DASH PRATIK SWARUP (IN)
GHORAI SOUMITRA (IN)
SHARMA BINOD (IN)
SREECHEM RESINS LTD (IN)
WO2015107811A1 | 2015-07-23 |
CN103613728A | 2014-03-05 | |||
CN107200994A | 2017-09-26 | |||
US20220186020A1 | 2022-06-16 | |||
CN104531020A | 2015-04-22 | |||
KR101547492B1 | 2015-08-26 | |||
JP5727241B2 | 2015-06-03 | |||
JP2012101279A | 2012-05-31 | |||
JP2003286503A | 2003-10-10 |
We claim: 1. An organic polymer of formula I Formula I wherein ‘n’ is 10-1000. 2. The organic polymer as claimed in claim 1, wherein the appearance of the polymer is a black viscous solution; and wherein the polymer is completely soluble in water. 3. The organic polymer as claimed in claim 1, wherein the viscosity of the polymer is 1.11 ± .03, wherein pH is 7.0 ± 1.0; and wherein specific gravity is 1200 ± 500 cps. 4. A method for preparing an organic polymer as defined in claim 1, the method comprising: x mixing phenol with formaldehyde in presence of a base to obtain phenolic resin solution; x mixing lignosulphonate with cardanol to obtain lignin cardanol solution; x mixing the phenolic resin solution with the lignin cardanol solution to obtain mixture 1; x heating the mixture 1 to about 65-85 ºC followed by cooling to obtain mixture 2; x distilling out for removal of excess reactants from the mixture 2 to obtain mixture 3; x cooling the mixture 3 followed by treatment with solvent and neutralizers to obtain mixture 4; x mixing the mixture 4 with hydrogen donor chemical solution in presence of a tackifier to obtain mixture 5; and x stabilizing the mixture 5 to obtain the polymer. 5. The method as claimed in claim 4, wherein the hydrogen donor chemical solution is octyl phenol or tetralin. 6. The method as claimed in claim 4, wherein the tackifier is a solution of glycol and ethylamine. 7. The method as claimed in claim 4, wherein a concentration of phenolic resin solution is about 60-70% and lignin cardanol solution is about 40-30%. 8. The method as claimed in claim 4, wherein the neutralizer is a base, wherein the base is either sodium hydroxide or potassium hydroxide. 9. A blend for the production of metallurgical coke, wherein the blend comprises: non-coking coal (NCC) at about 10-40 wt% with coking coal (CC) at about 60-90 wt%; and an organic polymer as defined in claim 1. 10. The blend as claimed in claim 9, wherein the organic polymer is 0.5 to 0.8 wt% of the blend. 11. The blend as claimed in claim 9, wherein non-coking coal has a crucible swelling number (CSN) <3. 12. The blend as claimed in claim 9, wherein crucible swelling number (CSN) of the blend is 5-7. 13. The blend as claimed in claim 9, wherein coke strength after reaction (CSR) of the coke made from the blend is about 53 to 55; wherein coke reactivity indices (CRI) of the coke made from the blend is about 30.0 to 30.6, and wherein fluidity of the blend is 200-800 ddpm. 14. A process for preparing a blend as defined in claim 9, wherein said process comprises mixing non-coking coal (NCC) at about 10-40 wt% with coking coal (CC) at about 60-90 wt% in presence of water and polymer as defined in claim 1. 15. The process as claimed in claim 14, wherein said process is carried out in an oven at a temperature ranging from about 800 ºC to 1000 ºC. |
wherein ‘n’ is 10 to 1000. In an embodiment of the present disclosure, the organic polymer is a black viscous solution with a viscosity of 1.11 ± .03; pH of 7.0 ± 1.0; and a specific gravity of 1200 ± 500 cps. In an embodiment of the present disclosure, the organic polymer is soluble in water. The present disclosure also relates to a method for preparing the organic polymer comprising: x mixing phenol with formaldehyde in presence of a base to obtain phenolic resin solution; x mixing lignosulphonate with cardanol to obtain lignin cardanol solution; x mixing the phenolic resin solution with the lignin cardanol solution to obtain mixture 1; x heating the mixture 1 to about 65-85 ºC followed by cooling to obtain mixture 2; x distilling out for removal of excess reactants from the mixture 2 to obtain mixture 3; x cooling the mixture 3 followed by treatment with solvent and neutralizers to obtain mixture 4; x mixing the mixture 4 with hydrogen donor chemical solution in presence of a tackifier to obtain mixture 5; and x stabilizing the mixture 5 to obtain the organic polymer. In an embodiment of the present disclosure, the hydrogen donor chemical solution is octyl phenol or tetralin. In an embodiment of the present disclosure, the reactants are phenol, formaldehyde, lignosulphonate and cardanol. In an embodiment of the present disclosure, the solvent is selected from a group comprising phenol or other phenolic derivatives. In an embodiment of the present disclosure, the neutralizer is a base. In another embodiment of the present disclosure, the base is either sodium hydroxide or potassium hydroxide. In another embodiment of the present disclosure, the solution of glycol and ethylamine acts as a tackifier. In another embodiment of the present disclosure, the tackifier is a solution of glycol and ethylamine. In another embodiment of the present disclosure, the concentration of the phenolic resin solution is about 60-70% and the lignin cardanol solution is about 30-40%. In another embodiment of the present disclosure, the base is sodium hydroxide. The present disclosure also relates to a blend for the production of metallurgical coke, wherein the blend comprises: ¾ non-coking coal (NCC) at about 10-40 wt% with coking coal (CC) at about 60- 90 wt%; and ¾ the organic polymer as defined above. ^ In another embodiment of the present disclosure, the organic polymer is at a concentration of about 0.5 to 0.8 wt% of the blend. In an embodiment of the present disclosure, the base added is 8-10% of the volume of the mixture. In an embodiment of the present disclosure, the coking coal comprises captive soft coal at a concentration of about 35 %, imported semi-soft coal at a concentration of about 25%, imported hard coking coal at a concentration of about 15% to 20%, and captive hard coking coal at a concentration of about 10%. In another embodiment of the present disclosure, the base blend comprises domestic coal at a concentration of about 20%, prime coking coal at a concentration of about 35%, weak coal at a concentration of about 20%, and semi-soft coal at a concentration of about 25% In another embodiment of the present disclosure, the trial blend comprises domestic coal at a concentration of about 20%, prime coking coal at a concentration of about 25%, weak coal at a concentration of about 30%, semi-soft coal at a concentration of about 25% and a polymer of formula I at a concentration of about 0.7%. In another embodiment of the present disclosure, the captive soft coal has CSN 5-6, the imported semi-soft coal has CSN 5-6, the imported hard coking coal has CSN 7-8, and the captive hard coking coal has CSN 6-7. In another embodiment of the present disclosure, the domestic soft coal has CSN 5-6, prime coking coal has CSN 7-8, and semi-soft coal has CSN 5-6. In another embodiment of the present disclosure, the non-coking coal has a crucible swelling number (CSN) <3. In another embodiment of the present disclosure, the crucible swelling number (CSN) of the blend is 5-7. In another embodiment of the present disclosure, the coke strength after reaction (CSR) of the coke made from the blend is about 53 to 55; wherein coke reactivity indices (CRI) of the coke made from the blend is about 30.0 to 30.6, and wherein fluidity of the blend is about 200-800 ddpm. The present disclosure also relates to a process for preparing the blend, wherein said process comprises mixing non-coking coal (NCC) at about 10-40 wt% with coking coal (CC) at about 60-90 wt% in presence of water and the organic polymer as defined above. In another embodiment of the present disclosure, the process is carried out in an oven at a temperature ranging from about 800 ºC to 1000 ºC. The organic polymer enables the generation of transferable hydrogen (H 2 ) in a specific temperature range during carbonization process. The presence of transferrable hydrogen is essential for making coking coal. In the case of non-coking coal, the transferrable hydrogen is largely consumed during the heating up to the start of fluidic temperature, while with strongly coking coal, this transferrable hydrogen could not be taken up to the same extent. Therefore, in the following heating period from the start of the fluid zone, enough transferrable hydrogen remains, and it can play a role to stabilize the cleaved fragment of coal. So, the organic polymer can generate hydrogen at the above-mentioned specific temperature range when mixed with a blend. Which in turn imparts fluidity to the coal matrix. This gives an opportunity to incorporate non-coking coal into the blend. Thus, the basis of the synthesis of organic polymer is that they release hydrogen in the plastic region of coal (400-600º C). In another embodiment, the organic polymer is added by replacing the coking coal. Examples: Example 1: General procedure for preparing the organic polymer of formula I: Phenol and formaldehyde were reacted in presence of a base to obtain a phenolic resin solution. Lignosulphonate is reacted with cardanol to obtain lignin cardanol solution. Phenolic resin solution is mixed with the lignin cardanol solution and heated up to a temperature of 70°C to activate an exothermic reaction in the system to obtain a mixture. Once the exothermic stage is reached, then the entire solution was cooled through limpet coils in the reactor as well as the cooling coils inside the reactor, so that, the entire exothermic reaction was completed below the temperature range of 80°C. However, the kinetics of the reaction was controlled through the desired amount of pressure between 2-6 kg/cm 2 in the reactor. Once the exothermic stage is over, the material is subjected to the vacuum distillation cycle for a period of 6-12 hours to remove the water from the reaction. Then the material is cooled down to 40°C and hydrogen donor solvent and neutralizers are added to complete the manufacturing process. Subsequently, the above mix is added to the hydrogen donor chemical solution and the entire reaction is completed in the bulk reactors over the next 4-7 hours. Intermittent samples are drawn during the reaction process for testing in the lab as per QC norms. The final mix is discharged and kept for the completion of the stabilization reaction. The discharged material is kept in a separate stabilization tank, where they attain stability at room temperature in approx.3-8 hours. Example 2: Procedure for preparing the organic polymer of formula I: Phenol (30-40 gm) and formaldehyde (150-160 ml) were reacted in presence of a base to obtain a phenolic resin solution (60-70%). Lignosulphonate (100gm) is reacted with cardanol (100gm) to obtain lignin cardanol solution (40-30%). Phenolic resin solution is mixed with the lignin cardanol solution to obtain mixture 1. Mixture 1 is heated to about 65-85 ºC followed by cooling to obtain mixture 2. Excess reactants of mixture 2 were distilled out to obtain mixture 3. Mixture 3 is subjected to cooling followed by treatment with sodium hydroxide solution to obtain mixture 4. Mixture 4 is treated with octyl phenol to obtain mixture 5. Mixture 5 is stabilized to obtain the organic polymer of formula I. Example 3: General Procedure for mixing coal with polymer Different coal (prime coking coal, medium coking coal, and weaker/non-coking coal) is mixed in specific proportions.10 % water was added to the mix for binding followed by the addition of 0.3-0.8% of the organic polymer of formula I in this mix. This is then mixed homogeneously. Stamping of the blend is done in order to achieve the required bulk density and it is then charged into the oven. The empty oven temperature is kept at 900 0 C to dry the blend and to obtain the final product. FTIR Spectra: The FTIR spectrum of SR 303 shows the peaks at 3299 cm -1 , which is associated with the O–H stretching vibration of the lignin/phenolic component present in the polymer. The peak at 2925 cm -1 is due to the aliphatic -CH modes, which indicates the successful polymerization of phenolic/lignin unit with formaldehyde monomer. An aromatic C=C stretching peak is observed at 1628 cm -1 . The emerging peak at 1435 cm -1 is attributed to -CH 2 deformation vibration. The peaks at 1340 cm -1 are associated with the C–H bending vibration. SR 303 shows the single bond C-O stretching vibrations of -CH 2 OH group or Carbon nanomaterial present at 1057 cm -1 and asymmetric stretching vibration of phenolic C-C-OH group at 1245 cm -1 . Carbonization study After complete characterization of the polymer, a series of carbonization tests were designed in the 7 kg carbolite oven. Several carbonization tests were conducted in the 7-kg test oven, under stamp charging conditions. A series of carbonization tests were carried out to study the influence of the organic polymer on the coke properties. Water was added to the coal blend to obtain the desired value of moisture content. The coal cake was made inside a cardboard box keeping the bulk density 1150 kg/m 3 . Tests were done with different blends. Initially, the test was carried out with a base blend (blend no 1). Then, the hard coking coal from the base blend is replaced by non-coking coal. An optimized quantity of organic polymer has been added to maintain the coke quality. Before charging the coal cake into the oven, it was ensured that the empty oven temperature is 900±5°C. After 5 h of carbonization time, the hot coke was pushed out and quenched with water. The coke samples were tested for coke strength after reaction (CSR) and CRI (coke reactivity indices). In Tata Steel, coke strength after the reaction has been done following the NSC method in which 200 g coke of 19-21 mm size is heated in a reaction tube (78 mm diameter X 210 mm length) at 1100 0 C for two hours during which CO 2 is passed at 5 l/min. The percentage loss in the weight of coke during the above reaction is reported as the coke reactivity test (CRI). The reacted coke is further tested by rotating in a I drum (127 mm diameter X725 mm length) for 30 min at a speed of 20 rpm. The coke is then screened on a 10 mm sieve and the % of + 10 mm fraction is reported as the coke strength after reaction (CSR). Researchers have been trying various methods on how to increase the coke strength of coal and there has been a continuous focus on how to increase efficiency and hence increase energy savings. Carbonization results: Different coals have been used for blend preparation. Coal A1 and A2 are captive and imported semi-soft coal respectively. Coal B1 is imported hard coking coal and coal B2 is captive hard coking coal. Coal C is non-coking coal. Characterization: The coals are characterized in terms of ash, volatile matter (VM), crucible swelling number (CSN), and fluidity. The details of the tests are as follows: Ash determination: Ash is determined by following ASTM standard D 3174-11.1 gm of 250 mm size sample is taken to a weighed capsule. Then the sample is placed in a cold muffle furnace and heated gradually at such a rate that the temperature reached 450 0 C to 500 0 C within 1 hr. At the end of the 2 hr, it will reach 950 0 C. After cooling, the weight of the sample is then measured, and ash is calculated by weight difference. VM determination: Ash is determined by following ASTM standard D 3175-11. In this test, 1 gm of 250 mm size sample is taken in a covered platinum crucible and heated in a furnace of 950 0 C for 7 min. The VM is calculated by weight difference. Crucible swelling number: Crucible swelling number test has been done by following ASTM D720-91 (2010) in which 1 gm of the sample (-0.212 mm size) is taken in a translucent squat-shaped silica crucible and the sample is leveled by tapping the crucible 12 times. The crucible is covered with a lid and heated under standard conditions, either by a special type of gas burner or muffle furnace. After the test, the shape of the coke button is compared with a standard chart, and accordingly, the crucible swelling number (0 to 9) is assigned to the coal sample. Table 1 presents the properties of different coal: Coal Ash VM Crucible Table 2 represents the blend composition and coking properties. Blend 1 2 3 4 Coal C-10 Coal C-9.3 Coal C-14.3 Polymer-0.7 Polymer-0.7 Blend 1 is the base blend of the coke plant. In blend 2, 10% of non-coking coal is added in place of imported hard coking coal. The result shows that the CSR value has dropped from 53.4 to 48. In blends 3 and 4, 0.7 % of the organic polymer has been added. There is an improvement in CSR value from 48 to 54.8 (blend 3) and 53.1 (blend 4) respectively. The result shows that the CRI value has increased from 29.8 to 33.6. In blends 3 and 4, 0.7 % of the organic polymer has been added. There is an improvement in CSR value from 33.6 to 30.1 (blend 3) and 30.6(blend 4) respectively. Results revealed that the addition of 10% poor coking coal in the blend along with 0.7% organic polymer is giving a similar value of CSR to the base blend. The above results indicate that a 0.7 % addition of the organic polymer has the potential to replace around 10% of prime hard coking coal with non-coking coal. Thus, it is evident that due to the addition of the organic polymer, there can be replacement of coking coal with non-coking coal and the CSN properties of coke obtained are industrially acceptable. Example 4: Plant trial study: Mixing and a dosing system has been developed near the conveyor belt of the coke plant. The organic polymer of formula I is pumped from the storage and sprayed on the conveyor belt in a concentration of about 0.5 to 0.8%. After spraying the organic polymer of formula I on coal, the coal mix goes to a crusher to crush it to a specific size. Then it goes for stamping and finally charging. 15000 Ton coal was raised for the trial. The percentage of the organic polymer was kept around 0.5 -0.8. 10 % of prime coking coal has been replaced by weak coking coal. Coke properties were satisfactory as provided below in the table 3 - Trial Blend Trial Blend B Bl nd without ol mer ith l m r Table 3 represents CSR values of coke blends with and without polymer From the above-provided table, it is evident that the base blend contains only 20% of weak coal along with 35% of prime coking coal and its CSR is 66.4. However, when the percentage of weak coal increased from 20 to 30%; and when the prime coking coal decreased from 35% to 25%, the CSR value (of trial blend without polymer) dropped from 66.4 to 62. However, upon the incorporation of 0.7% of the polymer of formula I, the CSR value (of trial blend with polymer) increased from 62 to 66.2, signifying the contributory role of polymer in improving the coking properties of the weak coal.