CN113549471B - Application of sunflower straw in catalyzing steam gasification of medium-low rank coal - Google Patents
Application of sunflower straw in catalyzing steam gasification of medium-low rank coal Download PDFInfo
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Abstract
The invention provides an application of sunflower straws in catalyzing low-rank coal steam gasification, belonging to the technical field of catalysts. The invention provides an application of sunflower straws in catalyzing low-order coal steam gasification, which is characterized in that the treated sunflower straws are dried, ground, screened and added into coal for steam co-gasification experiment, so that a gasification reaction temperature region is advanced, the steam gasification reaction rate is obviously accelerated, a water gas shift reaction is completed, the hydrogen yield is improved, the coal consumption is saved, the environment is protected, and the efficient utilization of biomass resources is realized. The invention provides a novel treatment mode for the treatment of biomass sunflower straws and the efficient utilization of medium-low-rank coal. The differences of the sunflower straw skin and core co-gasification are respectively found, experiments show that the sunflower straw core and the coal are obviously superior to the sunflower straw skin through the steam co-gasification, and the doping mass ratio of the straw to the coal is 3:1 to 1: 1.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to application of sunflower straws in catalyzing steam gasification of medium-low-rank coal.
Background
Biomass refers to various organisms produced through photosynthesis of the atmosphere, land, water and the like, crop straws are important components of the biomass, and the full utilization of the straws and the full exertion of the advantages of the straws gradually become important scientific research contents at present. The straws contain a large amount of lignin and cellulose, and also contain a certain amount of inorganic substances, such as potassium, sodium, calcium and the like, the content of the inorganic substances is different under different growth environments, most of the straws are burnt and wasted, and the least part of the straws are used as potassium fertilizer, so that the efficient utilization of the sunflower straw biomass has important significance.
China is one of the most abundant countries of coal resources in the world, and lignite is abundant in resources and mainly focuses on North China. With the increasing exhaustion of high-rank coal, the position of lignite and bituminous coal in the field of energy utilization is obviously improved. The lignite is high in volatile matter content, high in water content, low in heat value and poor in thermal stability to air, the water content of bituminous coal is slightly lower than that of lignite, volatile matter of medium-low-rank coal is higher than that of high-rank coal, and accordingly the high-rank coal is low in utilization rate as energy. Therefore, finding a method for efficiently recycling medium-low-rank coal has important significance for large-scale utilization of the medium-low-rank coal.
In the coal gasification process, a steam gasification technology is one of the cleanest technologies, and for medium-low-rank coal, alkali and alkaline earth metals are mostly used for catalyzing the lignite steam gasification process at the present stage, but some catalysts are expensive, so that it is very important to find a replaceable biomass straw.
Disclosure of Invention
In view of the above, the present invention aims to provide an application of sunflower straw in catalytic steam gasification of medium-low rank coal. The invention takes sunflower straws as a catalyst, and realizes the steam gasification of medium-low-rank coal.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of sunflower straws in catalyzing steam gasification of medium-low-rank coal.
Preferably, the sunflower stalks are pretreated as follows:
drying sunflower straws and separating skin from core in sequence to respectively obtain a skin component and a core component;
and respectively crushing and screening the skin component and the core component to obtain the sunflower straw skin and the sunflower straw core.
Preferably, the drying temperature is 105 ℃ and the drying time is 24 h.
Preferably, the particle size after screening is 200-300 meshes.
Preferably, the application comprises the steps of:
performing acid treatment on the medium and low rank coal to obtain a treated coal sample;
mixing sunflower straws with the treated coal sample to obtain a straw-containing coal sample;
and carrying out steam gasification reaction on the coal sample containing the straws.
Preferably, the mass ratio of the processed coal sample to the sunflower straw is 1: 1-3.
Preferably, the mass ratio of the processed coal sample to the sunflower straws is 1:1 or 1: 3.
Preferably, the medium-low rank coal is lignite or bituminous coal.
Preferably, hydrochloric acid is used for the acid treatment, the mass fraction of the hydrochloric acid is 18%, and the dosage ratio of the medium-low rank coal to the hydrochloric acid is 1g:10 mL.
Preferably, the parameters of the water vapor gasification reaction include: heating to 500 deg.C at 15 deg.C/min, heating to 900 deg.C at 2 deg.C/min, maintaining the temperature of 900 deg.C for 1h, and heating to 400 deg.C; the water pumping rate is 0.057 mL/min.
The invention provides an application of sunflower straws in catalyzing low-order coal steam gasification, which is characterized in that the treated sunflower straws are dried, ground, screened and added into coal for steam co-gasification experiment, so that a gasification reaction temperature region is advanced, the steam gasification reaction rate is obviously accelerated, the water gas shift reaction is completed, the coal consumption is saved, the environment is protected, and the efficient utilization of biomass resources is realized. The invention provides a novel treatment mode for the treatment of biomass sunflower straws and the efficient utilization of medium-low-rank coal.
Furthermore, the differences of the sunflower straw skin and core co-gasification are respectively found, and experiments show that the sunflower straw core and the water vapor co-gasification of the coal are obviously superior to the sunflower straw skin.
Drawings
FIG. 1 shows the steam gasification of the treated coal sample and the coal sample containing straw obtained in example 1 to produce H2Generating a rate map;
FIG. 2 is a graph showing the rate of CO formation by steam gasification of the coal samples treated and the coal samples containing straw obtained in example 1;
FIG. 3 shows the steam gasification of the treated coal sample and the coal sample containing straw obtained in example 1 to produce CH4To generate a rate map；
FIG. 4 is a diagram showing the steam gasification reaction of the treated coal sample and the coal sample containing straw obtained in example 1 to produce CO2Generating a rate map;
FIG. 5 is a graph of carbon yield from steam gasification of different coal samples in example 1;
FIG. 6 is a graph of the water vapor component ratios for different coal samples from example 1.
Detailed Description
The invention provides an application of sunflower straws in catalyzing steam gasification of medium-low-rank coal.
In the present invention, the sunflower straw is pretreated as follows:
drying sunflower straws and separating skin from core in sequence to respectively obtain a skin component and a core component;
and respectively crushing and screening the skin component and the core component to obtain the sunflower straw skin and the sunflower straw core.
In the present invention, the sunflower straw is preferably from the inner Mongolia region of China.
In the present invention, the drying temperature is preferably 105 ℃ and the drying time is preferably 24 hours.
The specific mode of the skin-core separation is not particularly limited, and the skin-core separation can be realized.
In the present invention, the crushing is preferably performed by using a crusher, and the present invention is not particularly limited to the specific mode of the crushing.
In the invention, the particle size after screening is preferably 200-300 meshes.
In a specific embodiment of the invention, the sunflower straw skins are denoted as SFS and the sunflower straw cores are denoted as SFC.
In the present invention, the application preferably comprises the steps of:
performing acid treatment on the medium-low rank coal to obtain a treated coal sample;
mixing sunflower straws with the treated coal sample to obtain a straw-containing coal sample;
and carrying out steam gasification reaction on the coal sample containing the straws.
The invention carries out acid treatment on medium and low rank coal to obtain a treated coal sample.
In the invention, the medium-low-rank coal is preferably bituminous coal or lignite, the bituminous coal is preferably from the Mongolian Huoyou, and the lignite is preferably Shengli lignite in the inner Mongolian east region.
In the invention, the medium-low rank coal preferably further comprises crushing, screening and drying which are sequentially carried out before the acid treatment.
The present invention is not particularly limited with respect to the specific manner of the crushing.
In the invention, the screening is preferably carried out to 200-300 meshes by a standard screening device.
In the present invention, the drying is preferably carried out in a forced air drying oven, the temperature of the drying is preferably 105 ℃, and the time is preferably 6 h.
In the invention, hydrochloric acid is preferably used for the acid treatment, the dosage ratio of the medium-low rank coal to the acid solution is preferably 1g:10mL, and the concentration of the hydrochloric acid is preferably 18 wt%. In the present invention, the acid treatment is used for eliminating the influence of the inherent minerals in the medium-low-rank coal on the catalytic performance and eliminating the influence of the aluminosilicate in the coal on the catalytic performance.
According to the invention, the medium-low rank coal and the acid liquor are preferably mixed and then are kept stand, then the mixture is washed to be neutral by water, and then the obtained coal sample is dried and sieved to obtain the treated coal sample.
In the present invention, the mixing is preferably performed at 100 r.min-1Stirring for 24 hours.
In the present invention, the water is preferably distilled water.
In the present invention, the washing preferably further comprises detecting halogen-free ions (chloride ions), more preferably detecting chloride ions with a silver nitrate solution.
In the present invention, the temperature of the re-drying is preferably 105 ℃ and the time is preferably 24 hours.
In the present invention, a sieve of 200 to 300 meshes is preferably used for the sieving.
After the processed coal sample is obtained, the sunflower straws are mixed with the processed coal sample to obtain the straw-containing coal sample.
In the invention, the mass ratio of the treated coal sample to the sunflower straws is preferably 1: 1-3, and more preferably 1:1 or 1: 3.
In the present invention, the mixing is preferably grinding, and the grinding is preferably followed by drying, wherein the drying temperature is preferably 105 ℃, and the drying time is preferably 1 h.
After the straw-containing coal sample is obtained, the invention carries out steam gasification reaction on the straw-containing coal sample.
In the present invention, the parameters of the steam gasification reaction preferably include: heating to 500 deg.C at 15 deg.C/min, heating to 900 deg.C at 2 deg.C/min, maintaining the temperature of 900 deg.C for 1h, and heating to 400 deg.C; the water pumping rate is 0.057 mL/min.
In the present invention, the steam gasification reaction is preferably carried out in a fixed bed reaction apparatus.
In the invention, the mixed gas obtained by the water vapor gasification reaction is preferably detected by gas phase spectrometry. The present invention is not limited to the specific detection method, and the method is well known to those skilled in the art.
To further illustrate the present invention, the following will describe in detail the application of sunflower straw in catalytic low-rank coal steam gasification in accordance with the present invention, but they should not be construed as limiting the scope of the present invention.
Examples
(1) Drying the obtained sunflower straws for 24h at 105 ℃ in a constant-temperature drying box, separating the skins and the cores of the sunflower straws, crushing the separated sunflower straws by using a crusher until the sunflower straws are powdery, screening the sunflower straws by using a screen, and selecting 200-300 meshes from the screen to obtain a sunflower straw skin and sunflower straw core sample, wherein the sunflower straw skins are recorded as SFS and the sunflower straw cores are recorded as SFC.
(2) Taking victory lignite in inner Mongolia region and Mongolia Huoshu bituminous coal as basic research coal samples, crushing the two basic coal samples, selecting 200-300 meshes by using a sieve, and drying for 6 hours in a constant-temperature drying oven at 105 ℃ to obtain two kinds of raw coalCoal samples, both of which need to be washed with hydrochloric acid in order to eliminate interference from the minerals inherent in lignite. Mixing with hydrochloric acid (18% by mass of hydrochloric acid, 5.819mol/L) at a ratio of 1g:10mL, at 100 r.min-1Stirring for 24h, standing for 3h, washing with distilled water to neutrality, and detecting no Cl with silver nitrate solution-Then, the obtained coal sample is placed in a drying box to be dried for 24 hours at 105 ℃, a 200-300-mesh sieve is used to obtain an acid-washed coal sample of the victory lignite and the Huo-Shu bituminous coal, and the acid-washed victory lignite is marked as SL+And the pickled Hushuo Bitumo coal was recorded as KS+。
(3) Mechanically mixing the sunflower straw peel and the victory lignite according to the mass mixing ratio of 1:1 and 1:3 respectively, fully grinding the mixture, placing the mixture in a drying box, and drying the mixture for 1 hour at 105 ℃ to obtain a sample SL + -SFS (1:1), wherein the SL + is SL+-SFS (1: 3); sufficiently grinding the victory lignite and the straw core according to the mass mixing ratio of 1:1 and 1:3 respectively, and drying the fully ground victory lignite and the straw core in a drying oven at 105 ℃ for 1 hour to obtain a sample SL+-SFC(1:1)，SL+SFC (1: 3). In the same manner, Huo-Shu bituminous coal was mechanically mixed with straw husk and core, and the samples obtained were respectively labeled KS+-SFS(1:1)，KS+-SFS(1:3)，KS+-SFC(1:1)，KS+-SFC(1:3)。
The obtained product was subjected to industrial analysis, and the results are shown in table 1. As can be seen from Table 1, Pickling Hushuo bituminous coal KS+Volatile component V ofdThe content is 17.94 percent and is lower than that of the victory lignite SL+38.30% of and KS+Fixed carbon of (2)cdThe content is 72.83 percent and is much higher than SL+51.56% of the total content of the volatile matters, the volatile content of the biomass is greatly improved with the addition of the biomass, the fixed carbon content is reduced, and the moisture M isadSlightly increased. Compared with the addition amount of coal and straw bark in a mass ratio of 1:1, when the addition amount is increased to 1:3, the fixed carbon content of the sample is further reduced.
TABLE 1 Industrial analysis results of the products
Rate of steam generation in steam gasification reaction-Single component analysis
The treated coal sample and the coal sample containing straw obtained in example 1 were subjected to gasification reaction in a fixed bed reactor, and the temperature rise program of the gasification reaction was set as follows:
heating to 500 deg.C at 15 deg.C/min, heating to 900 deg.C at 2 deg.C/min, maintaining the temperature of 900 deg.C for 1h, and heating to 400 deg.C; the water pumping rate is 0.057 mL/min.
FIGS. 1 to 4 show the generation of H by the steam gasification reaction of the treated coal sample and the coal sample containing straw obtained in example 12CO and CO2The generation rate of the biomass straw is shown in the figure, and H of eight samples can be seen in the figure after the biomass straw is added2Gasification reaction temperature zone compared with SL+And KS+All undergo different degrees of advancement, wherein SL+SFC (1:3) with KS+The reaction temperature zone of-SFC (1:3) is most obviously advanced, and the maximum gasification rate corresponds to the temperatures of 716 ℃ and 720 ℃ respectively, and is advanced by 180 ℃. The hydrogen generated by the reaction is improved, and the gas generation rate is obviously improved, so that the medium-low rank coal SL can be added by adding the biomass straws+，KS+The gasification performance of (2) is improved. Meanwhile, after the biomass straws are added, the co-gasification reaction performance of the straw core and the coal is superior to that of the straw skin and the coal under the condition of the same addition amount; under the addition of different proportions, the mass ratio of coal to straw is 1:3, the co-gasification reaction performance is better than that of coal and straw in a mass ratio of 1:1, co-gasification reactivity; in the co-gasification of the straw core and the coal, the gasification reaction temperature zone of the bituminous coal is slightly advanced compared with that of the lignite, and the maximum gasification rate is advanced by about 20-30 ℃ corresponding to the temperature. In addition, the composition of the steam gasification reaction generated gas of the coal sample is changed, SL+And KS+The steam gasification generated gas is mainly H2And CO is mainly used, a small amount of CO gas is generated when the biomass straws and the coal except the straw skins are CO-gasified with the coal, and the CO-gasification generated gas mainly contains H2And CO2Mainly, the generation means that the reaction path of the steam gasification reaction is changed by adding the biomass straws. It can be seen that co-gasification with coal by adding biomass straw may occurThe synergistic effect improves the gasification performance of low-rank coal gasification in a single use, and the method has important significance for high-value utilization of sunflower biomass straws and medium-low-rank coal.
Carbon yield
FIG. 5 is a graph showing the carbon yield in steam gasification of different coal samples in example 1, and it can be seen that the carbon yield increases with the increase in gasification temperature. As can be seen in the figure, with the addition of sunflower straw biomass, the gasification reaction performance of the eight samples is obviously improved and is obviously higher than that of SL+And KS+The reactivity of (a). SL when the carbon yield reaches 50%+-SFS(1:1)、SL+-SFS(1:3)、KS+-SFS(1:1)、KS+-SFS(1:3)、SL+-SFC(1:1)、SL+-SFC(1:3)、KS+-SFC(1:1)、KS+Significantly lower than SL for-SFC (1:3)+，KS+Especially SL+-SFC(1:3)、KS+SFC (1:3) corresponds to a temperature of 692 ℃ at 50% carbon conversion, 695 ℃ well below SL at 50% carbon conversion+，KS+The temperature of (2). This means that the core added with sunflower straw is better than the straw skin, and the gasification performance of coal is improved more obviously. The co-gasification reaction performance of the straw core and the coal is better than that of the straw skin and the coal under the condition of the same addition amount; under the addition of different proportions, the mass ratio of coal to straw is 1:3, the co-gasification reaction performance is better than that of coal and straw in a mass ratio of 1:1 co-gasification reactivity. When the water vapor vaporization temperature reaches 900 ℃, SL+-SFS(1:1)、SL+-SFS(1:3)、KS+-SFS(1:1)、KS+-SFS(1:3)、SL+-SFC(1:1)、SL+-SFC(1:3)、KS+-SFC(1:1)、KS+The carbon conversion of the SFC (1:3) has almost reached 100%, whereas SL+And KS+The carbon conversion of (a) is only about 81%. The biomass straw and the coal sample are co-gasified compared with SL+And KS+The carbon conversion rate is obviously improved and SL is obviously improved by the single gasification of the medium-low rank coal+And KS+The carbon yield rate does not increase sharply until 900 ℃ after 800 ℃. The method fully shows that the co-gasification of the biomass sunflower straws and the coal improves the gasification reactionThe performance should be maintained.
The ratio of each component of the generated gas
FIG. 6 is a graph showing the steam component ratios of different coal samples in example 1, from which SL is shown+And KS+Generated gas of (1) is mainly H2And CO, and the generated gas component is mainly changed into H along with the addition of the biomass straws2And CO2And when the mass ratio of the coal to the straw is 1: and more clearly at 3. SL (Long-side)+And KS+CO/H in the generated gas2Is about 1/1, but when the coal and biomass straw are co-gasified, H2And CO2Has an increased ratio of (A) to (B), and a greatly reduced CO, especially KS+-SFC(1:3)，SL+The SFC (1:3) sample is most obvious, and the carbon conversion chart shows that the adding amount ratio of coal to biomass straws is 1:3, the reaction performance of the coal sample using the sunflower straw core is optimal, and the lignite is slightly superior to the bituminous coal. Therefore, the biomass straw and coal can generate synergistic effect during co-gasification, and the reaction path is changed during gasification, so that the composition of the generated gas is changed.
Therefore, the sunflower straw gasification experiment is carried out by the sunflower straw gasification method together with the victory lignite and the Humajor bituminous coal. The addition of the sunflower straws has a very obvious catalytic action on the gasification reaction of the coal, and the co-gasification of the two kinds of coal and the biomass straws greatly improves the reaction temperature area and accelerates the reaction rate. Compared with the straw skin, the synergistic effect of the straw core and the coal is more obvious, the reaction performance is better when the addition amount is 3:1 of the biomass and the coal, the efficient utilization of the biomass straw and the medium-low-rank coal is realized, the coal consumption is reduced, and the energy is saved.
Detailed description of the preferred embodiment 1
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-order coal is realized by the following steps:
1) selecting victory lignite in inner Mongolia areas of China, crushing the victory lignite by a crusher, pre-drying the victory lignite in a forced air drying oven at 105 ℃, preparing the victory lignite into powder by a ball mill, screening the powder to 200-300 meshes by a standard screening device, and drying lignite particles for 6 hours at 105 ℃ to obtain raw coal of the victory lignite;
2) mixing the victory lignite with 18 wt.% hydrochloric acid according to a volume ratio of 1g: mixing the components in a proportion of 10mL, stirring the mixture for 24 hours at a rotating speed of 100r/min, standing the mixture for 6 hours, removing supernatant, and washing the mixture for multiple times by using deionized water until the mixture is AgNO3Absence of Cl after detection-If the coal sample exists, the coal sample is considered to be washed clean, then the filtered coal sample is dried for 24 hours at 105 ℃, and finally the coal sample is sieved to 200-300 meshes through a standard sieving machine to obtain a hydrochloric acid treated coal sample;
3) selecting sunflower straws, drying, crushing the straw skins of the sunflower straws by using a crusher until the straw skins are powdery, and selecting 200-300 meshes by using a sieve to obtain a sunflower straw skin sample.
4) Mechanically mixing sunflower straw bark and acid-washed lignite according to the mass mixing ratio of 1:1, fully grinding, drying in a drying oven at 105 ℃ for 1h to obtain a coal sample, and recording the coal sample as SL+-SFS(1:1)。
5) 0.15g of SL+-SFS (1:1) is placed in an electric heating furnace with high-purity argon as carrier gas and gas speed of 60mL min-1The system pressure is 0.4MPa, the temperature of the reactor is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ per minute-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature was kept constant at 900 ℃ for 1 hour, and the gas generated was monitored by gas chromatography.
Specific example 2
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-order coal is realized by the following steps:
1) selecting victory lignite in inner Mongolia areas of China, crushing the victory lignite by a crusher, pre-drying the victory lignite in a forced air drying oven at 105 ℃, preparing the victory lignite into powder by a ball mill, screening the powder to 200-300 meshes by a standard screening device, and drying lignite particles for 6 hours at 105 ℃ to obtain raw coal of the victory lignite;
2) mixing the victory lignite with 18-wt.% hydrochloric acid according to a volume ratio of 1g: mixing at a ratio of 10mL, stirring at 100r/min for 24h, and standingStanding for 6h, removing supernatant, and washing with deionized water for several times until AgNO3No Cl after detection-If the coal sample exists, the coal sample is considered to be washed clean, then the filtered coal sample is dried for 24 hours at 105 ℃, and finally the coal sample is sieved to 200-300 meshes through a standard sieving machine to obtain a hydrochloric acid treated coal sample;
3) the method comprises the steps of selecting sunflower straws, drying, crushing the sunflower straw skins with a crusher until the sunflower straw skins are powdery, and selecting 200-300 meshes with a sieve to obtain a sunflower straw skin sample.
4) Mechanically mixing sunflower straw bark and acid-washed lignite according to the mass mixing ratio of 1:3, fully grinding, drying in a drying oven at 105 ℃ for 1h to obtain a coal sample, and recording the coal sample as SL+-SFS(1:3)。
5) 0.15g of SL+-SFS (1:3) is placed in an electric heating furnace with high-purity argon as carrier gas and gas speed of 60mL min-1The system pressure is 0.4MPa, the temperature of the reactor is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ min-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature was kept constant at 900 ℃ for 1 hour, and the gas produced was monitored by gas chromatography.
Specific example 3
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-order coal is realized by the following steps:
1) selecting Huo Shuo bituminous coal in Mongolia, crushing the Huo Shuo bituminous coal by a crusher, pre-drying the crushed Huo Shuo bituminous coal in a blast drying box at 105 ℃, preparing the crushed Huo Shuo bituminous coal into powder by a ball mill, screening the powder to 200-mesh and 300-mesh by a standard screening device, and drying bituminous coal particles for 6 hours at 105 ℃ to obtain the Huo Shuo bituminous coal raw coal;
2) mixing Huo Shuo bituminous coal with 18 wt.% hydrochloric acid according to a volume ratio of 1g: mixing the components in a proportion of 10mL, stirring the mixture for 24 hours at a rotating speed of 100r/min, standing the mixture for 6 hours, removing supernatant, and washing the mixture for multiple times by using deionized water until the mixture is AgNO3Absence of Cl after detection-There, the coal sample is considered to be washed clean and then filtered at 105 deg.CDrying for 24h, and finally sieving to 200-300 meshes by using a standard sieving device to obtain a hydrochloric acid treatment coal sample;
3) the method comprises the steps of selecting sunflower straws, drying, crushing the sunflower straw skins with a crusher until the sunflower straw skins are powdery, and selecting 200-300 meshes with a sieve to obtain a sunflower straw skin sample.
4) Mechanically mixing sunflower straw bark and acid-washed bituminous coal at a mass mixing ratio of 1:1, fully grinding, drying at 105 deg.C for 1 hr in a drying oven to obtain coal sample, and recording as KS+-SFS(1:1)。
5) 0.15g of KS+-SFS (1:1) is placed in an electric heating furnace with high-purity argon as carrier gas and gas speed of 60mL min-1The system pressure is 0.4MPa, the temperature of the reactor is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ per minute-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature was kept constant at 900 ℃ for 1 hour, and the gas produced was monitored by gas chromatography.
Specific example 4
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-rank coal is realized by the following steps:
1) selecting Huo Shu Tu bituminous coal of Mongolian, crushing the Huo Shu Tu bituminous coal by a crusher, pre-drying the Huo Shu Tu bituminous coal in a blast drying oven at 105 ℃, preparing the Huo Shu Tu bituminous coal into powder by a ball mill, screening the powder to 200-300 meshes by a standard screening device, and drying bituminous coal particles for 6 hours at 105 ℃ to obtain Huo Shu Tu bituminous coal raw coal;
2) mixing Huo Shuo bituminous coal with 18 wt.% hydrochloric acid according to a volume ratio of 1g: mixing the components in a proportion of 10mL, stirring the mixture for 24 hours at a rotating speed of 100r/min, standing the mixture for 6 hours, removing supernatant, and washing the mixture for multiple times by using deionized water until the mixture is AgNO3Absence of Cl after detection-If the coal sample exists, the coal sample is considered to be washed clean, then the filtered coal sample is dried for 24 hours at 105 ℃, and finally the coal sample is sieved to 200-300 meshes through a standard sieving machine to obtain a hydrochloric acid treated coal sample;
3) the method comprises the steps of selecting sunflower straws, drying, crushing the sunflower straw skins with a crusher until the sunflower straw skins are powdery, and selecting 200-300 meshes with a sieve to obtain a sunflower straw skin sample.
4) The skin of sunflower straw was mechanically mixed with the acid-washed bituminous coal in a mass mixing ratio of 1:3, respectively, and the mixture was fully ground and then dried in a drying oven at 105 ℃ for 1h to obtain a coal sample, which was designated as KS + -SFS (1: 3).
5) 0.15g of KS+-SFS (1:3) is placed in an electric heating furnace, high-purity argon is used as carrier gas, and the gas speed is 60 mL/min-1The system pressure is 0.4MPa, the temperature of the reactor is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ per minute-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature was kept constant at 900 ℃ for 1 hour, and the gas produced was monitored by gas chromatography.
Specific example 5
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-rank coal is realized by the following steps:
1) selecting victory lignite in inner Mongolia areas of China, crushing the victory lignite by a crusher, pre-drying the victory lignite in a forced air drying oven at 105 ℃, preparing the victory lignite into powder by a ball mill, screening the powder to 200-300 meshes by a standard screening device, and drying lignite particles for 6 hours at 105 ℃ to obtain raw coal of the victory lignite;
2) mixing the victory lignite with 18 wt.% hydrochloric acid according to a volume ratio of 1g: mixing 10mL of the mixture, stirring the mixture for 24 hours at the rotating speed of 100r/min, standing the mixture for 6 hours, removing supernatant, and washing the mixture for multiple times by using deionized water until the AgNO is AgNO3Absence of Cl after detection-If the coal sample exists, the coal sample is considered to be washed clean, then the filtered coal sample is dried for 24 hours at 105 ℃, and finally the coal sample is sieved to 200-300 meshes through a standard sieving machine to obtain a hydrochloric acid treated coal sample;
3) selecting sunflower straws, drying, crushing the sunflower straw cores by using a crusher until the sunflower straw cores are powdery, and selecting 200-300 meshes by using a sieve to obtain a sunflower straw core sample.
4) Mixing sunflower stalk core with acid-washed brownMechanically mixing coal, namely fully grinding the victory lignite and the straw cores according to the mass mixing ratio of 1:1 respectively, and then drying the mixture in a drying oven at 105 ℃ for 1h to obtain a coal sample which is recorded as SL+-SFC(1:1)。
5) 0.15g of SL+-SFC (1:1) was placed in an electric furnace with high purity argon as carrier gas at a gas velocity of 60mL min-1The system pressure is 0.4MPa, the temperature of the reactor is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ per minute-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature was kept constant at 900 ℃ for 1 hour, and the gas produced was monitored by gas chromatography.
Specific example 6
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-rank coal is realized by the following steps:
1) selecting victory lignite in inner Mongolia areas of China, crushing the victory lignite by a crusher, pre-drying the victory lignite in a forced air drying oven at 105 ℃, preparing the victory lignite into powder by a ball mill, screening the powder to 200-300 meshes by a standard screening device, and drying lignite particles for 6 hours at 105 ℃ to obtain raw coal of the victory lignite;
2) mixing the victory lignite with 18 wt.% hydrochloric acid according to a volume ratio of 1g: mixing 10mL of the mixture, stirring the mixture for 24 hours at the rotating speed of 100r/min, standing the mixture for 6 hours, removing supernatant, and washing the mixture for multiple times by using deionized water until the AgNO is AgNO3Absence of Cl after detection-If the coal sample exists, the coal sample is considered to be washed clean, then the filtered coal sample is dried for 24 hours at 105 ℃, and finally the coal sample is sieved to 200-300 meshes through a standard sieving machine to obtain a hydrochloric acid treated coal sample;
3) selecting sunflower straws, drying, crushing the sunflower straw cores by using a crusher until the sunflower straw cores are powdery, and selecting 200-300 meshes by using a sieve to obtain a sunflower straw core sample.
4) Mechanically mixing sunflower straw cores and acid-washed lignite in a mass mixing ratio of 1:3, fully grinding, drying in a drying oven at 105 ℃ for 1h to obtain a coal sample, and recording the coal sample as SL+-SFC(1:3)。
5) 0.15g of SL+-SFC (1:3) is placed in an electric heating furnace, high-purity argon is used as carrier gas, and the gas speed is 60 mL/min-1The system pressure is 0.4MPa, the temperature of the reactor is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ per minute-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature was kept constant at 900 ℃ for 1 hour, and the gas produced was monitored by gas chromatography.
Specific example 7
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-rank coal is realized by the following steps:
1) selecting Huo Shu Tu bituminous coal of Mongolian, crushing the Huo Shu Tu bituminous coal by a crusher, pre-drying the Huo Shu Tu bituminous coal in a blast drying oven at 105 ℃, preparing the Huo Shu Tu bituminous coal into powder by a ball mill, screening the powder to 200-300 meshes by a standard screening device, and drying bituminous coal particles for 6 hours at 105 ℃ to obtain Huo Shu Tu bituminous coal raw coal;
2) mixing Huo Shuo bituminous coal with 18-wt.% hydrochloric acid according to a volume ratio of 1g: mixing the components in a proportion of 10mL, stirring the mixture for 24 hours at a rotating speed of 100r/min, standing the mixture for 6 hours, removing supernatant, and washing the mixture for multiple times by using deionized water until the mixture is AgNO3Absence of Cl after detection-If the coal sample exists, the coal sample is considered to be washed clean, then the filtered coal sample is dried for 24 hours at 105 ℃, and finally the coal sample is sieved to 200-300 meshes through a standard sieving machine to obtain a hydrochloric acid treated coal sample;
3) selecting sunflower straws, drying, crushing the sunflower straw cores by using a crusher until the sunflower straw cores are powdery, and selecting 200-300 meshes by using a sieve to obtain a sunflower straw core sample.
4) Mechanically mixing the cores of the sunflower straws with the acid-washed bituminous coal, wherein the mass mixing ratio of the Humajor bituminous coal to the straw cores is 1:1 respectively, fully grinding the mixture, and drying the mixture in a drying oven at 105 ℃ for 1h to obtain a coal sample, which is recorded as KS + -SFC (1: 1).
5) 0.15g of KS+-SFC (1:1) was placed in an electric furnace with high purity argon as carrier gas at a gas velocity of 60mL min-1The system pressure is 0.4MPa, and the reaction is carried outThe reactor temperature is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ min-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature was kept constant at 900 ℃ for 1 hour, and the gas produced was monitored by gas chromatography.
Specific example 8
A method for producing hydrogen by catalytic gasification of biomass straws and medium-low-order coal is realized by the following steps:
1) selecting Huo Shu Tu bituminous coal of Mongolian, crushing the Huo Shu Tu bituminous coal by a crusher, pre-drying the Huo Shu Tu bituminous coal in an air-blast drying oven at 105 ℃, preparing the Huo Shu Tu bituminous coal into powder by a ball mill, screening the powder to 200-300 meshes by a standard screening device, and drying bituminous coal particles for 6 hours at 105 ℃ to obtain raw Huo Shu Tu bituminous coal;
2) mixing Hushuo bituminous coal with 18 wt.% hydrochloric acid according to a volume ratio of 1g: mixing 10mL of the mixture, stirring the mixture for 24 hours at the rotating speed of 100r/min, standing the mixture for 6 hours, removing supernatant, and washing the mixture for multiple times by using deionized water until the AgNO is AgNO3Absence of Cl after detection-If the coal sample exists, the coal sample is considered to be washed clean, then the filtered coal sample is dried for 24 hours at 105 ℃, and finally the coal sample is sieved to 200-300 meshes through a standard sieving machine to obtain a hydrochloric acid treated coal sample;
3) selecting sunflower straws, drying, crushing the sunflower straw cores by using a crusher until the sunflower straw cores are powdery, and selecting 200-300 meshes by using a sieve to obtain a sunflower straw core sample.
4) Mechanically mixing sunflower straw core and acid-washed bituminous coal at a mass mixing ratio of 1:3, fully grinding, drying at 105 deg.C for 1 hr in a drying oven to obtain coal sample, and recording as KS+-SFC(1:3)。
5) 0.15g of KS+-SFC (1:3) is placed in an electric heating furnace, high-purity argon is used as carrier gas, and the gas speed is 60 mL/min-1The system pressure is 0.4MPa, the temperature of the reactor is heated from room temperature to 500 ℃, and the heating rate is 15 ℃ per minute-1Introducing deionized water, and then introducing deionized water at 2 ℃ for min-1The temperature is constantly 900 ℃ when the temperature is increased to 900 DEG CThe hold time was 1 hour and the gas evolution was monitored by gas chromatography.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (6)
1. An application of sunflower straw in catalyzing the steam gasification of medium-low rank coal,
the sunflower straws are pretreated by the following steps:
drying sunflower straws and separating skin from core in sequence to respectively obtain a skin component and a core component;
crushing and screening the core components to obtain sunflower straw cores;
the application specifically comprises the following steps:
performing acid treatment on the medium-low rank coal to obtain a treated coal sample;
mixing the sunflower straw cores with the treated coal sample to obtain a straw-containing coal sample; the mass ratio of the treated coal sample to the sunflower straw core is 1: 3;
and carrying out steam gasification reaction on the coal sample containing the straws.
2. Use according to claim 1, wherein the drying is carried out at a temperature of 105 ℃ for a period of 24 hours.
3. The use according to claim 1, wherein the sieved particle size is 200 to 300 mesh.
4. The use according to claim 1, wherein the medium-low rank coal is lignite or bituminous coal.
5. The use of claim 1, wherein the acid treatment uses hydrochloric acid, the mass fraction of the hydrochloric acid is 18%, and the dosage ratio of the medium-low rank coal to the hydrochloric acid is 1g:10 mL.
6. Use according to claim 1, wherein the parameters of the water vapour gasification reaction comprise: heating to 500 deg.C at 15 deg.C/min, heating to 900 deg.C at 2 deg.C/min, and holding the temperature at 900 deg.C for 1 h.
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