CN118851881B - A purification process for producing ethanol from synthesis gas - Google Patents
A purification process for producing ethanol from synthesis gas Download PDFInfo
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- CN118851881B CN118851881B CN202411323791.1A CN202411323791A CN118851881B CN 118851881 B CN118851881 B CN 118851881B CN 202411323791 A CN202411323791 A CN 202411323791A CN 118851881 B CN118851881 B CN 118851881B
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Abstract
本发明公开了一种合成气制乙醇的提纯工艺，属于乙醇提纯技术领域，用于解决现有技术中的吸附剂填料的孔隙率与比表面积低，合成气制备的粗乙醇精馏提纯的乙醇产品的纯度有待进一步提高的技术问题；本发明包括以下步骤：将改性膨润土、改性粉煤灰、淀粉和硅酸钠混合均匀后加入到反应釜中，向反应釜中加入去离子水，本发明是通过改性膨润土、改性粉煤灰、淀粉、硅酸钠与偏铝酸钠复配，制备多孔隙的亲水性吸附剂前驱体，通过壳聚糖与氧化锌对其进行改性，制备得到大比表面积与孔隙率的亲水性吸附剂填料，再优化现有技术中的乙醇精馏提纯工艺，降低乙醇产品中水分、甲醇、乙酸酯等杂质的含量，制备得到高纯度的工业乙醇产品。
The invention discloses a purification process for preparing ethanol from synthesis gas, belongs to the technical field of ethanol purification, and is used to solve the technical problem that the porosity and specific surface area of the adsorbent filler in the prior art are low, and the purity of the ethanol product obtained by distillation and purification of crude ethanol prepared from synthesis gas needs to be further improved. The invention comprises the following steps: modified bentonite, modified fly ash, starch and sodium silicate are uniformly mixed and added into a reactor, and deionized water is added into the reactor. The invention prepares a porous hydrophilic adsorbent precursor by compounding the modified bentonite, modified fly ash, starch, sodium silicate and sodium aluminate, and modifies the precursor by chitosan and zinc oxide to prepare a hydrophilic adsorbent filler with a large specific surface area and porosity, and then optimizes the ethanol distillation and purification process in the prior art to reduce the content of impurities such as water, methanol and acetate in the ethanol product, so as to prepare a high-purity industrial ethanol product.
Description
Technical Field
The invention relates to the technical field of ethanol purification, in particular to a purification process for preparing ethanol from synthesis gas.
Background
The method has the advantages that the synthetic gas is obtained by gasifying solid coal and coke, and the route for preparing the low-carbon alcohol by the synthetic gas is efficient and clean, has sustainable development and can also effectively improve the utilization rate of coal resources.
In the prior art, the synthetic gas is firstly prepared into methanol, the methanol is dehydrated to prepare dimethyl ether, and the dimethyl ether carbonylation and methyl acetate hydrogenation are carried out to prepare ethanol so as to avoid the problem of corrosion of acetic acid to equipment, reduce the requirement on equipment materials, and the hydrogenation difficulty of the methyl acetate is lower than that of the acetic acid, and the hydrogenation catalyst is mainly a non-noble metal catalyst taking Cu as an active component, so that the cost of the route is low and the economic competitiveness is strong;
however, the prepared ethanol is mixed with unreacted methanol, methyl acetate and byproducts of methyl formate, water and other alcohols generated in the reaction process, a rectifying tower is usually adopted for rectifying the crude ethanol in the prior art, impurities in the ethanol are separated from the ethanol by utilizing the difference of the boiling points of molecules, but methyl acetate and water contained in the crude ethanol prepared by the synthesis gas are azeotroped with the ethanol in the rectifying tower, a molecular sieve is usually adopted as a filler in the filler tower, the porosity and the specific surface area are low, the hydrophilicity and the selective adsorption of the methanol and the acetate are poor, the moisture content of the prepared ethanol product is high, and the purity of the ethanol product is still to be further improved.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a purification process for preparing ethanol from synthesis gas, which is used for solving the technical problems that the adsorbent filler in the prior art has low porosity and specific surface area, poor hydrophilicity and selective adsorption on methanol and acetate, the content of water, methanol and methyl acetate in an ethanol product prepared by rectifying and purifying crude ethanol prepared from synthesis gas is high, and the purity of the ethanol product needs to be further improved.
The invention aims at realizing the purification process for preparing ethanol from synthesis gas, which comprises the following steps:
S1, uniformly mixing modified bentonite, modified fly ash, starch and sodium silicate, adding the mixture into a reaction kettle, adding deionized water into the reaction kettle, stirring for 30-50min at room temperature, raising the temperature of the reaction kettle to 70-80 ℃, adding a sodium metaaluminate solution into the reaction kettle, stirring for 90-110min, evaporating the solvent under reduced pressure to obtain slurry with the water content of 10-20%, and roasting after granulation treatment to obtain an adsorbent precursor;
The synthesis reaction principle of the adsorbent precursor is as follows:
After the modified bentonite, the modified fly ash, the starch and the sodium silicate are uniformly mixed, deionized water is added for stirring, the raw materials are subjected to preliminary physical mixing and wetting under the action of water molecules, meanwhile, sodium silicate is dissolved in water to form silicate ions, and complex chemical reactions such as ion exchange, precipitation generation, complexation reaction and the like are carried out on the metaaluminate ions in the metaaluminate solution and silicate ions, calcium ions, aluminum ions and the like in a reaction system at high temperature (70-80 ℃), so that the intermolecular acting force is improved, the interaction between reaction products is enhanced by evaporating most of the aqueous solution, the reaction products are subjected to granulation through a granulator to form a particle blank with certain strength and structure, and then the particle blank is subjected to programmed heating treatment to further solidify, so that the decomposition of organic matters (starch), the rearrangement and sintering of inorganic mineral phases and the like are promoted to form a more compact and stable structure, and the structure of the particle blank is more stable, so that the adsorbent precursor with a porous structure is prepared.
S2, adding chitosan and glacial acetic acid solution into a reaction kettle, stirring until the system is dissolved, adding an adsorbent precursor and zinc oxide into the reaction kettle, performing ultrasonic dispersion for 30-50min, dropwise adding sodium hydroxide solution into the reaction kettle, performing ultrasonic dispersion for 40-60min after the dropwise addition is completed, and performing post-treatment to obtain an adsorbent filler;
the synthetic reaction principle of the adsorbent filler is as follows:
In the reaction process, chitosan and zinc oxide are dissolved in glacial acetic acid solution, uniform mixing of chitosan, zinc oxide and an adsorbent precursor is promoted through ultrasonic dispersion, the pH of a system is increased at any time, amino groups in chitosan molecules begin to be deprotonated, the original neutral or negatively charged state is restored, chitosan molecules interact with a porous structure of the adsorbent precursor through hydrogen bonds, electrostatic interactions or van der Waals forces and the like to form a chitosan coating layer, cross-linking reaction possibly occurs between chitosan molecules under alkaline conditions, the adsorbent precursor is coated to form a three-dimensional network structure, zinc ions and hydroxyl groups, amino groups and the like in the chitosan molecules are coordinated or chelated under alkaline conditions to form a stable compound, solids and liquid in the reaction mixture are separated through suction filtration, the filter cake is washed to be neutral through purified water to remove residual sodium hydroxide and other soluble impurities, then the interaction between solid particles is promoted to be gradually evaporated in the high-temperature drying process, and the adsorbent filler with stable structure and performance is formed.
S3, filling the adsorbent filler on a tower plate of the rectifying tower, and forming an adsorbent bed layer on the tower plate of the rectifying tower;
s4, conveying the crude ethanol into the rectifying tower from a feed pipe, purifying and rectifying the crude ethanol by the rectifying tower, discharging the finished ethanol from a discharge pipe of the rectifying tower, discharging light components from a top blow-down pipe of the rectifying tower, collecting heavy components at the bottom of the inner side of the rectifying tower, and discharging the heavy components from a bottom discharge pipe of the rectifying tower.
Further, in the step S1, the dosage ratio of the modified bentonite, the modified fly ash, the starch, the sodium silicate, the deionized water and the sodium metaaluminate solution is 7g to 3g to 0.6-0.8g to 3.5g to 12-14mL to 10g, the sodium metaaluminate solution is composed of sodium metaaluminate and deionized water according to the weight ratio of 1:9, the roasting treatment method comprises the steps of placing the granulated particles into a muffle furnace, increasing the temperature of the muffle furnace to 95-105 ℃ at the temperature increasing rate of 3-5 ℃ per minute, carrying out heat preservation treatment for 50-70min, increasing the temperature of the muffle furnace to 180-220 ℃ at the temperature increasing rate of 1-3 ℃ per minute, carrying out heat preservation treatment for 30-40min, increasing the temperature of the muffle furnace to 450-550 ℃ at the temperature increasing rate of 6-9 ℃ per minute, carrying out heat preservation treatment for 2-3h, naturally cooling to room temperature, and obtaining an adsorbent precursor, and in the step S2, carrying out suction treatment for 1-1.5g to 10g, transferring the dosage ratio of the chitosan, the glacial acetic acid solution, the adsorbent precursor, the zinc oxide and the sodium hydroxide solution to 50mL to the weight ratio of the adsorbent, carrying out suction filtration for 1-5.5 g to 50.0:0 mol/15 ℃ and drying the filter cake, and carrying out the water filtration for the purification treatment, and the filter cake after the water filtration, and the water filtration is completed to 60-0.5:0:0 mol, and the dry concentration of the filter cake is carried out after the water filtration, and the water filtration is completed.
Further, the number of the tower plates of the rectifying tower is 60, the height of the adsorbent bed layer on each tower plate is 7-10cm, the feeding pipe extends to the top of the 13 th tower plate from bottom to top, one end of the inside of the rectifying tower is positioned at the top of the 54 th tower plate from bottom to top, the reflux ratio inside the rectifying tower is 60, and the distillate feeding ratio is 0.105-0.110.
Further, the modified bentonite is obtained by processing the following steps:
a1, adding activated bentonite and calcium oxide into a ball mill, ball milling for 40-60min, and sieving with a 100-mesh sieve to obtain mixed powder;
A2, adding the mixed powder and deionized water into a reaction kettle, and stirring for 30-50min at room temperature to obtain a mixture;
And A3, paving the mixture in a constant temperature and humidity box, performing heat preservation and moisture preservation for 10-12h, and performing post treatment to obtain the modified bentonite.
The synthetic reaction principle of the modified bentonite is as follows:
Through ball milling and dispersing, calcium oxide is mixed and dispersed with activated bentonite in a physical embedding way, calcium oxide is an alkaline oxide, calcium hydroxide is generated by hydrolysis in water, the calcium hydroxide is adsorbed to interlayer active centers of the activated bentonite, a heat preservation and moisture preservation treatment stage is carried out under the constant temperature and humidity condition, and the calcium hydroxide generated by hydrolysis of the calcium oxide further promotes dissolution and reprecipitation of silicate minerals in the bentonite, so that hydration caused by hydroxide ions of the calcium hydroxide is avoided, calcium hydroxide is condensed in outer pore channels of the activated bentonite, the calcium hydroxide cannot diffuse into the pore channels of the activated bentonite, and alkaline calcium hydroxide is loaded inside and outside the pore channels of the activated bentonite, so that the modified bentonite is prepared.
In the step A3, the temperature of the constant temperature and humidity box is 65-75 ℃ and the humidity is 50-60%, after the treatment is finished, the temperature of the constant temperature and humidity box is reduced to room temperature, discharging is carried out, a modified bentonite crude product is obtained, the modified bentonite crude product and deionized water are added into a reaction kettle according to the weight ratio of 1g to 20mL, stirring and dispersing are carried out for 60-80min, suction filtration is carried out, a filter cake is dried after leaching by deionized water, the filter cake is transferred into a drying box with the temperature of 60-70 ℃, and vacuum drying is carried out to constant weight, and a 100-mesh screen is adopted, thus obtaining the modified bentonite.
Further, the preparation method of the activated bentonite comprises the steps of adding bentonite and hydrochloric acid into a reaction kettle, stirring, heating the reaction kettle to 75-85 ℃, preserving heat, stirring for 4-6h, and performing post-treatment to obtain the activated bentonite.
The synthesis reaction principle of the activated bentonite is as follows:
Bentonite mainly comprises phyllosilicate minerals such as montmorillonite and the like, and exchangeable cations (such as sodium, calcium, magnesium and the like) and interlayer water are contained in the phyllosilicate minerals, and the phyllosilicate minerals enable the bentonite to have good adsorptivity, expansibility and cation exchange capacity, hydrochloric acid is an inorganic acid with lower corrosiveness, through the concentration of carbonic acid hydrochloric acid, under the condition of avoiding excessive reaction caused by high-concentration acid, the exchange reaction between hydrogen ions and interlayer cations of the bentonite can be carried out at a relatively moderate rate, so that the hydrogen ions in the hydrochloric acid and the interlayer cations of the bentonite are subjected to ion exchange reaction, and the cations such as sodium, potassium, magnesium and the like are converted into soluble salts of the acid to be dissolved out, so that the bonding force between original layers is weakened, the lamellar lattice of the bentonite is split, the pore channels of the bentonite are dredged, and the activity of the bentonite is enhanced.
Further, the dosage ratio of the bentonite to the hydrochloric acid is 1g to 10mL, the mass fraction of the hydrochloric acid is 10-12%, the post-treatment in the preparation method of the activated bentonite comprises the steps of reducing the temperature of a reaction kettle to room temperature after the reaction is completed, carrying out suction filtration, washing a filter cake with purified water to neutrality, carrying out suction drying, transferring the filter cake into a drying box with the temperature of 70-80 ℃, and drying to constant weight to obtain the activated bentonite.
Further, the preparation method of the modified fly ash comprises the steps of adding the fly ash and the modifying liquid into a reaction kettle, stirring, reducing the temperature of the reaction kettle to 18-22 ℃, preserving heat, stirring for 120-160min, and post-treating to obtain the modified fly ash.
The synthetic reaction principle of the modified fly ash is as follows:
Fly ash is mainly composed of oxides and silicate minerals of elements such as silicon, aluminum, iron and the like, and the surface of the fly ash is usually provided with a certain charge and active sites. In alkaline environment, anions of sodium carbonate and sodium hydroxide can react with cations (such as cations of silicon and aluminum) on the surface of the fly ash, soluble salts such as sodium silicate and sodium aluminate are activated through dissociation or hydrolysis reaction to form ions or molecular forms which are easier to react, activated monomers are mutually close and are connected through chemical bonds to form small aggregates or 'cores', more monomers are added into the cores along with the progress of the reaction, the aggregates are gradually increased, cross-linking reaction can also occur between different aggregates, a three-dimensional network structure is formed on the surface of the fly ash, and the specific surface area and the porosity of the fly ash are improved.
Further, the dosage ratio of the fly ash to the modifying liquid is 1g to 15mL, the modifying liquid consists of sodium carbonate, sodium hydroxide and deionized water according to the dosage ratio of 5g to 1g to 50mL, the post treatment in the preparation method of the modified fly ash comprises the steps of after the reaction is completed, pumping filtration, washing a filter cake with deionized water to be neutral, pumping, transferring the filter cake into a drying box with the temperature of 85-95 ℃, drying to constant weight, and sieving the filter cake with a 100-mesh sieve to obtain the modified fly ash.
The invention has the following beneficial effects:
1. According to the purification process for preparing ethanol from synthesis gas, alkaline calcium hydroxide is loaded on activated bentonite to prepare modified bentonite, modified fly ash, starch and sodium silicate are mixed and then are compounded with sodium metaaluminate, and the subsequent treatments such as granulation and roasting are carried out to prepare the adsorbent filler, so that the original structure of raw materials is broken through in the preparation process of the modified fly ash and the modified bentonite, more micropores and mesopores are formed, the specific surface area and the porosity of the adsorbent filler are improved, the sufficient contact between the adsorbent and the adsorbate is facilitated, the adsorption efficiency is improved, the separation of methanol, methyl acetate and ethanol in crude ethanol is promoted, the high-purity ethanol product is prepared, the adsorbent filler optimizes the structure of the adsorbent in the preparation process, the adsorbent filler has stronger hydrophilicity, the adsorbent filler has better performance in the aspect of removing water in the crude ethanol, the rectification purification process parameters are optimized, the moisture in the crude ethanol can be effectively removed, and the water content of the ethanol product is reduced, and the high-purity industrial ethanol is obtained.
2. According to the purification process for preparing ethanol from the synthesis gas, the bentonite is modified by the hydrochloric acid, so that the porosity and activity of the activated bentonite are improved, calcium oxide solid and the activated bentonite are premixed, and then through wet maintenance, calcium hydroxide is further dissociated to release a large number of hydroxide ions, the hydroxide ions are adsorbed on the surface of the bentonite or enter the pore structure of the bentonite, and the hydroxide ions can form hydrogen bonds with water molecules, so that the interaction between a material and moisture is enhanced, and the hydrophilic performance of the modified bentonite is improved; according to XRD analysis, only the intensity of diffraction peaks before and after the modification of the fly ash is changed, no obvious new diffraction peaks appear, the mineral types of the fly ash before and after the modification are not changed, silicate in the fly ash is generally provided with a complex network structure, the silicate is formed by connecting silicon and oxygen atoms through covalent bonds, a three-dimensional framework is formed, sodium hydroxide is a strong alkali, when the sodium hydroxide contacts with the fly ash, hydroxide ions dissociated in aqueous solution attack silica bonds or silica-alumina bonds in silicate networks, silicate ions or aluminate ions are released, and simultaneously hydroxide ions are recombined with the ions, so that new compounds containing hydroxyl groups are formed, further the hydrophilic performance of the modified fly ash is further improved, the high porosity is matched with the high porosity of the compound, so that the adsorbent filler shows good porosity, the high porosity is favorable for reducing the diffusion resistance of adsorbent molecules in the adsorbent, the compound can reach adsorption sites more quickly, the adsorption efficiency is improved, the increase of the porosity means that more tiny space in the adsorbent is provided in the adsorbent, the surface area is increased, more adsorption sites are provided for adsorbing impurities, the adsorbent can more effectively promote the separation of ethanol products and impurities, and improve the purity of ethanol.
3. According to the purification process for preparing ethanol from the synthesis gas, silicate substances such as sodium silicate and the like in a mixed system of modified bentonite, modified fly ash, starch and sodium silicate can form silicate gel in water, the addition of sodium metaaluminate can further promote the gelation process, the components are tightly combined together to form an adsorbent precursor with a porous structure, the components are tightly combined through drying, the starch is used as a natural high molecular compound and has good cohesiveness and film forming property, in a reaction system, the starch can be used as a binder, inorganic particles such as modified bentonite, modified fly ash and the like and the adhesive such as sodium silicate are tightly combined together to form more uniform and stable slurry, the starch can be carbonized in the heating process to form a carbonaceous material with adsorption activity, and carbonization generates a microporous or mesoporous structure, the specific surface area and the porosity of the adsorbent precursor are increased, the separation and purification effects of the adsorbent filler on crude ethanol are further improved, the chitosan is a natural high molecular polysaccharide with rich hydroxyl groups, amino groups and the like, the functional groups can be combined with water molecules, acetic acid esters and the like to form the adsorption sites, the adsorption sites of the acetic acid and the zinc oxide and the impurities in the porous structure are selectively combined with the adsorption sites of the porous filler, and the adsorption sites of the acetic acid and the impurities are mutually-rich, and the adsorption sites of the adsorption sites and the adsorption sites of the acetic acid and the zinc oxide and the impurities are provided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a rectifying tower according to the present invention;
FIG. 2 is an XRD analysis spectrum of fly ash and modified fly ash according to the invention;
FIG. 3 is an infrared analysis spectrum of activated bentonite and modified bentonite in the present invention.
In the figure, 100 parts of methanol rectifying tower, 200 parts of feeding pipe, 300 parts of discharging pipe, 400 parts of blow-down pipe, 500 parts of discharging pipe.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of an adsorbent filler for purifying ethanol prepared from synthesis gas, which comprises the following steps:
S1, preparing modified fly ash
Uniformly mixing sodium carbonate, sodium hydroxide and deionized water according to the dosage ratio of 5g to 1g to 50mL to obtain a modified liquid;
1000g of fly ash and 15000mL of modifying liquid are weighed, added into a reaction kettle for stirring, the temperature of the reaction kettle is reduced to 18 ℃, the temperature is kept for stirring for 120min, after the reaction is completed, suction filtration is performed, a filter cake is washed to be neutral by deionized water and then is pumped to be dried, the filter cake is transferred into a drying box with the temperature of 85 ℃ for drying to constant weight, and the filter cake is screened by a 100-mesh screen to obtain the modified fly ash.
S2, preparing activated bentonite
1000G of bentonite and 10000mL of 10wt% hydrochloric acid are weighed, added into a reaction kettle for stirring, the temperature of the reaction kettle is increased to 75 ℃, the reaction kettle is kept warm and stirred for 4 hours, after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is pumped to dryness, and the filter cake is transferred into a drying box with the temperature of 70 ℃ and is dried to constant weight, so that the activated bentonite is obtained.
S3, preparing modified bentonite
Weighing 1000g of activated bentonite and 400g of calcium oxide, adding into a ball mill, ball milling for 40min, and sieving with a 100-mesh sieve to obtain mixed powder;
adding the mixed powder and deionized water into a reaction kettle according to the dosage ratio of 1g to 2mL, and stirring for 30min at room temperature to obtain a mixture;
laying the mixture in a constant temperature and humidity box, setting the temperature to be 65 ℃ and the humidity to be 50%, carrying out heat preservation and moisture preservation treatment for 10 hours, reducing the temperature of the constant temperature and humidity box to room temperature, and discharging to obtain a modified bentonite crude product;
adding the crude modified bentonite and deionized water into a reaction kettle according to the dosage ratio of 1g to 20mL, stirring and dispersing for 60min, carrying out suction filtration, leaching a filter cake by using deionized water, then pumping, transferring the filter cake into a drying box with the temperature of 60 ℃, carrying out vacuum drying to constant weight, and sieving by a 100-mesh screen to obtain the modified bentonite.
S4, preparing an adsorbent precursor
Uniformly mixing sodium metaaluminate and deionized water according to a weight ratio of 1:9 to obtain a sodium metaaluminate solution;
Weighing 1400g of modified bentonite, 600g of modified fly ash, 120g of corn starch and 700g of sodium silicate, uniformly mixing, adding 2400mL of deionized water into a reaction kettle, stirring for 30min at room temperature, increasing the temperature of the reaction kettle to 70 ℃, adding 2000g of sodium metaaluminate solution into the reaction kettle, stirring for 90min, steaming out the solvent under reduced pressure to obtain slurry with the water content of 10%, granulating to obtain spherical particle blanks with the particle size of 3-5mm, putting the particle blanks into a muffle furnace, increasing the temperature of the muffle furnace to 95 ℃ at the temperature increasing rate of 3 ℃ per min, carrying out heat preservation treatment for 50min, increasing the temperature of the muffle furnace to 180 ℃ at the temperature increasing rate of 1 ℃ per min, carrying out heat preservation treatment for 30min, increasing the temperature of the muffle furnace to 450 ℃ at the temperature increasing rate of 6 ℃ per min, carrying out heat preservation treatment for 2h, and naturally cooling to room temperature to obtain the adsorbent precursor.
S5, preparing adsorbent filler
Weighing 100g of chitosan and 5000mL of 3wt% glacial acetic acid solution, adding into a reaction kettle, stirring until the system is dissolved, adding 1000g of adsorbent precursor and 10g of zinc oxide into the reaction kettle, performing ultrasonic dispersion for 30min, dropwise adding 6000mL of 0.8mol/L sodium hydroxide solution into the reaction kettle, performing ultrasonic dispersion for 40min after the dropwise addition is completed, performing suction filtration, washing a filter cake with purified water to be neutral, performing suction drying, transferring the filter cake into a drying box with the temperature of 90 ℃, and drying to constant weight to obtain the adsorbent filler.
Example 2
The embodiment provides a preparation method of an adsorbent filler for purifying ethanol prepared from synthesis gas, which comprises the following steps:
S1, preparing modified fly ash
Uniformly mixing sodium carbonate, sodium hydroxide and deionized water according to the dosage ratio of 5g to 1g to 50mL to obtain a modified liquid;
1000g of fly ash and 15000mL of modifying liquid are weighed, added into a reaction kettle for stirring, the temperature of the reaction kettle is reduced to 20 ℃, the temperature is kept for stirring for 140min, after the reaction is completed, suction filtration is performed, a filter cake is washed to be neutral by deionized water and then is pumped to be dried, the filter cake is transferred into a drying box with the temperature of 90 ℃ for drying to constant weight, and the filter cake is screened by a 100-mesh screen to obtain the modified fly ash.
S2, preparing activated bentonite
1000G of bentonite and 10000mL of 11wt% hydrochloric acid are weighed, added into a reaction kettle for stirring, the temperature of the reaction kettle is increased to 80 ℃, the reaction kettle is kept warm and stirred for 5 hours, after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is pumped to dryness, and the filter cake is transferred into a drying box with the temperature of 75 ℃ and is dried to constant weight, so that the activated bentonite is obtained.
S3, preparing modified bentonite
Weighing 1000g of activated bentonite and 400g of calcium oxide, adding into a ball mill, ball milling for 50min, and sieving with a 100-mesh sieve to obtain mixed powder;
Adding the mixed powder and deionized water into a reaction kettle according to the dosage ratio of 1g to 2mL, and stirring for 40min at room temperature to obtain a mixture;
laying the mixture in a constant temperature and humidity box, setting the temperature to be 70 ℃ and the humidity to be 55%, carrying out heat preservation and moisture preservation treatment for 11 hours, reducing the temperature of the constant temperature and humidity box to room temperature, and discharging to obtain a modified bentonite crude product;
Adding the crude modified bentonite and deionized water into a reaction kettle according to the dosage ratio of 1g to 20mL, stirring and dispersing for 70min, carrying out suction filtration, leaching a filter cake by using deionized water, then pumping, transferring the filter cake into a drying box with the temperature of 65 ℃, carrying out vacuum drying to constant weight, and sieving by a 100-mesh screen to obtain the modified bentonite.
S4, preparing an adsorbent precursor
Uniformly mixing sodium metaaluminate and deionized water according to a weight ratio of 1:9 to obtain a sodium metaaluminate solution;
Weighing 1400g of modified bentonite, 600g of modified fly ash, 140g of tapioca starch and 700g of sodium silicate, uniformly mixing, adding 2600mL of deionized water into a reaction kettle, stirring at room temperature for 40min, increasing the temperature of the reaction kettle to 75 ℃, adding 2000g of sodium metaaluminate solution into the reaction kettle, stirring for 100min, steaming under reduced pressure to remove the solvent to obtain slurry with the water content of 15%, granulating to obtain spherical particle blanks with the particle size of 3-5mm, putting the particle blanks into a muffle furnace, increasing the temperature of the muffle furnace to 100 ℃ at the temperature increasing rate of 4 ℃ per min, carrying out heat preservation treatment for 60min, increasing the temperature of the muffle furnace to 200 ℃ at the temperature increasing rate of 2 ℃ per min, carrying out heat preservation treatment for 35min, increasing the temperature of the muffle furnace to 500 ℃ at the temperature increasing rate of 7.5 ℃ per min, carrying out heat preservation treatment for 2.5h, and naturally cooling to room temperature to obtain the adsorbent precursor.
S5, preparing adsorbent filler
Weighing 150g of chitosan and 5000mL of 5wt% glacial acetic acid solution, adding into a reaction kettle, stirring until the system is dissolved, adding 1000g of adsorbent precursor and 15g of zinc oxide into the reaction kettle, performing ultrasonic dispersion for 50min, dropwise adding 6000mL of 1.2mol/L sodium hydroxide solution into the reaction kettle, performing ultrasonic dispersion for 60min after the dropwise addition is completed, performing suction filtration, washing a filter cake with purified water to be neutral, performing suction drying, transferring the filter cake into a drying box with the temperature of 100 ℃, and drying to constant weight, thus obtaining the adsorbent filler.
Example 3
The embodiment provides a preparation method of an adsorbent filler for purifying ethanol prepared from synthesis gas, which comprises the following steps:
S1, preparing modified fly ash
Uniformly mixing sodium carbonate, sodium hydroxide and deionized water according to the dosage ratio of 5g to 1g to 50mL to obtain a modified liquid;
1000g of fly ash and 15000mL of modifying liquid are weighed, added into a reaction kettle for stirring, the temperature of the reaction kettle is reduced to 22 ℃, the temperature is kept for 160 minutes for stirring, after the reaction is completed, suction filtration is performed, a filter cake is washed to be neutral by deionized water and then is pumped to be dried, the filter cake is transferred into a drying box with the temperature of 95 ℃, and is dried to constant weight, and the filter cake is screened by a 100-mesh screen to obtain the modified fly ash.
S2, preparing activated bentonite
1000G of bentonite and 10000mL of 12wt% hydrochloric acid are weighed, added into a reaction kettle for stirring, the temperature of the reaction kettle is increased to 85 ℃, the reaction kettle is kept warm and stirred for 6 hours, after the reaction is completed, the temperature of the reaction kettle is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is pumped to dryness, and the filter cake is transferred into a drying box with the temperature of 80 ℃ and is dried to constant weight, so that the activated bentonite is obtained.
S3, preparing modified bentonite
Weighing 1000g of activated bentonite and 400g of calcium oxide, adding into a ball mill, ball milling for 60min, and sieving with a 100-mesh sieve to obtain mixed powder;
Adding the mixed powder and deionized water into a reaction kettle according to the dosage ratio of 1g to 2mL, and stirring for 50min at room temperature to obtain a mixture;
laying the mixture in a constant temperature and humidity box, setting the temperature to be 75 ℃ and the humidity to be 60%, carrying out heat preservation and moisture preservation treatment for 12 hours, reducing the temperature of the constant temperature and humidity box to room temperature, and discharging to obtain a modified bentonite crude product;
Adding the crude modified bentonite and deionized water into a reaction kettle according to the dosage ratio of 1g to 20mL, stirring and dispersing for 80min, carrying out suction filtration, leaching a filter cake by using deionized water, then pumping, transferring the filter cake into a drying box with the temperature of 70 ℃, carrying out vacuum drying to constant weight, and sieving by a 100-mesh screen to obtain the modified bentonite.
S4, preparing an adsorbent precursor
Uniformly mixing sodium metaaluminate and deionized water according to a weight ratio of 1:9 to obtain a sodium metaaluminate solution;
Weighing 1400g of modified bentonite, 600g of modified fly ash, 160g of wheat starch and 700g of sodium silicate, uniformly mixing, adding 2800mL of deionized water into a reaction kettle, stirring at room temperature for 50min, increasing the temperature of the reaction kettle to 80 ℃, adding 2000g of sodium metaaluminate solution into the reaction kettle, stirring for 110min, steaming under reduced pressure to remove a solvent, obtaining slurry with the water content of 20%, granulating, obtaining spherical particle blanks with the particle size of 3-5mm, placing the particle blanks into a muffle furnace, increasing the temperature of the muffle furnace to 105 ℃ at the temperature increasing rate of 5 ℃ per min, carrying out heat preservation treatment for 70min, increasing the temperature of the muffle furnace to 220 ℃ at the temperature increasing rate of 3 ℃ per min, carrying out heat preservation treatment for 40min, increasing the temperature of the muffle furnace to 550 ℃ at the temperature increasing rate of 9 ℃ per min, carrying out heat preservation treatment for 3h, and naturally cooling to room temperature to obtain the adsorbent precursor.
S5, preparing adsorbent filler
Weighing 150g of chitosan and 5000mL of 5wt% glacial acetic acid solution, adding into a reaction kettle, stirring until the system is dissolved, adding 1000g of adsorbent precursor and 15g of zinc oxide into the reaction kettle, performing ultrasonic dispersion for 50min, dropwise adding 6000mL of 1.2mol/L sodium hydroxide solution into the reaction kettle, performing ultrasonic dispersion for 60min after the dropwise addition is completed, performing suction filtration, washing a filter cake with purified water to be neutral, performing suction drying, transferring the filter cake into a drying box with the temperature of 100 ℃, and drying to constant weight, thus obtaining the adsorbent filler.
Example 4
The embodiment provides a purification process for preparing ethanol from synthesis gas, which comprises the following steps:
Step one, selecting a plate column with the number of plates of 60 as a rectifying column 100, arranging a feeding pipe 200 and a discharging pipe 300 which are communicated with the inside of the rectifying column 100 on the outer wall of the rectifying column 100, wherein the feeding pipe 200 extends to the top of a 13 th column plate with one end of the inside of the rectifying column 100 positioned from bottom to top, the discharging pipe 300 extends to the top of a 54 th column plate with one end of the inside of the rectifying column 100 positioned from bottom to top, arranging a blow-down pipe 400 on the top of the rectifying column 100, and arranging a discharging pipe 500 on the bottom of the rectifying column 100;
Step two, filling the adsorbent filler prepared in the embodiment 1 on a column plate of the rectifying column 100, and forming an adsorbent bed layer with the thickness of 7cm on the top of each column plate of the rectifying column 100;
Step three, crude ethanol is conveyed into the rectifying tower 100 from a feed pipe 200, the reflux ratio in the rectifying tower 100 is 60, the distillate feed ratio is 0.105, finished ethanol is discharged from a discharge pipe 300 of the rectifying tower 100 after purified and rectified by the rectifying tower 100, light components are discharged from a discharge pipe 400 at the top of the rectifying tower 100, heavy components collected at the bottom of the inner side of the rectifying tower 100 are discharged from a discharge pipe 500 at the bottom of the rectifying tower 100.
Example 5
The embodiment provides a purification process for preparing ethanol from synthesis gas, which comprises the following steps:
Step one, selecting a plate column with the number of plates of 60 as a rectifying column 100, arranging a feeding pipe 200 and a discharging pipe 300 which are communicated with the inside of the rectifying column 100 on the outer wall of the rectifying column 100, wherein the feeding pipe 200 extends to the top of a 13 th column plate with one end of the inside of the rectifying column 100 positioned from bottom to top, the discharging pipe 300 extends to the top of a 54 th column plate with one end of the inside of the rectifying column 100 positioned from bottom to top, arranging a blow-down pipe 400 on the top of the rectifying column 100, and arranging a discharging pipe 500 on the bottom of the rectifying column 100;
step two, filling the adsorbent filler prepared in the embodiment 2 on a column plate of the rectifying column 100, and forming an adsorbent bed layer with the thickness of 8.5cm on the top of each column plate of the rectifying column 100;
Step three, crude ethanol is conveyed into the rectifying tower 100 from a feed pipe 200, the reflux ratio in the rectifying tower 100 is 60, the distillate feed ratio is 0.107, finished ethanol is discharged from a discharge pipe 300 of the rectifying tower 100 after purified and rectified by the rectifying tower 100, light components are discharged from a discharge pipe 400 at the top of the rectifying tower 100, heavy components collected at the bottom of the inner side of the rectifying tower 100 are discharged from a bottom discharge pipe 500 of the rectifying tower 100.
Example 6
The embodiment provides a purification process for preparing ethanol from synthesis gas, which comprises the following steps:
Step one, selecting a plate column with the number of plates of 60 as a rectifying column 100, arranging a feeding pipe 200 and a discharging pipe 300 which are communicated with the inside of the rectifying column 100 on the outer wall of the rectifying column 100, wherein the feeding pipe 200 extends to the top of a 13 th column plate with one end of the inside of the rectifying column 100 positioned from bottom to top, the discharging pipe 300 extends to the top of a 54 th column plate with one end of the inside of the rectifying column 100 positioned from bottom to top, arranging a blow-down pipe 400 on the top of the rectifying column 100, and arranging a discharging pipe 500 on the bottom of the rectifying column 100;
Step two, filling the adsorbent filler prepared in the embodiment 3 on a column plate of the rectifying column 100, and forming an adsorbent bed layer with the thickness of 10cm on the top of each column plate of the rectifying column 100;
Step three, crude ethanol is conveyed into the rectifying tower 100 from a feed pipe 200, the reflux ratio in the rectifying tower 100 is 60, the distillate feed ratio is 0.110, finished ethanol is discharged from a discharge pipe 300 of the rectifying tower 100 after purified and rectified by the rectifying tower 100, light components are discharged from a discharge pipe 400 at the top of the rectifying tower 100, heavy components collected at the bottom of the inner side of the rectifying tower 100 are discharged from a discharge pipe 500 at the bottom of the rectifying tower 100.
Comparative example 1
The present comparative example differs from example 6 in that the adsorbent filler prepared in example 3 was used in preparation, step S1 was omitted, and the fly ash in step S1 was used instead of the modified fly ash in step S4.
Comparative example 2
The present comparative example differs from example 6 in that the adsorbent filler prepared in example 3 was used in preparation, step S2 was omitted, and the bentonite in step S2 was used instead of the modified bentonite in step S3.
Comparative example 3
This comparative example differs from example 6 in that the adsorbent filler prepared in example 3 was used in the preparation, and in step S3, a mixture was prepared by stirring and mixing a mixture composed of 400g of calcium hydroxide, 2800mL of water and 1000g of activated bentonite.
Comparative example 4
The present comparative example differs from example 6 in that the adsorbent filler prepared in example 3 was used at the time of preparation, and in step S5, no zinc oxide was added.
Performance test:
Determination of pore size distribution and porosities of solid Material by reference to Standard GB/T21650.1-2008 mercury porosimetry and gas adsorption part 1 mercury porosimetry specific surface areas and porosities of the adsorbent fillers used in examples 4-6 and comparative examples 1-4 were tested, the specific test results are shown in Table 1;
The mass fraction of the static water adsorption amount and the dynamic water adsorption rate of the adsorbent fillers used in examples 4 to 6 and comparative examples 1 to 4 were tested with reference to the standard GB/T6287-2021 molecular sieve static Water adsorption determination method, and the specific test results are shown in Table 1;
The finished ethanol products prepared in examples 4-6 and comparative examples 1-4 were tested for moisture, methanol, acetate content and ethanol content with reference to the standard GB/T6820-2016 Industrial ethanol, and the specific test results are shown in Table 2.
TABLE 1 Performance test data sheet for adsorbent packing
TABLE 2 quality control data sheet for finished ethanol
Data analysis:
Comparing and analyzing the data in the table 1 and the table 2, the specific surface area of the prepared adsorbent filler reaches 815m 2/g, the porosity reaches 66.2%, the static water adsorption capacity reaches 46.2%, the adsorbent filler is used as a filler tower filler, the ethanol prepared from the synthesis gas is rectified and purified, the prepared ethanol content reaches 99.81%, the water content is reduced to 0.04%, the methanol content is reduced to 18.7mg/L, the acetate content is reduced to 96.7mg/L, and various performance parameters are better than those of the comparative example.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (6)
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