METHODOLOGY FOR UPGRADING AND CLEANING OF USED TIRES, WASTE LUBRICANTS AS WELL AS ANY KIND OF OILS AND FATS FOR UTILIZATION AS FEEDSTOCK IN THERMOCHEMICAL CONVERSION PROCESSES

Abstract

A methodology for cleaning and upgrading any kind of tires (cars, motorcycles, trucks, etc.), any kind of waste lubricants (internal combustion engines, industrial parts), any kind of oils as well as plant and animal fats by means of removal of the inorganic elements (potassium, sodium, chlorine, sulfur, phosphorus and heavy metals such as Pb, Cu, Cd, Zn, Hg, Mn, etc.) and the simultaneous addition of new such as calcium, magnesium and ammonium, in order to produce a clean and upgraded rubber material, lubricant as well as fat/oil, which can be used as raw material in thermochemical conversion processes such as flash (t<1 sec)/fast pyrolysis.

Claims

1. Methodology for cleaning and upgrading any kind of tires, any kind of waste lubricants (internal combustion engines, industrial parts), any kind of oils as well as plant and animal fats by means of removal of the inorganic elements (potassium, sodium, chlorine, sulfur, phosphorus and heavy metals) and the simultaneous addition of new such as calcium, magnesium, aluminum and ammonium, utilizing inorganic and/or organic calcium and/or magnesium and/or aluminum and/or ammonium salts and/or salt/acid mixtures in order to produce a clean and upgraded fat/oil/rubber/lubricant material, which can be used as raw material in thermochemical conversion processes such as flash (t<1 sec)/fast pyrolysis (1<t<10 sec), as well as in the gasification for the production of hydrogen-rich gas and liquid hydrocarbons which can be further upgraded by applying commercially available thermochemical conversion technologies for the production of pure hydrogen, liquid fuels, chemicals and energy with great economic and environmental benefits. The treatment is carried out either at atmospheric pressure and temperatures (10-99 C.) or at elevated pressure (2-45 atm) and temperatures (110-250 C.) using special high pressure and temperature reactors. Treatment time could vary from 1 min up to 2 h.

2. Method according to claim 1 where the intended purpose is achieved by leaching of the raw used tires, any kind of waste lubricants (internal combustion engines, industrial parts), as well as fats and oils with aqueous solutions of inorganic and/or organic salts.

3. Method according to claims 1 and 2 where both organic and inorganic acid/salt mixtures are used in the process to achieve the desired result considering that the proportion of acid is limited to less than 30% of the total mixture on a weight basis.

4. Method according to claims 1, 2 and 3 where the leaching process takes place at atmospheric pressure or at elevated pressure.

5. Method according to claims 1, 2, 3 and 4 where the different types of any kind of waste lubricants (internal combustion engines, industrial parts), plant and animal origin fats and oils undergo leaching with an aqueous solution of organic and/or inorganic compounds. Regarding organic and/or inorganic compounds, they are/can be used any water-soluble organic/inorganic salts of calcium, magnesium and ammonium in proportions of 0.07 up to 1.5% weight basis in aqueous solution. Also all organic and/or inorganic acids that create water-soluble salts with one of the aforementioned cations.

6. Method according to claims 1, 2, 3 and 4 where the different types of used tires undergo leaching with an aqueous solution of organic and/or inorganic compounds.. Regarding organic and/or inorganic compounds, they are/can be used any water-soluble organic/inorganic salts of calcium, magnesium and ammonium in proportions of 0.5 up to 4% weight basis in aqueous solution. Also all organic and/or inorganic acids that create water-soluble salts with one of the aforementioned cations.

7. Method according to claims 1 to 6 where the utilized water-soluble organic and/or inorganic acids are necessary to be used combined to one/some of the water soluble organic and/or inorganic salts to achieve the desired result while the water soluble organic and/or inorganic salts can be utilized without the addition of water-soluble organic and/or inorganic acid.

8. Method according to claims 1 to 7 where the specific organic and/or inorganic compounds are used in proportions ranging from 0.1% to 99% to form the active substance used in the aqueous solution creation.

9. Method according to claims 1 to 8 where the specific organic and/or inorganic compounds are used in sequential order for executing successive extractions to achieve the desired result. The applied proportions and the use of successive extractions or not depend on the type and composition of the treated material as well as the desirable properties of the treated material.

10. Method according to claims 1 to 9 in which any kind of water from the public water system, source, etc., can be employed to create the aqueous solution where the oil-fatty/aqueous phase ratio can range from 15 grams per liter to 800 grams per liter. In case of used tires, it can range from 15 grams per liter to 750 grams per liter.

11. Method according to claims 1 to 10 where the best results are achieved when the oil-fatty/aqueous phase ratio ranges from 140 grams per liter to 800 grams per liter. In case of used tires it ranges from 140 grams per liter to 750 grams per liter.

12. Method according to claims 1 to 11 where the pretreatment temperature varies from 10 C. up to 99 C.

13. Method according to claims 1 to 12 where the best results are achieved at temperature range from 20 C. up to 45 C.

14. Method according to claims 1 to 13 where the pretreatment time of the material ranges from 5 minutes to 30 minutes.

15. Method according to claims 1 to 14 where the best results are achieved for pretreatment time ranging from 5 minutes to 20 minutes by ensuring vigorous agitation in the reactor and/or intense mixing conditions of the pretreated material with the aqueous solution.

16. Method according to claims 1, 2, and 15 where the leaching pretreatment is carried out by applying commercial reactors which are already in use in various industrial applications and in any application that requires liquid/liquid and/or solid/liquid extraction.

17. Method according to claims 1 and 2 where leaching is carried out by applying higher pressures and temperatures and using special reactors. In this case, the reactor illustrated in FIG. 1 operating at temperatures between 110-150 C. and pressure 2-7 atm is the optimum solution.

18. Method according to claims 1, 2, and 17 where the reaction is carried out at temperatures between 110-150 C. and pressure 2-7 atm so that the aqueous phase remains in the liquid form and is not converted to gas.

19. Method according to claims 1, 2, 17 and 18 where the reaction time is limited below 5 minutes, the oil-fatty/aqueous phase ratio ranges from 15 grams per liter to 800 grams per liter while in case of tires, the solid/liquid ratio ranges from 15 grams per liter to 750 grams per liter, and the concentration of inorganic and/or organic salts, acids/salts remains below 1.5% weight basis where better results are obtained for concentrations of 0.5-1% weight basis in case of any kind of waste lubricants (internal combustion engines, industrial parts), fats/oils, while in case of tires, the concentration of inorganic and/or organic salts, acids/salts ranges from 0.5 to 4% weight basis.

20. Method according to claims 1, 2, 17, 18 and 19 where after the end of the leaching pretreatment process either at atmospheric or at elevated pressure, the fatty/oil phase is separated from the aqueous phase by using gravity separation tanks or by centrifugation.

21. Method according to claims 1 to 20 where during the treatment with the aqueous solution of the organic and/or inorganic solvent, the water soluble alkali metals, sulfur, phosphorus, heavy metals (Cu, Pb, Zn, Cr, Hg etc.), and the chlorine are transferred into the aqueous phase and removed from the pretreated material.

22. Method according to claims 1 to 21 where the aqueous residue remaining after separation of the organic and/or inorganic compounds used to create the aqueous solvent for the pretreatment of various materials is rich in alkali metals, chlorine, sulfur and phosphorus and is utilized as high quality fertilizer.

23. Method according to claims 1 and 17 where the high pressure reactor consists of two separate reactors in a parallel mode. Each reactor contains an initial mixing vessel where the aqueous and solid/oil/fatty phase are mixed with organic and/or inorganic solvents at temperatures between 50-80 C.

24. Method according to claims 1, 17 and 23 in which the solution is fed to the pressurized reactor using a pressure pump where the conditions are already 110-150 C. and 2-7 atm. The treated material reaction is now shorter than 5 minutes followed by the immediate expansion of the solution in a cooling pressurized tank where the solution temperature is instantly limited to 70 C. to prevent evaporation of the aqueous phase.

25. Method according to claims 1, 17, 23 and 24 where the parallel reactor operates one step back from the initial reactor in order to realize a process which is semi-batch but in progress at any time.

26. Method according to claims 1, 17, 23, 24 and 25 where the pressurized reactors as shown in FIG. 1 are equipped with a second direct discharge valve which communicates with the interior of the reactor via a pipeline at the end of which there is a 40 micron diameter solids filter. The immediate depressurization caused by the discharge valve opening after the end of the treatment process results in solid/liquid separation letting the liquid to be concentrated and cooled in the recover tank before being recycled into the process as shown in FIG. 1 while the solid product is removed in the second phase by opening the valve of the pressurized reactor's bottom.

27. Method according to claims 1 to 26 which involves the incorporation of calcium and/or magnesium and/or ammonium ions in the treated material structure, realizing the simultaneous removal of all chlorine, 100% of active alkali metals, 60-100% of sulfur, 30-90% of phosphorus and 30-85% of heavy metals from the treated material.

28. Method according to claims 1 to 17 where leaching is carried out by applying elevated pressures and temperatures using commercially available reactors operating at high pressures (2-100 atm) and temperatures (110-250 C.).

Description

EXAMPLE 1

[0028] Used motorcycle tires are treated at atmospheric conditions utilizing calcium nitrate as solvent. The applied conditions are the following: temperature 80 C., solid/liquid ratio 15% w/w dry basis, agitator use at 500 rpm, leaching time 20 minutes, solvent concentration 3% w/w, material particle size <5 mm. After the pretreatment, the sample is filtered and dried at 50 C. After the pretreatment, 1.5% weight increase of the treated dry material is noticed because of the calcium absorption by the material. Sample analysis by electron microscopy, SEM-EDX confirms the significantly increased calcium concentration in the sample as well as the absence of chlorine and alkali metals while the sulfur concentration appears to be significantly reduced by 10-20%. Then both the untreated and the treated material are used in fast pyrolysis tests (t=2 sec) at 600 C. and 800 C. These tests showed that the material conversion into gaseous and liquid products was increased from 35.7 to 62.5% at 600 C. and from 75 to 91.1% at 800 C. after pretreatment. At the same time, although SO.sub.2 was produced in the final gaseous and liquid products during pyrolysis of the raw material, there was no presence of SO.sub.2 in case of the treated material. Additionally, the production of liquid hydrocarbons appears to be decreased by more than 70% in case of the treated sample while the primary end product is a gas mixture rich in H.sub.2, CO, CH.sub.4, and other hydrocarbons.

EXAMPLE 2

[0029] Used motorcycle tires are treated at elevated pressure using the reactor shown in FIG. 1 utilizing calcium chloride as solvent. The applied conditions are the following: temperature 140 C., pressure 7 atm, solid/liquid ratio 25% w/w dry basis, leaching time 4.5 minutes, solvent concentration 4% w/w, material particle size <5 mm. After the pretreatment, the sample is dried at 50 C. After the pretreatment, 1.9% weight increase of the treated dry material is noticed because of the calcium absorption by the material. Sample analysis by electron microscopy, SEM-EDX confirms the significantly increased calcium concentration in the sample as well as the absence of chlorine and alkali metals while the sulfur concentration appears to be significantly reduced by 15-30%. Then both the untreated and the treated material are used in fast pyrolysis tests (t=2 sec) at 600 C. and 800 C. These tests showed that the material conversion into gaseous and liquid products was increased from 35.7 to 73% at 600 C. and from 75 to 93% at 800 C. after pretreatment. At the same time, although SO.sub.2 was produced in the final gaseous and liquid products during pyrolysis of the raw material, there was no presence of SO.sub.2 in case of the treated material. Additionally, the production of liquid hydrocarbons appears to be decreased by more than 80% in case of the treated sample while the primary end product is a gas mixture rich in H.sub.2, CO, CH.sub.4, and other hydrocarbons.

EXAMPLE 3

[0030] Waste cooking oil from waste cooking oil recycling company RENOVOIL is treated at atmospheric conditions utilizing calcium acetate as solvent. The applied conditions are the following: temperature 30 C., oil/liquid ratio 25% weight basis, agitator use at 500 rpm, leaching time 20 minutes, solvent concentration 3% w/w. After the pretreatment, the sample is separated from the liquid phase using a separating funnel. The concentrations of chlorine, sulfur, alkali metals, calcium, magnesium, heavy metals, etc., in both raw and treated oil are determined by using ion chromatography and ICP-AES. The results show 99.9% chlorine removal, more than 35% sulfur removal, alkali metals removal by more than 55% for sodium and 99% for potassium while heavy metals removal such as V, Cu, Ba, Mo, Mn ranges from 30-80%. At the same time, the calcium concentration in the treated oil is significantly increased. Then both the untreated and the treated material are used in fast pyrolysis tests (t=2 sec) at 600 C. and 800 C. These tests showed that the material conversion into gaseous and liquid products was increased from 40 to 75% at 600 C. and from 55 to 90% at 800 C. after pretreatment. At the same time, although SO2 was produced in the final gaseous and liquid products during pyrolysis of the raw material, there was no presence of SO.sub.2 in case of the treated material. Additionally, the production of liquid hydrocarbons appears to be decreased by more than 75% in case of the treated sample for both temperatures while the primary end product is a gas mixture rich in H.sub.2, CO, CH.sub.4, and other hydrocarbons.

EXAMPLE 4

[0031] Waste cooking oil from waste cooking oil recycling company RENOVOIL is treated at elevated pressure using the reactor shown in FIG. 1 utilizing calcium chloride as solvent. The applied conditions are the following: temperature 140 C., pressure 6 atm, oil/liquid ratio 25% weight basis, leaching time 4.5 minutes, solvent concentration 2.5% w/w. After the pretreatment, the sample is separated from the liquid phase using a separating funnel. The concentrations of chlorine, sulfur, alkali metals, calcium, magnesium, heavy metals, etc., in both raw and treated oil are determined by using ion chromatography and ICP-AES. The results show 99.9% chlorine removal, more than 35% sulfur removal, alkali metals removal by more than 55% for sodium and 99% for potassium while heavy metals removal such as V, Cu, Ba, Mo, Mn ranges from 30-80%. At the same time, the calcium concentration in the treated oil is significantly increased. Then both the untreated and the treated material are used in fast pyrolysis tests (t=2 sec) at 600 C. and 800 C. These tests showed that the material conversion into gaseous and liquid products was increased from 40 to 75% at 600 C. and from 55 to 90% at 800 C. after pretreatment. At the same time, although SO.sub.2 was produced in the final gaseous and liquid products during pyrolysis of the raw material, there was no presence of SO.sub.2 in case of the treated material. Additionally, the production of liquid hydrocarbons appears to be decreased by more than 75% in case of the treated sample for both temperatures while the primary end product is a gas mixture rich in H.sub.2, CO, CH.sub.4, and other hydrocarbons.

EXAMPLE 5

[0032] Corn oil is treated at atmospheric conditions utilizing initially citric acid and then calcium acetate as solvent. Each wash is carried out separately while the treated material is separated from the first solvent using a separating funnel before being treated with the second. The applied conditions are the following: temperature 30 C. for citric acid and 20 C. for calcium acetate as solvents, oil/liquid ratio 25% weight basis, agitator use at 500 rpm, leaching time 20 minutes (10 minutes with the acid and 10 minutes with the acid salt), citric acid concentration 0.25% weight basis, calcium acetate concentration 0.2% weight basis. After the pretreatment, the sample is separated from the liquid phase using a separating funnel. The concentrations of chlorine, sulfur, alkali metals, calcium, magnesium, heavy metals, etc., in both raw and treated oil are determined by using ion chromatography and ICP-AES. The results show 99.9% chlorine removal, more than 40% sulfur removal, more than 25% phosphorus removal, alkali metals removal by more than 60% for sodium and 99% for potassium while heavy metals removal such as V, Cu, Ba, Mo, Mn ranges from 30-90%. At the same time, the calcium concentration in the treated oil is significantly increased. Then both the untreated and the treated material are used in fast pyrolysis tests (t=2 sec) at 600 C. and 800 C. These tests showed that the material conversion into gaseous and liquid products was increased from 45 to 73% at 600 C. and from 51 to 92% at 800 C. after pretreatment. Additionally, the production of liquid hydrocarbons appears to be decreased by more than 78% in case of the treated sample for both temperatures while the primary end product is a gas mixture rich in H.sub.2, CO, CH.sub.4, and other hydrocarbons.

EXAMPLE 6

[0033] Sunflower oil is treated at atmospheric conditions utilizing calcium acetate/magnesium acetate ratio: 60/40 as solvent. The applied conditions are the following: temperature 30 C., oil/liquid ratio 65% weight basis, agitator use at 500 rpm, leaching time 20 minutes, solvent concentration 4% weight basis. After the pretreatment, the sample is separated from the liquid phase using a separating funnel. The concentrations of chlorine, sulfur, alkali metals, calcium, magnesium, heavy metals, etc., in both raw and treated oil are determined by using ion chromatography and ICP-AES. The results show 99.9% chlorine removal, more than 30% sulfur removal, alkali metals removal by more than 75% for sodium and 99% for potassium while heavy metals removal such as V, Cu, Ba, Mo, Mn ranges from 30-85%. At the same time, the calcium as well as the magnesium concentration in the treated oil is significantly increased. Then both the untreated and the treated material are used in fast pyrolysis tests (t=2 sec) at 600 C. and 800 C. These tests showed that the material conversion into gaseous and liquid products was increased from 44 to 77% at 600 C. and from 49 to 89% at 800 C. after pretreatment. Additionally, the production of liquid hydrocarbons appears to be decreased by more than 80% in case of the treated sample for both temperatures while the primary end product is a gas mixture rich in H.sub.2, CO, CH.sub.4, and other hydrocarbons.