Method for preparing nut coke by recovering coke powder

Abstract

The invention discloses a method for preparing coke nuts by recovering coke powder, and relates to the technical field of energy utilization. The coke nut prepared by the invention comprises the following raw materials in parts by weight: 160-200 parts of coke powder, 0-40 parts of coke ash, 10-20 parts of a binder, 10-20 parts of dilute phosphoric acid and 10-20 parts of dilute sulfuric acid. Wherein the binder is prepared from the following raw materials in parts by weight: 15 to 18 parts of corn straw coke, 20 to 25 parts of diatomite, 35 to 40 parts of modified calcium bentonite, 8 to 10 parts of sodium carboxymethyl cellulose, 5 to 8 parts of corn straw tar and 6 to 8 parts of water; the corn straw coke and the corn straw tar both come from agricultural wastes and are recycled together with waste residue coke powder in electric furnace smelting, so that energy waste is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of energy utilization, in particular to a method for recovering coke powder to prepare coke cubes. Background Art

[0002] Yellow phosphorus is an extremely important basic industrial raw material, mainly used in fertilizers, medicines, pesticides, etc. As an important intermediate product of phosphorus chemical industry, it is energy-intensive and highly polluting. In the smelting of yellow phosphorus, the electric furnace method adds a mixture of phosphate ore, silica and coke into an electric furnace, and the graphite electrodes passing through the furnace cover convert electrical energy into thermal energy, thereby heating the mixture to a molten state, causing a reduction reaction, sublimating the elemental phosphorus, and then condensing, separating and refining the phosphorus-containing gas to obtain elemental phosphorus. This method has a high actual yield and high product purity, but in the cost structure, electricity cost is the largest cost, accounting for about 37% of the total cost, followed by phosphate ore and coke; During the electric furnace smelting process, coke participates in the reaction as a reducing agent, and part of the coke will be converted into coke powder, which will be discharged from the electric furnace together with the slag. Since the coke powder contains unreacted carbon elements, the present invention aims to solve the problem of recycling and reusing the unreacted coke powder in the slag, reduce resource waste and improve economic benefits. Summary of the invention

[0003] The object of the present invention is to provide a method for recovering coke powder and preparing coke diced, so as to solve the problems raised in the prior art.

[0004] To achieve the above object, the present invention provides the following technical solutions: A method for recovering coke powder and preparing coke diced, the specific steps are as follows: Step 1: Add diatomaceous earth, modified calcium-based bentonite and sodium carboxymethyl cellulose into electric furnace wastewater in sequence, mix and stir for 30-40 minutes, then add corn straw coke and corn straw tar and continue stirring for 1-2 hours to obtain a binder; Step 2: Stir the coke powder, coke ash, dilute phosphoric acid and dilute sulfuric acid for 30-40 minutes, then add the binder prepared in step 1 and continue stirring for 1-2 hours, press into small balls, sieve and dry to obtain coke cubes; wherein the particle size of the coke cubes is 5mm-25mm.

[0005] The raw materials of coke diced include 160-200 parts of coke powder, 0-40 parts of coke ash, 10-20 parts of binder, 10-20 parts of dilute phosphoric acid, and 10-20 parts of dilute sulfuric acid by weight. The raw materials of the binder include 15-18 parts of corn straw coke, 20-25 parts of diatomaceous earth, 35-40 parts of modified calcium-based bentonite, 8-10 parts of sodium carboxymethyl cellulose, 5-8 parts of corn straw tar, and 6-8 parts of electric furnace wastewater by weight.

[0006] The preparation steps of modified calcium-based bentonite are: Sodium polyacrylate, polyanionic cellulose and N,N-methylenebisacrylamide were added to water in sequence and stirred and mixed, and then calcium bentonite was slowly added in batches. The temperature was raised to 50-60°C and stirred for reaction for 1-2 hours to obtain a slurry, which was dried in an oven for 24 hours and ground through a 200-mesh sieve to obtain modified calcium bentonite.

[0007] Furthermore, the weight proportions of the raw materials in the preparation step of the modified calcium-based bentonite are: 0.3-0.5 parts of sodium polyacrylate, 1-2 parts of polyanionic cellulose, 0.01-0.02 parts of N,N-methylenebisacrylamide, 95-100 parts of water, and 6-11 parts of calcium-based bentonite.

[0008] The preparation steps of corn straw coke and corn straw tar in the binder are as follows: Step S1: crushing the corn stalks, passing through an 80-100 mesh sieve, performing hydrothermal pretreatment, placing in deionized water, heating to 180-240° C. at a rate of 10° C. / min, keeping warm for 1-2 hours, filtering, placing in 60° C. hydrochloric acid for pickling for 2-3 hours, washing and drying, adding a liquefier and a catalyst for liquefaction, passing into a protective atmosphere, liquefying at 200° C. for 2-3 hours, obtaining crude corn stalk tar, and purifying; Step S2: washing the remaining solids in step S1 with water and then performing high-temperature decomposition, decomposing at 500-550° C. for 30 min in a protective atmosphere, grinding and sieving for deashing, placing in a mixed acid solution, shaking for 5-6 days, washing and drying to obtain corn straw char.

[0009] Furthermore, in step S1, corn straw tar and anhydrous ethanol are mixed in a volume ratio of 1:0.5, stirred at 50° C. for 1 h, and then distilled under reduced pressure at 0.04 MPa to obtain corn straw tar; Furthermore, the mixed acid solution in step S2 is a composite combination of hydrochloric acid and hydrofluoric acid; wherein the concentration of hydrochloric acid is 1-2 mol / L, and the volume fraction of hydrofluoric acid is 10-20%; and the solid-liquid ratio during deashing is 1:20.

[0010] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention adds a variety of additives to the recovered coke powder to make coke cubes, thereby realizing the recycling and reuse of the coke powder and reducing resource loss; the added corn straw coke and corn straw tar make full use of agricultural waste and have both environmental and economic advantages.

[0011] 2. The bentonite in the binder is modified to increase the active groups, improve the wettability of the powder, and increase the bonding strength. The addition of corn straw tar improves the bonding performance of the binder. At the same time, corn straw tar has a high calorific value, which increases the heat output during smelting. Corn straw coke has a fluffy porous structure, which regulates the porosity of the coke and improves the reaction activity of the coke in electric furnace smelting to a certain extent. The organic binder and the inorganic binder work together to improve the compressive strength of the coke. DETAILED DESCRIPTION

[0012] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative work shall fall within the scope of protection of the present invention.

[0013] In the embodiment, coke powder and coke ash are both from factory electric furnace smelting waste slag, which are crushed to a particle size of 3-10 mm; Sodium polyacrylate with an average Mw of 2100 and polyanionic cellulose with a viscosity of 600-1000 mPa.s were purchased from Shanghai Aladdin Biochemical; diatomaceous earth 325 mesh and calcium-based bentonite 325 mesh were purchased from Lingshou Tianlong Mineral Products.

[0014] The preparation steps of modified calcium-based bentonite are as follows: 0.5 parts of sodium polyacrylate, 2 parts of polyanionic cellulose and 97.5 parts of deionized water are weighed by weight, mixed and stirred, heated to 60°C, 0.01 parts of N,N-methylenebisacrylamide are added, 10 parts of calcium-based bentonite are slowly added in batches, stirred and reacted for 1 hour to obtain a slurry, dried in an oven for 24 hours, ground through a 200-mesh sieve, and obtained modified calcium-based bentonite.

[0015] Example 1: Preparation of chopped coke, the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 20 parts of diatomaceous earth, 35 parts of modified calcium-based bentonite and 8 parts of sodium carboxymethyl cellulose in parts by weight, add them into 6 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 1 hour to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 12 parts of dilute phosphoric acid and 13 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 15 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0016] Example 2: Preparation of chopped coke, the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 25 parts of diatomaceous earth, 40 parts of modified calcium-based bentonite and 10 parts of sodium carboxymethyl cellulose in parts by weight, add them into 8 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 8 parts of corn straw tar and continue stirring for 1 hour to obtain a binder; Step 4: Weigh 180 parts of coke powder, 20 parts of coke ash, 20 parts of dilute phosphoric acid and 20 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 20 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0017] Example 3: Preparation of chopped coke, the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 25 parts of diatomaceous earth, 35 parts of modified calcium-based bentonite and 10 parts of sodium carboxymethyl cellulose in parts by weight, add them into 8 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 1 hour to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 20 parts of dilute phosphoric acid and 20 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 18 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0018] Example 4: Preparation of chopped coke, the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 25 parts of diatomaceous earth, 38 parts of modified calcium-based bentonite and 10 parts of sodium carboxymethyl cellulose in parts by weight, add them into 6 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 1 hour to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 18 parts of dilute phosphoric acid and 18 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 15 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0019] Example 5: Preparation of chopped coke, the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 25 parts of diatomaceous earth, 35 parts of modified calcium-based bentonite and 10 parts of sodium carboxymethyl cellulose in parts by weight, add them into 6 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 2 hours to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 15 parts of dilute phosphoric acid and 15 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 15 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0020] Example 6: Preparation of chopped coke, the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 22 parts of diatomaceous earth, 35 parts of modified calcium-based bentonite and 10 parts of sodium carboxymethyl cellulose in parts by weight, add them into 6 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 1 hour to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 12 parts of dilute phosphoric acid and 15 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 13 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0021] Example 7: Preparation of chopped coke, the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 20 parts of diatomaceous earth, 35 parts of modified calcium-based bentonite and 10 parts of sodium carboxymethyl cellulose in parts by weight, add them into 6 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 1 hour to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 15 parts of dilute phosphoric acid and 12 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 13 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0022] Comparative Example 1: Referring to Example 1, the number of binders was adjusted to 5 parts, and the specific steps were as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 20 parts of diatomaceous earth, 35 parts of modified calcium-based bentonite and 8 parts of sodium carboxymethyl cellulose in parts by weight, add them into 6 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 1 hour to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 12 parts of dilute phosphoric acid and 13 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 5 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0023] Comparative Example 2: Referring to Example 1, the number of parts of the binder is adjusted to 25 parts, and the specific steps are as follows: Step 1: crush the corn stalks, pass through a 100-mesh sieve, perform hydrothermal pretreatment, place in deionized water, heat to 220°C at a rate of 10°C / min, keep warm for 2h, filter, place in 60°C hydrochloric acid for pickling for 2h, wash with water, dry, place in a reactor, add diethylene glycol, 1,2-propylene glycol and concentrated sulfuric acid in a volume ratio of 1:2, liquefy at a solid-liquid ratio of 1:5, pass into a protective atmosphere, liquefy at 200°C for 2h to obtain crude corn stalk tar, mix the crude corn tar and anhydrous ethanol in a volume ratio of 1:0.5, stir at 50°C under normal pressure for 1h, and distill under reduced pressure at 0.04MPa to obtain corn stalk tar; Step 2: The remaining solids after the liquefaction reaction in step 1 are washed with water and then subjected to high-temperature decomposition, decomposed at 550° C. for 30 min in a nitrogen atmosphere, ground and sieved for deashing, placed in a mixed acid solution of 1 mol / L hydrochloric acid and 15% hydrofluoric acid at a solid-liquid ratio of 1:20, shaken for 5 days, washed and dried to obtain corn straw char; Step 3: Weigh 20 parts of diatomaceous earth, 35 parts of calcium bentonite and 8 parts of sodium carboxymethyl cellulose in parts by weight, add them into 6 parts of electric furnace wastewater in turn, mix and stir for 30 minutes, then add 18 parts of corn straw coke and 6 parts of corn straw tar and continue stirring for 2 hours to obtain a binder; Step 4: Weigh 160 parts of coke powder, 40 parts of coke ash, 12 parts of dilute phosphoric acid and 13 parts of dilute sulfuric acid by weight, place them in a horizontal twin-shaft mixer and stir for 30 minutes, then add 25 parts of the binder prepared in step 3 and continue stirring for 2 hours, press them into small balls with a roller press, sieve them and dry them with a hot air dryer to obtain coke cubes.

[0024] Detection test Coke powder granulation quality index: 1. At room temperature, after the sample is freely dropped from a height of 1.5m to a 10mm thick steel plate, the integrity rate must be greater than 90%; 2. Place the sample in a high-temperature furnace (purge with argon for 30 minutes before heating to remove the air in the furnace), heat the high-temperature furnace from room temperature to 100℃ at a rate of 5℃ / min and keep constant temperature for 10min, 175℃ for 30min, and 950℃ for 10min, then cool to room temperature, take out and measure the strength: 100℃, ≥10kgf; 175℃, ≥10kgf; 950℃ is greater than or equal to 40kgf.

[0025] Five samples of the coke diced prepared in Examples 1-7 and Comparative Examples 1-2 were taken from each group for testing. The results are shown in Table 1, and all data are average values.

[0026]

[0027] Conclusion: By comparing Examples 1-7, it can be seen that Example 1 has better effects than the other examples, and provides a set of relatively excellent raw material ratios; the data of Examples 1-7 all meet the granulation standard; Comparative Examples 1 and 2 adjust the number of binders in Example 1, and the increase or decrease has an impact on the forming of the coke, the material integrity rate is reduced, and it is easy to break; at the same time, at several groups of temperatures, the strength is also reduced accordingly, and the granulation standard is not met.

[0028] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for recovering coke powder to prepare coke cubes, characterized in that: The specific steps are as follows: Step 1: Add diatomaceous earth, modified calcium-based bentonite and sodium carboxymethyl cellulose into electric furnace wastewater in sequence, mix and stir for 30-40 minutes, then add corn straw coke and corn straw tar and continue stirring for 1-2 hours to obtain a binder; Step 2: Stir the coke powder, coke ash, dilute phosphoric acid and dilute sulfuric acid for 30-40 minutes, then add the binder prepared in step 1 and continue stirring for 1-2 hours, press into small balls, sieve and dry to obtain coke cubes; The particle size of the chopped coke is 5mm-25mm.

2. The method for recovering coke powder to prepare coke diced according to claim 1, characterized in that: The raw materials of the coke diced include 160-200 parts of coke powder, 0-40 parts of coke ash, 10-20 parts of a binder, 10-20 parts of dilute phosphoric acid, and 10-20 parts of dilute sulfuric acid in parts by weight.

3. The method for recovering coke powder to prepare coke diced according to claim 1, characterized in that: The raw materials of the binder include 15-18 parts of corn straw coke, 20-25 parts of diatomaceous earth, 35-40 parts of modified calcium-based bentonite, 8-10 parts of sodium carboxymethyl cellulose, 5-8 parts of corn straw tar, and 6-8 parts of electric furnace wastewater in parts by weight.

4. The method for recovering coke powder to prepare coke diced according to claim 1, characterized in that: The preparation steps of the modified calcium-based bentonite are: Sodium polyacrylate, polyanionic cellulose and N,N-methylenebisacrylamide were added to water in sequence and stirred and mixed, and then calcium bentonite was slowly added in batches. The temperature was raised to 50-60°C and stirred for reaction for 1-2 hours to obtain a slurry, which was dried in an oven for 24 hours and ground through a 200-mesh sieve to obtain modified calcium bentonite.

5. The method for recovering coke powder to prepare coke cubes according to claim 4, characterized in that: The invention comprises, by weight, 0.3-0.5 parts of sodium polyacrylate, 1-2 parts of polyanionic cellulose, 0.01-0.02 parts of N,N-methylenebisacrylamide, 95-100 parts of water and 6-11 parts of calcium-based bentonite.

6. The method for recovering coke powder to prepare coke diced according to claim 1, characterized in that: The preparation steps of the corn straw coke and corn straw tar are as follows: Step S1: crushing corn stalks, passing through an 80-100 mesh sieve, performing hydrothermal pretreatment, placing in deionized water, heating to 180-240° C. at a rate of 10° C. / min, keeping warm for 1-2 hours, filtering, placing in 60° C. hydrochloric acid for pickling for 2-3 hours, washing and drying, adding a liquefier and a catalyst for liquefaction, passing into a protective atmosphere, liquefying at 200° C. for 2-3 hours, obtaining crude corn stalk tar, and purifying to obtain corn stalk tar; Step S2: washing the remaining solids in step S1 with water and then performing high-temperature decomposition, decomposing at 500-550° C. for 30 min in a protective atmosphere, grinding and sieving for deashing, placing in a mixed acid solution, shaking for 5-6 days, washing and drying to obtain corn straw char.

7. The method for recovering coke powder to prepare coke diced according to claim 6, characterized in that: Purification in step S1: Crude corn straw tar and anhydrous ethanol are mixed in a volume ratio of 1:0.5, stirred at 50° C. for 1 h under normal pressure, and then distilled under reduced pressure at 0.04 MPa to obtain corn straw tar.

8. The method for recovering coke powder to prepare coke diced according to claim 6, characterized in that: The mixed acid solution in step S2 is a composite combination of hydrochloric acid and hydrofluoric acid; wherein the concentration of hydrochloric acid is 1-2 mol / L, and the volume fraction of hydrofluoric acid is 10-20%; and the solid-liquid ratio during deashing is 1:20.

Images