CN106064100A - A kind of processing method of base metal catalysts washing recovered liquid - Google Patents
A kind of processing method of base metal catalysts washing recovered liquid Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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Abstract
The present invention relates to catalytic gasification technical field, particularly relate to the processing method of a kind of base metal catalysts washing recovered liquid.The alkali metal that can make the catalytically inactive in washing recovered liquid exchanges in the form of an ion to the surface of the first raw material, presented in having catalysis activity, improves the catalysis activity reclaiming catalyst, reduces financial cost.The catalysis activity overcoming recovery catalyst in prior art is relatively low, needs extra supplementary potassium carbonate so that the still higher defect of financial cost.A kind of processing method of base metal catalysts washing recovered liquid, including: step 1) using the low-order coal coal dust containing oxygen-containing functional group or/and biomass powder is mixed and stirred for uniformly as the first raw material and calcium oxide or calcium hydroxide in presence of water, standing brings it about the first reaction, it is thus achieved that the first material；Step 2) pending washing recovered liquid is mixed as the second raw material and the first material, and under agitation bring it about the second reaction, it is thus achieved that the second material.
Description
Technical field
The present invention relates to catalytic gasification technical field, particularly relate to the process side of a kind of base metal catalysts washing recovered liquid
Method.
Background technology
The reaction of catalytic coal gasifaction methane typically requires addition catalyst, through great many of experiments discovery, potassium carbonate
Catalysis activity is optimal, but owing to it is relatively costly, needs to recycle the catalyst in catalytic gasification lime-ash.
Catalyst in existing catalytic gasification lime-ash is in a large number with the sylvite of catalytically inactive (for example: potassium sulfide, sulfuric acid
Potassium and potassium chloride etc.) exist, the especially amount with potassium sulfate is in the majority so that carry out washing reclaimed sylvite to catalytic gasification lime-ash
Catalysis activity is substantially reduced, it is difficult to directly apply in catalytic coal gasifaction, anti-using the sylvite reclaiming to carry out catalytic coal gasifaction
At once, often also need to supplement fresh potassium carbonate catalyst so that financial cost is still higher.
Content of the invention
Embodiments of the invention provide the processing method of a kind of base metal catalysts washing recovered liquid, can make described washing
The alkali metal of the catalytically inactive in recovered liquid exchanges in the form of an ion to the surface of described first raw material, to have catalysis activity
Presented in, improve the catalysis activity reclaiming catalyst, reduce financial cost.
For reaching above-mentioned purpose, embodiments of the invention adopt the following technical scheme that
The embodiment of the present invention provides the processing method of a kind of base metal catalysts washing recovered liquid, and pending washing is reclaimed
Potassium ion containing catalytically inactive in liquid, comprising:
Step 1) using the low-order coal coal dust containing oxygen-containing functional group or/and biomass powder as the first raw material and calcium oxide or
Person's calcium hydroxide is mixed and stirred for uniformly in presence of water so that it is the first reaction occurs, it is thus achieved that the first material；
Step 2) pending washing recovered liquid is mixed as the second raw material with described first material so that it is occur second
Reaction, it is thus achieved that the second material.
Preferably, in described step 1) also include before: detect the potassium ion of catalytically inactive in described second raw material
Content, determines the use of described calcium oxide or calcium hydroxide according to the content of the potassium ion of catalytically inactive in described second raw material
Amount, and the consumption of described first raw material is determined according to the consumption of described calcium oxide or calcium hydroxide.
Optionally, described according to the content of the potassium ion of catalytically inactive in described second raw material determine described calcium oxide or
The consumption of person's calcium hydroxide specifically includes:
According to the content of oxygen-containing functional group in described first raw material and described potassium ion and described calcium oxide or hydrogen-oxygen
Change calcium ion in calcium and the stoichiometric proportion of the second reaction occurs, calculate the consumption of described calcium oxide or calcium hydroxide.
Preferably, described determine that the consumption of described first raw material is concrete according to the consumption of described calcium oxide or calcium hydroxide
Including: the described low-order coal coal dust containing oxygen-containing functional group of sampling detection or/and the content of oxygen-containing functional group in biomass powder, and
There is the first reaction in the consumption according to described calcium oxide or calcium hydroxide and described calcium ion and described oxygen-containing functional group
Stoichiometric proportion, calculates the consumption of described first raw material.
Preferably, described method also includes: step 3) by described second material with treat that catalytic gasification raw coal is mixed and stirred for
Uniformly, it is dried, it is thus achieved that the catalytic gasification raw material of catalyst load.
Optionally, in described calcium oxide or calcium hydroxide calcium ion with in described first raw material oxygen-containing functional group mole
Ratio is 0.2-0.5.
Preferably, in described calcium oxide or calcium hydroxide calcium ion and catalytically inactive in described second raw material potassium from
The mol ratio of son is 0.5-4.
It is further preferred that the particle diameter of described first raw material is less than or equal to 5mm.
Optionally, described water and the mass ratio of described first raw material are 0.5-1.
Preferably, described step 1) also include before:
Calcium hydroxide or calcium oxide are dissolved in described water at 20-95 DEG C, it is thus achieved that the water of calcium hydroxide or calcium oxide
Solution.
Optionally, the described particle diameter treating catalytic gasification raw coal is less than or equal to 5mm.
The processing method of a kind of base metal catalysts washing recovered liquid that the embodiment of the present invention provides, by by described first
Raw material and calcium hydroxide or calcium oxide mix in presence of water, and the calcium in described calcium hydroxide can be oxygen-containing with described
There is ion-exchange reactions in functional group, generates calcium salt (calcium generates) and water with reactions such as the carboxyl on the first raw material surface, hydroxyls, from
And the calcium in calcium hydroxide can be promoted to transfer to the ature of coal surface of the first raw material, afterwards by the first of ature of coal surface calcium ions
The washing recovered liquid mixing of raw material and described base metal catalysts, under agitation, calcium ion can be washed in recovered liquid with described
Catalytically inactive alkali metal ion generation ion exchange so that the alkali metal of catalytically inactive exchanges in the form of an ion to institute
State the surface of the first raw material, presented in there is catalysis activity such that it is able to improve the catalysis activity reclaiming catalyst, subtract
It is catalyzed cost less.The catalysis activity overcoming recovery catalyst in prior art is relatively low, needs extra supplementary potassium carbonate so that urge
This still higher defect of chemical conversion.
Brief description
The flow chart of the processing method of a kind of base metal catalysts washing recovered liquid that Fig. 1 provides for the embodiment of the present invention；
The flow process of the processing method of the another kind of base metal catalysts washing recovered liquid that Fig. 2 provides for the embodiment of the present invention
Figure.
Detailed description of the invention
Below in conjunction with the accompanying drawings the processing method of the washing recovered liquid of the base metal catalysts that the embodiment of the present invention provides is entered
Row describes in detail.
In describing the invention, term " first ", " second " are only used for describing purpose, and it is not intended that indicate or dark
Show relative importance or the implicit quantity indicating indicated technical characteristic.Thus, " first ", the feature of " second " are defined
Can express or implicitly include one or more this feature.
The embodiment of the present invention provides the processing method of a kind of base metal catalysts washing recovered liquid, and pending washing is reclaimed
In liquid, the potassium ion containing catalytically inactive, sees Fig. 1, comprising:
Step 1) using the low-order coal coal dust containing oxygen-containing functional group or/and biomass powder as the first raw material and calcium oxide or
Person's calcium hydroxide is mixed and stirred for uniformly in presence of water so that it is the first reaction occurs, it is thus achieved that the first material；
Step 2) pending washing recovered liquid is mixed as the second raw material with described first material so that it is occur second
Reaction, it is thus achieved that the second material.
The processing method of a kind of base metal catalysts washing recovered liquid that the embodiment of the present invention provides, by by described first
Raw material and calcium hydroxide or calcium oxide mix in presence of water, and the calcium in described calcium hydroxide can be oxygen-containing with described
There is ion-exchange reactions in functional group, generates calcium salt (calcium generates) and water with reactions such as the carboxyl on the first raw material surface, hydroxyls, from
And the calcium in calcium hydroxide can be promoted to transfer to the ature of coal surface of the first raw material, afterwards by the first of ature of coal surface calcium ions
The washing recovered liquid mixing of raw material and described base metal catalysts, under agitation, calcium ion can be washed in recovered liquid with described
Catalytically inactive alkali metal ion generation ion exchange so that the alkali metal of catalytically inactive exchanges in the form of an ion to institute
State the surface of the first raw material, presented in there is catalysis activity such that it is able to improve the catalysis activity reclaiming catalyst, subtract
It is catalyzed cost less.The catalysis activity overcoming recovery catalyst in prior art is relatively low, needs extra supplementary potassium carbonate so that urge
This still higher defect of chemical conversion.
Wherein, described oxygen-containing functional group can be carboxyl (-COOH), hydroxyl (-OH), sulfonic acid (-SO3H) or sulfinic acid
(-SOOH), exemplary, when described oxygen-containing functional group is carboxyl or hydroxyl, described first reaction is as follows respectively, raw
Become calcium salt and water.
2R-COOH+Ca(OH)2→(R-COO)2Ca2++2H2O (I)
2R-OH+Ca(OH)2→(R-O)2Ca2++2H2O (II)
As a example by described washing recovered liquid, the alkali metal salt of catalytically inactive is as potassium sulfate, described second reaction is respectively such as
Shown in lower, generate calcium sulfate precipitation and there is the sylvite of catalysis activity.
(R-COO)2Ca2++K2SO4→2R-COO-K+CaSO4 (III)
(R-O)2Ca2++K2SO4→2R-O-K+CaSO4 (IV)
Wherein it is desired to explanation, the generation calcium sulfate that reacts of potassium sulfate and the calcium salt in described washing recovered liquid sinks
Form sediment, reaction can be promoted to move right, so that the surface that the potassium ion in potassium sulfate is exchanged to described first raw material.And
In described washing recovered liquid the sylvite (for example: potassium chloride etc.) of other catalytically inactives with calcium salt owing to ion exchange potential is relatively low,
Therefore ion-exchange reactions also can occur so that the potassium ion in the sylvite of other catalytically inactives is exchanged to described first
The surface of raw material.
Wherein, the consumption of described first raw material and described calcium hydroxide or calcium oxide is not limited, as long as above-mentioned
The first reaction and the second reaction i.e. can be occurred under experiment condition respectively to generate the existence of the alkali metal ion with catalysis activity
Form.
In one embodiment of the invention, in described step 1) also include before: detect in described second raw material and live without catalysis
The content of the potassium ion of property, in described second raw material, the content of the potassium ion of catalytically inactive determines described calcium oxide or hydrogen-oxygen
Change the consumption of calcium, and determine the consumption of described first raw material according to the consumption of described calcium oxide or calcium hydroxide.
In embodiments of the present invention, it can be avoided that reaction not exclusively makes the existence with the alkali metal ion of catalysis activity
Form conversion ratio is low, and the consumption of calcium hydroxide or calcium oxide and the consumption of described first raw material is excessive causes waste, and
It is possible to affect the carrying out of subsequent catalyst gasification reaction.
Wherein, in described washing recovered liquid, the content of the potassium ion of catalytically inactive can pass through the chromatography of ions and titration
Method combines and detects, and concrete assay method can refer to standard GB/T 15454-2009, MT/T252-2000, GB/T 15452-
1995 etc. are carried out, and the content of described oxygen-containing functional group can calculate method, selective reagent reaction method and instrument by empirical equation
Analytic approach is measured, exemplary, and carboxyl can refer to standard GB/T 10338-2008, and hydroxyl can pass through GB/T 12442-
1990 are measured.Selective reagent reaction method refers to utilize some reagent only reacting with some particular functional group to determine coal
The method of middle oxygen-containing functional group, comprising: potentiometric titration etc., for example: determine that hydroxyl can pass through acetylation or deuterate is made
With carrying out, determine that phenolic hydroxyl group can be replaced by methylation reaction, barium hydroxide, ketenes acetylation titration is carried out, and determines carboxylic
Base can be carried out by decarboxylation reaction, iodometry, ion-exchange etc., determines that carbonyl can pass through oximation, cyanogen
Change effect is carried out.
In one embodiment of the invention, the described content according to the potassium ion of catalytically inactive in described second raw material determines
The consumption of described calcium oxide or calcium hydroxide specifically includes:
According to the content of the potassium ion of catalytically inactive in described second raw material and described potassium ion and described calcium ion
There is the stoichiometric proportion of the second reaction, calculate the consumption of calcium oxide or calcium hydroxide.
In embodiments of the present invention, generation ion completely can accurately be calculated according to the chemical equation of described second reaction
The described calcium hydroxide of clearing house needs or the consumption of calcium oxide.
In another embodiment of the present invention, described determine described first according to the consumption of described calcium oxide or calcium hydroxide
The consumption of raw material specifically includes: the described low-order coal coal dust containing oxygen-containing functional group of sampling detection is or/and oxygen-containing in biomass powder
The content of functional group, and according to the consumption of described calcium oxide or calcium hydroxide and described calcium ion and described oxygen-containing functional group
There is the stoichiometric proportion of the first reaction, calculate the consumption of described first raw material.
In embodiments of the present invention, generation ion completely can accurately be calculated according to the chemical equation of described first reaction
The consumption of described first raw material that clearing house needs.
In one embodiment of the invention, in described calcium oxide or calcium hydroxide, calcium ion and nothing in described second raw material are urged
The mol ratio of the potassium ion changing activity is 0.5-4.
Can be learnt by reactional equation formula (III) and (IV): the chemistry of described calcium ion and described potassium ion complete exchange
Metering ratio is 0.5, and therefore, in embodiments of the present invention, the ratio properly increasing calcium ion can improve calcium ion and potassium ion
Exchange efficiency.
Preferably, the calcium ion in described calcium oxide or calcium hydroxide and catalytically inactive in described washing recovered liquid
The mol ratio of potassium ion is 0.5-2.Too high being unfavorable for of calcium ion consumption reduces cost.
In another embodiment of the present invention, in described calcium oxide or calcium hydroxide, calcium ion contains in described first raw material
The mol ratio of oxygen functional group is 0.2-0.5.
Can be learnt by reactional equation formula (I) and (II): the chemistry meter that calcium ion and described oxygen-containing functional group react
Amount ratio is 0.5, and therefore, in embodiments of the present invention, the amount properly increasing described oxygen-containing functional group can increase having of calcium ion
Effect exchange capacity.
In one embodiment of the invention, the particle diameter of described first raw material is less than or equal to 5mm.
In embodiments of the present invention, owing to the particle diameter of described first raw material is less, by described first raw material and described hydrogen
During calcium oxide or calcium oxide carry out mix and blend in presence of water, enable to calcium ion and divide as homogeneously as possible
It is dispersed in the surface of described first raw material, improve effective exchange capacity of calcium ion.
In another embodiment of the present invention, described water is 0.5-1 with the mass ratio of described first raw material.Under this ratio,
Ensure that described first raw material, by water complete wetting, improves the reaction effect of the described first reaction, the water yield is excessive, can improve
Operating cost.
Wherein, the addition manner of described water is not limited, can by described first raw material and described calcium hydroxide or
Water is added, it is also possible to after described calcium hydroxide or calcium oxide are added to the water after calcium oxide mixing, then by described first former
Material is added thereto, it is of course also possible to add water in described first raw material, more described calcium hydroxide or calcium oxide is added it
In.
In another embodiment of the present invention, described step 1) before also include: by calcium hydroxide or calcium oxide at 20-95
It DEG C is dissolved in described water, it is thus achieved that the aqueous solution of calcium hydroxide or calcium oxide.
By being dissolved in described water calcium hydroxide or calcium oxide at 20-96 DEG C, it is possible to increase the dissociation effect of calcium ion
Rate, improves the ion exchange ratio of calcium ion, in addition, during dissolving described calcium hydroxide or calcium oxide, temperature is too low
Being unfavorable for the dissociation of calcium ion, temperature is too high can improve operating cost.
Wherein it is desired to explanation, described second material can be directly used in catalytic gasification, certainly through being dried, it is possible to
With with treat that catalytic gasification raw coal mixes so that alkali metal is to have the form of catalysis activity as described catalytic gasification raw coal for the treatment of
Catalyst brings it about catalytic gasification reaction.
Also, it should be noted owing to described second material containing calcium salt (such as calcium sulfate, calcium chloride etc.), therefore, will
Described second dry materials be directly used in catalytic gasification or by described second material with described after catalytic gasification raw coal mixes,
Can also increase described first raw material or the ash fusion point treating catalytic gasification raw coal, ash fusion point, also known as coal ash melting property, refers to solid
Ash content in fluid fuel, after reaching uniform temperature, deforms, and temperature when softening and melt is so, relatively low in temperature
Slagging scorification can be reduced when reacting at a temperature of catalytic gasification.
In one embodiment of the invention, seeing Fig. 2, described method also includes: step 3) by described second material with wait to urge
Change gasification raw coal and be mixed and stirred for uniformly, be dried, it is thus achieved that the catalytic gasification raw material of catalyst load.
In embodiments of the present invention, by with described, described second material is treated that catalytic gasification raw coal is mixed and stirred for all
Even, can be straight by the base metal catalysts (for example: potassium carbonate, potassium hydroxide) with catalysis activity in described washing recovered liquid
Connect and treat on catalytic gasification raw coal described in being supported on, and also can be by the alkali metal with catalysis activity in described second material
Existence form be also mixed into described in treat in catalytic gasification raw coal, treat catalytic gasification raw coal for occurring catalytic gasification to react described
When, the alkali metal with catalysis activity can migrate in catalytic gasification raw coal described treating, has preferably catalysis activity.
In one embodiment of the invention, the described particle diameter treating catalytic gasification raw coal is less than or equal to 5mm.Enable to described water
Wash the alkali metal salt with catalysis activity in recovered liquid and the having of surface of described first raw material is catalyzed active alkali metal
With described, salt treats that catalytic gasification raw coal is fully contacted, improve the dispersion effect of catalyst, carry high catalytic activity.
In another embodiment of the present invention, the water content of the catalytic gasification raw material of described catalyst load is less than or equal to 5%.
The catalytic gasification raw material of this catalyst load can be passed directly in gasification furnace and carry out catalytic gasification reaction.
Hereinafter, the embodiment of the present invention will the present invention will be described by embodiment and comparative example.These embodiments are only
The example proposing to illustrate the present invention, those skilled in the art are not it is appreciated that the scope of the present invention is by these
The restriction of embodiment.
It should be noted that in order to the objective technique effect to the embodiment of the present invention illustrates, described reference examples and reality
Execute and treat that catalytic gasification raw coal is same coal employed in example.
Comparative example 1
Detect the content of potassium ion in the washing recovered liquid of described base metal catalysts, and by its with treat catalytic gasification raw coal
(according to potassium carbonate (potassium ion is all converted according to potassium carbonate) with treat catalytic gasification raw coal quality than for 1:10) mix, make
Base metal catalysts in described washing recovered liquid be directly carried on described in treat on catalytic gasification raw coal, be dried, or aqueous
The catalytic gasification raw material of the catalyst load less than or equal to 5% for the amount.Measure the ash fusion point such as table 1 below institute before and after the load of its catalyst
Show:
Table 1
| Reference examples 1 | Deformation temperature DT | Softening temperature ST | Hemispherical fusion temperature HT | Flowing temperature FT |
| Before load | 1144 | 1264 | 1318 | 1355 |
| After load | 1008 | 1034 | 1076 | 1131 |
As shown in Table 1: the ash fusion point of the catalytic gasification raw material of catalyst load is substantially reduced.
The catalytic gasification raw material of described catalyst load is passed through at 700 DEG C in catalytic gasification fluidized-bed gasification furnace, pressure
For carrying out catalytic gasification reaction under 3.5MPa, wherein, gasifying agent steam and the catalytic gasification raw material of described catalyst load
Mass ratio is 1.5, and the solid phase time of staying is 2h, in the process, discharges part clinker, and finally giving its efficiency of carbon con version is
82%, in product gas, the content of methane is 13%.
Comparative example 2
Detect the content of potassium ion in the washing recovered liquid of described base metal catalysts and the existence form of potassium, it is thus achieved that potassium
Ion is mainly presented in potassium carbonate, potassium hydroxide and potassium sulfate, and wherein, potassium sulfate catalytically inactive, in potassium sulfate
Potassium accounts for 20% (mol ratio) of total potassium content in washing recovered liquid, by the potassium sulfate of catalytically inactive according to the mole of potassium ion
Conversion is the quality of potassium carbonate, and supplements this part potassium carbonate in washing recovered liquid, by the washing recovered liquid being obtained with treat
Catalytic gasification raw coal (according to potassium carbonate (potassium is all converted according to potassium carbonate) with to treat catalytic gasification raw coal quality ratio be 1:
10) mix, be dried, it is thus achieved that the catalytic gasification raw material of the catalyst load less than or equal to 5% for the water content.Its ash fusion point such as table 2 below
Shown in:
Table 2
| Reference examples 2 | Deformation temperature DT | Softening temperature ST | Hemispherical fusion temperature HT | Flowing temperature FT |
| After load | 987 | 1004 | 1036 | 1051 |
Can be learnt by table 2: the ash fusion point of the catalytic gasification raw material supplementing the load of potassium carbonate rear catalyst reduces further.
The catalytic gasification raw material of described catalyst load is passed through at 700 DEG C in catalytic gasification fluidized-bed gasification furnace, pressure
For carrying out catalytic gasification reaction under 3.5MPa, wherein, gasifying agent steam and the catalytic gasification raw material of described catalyst load
Mass ratio is 1.5, and the solid phase time of staying is 2h, in the process, discharges part clinker, and finally giving its efficiency of carbon con version is
93%, in product gas, the content of methane is 21%.
Embodiment 1
Embodiment 1 is essentially identical with described comparative example 2, except for the difference that: the side that embodiment 1 is provided by the embodiment of the present invention
Described washing recovered liquid is processed by method.
Concrete, the consumption of calcium hydroxide is determined according to the amount of the potassium sulfate of catalytically inactive in described washing recovered liquid,
By determine consumption calcium hydroxide soluble in water at 20 DEG C, keep calcium ion with the mol ratio of the potassium ion in described potassium sulfate be
0.5, it is thus achieved that the aqueous solution, described water is 0.5 with the mass ratio of following selected low-order coal coal dust.
Choose a kind of low-order coal, crush, sieve after acquisition particle diameter be less than or equal to the coal dust of 5mm, detect described low order
The oxygen-containing functional group content on the surface of coal, it is thus achieved that the content sum of carboxyl and hydroxyl is 2.47mol/kg coal, according to described calcium from
The consumption of son determines the consumption of described low-order coal so that calcium ion is 0.5 with the mol ratio of described oxygen-containing functional group.
The low-order coal and the described aqueous solution that determine consumption stirs in premixed device wet mixing to uniformly, standing 2h, it is thus achieved that the
Described first material is mixed by one material with described washing recovered liquid, and stirring obtains the second material；By described second material and institute
State and treat that catalytic gasification raw coal (according to potassium carbonate (all converting potassium according to potassium carbonate) with treating catalytic gasification raw coal quality ratio is
1:10) mix, be dried, it is thus achieved that the catalytic gasification raw material of the catalyst load less than or equal to 5% for the water content.Its ash fusion point such as following table
Shown in 3:
Table 3
| Embodiment 1 | Deformation temperature DT | Softening temperature ST | Hemispherical fusion temperature HT | Flowing temperature FT |
| After load | 1284 | 1314 | 1348 | 1365 |
Can be learnt by table 3: the washing recovered liquid after processing be carried on described on catalytic gasification raw coal when, its ash is molten
Point increases.
The catalytic gasification raw material of the catalyst load being obtained is passed through at 700 DEG C in catalytic gasification fluidized-bed gasification furnace,
Pressure is to carry out catalytic gasification reaction under 3.5MPa, and wherein, the catalytic gasification that gasifying agent steam loads with described catalyst is former
The mass ratio of material is 1.5, and the solid phase time of staying is 2h, in the process, does not finds slagging scorification phenomenon, finally gives its efficiency of carbon con version
Being 92%, in product gas, the content of methane is 21%.
Embodiment 2
First raw material and institute described in the processing procedure with washing recovered liquid described in described embodiment 1 for the described embodiment 2
State the consumption slightly difference of calcium hydroxide or calcium oxide.
Described embodiment 2 particularly as follows: calcium hydroxide is soluble in water at 95 DEG C, formed calcium hydroxide aqueous solution, described water with
The mass ratio of described low-order coal coal dust is 1, and described calcium ion is 0.5 with the mol ratio of oxygen-containing functional group in described low-order coal, institute
The mol ratio stating calcium ion with potassium ion in the potassium sulfate of described catalytically inactive is 2, and the efficiency of carbon con version of final coal is 93%, first
Alkane productivity is 20%, without slagging scorification phenomenon during catalytic gasification.
Embodiment 3
First raw material and institute described in the processing procedure with washing recovered liquid described in described embodiment 1 for the described embodiment 3
State the consumption slightly difference of calcium hydroxide or calcium oxide.
Described embodiment 3 particularly as follows: calcium hydroxide is soluble in water at 60 DEG C, forms calcium hydroxide aqueous solution, described water
Mass ratio with described low-order coal coal dust is 0.8, and described calcium ion with the mol ratio of oxygen-containing functional group in described low-order coal is
0.4, described calcium ion is 1 with the mol ratio of potassium ion in the potassium sulfate of described catalytically inactive, and the efficiency of carbon con version of final coal is
92%, methane production is 21%, without slagging scorification phenomenon during catalytic gasification.
Embodiment 4
First raw material and institute described in the processing procedure with washing recovered liquid described in described embodiment 1 for the described embodiment 4
State the consumption slightly difference of calcium hydroxide or calcium oxide.
Described embodiment 4 particularly as follows: calcium hydroxide is soluble in water at 25 DEG C, forms calcium hydroxide aqueous solution, described water
Mass ratio with described low-order coal coal dust is 0.5, and described calcium ion with the mol ratio of oxygen-containing functional group in described low-order coal is
0.2, described calcium ion is 4 with the mol ratio of potassium ion in the potassium sulfate of described catalytically inactive, and the efficiency of carbon con version of final coal is
95%, methane production is 22%, without slagging scorification phenomenon during catalytic gasification.
Conclusion: described washing recovered liquid, can be by the alkali of catalytically inactive in described washing recovered liquid after processing
Metal is presented in having catalysis activity, and is supported on the surface of described first raw material, and by itself and described gas to be catalyzed
Change raw coal mixing so that the described alkali-metal existence form with catalysis activity be supported on described in treat the table of catalytic gasification raw coal
Face, it is possible to increase reclaim the catalysis activity of catalyst so that efficiency of carbon con version and the methane production of coal are obtained with supplementary potassium carbonate
Efficiency of carbon con version and methane production suitable such that it is able to reduce catalysis cost, and, due to the existence of calcium salt, additionally it is possible to reduce
Slagging scorification phenomenon.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any
Those familiar with the art, in the technical scope that the invention discloses, can readily occur in change or replace, should contain
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with described scope of the claims.
Claims (11)
1. the processing method of a base metal catalysts washing recovered liquid, it is characterised in that contain in pending washing recovered liquid
There is the potassium ion of catalytically inactive, comprising:
Step 1) using the low-order coal coal dust containing oxygen-containing functional group or/and biomass powder is as the first raw material and calcium oxide or hydrogen
Calcium oxide is mixed and stirred for uniformly in presence of water so that it is the first reaction occurs, it is thus achieved that the first material；
Step 2) pending washing recovered liquid is mixed as the second raw material with described first material so that it is generation second is anti-
Should, it is thus achieved that the second material.
2. processing method according to claim 1, it is characterised in that
In described step 1) also include before: detect the content of the potassium ion of catalytically inactive in described second raw material, according to institute
The content stating the potassium ion of catalytically inactive in the second raw material determines the consumption of described calcium oxide or calcium hydroxide, and according to institute
The consumption stating calcium oxide or calcium hydroxide determines the consumption of described first raw material.
3. processing method according to claim 2, it is characterised in that
Described determine described calcium oxide or calcium hydroxide according to the content of the potassium ion of catalytically inactive in described second raw material
Consumption specifically include:
Occur with described calcium ion according to content and the described potassium ion of the potassium ion of catalytically inactive in described second raw material
The stoichiometric proportion of the second reaction, calculates the consumption of calcium oxide or calcium hydroxide.
4. processing method according to claim 3, it is characterised in that
Described determine that the consumption of described first raw material specifically includes according to the consumption of described calcium oxide or calcium hydroxide: sampling inspection
Survey the described low-order coal coal dust containing oxygen-containing functional group or/and the content of oxygen-containing functional group in biomass powder, and according to described oxygen
There is the stoichiometric proportion of the first reaction in the consumption of change calcium or calcium hydroxide and described calcium ion and described oxygen-containing functional group,
Calculate the consumption of described first raw material.
5. processing method according to claim 1, it is characterised in that described method also includes:
Step 3) by described second material with treat that catalytic gasification raw coal is mixed and stirred for uniformly, be dried, it is thus achieved that catalyst load
Catalytic gasification raw material.
6. the processing method according to any one of claim 1-4, it is characterised in that
In described calcium oxide or calcium hydroxide, calcium ion and the mol ratio of oxygen-containing functional group in described first raw material are 0.2-
0.5。
7. the processing method according to any one of claim 1-4, it is characterised in that
The mol ratio of the potassium ion of catalytically inactive in calcium ion and described second raw material in described calcium oxide or calcium hydroxide
For 0.5-4.
8. processing method according to claim 1, it is characterised in that
The particle diameter of described first raw material is less than or equal to 5mm.
9. processing method according to claim 1, it is characterised in that
Described water is 0.5-1 with the mass ratio of described first raw material.
10. the processing method according to claim 1 or 9, it is characterised in that
Described step 1) also include before:
Calcium hydroxide or calcium oxide are dissolved in described water at 20-95 DEG C, it is thus achieved that the aqueous solution of calcium hydroxide or calcium oxide.
11. processing methods according to claim 5, it is characterised in that
The described particle diameter treating catalytic gasification raw coal is less than or equal to 5mm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107159180A (en) * | 2017-06-01 | 2017-09-15 | 新奥科技发展有限公司 | A kind of catalyst recovery process |
| CN108067216A (en) * | 2017-12-19 | 2018-05-25 | 新奥科技发展有限公司 | The recovery method of base metal catalysts in a kind of catalytic coal gasifaction lime-ash |
| CN114433140A (en) * | 2020-10-30 | 2022-05-06 | 中国石油化工股份有限公司 | Biological coke gasification catalyst and biological coke catalytic raw material |
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| CN104043485A (en) * | 2014-06-09 | 2014-09-17 | 新奥科技发展有限公司 | Catalyst recovering and loading method |
| CN104449865A (en) * | 2014-10-16 | 2015-03-25 | 中国科学院山西煤炭化学研究所 | Method for improving catalytic coal gasification activity and catalyst recovery rate |
| CN104759249A (en) * | 2015-04-07 | 2015-07-08 | 新奥科技发展有限公司 | Recycling method of catalytic gasification coal slag and activated residues of catalytic gasification coal slag |
| CN105396574A (en) * | 2015-11-25 | 2016-03-16 | 杨秋良 | Method for recycling composite coal gasification catalyst |
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| CN104043485A (en) * | 2014-06-09 | 2014-09-17 | 新奥科技发展有限公司 | Catalyst recovering and loading method |
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| CN104759249A (en) * | 2015-04-07 | 2015-07-08 | 新奥科技发展有限公司 | Recycling method of catalytic gasification coal slag and activated residues of catalytic gasification coal slag |
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| CN107159180A (en) * | 2017-06-01 | 2017-09-15 | 新奥科技发展有限公司 | A kind of catalyst recovery process |
| CN108067216A (en) * | 2017-12-19 | 2018-05-25 | 新奥科技发展有限公司 | The recovery method of base metal catalysts in a kind of catalytic coal gasifaction lime-ash |
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