Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/40—Ethylene production

Definitions

• This invention relates to the preparation of unsaturated hydrocarbons from oxygen-containing organic materials. It pertains particularly to the preparation of low molecular weight, unsaturated hydrocarbons such as acetylene and ethylene.
• Afurther important object of the invention is the provision of a process for making unsaturated hydrocarbons from pulp mill spent liquors, which process may be operated as an adjunct of paper mill pulping procedures, without abnormal loss of pulping chemicals, and without destroying the delicate chemical balance which must be preserved during the pulping process.
• unsaturated hydrocarbons such as acetylene and ethylene may be obtained in yields of up to 50% of the theoretical by a process which, broadly considered, comprises reducing the material to finely divided form, heating it rapidly in a substantially inert gaseous environment to a selected temperature of at least 1000 F., maintaining it at the selected temperature until a substantial proportion of it has been converted to a reaction product including the desired unsaturated hydrocarbons, rapidly cooling the reaction product, and separating the unsaturated hydrocarbon components from it.
• the process comprises cooking lignocellulose in an aqueous medium with a predetermined proportion of an inorganic lignocellulose pulping agent for substantial separation of the lignin from the cellulose, separating the resulting cellulosic pulp from the residual spent liquor, separating the inorganic salt content of the liquor and returning it to the pulping of a further quantity of the lignocellulose, separating the lignin content of the liquor as a finely divided solid, and then pyrolyzing the solid in a substantially inert gaseous en- 3,148,227 Patented Sept. 8, 1964 vironment as set forth above.
• the unsaturated hydrocarbon products may be manufactured Without abnormal loss of pulping chemicals and without destroying the material balance in the digesters.
• the alkali lignins including soda lignin and kraft lignin, are eminently suitable for the present purpose. These preferably are treated first for removal of their inorganic salt content, which then may be cycled to the chemical recovery system of the pulp mill.
• sulfonated lignins contained in sulfite spent liquor may be employed, keeping in mind that the sulfur contained in such liquor may serve as a hydrogen scavenger during the pyrolysis reaction, thus reducing correspondingly the yield of unsaturated hydrocarbon products.
• sulfur contained in such liquor may serve as a hydrogen scavenger during the pyrolysis reaction, thus reducing correspondingly the yield of unsaturated hydrocarbon products.
• the pulping spent liquors are evaporated or chemically treated for separation of the solid lignins. These then are dried sufficiently to convert them to a finely divided powder which may be handled easily.
• lignocellulose materials such as the woods and barks of various tree species, and various non-woody plant materials such as bagasse, straw and cornstalks, are also applicable broadly to the purposes of the present invention.
• these materials first are dried, if desired, and reduced to finely divided form in any suitable grinding or comminuting apparatus. Although the degree of subdivision is variable, depending upon the nature of the materials and the reaction conditions, in general it is preferred to reduce them to a particle size of not over 20 mesh, U.S. Sieve Series.
• the various carbohydrates such as sugars, starch and, particularly, cellulose, also are applicable as starting materials for the presently described process.
• the materials first are reduced to a dry powder, preferably one having a particle size of not over 20 mesh, U.S. Sieve Series.
• the selected starting material is introduced into a reaction zone containing a substantially inert, or at least nondetrimental, gas such as helium, carbon monoxide, argon, or neon. Nitrogen also may be employed, although in this case hydrogen cyanide may be formed as a by-product.
• the solid material is introduced into the reaction zone by entraining it in a stream of the selected gaseous carrier.
• the reaction zone may be heated to the desired level and in any suitable manner, as by partial combustion of the reacting material, indirect combustion, electrical resistance heating, electric arc heating, etc.
• the temperature of the material be elevated rapidly in the reaction zone to a level of at least 1000*" F. If this is not done, the usual oxygen-containing pyrolysis products of lignin and woody materials are obtained. These include tars, resins, pyroligneous acids and the like.
• reaction mixture is cooled rapidly, preferably by quenching it in a spray of Water or other liquid, or by passing it through a heat exchanger cooled eflioiently by water or other cooling medium.
• the gaseous components of the reaction mixture are separated from any suspended carbon which may have been formed.
• the acetylene and ethylene products are recovered and separated from each other by any of the methods conventionaly employed for this purpose.
• Example 1 A 4-way T reactor was fitted with two tungsten wires connected to a high voltage source. An arc was struck between the wires. Dry powdered kraft lignin obtained by the acidification of kraft black liquor was blown through the are using helium as a carrier gas. The maximum temperature of the arc was about 3600 F. An analysis of the gaseous product indicated an acetylene yield of 14%.
• Example 2 This example illustrates the application of resistance heating to the presently described process.
• a 4-way T tube reactor was placed a coil wound with A diameter No. 28 tungsten wire.
• the coil was connected to copper wire sealed into the system and a current of 500 watts passed through the coil, the temperature of which reached a level of from 35004500 F.
• Precipitated kraft lignin was blown onto the coil using helium as a gaseous carrier. The gases were removed from the reaction zone immediately and collected over saturated brine. An acetylene yield of 23% was obtained.
• Example 3 A furnace consisting of a 1" ceramic tube surrounded by a A" layer of flake graphite held in place by an alumina cylinder was heated with Rf current. The heating zone was 5" long and was packed loosely for about one-half its distance with broken ceramic. Water cooled copper tubes communicated with the ceramic tube at its upstream and downstream ends. Means were provided for admitting the powdered feed in an inert carrier gas at a controlled flow rate, thereby enabling various residence times in the furnace.
• Example 4 The procedure of Example 3 was repeated, heating the furnace to 2100 F. 2.6 grams of dry, precipitated kraft lignin were added in 30 seconds with a helium flow rate l of 2700 nil/min. In this case a 3.5% yield of acetylene and a 7.2% yield of ethylene were obtained.
• Example 5 The procedure of Example 3 again was repeated, with the furnace heated to 2600" F. and the helium flow rate adjusted to 2700 mL/min. Under these conditions, 1.8 grams of powdered Douglas fir wood were passed through the system in about 2 minutes. An acetylene yield of 13% and an ethylene yield of 4.6% were obtained. Bubbling the gaseous product through silver nitrate test solution resulted in the formation of a characteristic precipitate of solid silver carbide-silver nitrate.
• Example 6 Into the furnace of Example 3 heated to 2700 F. using a helium flow of 4000 ml./min. were passed 2 grams of -mesh whole bagasse in about 3 minutes. An acetylene yield of 15% was obtained.
• Example 7 Using the furnace and conditions of Example 3, 2 grams of 60-mesh Douglas fir bark was passed through the furnace. A yield of 12.5% acetylene was obtained.
• Example 8 A plasma was made by passing argon through a 1 quartz tube surrounded by a 17-turn water-cooled copper tubing coil connected to a radio frequency generator. The temperature of the plasma was from 4000 F. to 5000 F. Careful addition of 0.3 gram powdered bagasse into the plasma in about 3 minutes resulted in collection of a 17% yield of acetylene. There was no evidence of the formation of any ethylene or methane.
• oxygen-containing organic material comprises a lignin-containing pulping spent liquor.
• reaction product is cooled rapidly by quenching it in water.
• the process of making unsaturated hydrocarbons of the groups consisting of acetylene and ethylene which comprises cooking lignocellulose in an aqueous medium with a predetermined proportion of an inorganic lignocellulose pulping agent for substantial separation of the lignin from the cellulose, separating the resulting cellulosic pulp from the residual spent liquor, separting the inorganic compound content of the liquor and returning it to the pulping of a further quantity of lignocellulose, separating the lignin content of the liquor as a finely divided solid, rapidly heating the solid lignin in a substantially inert gaseous environment to a selected temperature of at least 1000 F., maintaining the lignin solids at the selected temperature for a time of from 10- seconds to about 10 seconds, thereby converting a substantial proportion thereof to a reaction product including the unsaturated hydrocarbon, rapidly cooling the reaction product, and separating the unsaturated hydrocarbon therefrom.
• the inorganic lignocellulose pulping agent comprises a soda pulping agent.
• the inorganic lignocellulose pulping agent comprises a sulfite pulping agent.
• the inorganic lignocellulose pulping agent comprises a sulfite pulping agent and including the step of desulfonating the spent liquor preliminary to separating the lignin solids.

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Cited By (11)

Citations (5)

• 0
  • NL NL277991D patent/NL277991A/xx unknown
• 1961
  • 1961-05-04 US US107658A patent/US3148227A/en not_active Expired - Lifetime

Patent Citations (5)

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