PROCESS OF CATALYTIC CRACKING OF SOLID WASTE FROM PINE DERIVATIVES INDUSTRY

Abstract

A process for catalytic cracking of waste originating from pine processing industry for producing a mixture of chemical compounds, e.g., components for formulation of adhesives, foams, antioxidants, sugars, among others. Optionally, additional steps can be added to the process for processing the obtained mixtures in order to obtain purer fractions with greater commercial interest and value.

Claims

1-6. (canceled)

7. A process of catalytic cracking of waste originating from pine processing industry, which may, or not, contain plastics, paper or glue residues for obtaining chemical products, which are stable, sustainable and cost-effective, comprising the following steps: a) grinding waste originating from pine processing industry into a particle size between 0.5 mm and 75 mm; b) spraying a solution of a solvent selected, from crude glycerol and glycerol derivatives, lactates and respective citrates, fatty acids, Tall oil, as well as esters or lactones thereof, glycerol carbonate, solketal among others, said solvents being used pure or in mixtures, and a catalyst in homogeneous phase over the waste originating from pine processing industry; c) introducing the mixture of step b) into a first reactor at temperatures between 80° C. and 250° C.; d) maintaining the mixture of step b) under vigorous stirring at atmospheric pressure in a first reactor for a period of time between 30 minutes and 180 minutes; e) removing the solid residues obtained from the mixture of step d) by physical processes; f) reintroducing the solid residues obtained in step e) into the first reactor; g) introducing the liquid fraction obtained in step e) into a second reactor at temperatures between 80° C. and 250° C.; h) maintaining the liquid fraction of step e) in the second reactor for a period of time between 30 minutes and 180 minutes; i) removing the solid residues obtained from the mixture of step h) by physical processes; j) storing the liquid mixture obtained in step i) in a storage tank, the liquid mixture i.e. bio-oil; wherein, in order to avoid thermo-oxidative degradation, all the process is carried out under a nitrogen atmosphere with flow rates between 3 m3/h and 5 m3/h.

8. The process according to claim 7, further comprising: k) washing the liquid fraction obtained in step i) with water; l). separating the aqueous and organic phases obtained in step k); m) drying by distillation, at atmospheric pressure and single column, the organic fraction obtained in step 1); n) fractionating the dried organic fraction obtained in step m) by fractional distillation, with a plate column, under vacuum and at temperatures between 100° C. and 250° C.; and o) storing in tanks the distilled fractions obtained in step n) and from the aqueous fraction in step k).

9. The process according to claim 7, wherein in step c) the first reactor is at temperatures, preferably between 120 and 170° C.

10. The process according to claim 7, wherein the waste originating from pine processing industry may have a moisture content between 5% and 55%, may, or not, contain plastics, paper or glue residues, includes: pine bark, pinecones, pine nut shells, sawdust, abrasion dust from chipboards, pine chips, waste originating from manufacture of pine wood furniture, pine needles, stumps, among others.

11. The process according to claim 7, wherein solketal, glycerol carbonate, glycerol formate, glycerol, Tall oil are employed as solvents.

12. The process according to claim 7 wherein the catalytic cracking occurs in steps b), c), d), e), g) and h) with a catalyst in homogeneous phase selected from trichloroacetic acid, nitric acid, hydrofluoric acid, sulfuric acid, p-toluenesulphonic acid, triflic acid and, generally peracids and superacids, metal or semimetal carbonates in an amount varying between 0.05% and 1.5% (w/w) of weight of catalyst relative to the total weight of the reaction mixture.

Description

EXAMPLES

Example 1

[0035] In an initial phase, 600 kg of pine nutshell (10 mm particles), with 14% of moisture, were slowly and continuously added, through a feeder screw where 20% of a 1% solution of trichloroacetic acid in turpentine is introduced, into a first reactor containing 200 kg of turpentine and at a temperature of 160° C., with mechanical stirring. After 75 minutes the mixture is pumped into a basket filter where solid particles larger than 7 mm are separated, which are returned to the first reactor, while the liquid fraction and particles smaller than 7 mm are conveyed to a second reactor. The second reactor is kept at 170° C. with vigorous mechanical stirring, and after 60 minutes the mixture is conveyed to a basket filter where all solid particles are removed and returned to the second reactor, with the bio-oil being subsequently pumped into a storage tank. The obtained bio-oil presented 0.70% of water and 0.61% of ashes. The bio-oil was obtained with a 93% yield. The overall process is conducted under inert atmosphere by injecting nitrogen at 3.9 m3/h.

Example 2

[0036] In an initial phase, 600 kg of pine tree bark, with 18% of moisture, reduced to particles with 25 mm granulometry, were slowly and continuously added, through a feeder screw where 25% of a 1.5% solution of trichloroacetic acid in solketal is introduced, into a first reactor containing 200 kg of solketal and at a temperature of 165° C., with mechanical stirring. After 80 minutes the mixture is pumped into a basket filter where solid particles larger than 7 mm are separated, which are returned to the first reactor, while the liquid fraction and particles smaller than 7 mm are conveyed to a second reactor. The second reactor is kept at 165° C. with vigorous mechanical stirring, and after 55 minutes the mixture is conveyed to a basket filter where all solid particles are removed and returned to the second reactor, with the bio-oil being subsequently pumped into a storage tank. The obtained bio-oil presented 0.62% of water and 0.91% of ashes. The bio-oil was obtained with a 91% yield. The overall process is conducted under inert atmosphere by injecting nitrogen at 3.5 m.sup.3/h.

Example 3

[0037] In an initial phase, 600 kg of pine wood residues, with 25% of moisture, were reduced to particles of 35 mm granulometry, were slowly and continuously added, through a feeder screw where 20% of a 0.75% solution of trichloroacetic acid in glycerol carbonate is introduced, into a first reactor containing 200 kg of glycerol carbonate and at a temperature of 135° C., with mechanical stirring. After 90 minutes the mixture is pumped into a basket filter where solid particles larger than 7 mm are separated, which are returned to the first reactor, while the liquid fraction and particles smaller than 7 mm are conveyed to a second reactor. The second reactor is kept at 135° C. with vigorous mechanical stirring, and after 60 minutes the mixture is conveyed to a basket filter where all solid particles are removed and returned to the second reactor, with the bio-oil being subsequently pumped into a storage tank. The obtained bio-oil presented 0.34% of water and 0.41% of ashes. The bio-oil was obtained with a 97% yield. The overall process is conducted under inert atmosphere by injecting nitrogen at 4.5 m.sup.3/h.

Example 4

[0038] In an initial phase, 700 kg of pinecones, ground and sieved at 50 mm, were added, through a feeder screw, where a mixture of 1% trichloroacetic acid in turpentine is also introduced, into a first reactor containing 210 kg and at a temperature of 160° C., with mechanical stirring. After 75 minutes the mixture is pumped into a basket filter where solid particles larger than 7 mm are separated, which are returned to the first reactor, while the liquid fraction and particles smaller than 7 mm are conveyed to a second reactor. The second reactor is kept at 170° C. with vigorous mechanical stirring, and after 60 minutes the mixture is conveyed to a basket filter where all solid particles are removed and returned to the second reactor, with the bio-oil being subsequently pumped into a storage tank. The obtained bio-oil presented 0.82% of water and 0.89% of ashes. The bio-oil was obtained with a 91% yield Then, the obtained liquid product is fed to a distillation column at atmospheric pressure. Three fractions are obtained. One in the range 100-200° C. (10%), another in the range above 200° C. and below 300° C. (32%), and a solid fraction that corresponds to the bituminous that remains in the bottom of the column (58%).