm) by olivine original stone 1 time, and in the 2nd pulverising step
In be ground into the size of about 100~400 μm (in particular about 200~300 μm).
According to an embodiment, for manufacture catalyst natural minerals particle exemplary group at such as following table 2 institute
Show
【Table 2】
| Ingredient (wt%) | Natural zeolite | Dolomite (form after calcining) | Olivine |
| SiO2 | About 64~68 | About 1~3 | About 30~34 |
| Al2O3 | About 11~15 | About 0~1.5 | About 0~2 |
| Fe2O3 | About 2~6 | About 0~1 | About 28~32 |
| CaO | About 0.5~4.5 | About 55~65 | About 0~2 |
| MgO | About 0~2 | About 30~40 | About 33~37 |
| Na2O | About 1~5 | About 0~1 | About 0~1 |
| K2O | About 8.5~12.5 | About 0~1 | About 0~1 |
| It is other | About 0~1 | About 0~1 | About 0~1 |
As recorded in above-mentioned table, natural zeolite is with SiO2And Al2O3For principal component, contain a small amount of alkali metal oxide
(Na2O and K2O).On the other hand, dolomite mainly contains Ca and Mg, in addition, olivine mainly contains SiO2、Fe2O3And MgO.Cause
This, utilizes independent natural minerals, it is difficult to obtain simultaneously containing the Fe of certain level2O3, MgO and K2The catalyst of O forms.This reality
It applies in scheme, at least one of Fe, Mg and K ingredient can be made to be carried on natural minerals particle and meet desired activity
The content of ingredient.As the method for the load for passing through active constituent in this way, following 2 kinds of illustrative methods can be used.
According to an embodiment, the precursor solution that active constituent can be manufactured, by carrying method well known in the art,
Dipping (in particular wetness impregna-tion), ion exchange (for example, be recorded in U.S. Patent No. 3,140,249, the 3rd, 140,
In multiple documents such as No. 251, above-mentioned document is contained in the present invention with reference), spray drying etc., make above-mentioned active constituent
Precursor solution load (or attachment) is on natural minerals particle.As the precursor of active constituent, it can be used and be dissolvable in water solvent
The salt (for example, the inorganic salts such as the organic salts such as acetate, oxalates and/or nitrate) of the metal of (for example, water or organic solvent),
Hydride (hydrides), fluoride (fluorides), chloride (chlorides), bromide (bromides), iodide
(iodides), oxide (oxides), sulfide (sulfides), carbonyls (carbonyls), complex compound
(complexes) etc., but it is not necessarily limited to this.In specific embodiments, the precursor solution of above-mentioned active constituent can be
Metal salt (specifically, as water-soluble metal salt, such as there is into FeCl2、MgCl2Deng) it is dissolved in aqueous solution shape made of water
State.About this, the concentration of metal precursor in the solution for example can be about 1~10N (in particular about 2~8N, more specifically about
3~6N) range.
According to optional embodiment, olivine contains comparatively large number of Mg and Fe ingredient, correspondingly can be used
The dissolution fluid (leachate) that Mg and/or Fe ingredient dissolution (leaching) is obtained is carried on natural zeolite particle.About this, it is
The amount for adjusting loaded active constituent, a part of active constituent in dissolution fluid at least can locally be removed, example
Such as in order to reduce the Fe content in dissolution fluid, ammonium hydroxide can be added.
According to specific embodiment, can replace olivine makes ferronickel slag (Ferro- as steel plant's waste
Nickle Slag) it dissolves out and loads.Ferronickel slag is the slag generated during manufacturing the alloy of nickel and iron, such as following Table 3 institute
Show containing a large amount of MgO, additionally contains considerable amount of Fe2O3。
【Table 3】
| Ingredient | Content (wt%) |
| SiO2 | 51.3 |
| Al2O3 | 3.91 |
| Fe2O3 | 7.83 |
| CaO | 0.49 |
| MgO | 34.0 |
| Na2O | 0.36 |
| K2O | 0.07 |
| It is other | 0.03 |
As shown in the above Table, ferronickel slag is similar in terms of composition with olivine, therefore can use the dissolution fluid of ferronickel slag
Olivine is replaced, load liquid is obtained.
According to exemplary implementation scheme, by handling olivine or ferronickel slag by sour (for example, sulfuric acid, hydrochloric acid, nitric acid etc.),
Mg and/or Fe can be made to dissolve out.At this point, the concentration of acid for example can be about 1~10N, in particular about 2~8N, more specifically
The range of about 3~6N.
The partial size of olivine or ferronickel slag for example can be about 100~400 μm, in particular about 200~300 μm of model
It encloses.In addition, leaching temperature and time for example can be about 50~100 DEG C (in particular about 60~95 DEG C) and about 2~6 hours
(in particular about 3~5 hours).
In above-mentioned loading process, preferably make active constituent with particle (for example, being approximately less than equal to 3nm, in particular about
Partial size less than or equal to 2nm) form as far as possible uniformly or high degree of dispersion be carried on natural minerals particle surface.
If being utilized (i) metal precursor solutions or the dipping, ion exchange, spray drying of (ii) dissolution fluid etc. in this way
And meet the compositing range of desired active constituent, then precursor etc. can be made to turn by executing drying and calcination step later
Oxide form is turned to, gasifying catalyst is obtained.At this point it is possible to which drying temperature is adjusted to for example, about 80~120 DEG C (specifically
It is about 95~110 DEG C, more specifically about 100~105 DEG C), furthermore, it is possible to by calcination temperature under conditions of for oxygen supply (air)
It is adjusted to the range of for example, about 800~1200 DEG C (in particular about 900~1000 DEG C, more specifically about 940~960 DEG C), but
The present invention is not limited thereto.
On the other hand, as described above, having the bed for being suitable for fluidized-bed reactor in order to obtain after loading active constituent
Expect the catalyst of the size of (quicksand), additional sorting (or classification) process in the property of can choose ground.In this case, may be used
To use common sieve (sieve) or screening plant (for example, wire mesh screen etc.).
Gasification process
In this specification, " carbon raw material " is interpreted as solid phase, liquid phase comprising can be used for generating synthetic gas in a broad sense
And the carbonaceous material of gas phase.Such carbonaceous material is not necessarily limited to particular types, but can enumerate biomass (draft class,
The vegetable matters such as wooden class and animal matter), coal, organic waste, shale oil, coke, tar etc., can individually or
Two or more is applied in combination.As a result, hereinafter, although being illustrated centered on coal, present invention is obviously not limited to coals.
" coal " can be understood as including anthracite, bituminous coal (pitch coal, lignite, peat etc.), rudimentary active carbon etc..As a result,
Although being not limited to the coal of specific rank, from the aspect of improving economy, preferably (relatively waved using rudimentary coal as far as possible
Content height, the content of fixed carbon for sending out ingredient are low).
On the basis of all coal weight, the carbon content in coal for example can be about 20~about 90 weight %, be specifically about
The range of 30~about 80 weight %, more specifically about 40~about 70 weight %.In addition, coal may include example in terms of drying schedule
Such as from about it is less than or equal to the ash content of 20 weight %, in particular about 5~about 16 weight %, more specifically about 9~about 11 weight %
(ash) ingredient.Typically, silica, calcium oxide and iron oxide are contained with sizable ratio in above-mentioned ash content, and contained
The ingredients such as a small amount of potassium oxide, magnesia, titanium dioxide, zinc oxide.
In the case where rudimentary coal, due to containing largely (for example, about 10~70 weight %, in particular about 20~50
Weight %, more specifically about 20~40 weight %) moisture, therefore be preferably dried before being supplied to gasification reactor.
In addition, in order to successfully carry out conveying and gasification reaction, utilizing ball mill, hammering in advance to the property of can choose for coal
The pulverizing tools such as formula pulverizer, jaw crusher (Jaw crasher) and obtain particle, and led with the particle shape obtained in this way
Enter in drying machine.
On the other hand, the bed material of fluidized bed is formed in previous fluidized-bed gasifier by coal and quartz sand (silica
Sand) or lime stone (limestone) formation, but in the present embodiment, catalyst can replace previous bed material constitute at
Divide at least part (or even full dose) of (for example, quartz sand or lime stone as quicksand).In particular, the ratio of above-mentioned catalyst
Heat is about 1.4~1.43kJkg-1·K-1, it is identical as quartz sand specific heat or its more than, therefore be suitable as heat transmitting be situated between
Matter.
According to exemplary implementation scheme, in fluidized bed gasifying process, coal can be with the physical mixture shape with catalyst
State is introduced separately in gasification reactor.
In the case where physical mixture form, it can be and mixed coal particle and catalyst particle according to set ratio
Afterwards, by its to gasification reactor supply mode.At this point, the content of the catalyst particle in mixture for example can be about 10~
The range of 70 weight %, in particular about 10~60 weight %, more specifically about 20~40 weight %.
On the other hand, in the case where catalyst and coal to be separately supplied, from least one in gasifier, it is specifically
Multiple injection phases that gasifier has put into suitable catalyst.It is carried out with making alkali metal salt be impregnated in coal particle surface
The previous mode of load is compared, and such catalyst supply mode can largely simplify technique, and can mention
For following advantage：By making the investment position diversification of catalyst, optimal gasification process can be embodied.
On the other hand, gasification reaction temperature can for example, about 600~1100 DEG C, be specifically about 700~1000 DEG C, more
Specifically set in the range of about 850~950 DEG C.Reaction pressure is not particularly limited, but for example can be about 0.1~
4.5MPa, in particular 0.8~4MPa, the more specifically about range of 2.5~3.5MPa.
On the other hand, gasifying agent mainly includes steam, can contain aerobic or air (for example, passing through air-blowing), and then may be used also
Selectively to include a small amount of carbon dioxide.According to circumstances, the partial pressure tune using the inert gases such as nitrogen, argon gas can be passed through
Section, to adjust the quantity of steam in conversion zone.At this point, the supply ratio of steam/carbon such as can be about being less than with molar basis
Equal to 1.05, in particular about 0.51~1.03, more specifically about 0.6~0.7 range.
Typically, in steam gasification reaction path, the efficiency of carbon con version of coal can be typically at least about 80%, specifically
It is at least about 90%, more specifically at least about 97%.In addition, the H in the gas (synthetic gas) generated2/ CO molar ratio is such as
It can be about 0.3~about 0.7, more specifically about 0.4~0.6 range.
Fig. 2 diagrammatically shows the gasification process according to exemplary implementation scheme.
As shown in the above Fig., it will be supplied to pulverizer (1) along pipeline (100) as the coal of base feed, thus by making
At the coal particle of for example, about 50~6000 μm (in particular about 50~2000 μm, more specifically about 100~1000 μm).It will be above-mentioned
Smashed coal particle imports the first drying machine (2) along pipeline (101), reduces the moisture in coal to for example, about 18~25%
(in particular about 20~25%), at this point, the first drying machine (2) for example can be fluid bed dryer, rotary dryer, tubulation
Rotary dryer etc..
Later, 1 coal after dry is conveyed along pipeline (102) and is stored in the first storage hopper (3), then along pipe
Line (103) imports flash dryer (3), is specifically able to while the upward side direction in downside from flash dryer is mobile
It is dry.In the case where flash dryer (3), the volatile ingredient in coal is remained untouched within the short residence time due to having
Ground remains in coal and only by the characteristic of moisture removal, therefore is advantageous.The moisture in coal particle after drying final in this way
Such as it can be about being less than or equal to 4% (being in particular approximately less than equal to 2%).Coal particle after above-mentioned drying is passed through into pipeline
(104) it is stored in the 2nd storage hopper (5), feeder (6) is delivered to by pipeline (105) later.It can be by above-mentioned drying
Coal afterwards is supplied with set amount into fluidized-bed gasifier (8) by feeder along pipeline (106).
On the other hand, new gasifying catalyst (107) is supplied first to catalyst hooper and batcher (7), with such as rear institute
After stating catalyst (114) combination recycled like that, pass through pipeline (108) supply to fluidized bed gasification reactor (8).
According to embodiment illustrated, pipeline (109) will be passed through to gasification reactor (8) as the oxygen of gasifying agent and steam
Supply generates after reaction with CO and H2For principal component, further contain CH4And CO2Synthetic gas.At this point, in gasification reaction
In, promoted by means of catalyst for the CO in synthetic gas2CO2Gasification reaction and/or CH4CO2Modified-reaction, display
Out from the CH in the synthetic gas that gasification reactor (8) are discharged4And CO2It reduces and CO and H2The increased characteristic of generation.
Synthetic gas and small ash content (or cigarette ash) in gasification product are arranged from the upper effluent (110) of gasification reactor (8)
Out, and catalyst and coarse ash (coarse ash) are discharged from lower effluent (112).
Upper effluent (110) is transported to particle control equipment (particulate control device, PCD) or eddy flow
Separator (9) and remove the solid content (particle-like substance) for being mixed into such as small ash content in synthetic gas etc.On at this point,
The removal rate of solid content particle for example can be at least about 90% (in particular at least about 95%) in effluent (110).Separation
Small ash content imports catalyst-ash content current divider (10) by pipeline (113) and the lower effluent (112) of gasifier together.
Above-mentioned catalyst-ash content current divider (10) functions as follows：Such as by using nitrogen (or air) as conveying
Fluid separates and recovers catalyst according to specific gravity (partial size) difference with ash content, and the catalyst-ash content current divider (10) specifically may be used
Think gas cyclone current divider.As previously mentioned, natural minerals have specific gravity and big partial size significantly high compared with ash content, therefore hold
Easily separated catalyst, it is convenient to omit needed for separating high price catalyst with the condensation product of ash content from previous alkali metal salt catalyst
Treatment catalyst recovery process.
Be recycled to from the catalyst of ash separation along pipeline (114) in catalyst hooper and batcher (7) and with it is new
Catalyst combination.
On the other hand, in particle control equipment (9), pass through pipeline (111) quilt with the gas componant of small ash separation
It imports sour gas removal device (11), to remove sour gas contained in gas (for example, CO2、H2S etc.).According to showing
Example property embodiment, sour gas removal can be used absorbent and executed with multistage segmented mode.Such as in the first absorption plant/vapour
It mentions in section, separation first is rich in H2The stream of S.At this point, as H2S absorbent, can be used solvent or solid phase absorbents (for example,
ZnO desulphurization catalyst etc.), isolated H2S can be efficiently used to be manufactured in element sulphur.
Then, in the second absorption plant, H is absorbed2CO in the synthetic gas of S reduction2, formed and be rich in CO2Solvent and
Clean synthetic gas, it is above-mentioned to be rich in CO2Solvent CO is separated into stripping2And solvent.At this point, as CO2Absorbent,
Amine solvent (in particular MEA, DEA, TEA etc.) can be used for example.Above-mentioned isolated CO2It is recycled by pipeline (115)
It may be used as CO into gasifier2Gasification reaction and/or CH4CO2The reactant of modified-reaction.
Then, clean synthetic gas is selectively imported into WGS reactor (12) by pipeline (116), according to following
Reaction equation 9 can increase the hydrogen content in synthetic gas.
[reaction equation 9]
CO+H2O→CO2+H2
The present invention will be definitely understood by following embodiments, and following embodiments are only in order to illustrate this hair
It is bright, it is no intended to limit the scope of the invention.
Before manufacture is according to the catalyst of the present embodiment, natural minerals are handled respectively as steps described below, are come
Manufacture can be used as the particle of supporter.
(i) natural minerals
Natural zeolite：In QingBei, Korea, clinoptilolite (the Si/Al molar ratio of celebrating state area production：5~5.5)
Dolomite：It is produced in Zhong Beidi valley area of South Korea
Olivine：It is produced in NORTH CHINA area
* (ii) utilizes jaw crusher, and each natural minerals original mountain flour is broken into about 1mm size, utilizes disc mill later
(disk mill) is ground into the natural minerals particle of about 150~200 μ m in size for 2 times.Then, in air (or nitrogen) atmosphere and
Under the conditions of 350 DEG C of temperature, heat treatment 2 hours is carried out to natural zeolite and olivine.On the other hand, in oxygen atmosphere and 950
DEG C temperature under the conditions of, to dolomite carry out heat treatment 2 hours.Particle sorting (sieving) after above-mentioned heat treatment is obtained
There must be the natural minerals particle of about 150~180 μm of partial sizes.By the composition of the natural minerals particle after above-mentioned heat treatment and melting
Characteristic is shown in following table 4 and table 5.
【Table 4】
| Ingredient (wt%) | Natural zeolite | Dolomite (calcined form) | Olivine |
| SiO2 | 66.52 | 1.35 | 32.00 |
| Al2O3 | 12.87 | 0.68 | 0.64 |
| TiO2 | 0.24 | - | - |
| Fe2O3 | 3.91 | 0.70 | 30.54 |
| CaO | 2.40 | 60.30 | 1.20 |
| MgO | 0.71 | 36.27 | 35.41 |
| Na2O | 2.94 | - | - |
| K2O | 10.40 | 0.70 | - |
| NiO | - | - | 0.21 |
| V2O5 | - | - | - |
| MoO3 | - | - | - |
【Table 5】
| Natural zeolite | Dolomite (calcined form) | Olivine | |
| I.D.T | 1130℃ | 1430℃ | 1140℃ |
| S.T | 1350℃ | - | 1160℃ |
| H.T | 1430℃ | - | 1180℃ |
| F.T | - | - | 1380℃ |
In addition, natural zeolite, dolomite (calcined form) and the respective BET specific surface area of olivine (utilize
The ASAP 2020 of Micromeritics company is measured) it is 38.0m2/g、6.9m2/ g and 4.6m2/g。
In the present embodiment, raw material of the lignite (lignite) of Inner Mongolia as gasification reaction is used, and gasifying
Moisture is eliminated before reaction.The character of dry front and back is shown in following table 6.
【Table 6】
Embodiment 1
Utilize the manufacture (1) of the catalyst of natural zeolite
As Fe precursor aqueous solution, FeCl is prepared2·4H2Fe (the frerrous chloride tetrahydrate of three electricity Chun medicine companies of O
(Iron (II) chloride tetrahydrate), 99%), and as Mg precursor aqueous solution, prepare MgCl2·6H2O's
Mg (magnesium chloride hexahydrate (Magnesium chloride hexahydrate) of three electricity Chun medicine companies, 98%).
Later, as previously mentioned, in the beaker of the natural zeolite particle 100g investment 1L after being heat-treated at 350 DEG C, so
Add above-mentioned Fe precursor aqueous solution 125g and Mg precursor aqueous solution 94g respectively afterwards.Said mixture is stirred 6 hours at 75 DEG C
After be filtered, at 105 DEG C by filtrate it is dry after, calcined under the conditions of air atmosphere and 900 DEG C of temperature, thus
Manufacture gasifying catalyst.
Using ICP-OES (720ICP-OES of Agilent Technologies), catalyst composition is analyzed, is as a result confirmed
To the Fe of the MgO containing 20.5 weight %, 27.0 weight %2O3And 10.2 weight % K2O。
Embodiment 2
Utilize the manufacture of the catalyst of dolomite
As Fe precursor aqueous solution, FeCl is prepared2·4H2Fe (the frerrous chloride tetrahydrate of three electricity Chun medicine companies of O
(Iron (II) chloride tetrahydrate), 99%), and as K precursor aqueous solution, having prepared the K of KCl, (three electricity are pure
Medicine company potassium chloride (Potassium chloride), 99.5%).
Later, it by the beaker of the dolomite particles 100g investment 1L after above-mentioned calcination processing, then adds respectively above-mentioned
Fe precursor aqueous solution 125g and K precursor aqueous solution 74g.It is filtered after stirring said mixture 6 hours at 75 DEG C,
By after the drying of obtained solid content at 105 DEG C, calcined under the conditions of air atmosphere and 950 DEG C of temperature, to manufacture
Catalyst.
Using ICP-OES (720ICP-OES of Agilent Technologies), catalyst composition is analyzed, is as a result confirmed
To the Fe of the MgO containing 24.0 weight %, 27.5 weight %2O3And 10.5 weight % K2O。
Embodiment 3
Utilize the manufacture of natural zeolite and the catalyst of the dissolution fluid of olivine
By in the beaker of the olivine particle 100g investment 1L of above-mentioned manufacture, 5N hydrochloric acid 400ml is then added, at 90 DEG C
Then acid treated mixture is filtered and separates and recovers dissolution fluid by stirring 3 hours.
The content of the element (ion) extracted from the dissolution fluid sample (5ml) of recycling is shown in following table 7.
【Table 7】
| Element (ion) | Mg | Ca | Fe | Al | Si |
| Content (wt%) | 0.60 | 0.01 | 0.21 | 0.03 | 0.51 |
By in the beaker of the natural zeolite particle 100g investment 1L of above-mentioned manufacture, above-mentioned dissolution fluid 200ml is then added.It
Afterwards, it is filtered after 6 hours being stirred the mixture at 75 DEG C, after drying obtained solid content at 105 DEG C, in air
It is calcined under the conditions of atmosphere and 900 DEG C of temperature, to manufacture catalyst.
Using ICP-OES (720ICP-OES of Agilent Technologies), catalyst composition is analyzed, is as a result confirmed
To the Fe of the MgO containing 22.5 weight %, 27.1 weight %2O3And 11.8 weight % K2O。
Embodiment 4
Utilize the manufacture (2) of the catalyst of natural zeolite
As Fe precursor aqueous solution, the Fe (iron hydroxide (Iron (III) of three electricity Chun medicine companies of FeO (OH) is prepared
Hydroxide, 99%), as Mg precursor aqueous solution, prepared Mg (OH)2The Mg (magnesium hydroxide of three electricity Chun medicine companies
(magnesium hydroxide), 95%), and as K precursor aqueous solution, prepare K2CO3K (three electricity Chun medicine companies
Potassium carbonate (Potassium Carbonate), 99.5%).
Later, as previously mentioned, in the beaker of the natural zeolite particle 100g investment 1L after being heat-treated at 350 DEG C, so
The above-mentioned Mg precursor 20g of back loading passes through firing in 2 hours at 400 DEG C, loads Fe precursor 15g, 5 hours dry at 75 DEG C
Afterwards, K precursor 5g is impregnated with aqueous solution state.Under the conditions of air atmosphere and 900 DEG C of temperature, said mixture is forged
It burns 2 hours, to manufacture gasifying catalyst (being named as MNZ04 catalyst).
Embodiment 5
Utilize the manufacture (3) of the catalyst of natural zeolite
As Fe precursor aqueous solution, the Fe (iron hydroxide (Iron (III) of three electricity Chun medicine companies of FeO (OH) is prepared
Hydroxide, 99%), as Mg precursor aqueous solution, prepared Mg (OH)2The Mg (magnesium hydroxide of three electricity Chun medicine companies
(magnesium hydroxide), 95%), and as K precursor aqueous solution, prepare K2CO3K (three electricity Chun medicine companies
Potassium carbonate (Potassium Carbonate), 99.5%).
Later, as previously mentioned, in the beaker of the natural zeolite particle 100g investment 1L after being heat-treated at 350 DEG C, so
The above-mentioned Mg precursor 20g of back loading passes through firing in 2 hours at 400 DEG C, loads Fe precursor 15g, 5 hours dry at 75 DEG C
Afterwards, K precursor 5g is impregnated with aqueous solution state.Under the conditions of air atmosphere and 900 DEG C of temperature, said mixture is forged
It burns 2 hours, to manufacture gasifying catalyst.
From the aspect of activation, for calcined catalyst, at normal pressure, 350 DEG C, in H2/N2Mixed gas is (mixed
Composition and division in a proportion example is 1:1) flow is further progress pretreatment in the reducing atmosphere of 100ml/min.
Embodiment 6
Gasification reaction experiment
In the present embodiment, in order to evaluate a possibility that being applied to gasification process, execution used solidification bed gasifier and
And the laboratory test (950 DEG C, 1 atmospheric pressure) of un-fluidized-bed.Using the catalyst respectively manufactured by Examples 1 to 5, use
By coal and catalyst with weight basis 1:1 mixed sample.
Specific gasification reaction conditions and steps are as follows.
To the diameter for solidifying bed form be 1/2 inch, length is in 760mm microreactor, load the mixed of coal and catalyst
Sample 5g is closed, then on one side by N2With He gas respectively with the injection of 50ml/min flow, risen on one side with 5 DEG C/min from room temperature 1 time
Temperature is to 600 DEG C.In this process, by moisture drying existing for coal and catalytic inner, when inside reactor temperature reaches 600 DEG C
When, temperature is kept for 120 minutes on one side, is on one side pyrolyzed volatile ingredient present in coal.Later, implement to rise for 2 times with 5 DEG C/min
Temperature closes the counterbalance valve (back pressure valve, BPV) of reactor rear end, to make to react to 950 DEG C at the same time
Device internal pressure rises.
If temperature of reactor and pressure become stable under implementation condition, to provide that flow condition is injected by MFC
CO2Gas, and by injecting high steam using HPLC pump supply distilled water.By CO2Gas and steam are supplied to reactor
Afterwards, in order to stabilize, maintenance 120 minutes or more gasification reaction time.
With regard to CO2For gasification reaction experiment, if the CO measured after reacted device2Gas concentration is infused close to reactor
The CO entered2Gas concentration, the then carbon and CO being considered as in coal2Between reaction be fully completed, block gas later, gradually decrease anti-
Device temperature is answered, opens BPV to gradually decrease reactor pressure.
Embodiment 7
It is recycled after gasification reaction by means of the catalyst of magnetic force
The catalyst manufactured in embodiment 1,4~5 is recycled into ash content according to progress gasification reaction the step of embodiment 6 later
(including natural zeolite catalyst) passes through magnetic force (utilizing neodium magnet) for the ash of coal using the ash content as object as shown in Figure 6
It is divided into point and is separated with the natural zeolite catalyst coated with Fe.
The catalyst manufactured in Examples 1 to 5 can be recycled according to the step of Fig. 6 from ash content of coal, in the present embodiment, by
It, not only can be according to the specific gravity or size distribution of ash content and catalyst in natural zeolite magnetic precursor remained on surface
Difference, and recycling catalyst is easy by magnetic.
Fig. 7 is the figure for showing results of grain size analysis, and the granularity is to mix MNZ04 catalyst with Inner Mongol lignite
Sample be object, after gasification reaction, using Particle Size Analyzer (Particle Size Analyzer), respectively for
It remaining residue (mixture of ash content and MNZ04 catalyst) and is isolated using the neodium magnet recorded in embodiment 7
At after ash content and MNZ04 catalyst ash content and MNZ04 catalyst be measured.
Screening possibility by this magnetic force can use the screening machine by means of electromagnetic force in practical commercial technique
To replace catalyst-ash content current divider (10) of Fig. 2 as gas cyclone current divider.
Comparative example 1
Catalyst is not used, in addition to this, according to step same as Example 6, executes gasification reaction.
By using the CO of the catalyst manufactured respectively according to Examples 1 to 3 and comparative example 12Gasification reaction experiment and
Obtained CO conversion reaction speed (rCO) and in CO2By CO when gasification reaction is tested2While influx maintains certain level
Sustainable supply and the CO measured at any time2The result of discharge rate is shown in Fig. 3 a and Fig. 3 b.
It is confirmed by Fig. 3 a, having used makes active constituent be carried on natural minerals particle and by MgO, Fe2O3And K2O is adjusted
For specific composition range catalyst Examples 1 to 3 compared with the comparative example 1 of unused catalyst, show it is high by about 1.5~
2 times of gasification activity.
In addition, using 4 kinds of catalyst, showing to be inclined to as follows according to Fig. 3 b：In initial reaction stage, coal
In carbon and CO2Reaction is carried out to which CO hardly be discharged2, but reduced with the progress of reaction and as the carbon of reactant, by
This CO being discharged2Amount gradually increases.However, compared with comparative example 1, reaching CO in the case where Examples 1 to 32The limit
The time of discharge rate substantially reduces, this expression is improved for CO2Gasification activity.
In this way, judging by above-mentioned experimental result, it can expect that the yield of synthetic gas improves in Examples 1 to 3,
The size of riser can be reduced in fluidized bed gasifying process from now on, therefore equipment investment cost can be reduced.
Furthermore it confirms, although CO2Positive reaction usually occurs at a high temperature of 1200 DEG C or more for gasification reaction, but even if
Under about 950 DEG C of lower gasification temperature, excellent activity can be also obtained.It so, it is possible to reduce operation temperature, therefore energy
Enough make thermal energy investment and loss reduction, this is advantageous in terms of improving process efficiency and maintenance device.
Embodiment 8
It, will be according to the anti-of the gasification reactor of embodiment 6 using the catalyst manufactured respectively according to Examples 1 to 5 as object
It answers temperature to be fixed as 950 DEG C, reaction pressure is changed into 1 atmospheric pressure, 8.5 atmospheric pressure and 30 atmospheric pressure, and carry out gas
Change reaction.Under the above conditions, the synthetic gas for imitating commercial process is formed and is supplied, in order to evaluate CH4CO2Modified-reaction
Activity determines CO2、CO、H2And CH4Respective composition variation.Its result is shown in together with ASPEN analog result Fig. 4 a~
Fig. 4 d.
According to above-mentioned figure, the CH that is carried out in the presence of according to the catalyst of Examples 1 to 54CO2Modified-reaction result
It is, although the thermodynamical equilibrium under the conditions of not reaching corresponding operating forms (analogue value), with progress CO2-CH4Reaction,
CO2And CH4Concentration reduce, and CO and H2Concentration increases.This indicate according to Examples 1 to 5 manufacture based on natural minerals
Catalyst under the conditions of relatively low gasification reaction temperature have improved CH4CO2Modified reactivity,
As a result, increasing the CO and H in final synthetic gas2Production quantity, and can reduce CO2Discharge.
On the other hand, by catalyst manufactured according to Example 1 and from being captured according to the gasification reaction product of embodiment 6
The density and granularity (d of coarse ash50) it is shown in following table 8.
【Table 8】
| Embodiment 1 | Coarse ash | |
| Bulk density (g/cm3) | 1500 | 753 |
| Density (g/cm3) | 2650 | 1922 |
| d50(μm) | 120 | 104 |
In addition, by catalyst manufactured according to Example 1 and from the cinder captured according to the gasification reaction product of embodiment 6
The particle size distribution characteristics divided are shown in Fig. 5.
It is confirmed by above-mentioned table 8 and Fig. 5, it is close according to the catalyst of embodiment 1 compared with the ash content generated by gasification reaction
It spends (specific gravity) and partial size is significantly big.As a result, by the easy lock out operation using common swirl separator, can be easy point
From with the catalyst and ash content that are discharged after recycling gasification reaction, can be by the catalyst recycle of recycling in gasification reaction.
Those skilled in the art can be wrapped with simple deformation or change of the invention easy to use, this deformation or change
Containing within the scope of the invention.
Claims (25)
1. a kind of gasifying catalyst is MgO, 25~35 weight % containing 15~25 weight % on the basis of catalyst weight
Fe2O3And 10~20 weight % K2The gasification reaction catalyst of O, selected from by natural zeolite, olivine and dolomite group
At at least one of group natural minerals particle on load MgO, Fe2O3And K2At least one of O is formed.
2. gasifying catalyst according to claim 1, which is characterized in that
The range that the specific gravity of the catalyst is 2~3.5.
3. gasifying catalyst according to claim 1, which is characterized in that
The partial size d of the catalyst50For 120~240 μm of range.
4. gasifying catalyst according to claim 1, which is characterized in that
In the natural zeolite, the content of Na, K or their combination is at least 5 weight %, Si/Al molar ratios and is at least 5.
5. gasifying catalyst according to claim 1, which is characterized in that
The natural zeolite has 2~6 Mohs' hardness, 2~2.8 specific gravity and at least 1130 DEG C of IDT fusing point.
6. gasifying catalyst according to claim 1, which is characterized in that
The dolomite has 3~4 Mohs' hardness, 2.5~3.5 specific gravity and 1400~1480 DEG C of IDT fusing point.
7. gasifying catalyst according to claim 1, which is characterized in that
The olivine has 6~7 Mohs' hardness, 3.2~3.5 specific gravity and 1130~1170 DEG C of IDT fusing point.
8. a kind of method for manufacturing gasifying catalyst comprising：
The step of natural minerals original stone selected from least one of the group being made of natural zeolite, olivine and dolomite is provided
Suddenly；
The step of natural minerals original stone is crushed and natural minerals particle is provided；And
According to the Fe of MgO, 25~35 weight % containing 15~25 weight % on the basis of the catalyst weight2O3And 10~
The K of 20 weight %2The mode of O makes selected from by MgO, Fe2O3And K2At least one of the group of O composition active constituent is carried on day
Step on right mineral particle.
9. according to the method described in claim 8, it is characterized in that, the step of offer natural minerals particle include：
The step of being ground into 1~5mm size for described natural minerals original stone 1 time；
The step of being ground into 100~240 μ m in size for described 1 time smashed natural minerals particle 2 times；And
The step of described 2 times smashed natural minerals particles are heat-treated under oxidizing atmosphere or reducing atmosphere.
10. according to the method described in claim 9, it is characterized in that,
The natural minerals are natural zeolite and olivine, and the heat treatment step is in 0.5~5 atmospheric pressure and 300~400 DEG C
It is executed under the conditions of temperature.
11. according to the method described in claim 9, it is characterized in that,
The natural minerals are dolomite, and the heat treatment step is held under the conditions of oxidizing atmosphere and 800~1200 DEG C of temperature
Row.
12. according to the method described in claim 8, it is characterized in that, the step of loading the active constituent includes：
The step of manufacturing the precursor solution of active constituent；
The precursor solution of the active constituent is attached to the natural minerals grain by dipping, ion exchange or spray drying
The step of son；And
The step of natural minerals particle for being attached with the active constituent is dried and is calcined.
13. the method for manufacture gasifying catalyst according to claim 12, which is characterized in that
The step of loading the active constituent further comprise：After calcining step, in H2/N2The reducing atmosphere of mixed gas
Under pretreated step is carried out to calcined catalyst.
14. according to the method for claim 12, which is characterized in that
The precursor solution of the active constituent is that the water-soluble metal salt of active constituent is dissolved in water to form.
15. according to the method described in claim 8, it is characterized in that,
The natural minerals are natural zeolite, and the step of loading the active constituent includes：
The step of sour processing is carried out to olivine or ferronickel slag and obtains the dissolution fluid containing Mg and Fe；
The step of dissolution fluid is attached to the natural minerals particle by dipping, ion exchange or spray drying；And
The step of natural minerals particle for being attached with the active constituent is dried and is calcined.
16. according to the method for claim 15, which is characterized in that
In the step of obtaining the dissolution fluid, acid processing in 2~6 hours is carried out at 50~100 DEG C.
17. according to the method for claim 15, which is characterized in that
The acid is hydrochloric acid, sulfuric acid, nitric acid or their combination, the concentration with 1~10N.
18. a kind of catalyst gasification process comprising following steps：
Fe as MgO, 25~35 weight % containing 15~25 weight % on the basis of catalyst weight2O3And 10~20 weight
Measure the K of %2The gasification reaction catalyst of O, using in the group being made of natural zeolite, olivine and dolomite at least
MgO, Fe are loaded on a kind of particle of natural minerals2O3And K2Catalyst made of at least one of O is as bed material or quicksand
At least partially, carbonaceous base feed is made to gasify in fluidized bed gasification reactor.
19. catalyst gasification process according to claim 18, which is characterized in that
The carbonaceous base feed is coal, and the carbon content in the coal is 20~90 weight %, with drying schedule contain less than etc.
In the ash content of 20 weight %.
20. catalyst gasification process according to claim 19, which is characterized in that
The coal and catalyst (i) are imported in the form of physical mixture in fluidized bed gasification reactor or (ii) by coal and
Catalyst is directed respectively into fluidized bed gasification reactor.
21. catalyst gasification process according to claim 20, which is characterized in that
In the physical mixture of the coal and catalyst, the content of catalyst is 10~70 weight %.
22. catalyst gasification process according to claim 19, which is characterized in that further comprise：
From the step of the combination of the product separating synthetic gas body of the catalyst gasification reaction and catalyst and ash content；
The step of separating the catalyst and the ash content respectively according to the difference or magnetic force of density or partial size；And
The isolated catalyst is recycled to the step in fluidized bed gasification reactor.
23. catalyst gasification process according to claim 19, which is characterized in that
The gasification reaction executes at 600~1100 DEG C of temperature and the pressure of 0.1~4.5MPa.
24. catalyst gasification process according to claim 23, which is characterized in that
The gasification reaction executes under conditions of gasification reaction agent of the supply comprising oxygen and steam.
25. catalyst gasification process according to claim 24, which is characterized in that
The gasification reaction agent further includes carbon dioxide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140079162 | 2014-06-26 | ||
| KR10-2014-0079162 | 2014-06-26 | ||
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| CN108993484A (en) * | 2018-07-03 | 2018-12-14 | 昆明超晶科技有限公司 | A method of palladium carbon catalyst is prepared with chloronitrobenzene selective hydrogenation |
| CN110721691B (en) * | 2019-11-12 | 2020-07-24 | 中南大学 | CFAN catalyst, preparation thereof and application thereof in methane hydrogen production |
| CN113046131A (en) * | 2019-12-27 | 2021-06-29 | 陕西博瑞新环保科技有限公司 | Miniature distributed harmless garbage cracking and gasifying device |
| CN113477190B (en) * | 2021-06-16 | 2023-03-17 | 东南大学 | Method for preparing methane gas from solid waste in two-stage mode |
| CN113893854B (en) * | 2021-10-18 | 2023-09-26 | 广东鹏凯智能装备制造有限公司 | Supported binary metal oxide catalyst and preparation method and application thereof |
| US20230150823A1 (en) * | 2021-11-16 | 2023-05-18 | Dennis Schuetzle | CO2 hydrogenation catalysts for the commercial production of syngas |
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