USRE24293E - Method of improving the yield of - Google Patents
Method of improving the yield of Download PDFInfo
- Publication number
- USRE24293E USRE24293E US24293DE USRE24293E US RE24293 E USRE24293 E US RE24293E US 24293D E US24293D E US 24293DE US RE24293 E USRE24293 E US RE24293E
- Authority
- US
- United States
- Prior art keywords
- sulfide
- methyl
- methyl sulfide
- sulfate
- liquor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- QMMFVYPAHWMCMS-UHFFFAOYSA-N methyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 26
- 239000002699 waste material Substances 0.000 description 13
- 229920002678 cellulose Polymers 0.000 description 11
- 239000001913 cellulose Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000029087 digestion Effects 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 241001062472 Stokellia anisodon Species 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical class [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N Ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- FRLJSGOEGLARCA-UHFFFAOYSA-N Cadmium sulfide Chemical compound [S-2].[Cd+2] FRLJSGOEGLARCA-UHFFFAOYSA-N 0.000 description 1
- AGVJBLHVMNHENQ-UHFFFAOYSA-N Calcium sulfide Chemical compound [S-2].[Ca+2] AGVJBLHVMNHENQ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N Methyl bisulfate Chemical class COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 102000018210 Recoverin family Human genes 0.000 description 1
- 108010076570 Recoverin family Proteins 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229940055700 calcium sulfide Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
Definitions
- methyl sulfide may be considered a useful starting material for the preparation of valuable products, particularly methyl sulfoxide.
- the present invention has for its object to provide a method of improving the yield of methyl sulfide obtained by heating waste liquors from the manufacture of cellulose, from an insignificant amount to quantities, which are sufiicient to make possible the production of methyl sulfoxide and other valuable substances in considerable quantities. This is accomplished by heating the waste liquors in the presence of metal sulfides or other substances containing inorganic sulfidic or hydrosulfidic sulfur, which has proved to be particularly capable of splitting off the methoxyl of the lignin to form methyl sulfur compounds.
- sodium sulfide or a substance containing sodium sulfide for instance soda smelt from sulfate cellulose production, is added to evaporated black liquor from sulfate cellulose digestion.
- black liquor derived from cellulose digestion with soda liquor free from sulfur may be used or even sulfite waste liquor, and the waste liquors may be concentrated or unconcentrated.
- the sodium sulfide may be replaced by sulfides of other metals, e. g. by calcium sulfide or by ammonium hydrosulfide.
- alkalies and sulfur may be added in another form, e. g. as sodium hydroxide and sulfur or in the form of thiosulfates of various metals. Particularly when sulfite waste liquor is treated lime and sulfur may advantageously be added.
- the process may be carried out at normal or superatmospheric pressure in accordance with previously known principles (see for instance the U. S. Patents Nos. l;680,540, 1,772,216 and 1,795,557).
- the heating is carried to a temperature of between 150 and 500 C., preferably between 250 and 350 C.
- methyl sulfide a certain amount of methyl mercaptan is formed in the heat treatment.
- This substance may to a substantial extent be transformed into methyl sulfide by means of procedures which are known per se, for instance by passing the mercaptan over heated metal sulfide catalysts or by reaction with alkali salts of methyl sulfuric acid.
- the black liquor may be subjected to combustion as in the conventional sulfate process, if desired after being treated to yield other useful products such as acetone, butanone etc. in accordance with known methods.
- a special advantage of the present method is that the amount of sodium sulfide required is comparatively little and may be added in the form of soda smelt of the kind that is produced in the usual sulfate cellulose process. Thus, no other chemicals are needed for the production of methyl sulfide than sodium sulfate that is always added to replace the loss of alkali and sulfur in technical sulfate cellulose production.
- the method of producing methyl sulfide which comprises adding an inorganic sulfide to waste liquor from alkaline cellulose digestion, heating the mixture at a temperature between C. and 500 C., and recovering the methyl sulfide formed thereby.
- the method of producing methyl sulfide which comprises adding an inorganic sulfide to sulfate waste liquor, heating the mixture at a temperature between 150 C. and 500 C., and recovering the methyl sulfide formed thereby.
- the method of producing methyl sulfide which comprises adding an inorganic sulfide to concentrated waste liquor, heating the mixture at a temperature between 150" C. and 500 C., and recovering the methyl sulfide formed thereby.
- the method of producing methyl sulfide which comprises adding sodium sulfide to waste liquor from alkaline cellulose digestion, heating the mixture at a temperature between 150 C. and 500 C., and recovering the methyl sulfide formed thereby.
- the method of producing methyl sulfide which comprises adding sodium sulfide to concentrated sulfate black liquor, heating the mixture at a temperature between 150 C. and 500 C., and recovering the methyl sulfide formed thereby.
- the method of producing methyl sulfide which comprises adding sodium sulfide to sulfate black liquor, heating the mixture at a temperature between 250 C. and 350 C., and recovering the methyl sulfide formed thereby.
- the method of treating alkaline waste liquor from cellulose digestion which comprises reacting said liquor with a substance containingjnorganic sulfidic sulfur at a temperature ofjrom 250 C. t0 350 C., and reco verin g methyl sulfide and methyl mercqptan formed thereby.
Description
United States Patent 24,293 METHOD OF llVlPROVlNG THE YIELD OF METHYL SULFIDE OBTAINED BY HEAT- ING WASTE LIQUORS FROM CELLULOSE MANUFACTURE BY ADDING 'INOR- GANIC SULFIDES Erik Karl Mauritz Hiigglund, Stockholm, Sweden, and
Terje Ulf Eugen Enkvist, Helsingfors, Finland, assiguors to Svenska Cellulosaforeningens Centrallaboratorium (Cellulosaindustriens Centrallaboratorium), Stockholm, Sweden, a Swedish firm No Drawing. Original No. 2,711,430, dated June 21, 1955, Serial No. 223,444, April 27, 1951. Application for reissue June 13, 1956, Serial No. 591,257
Claims priority, application Sweden June 27, 1950 9 Claims. (Cl. 260-609) Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
It is known that when waste liquors from the cellulose manufacture are heated, small quantities of methyl sulfide may be formed. This substance has for a long time been considered an objectionable by-product, the amount of which it has been attempted to reduce as far as possible with various means. Now, however, the methyl sulfide may be considered a useful starting material for the preparation of valuable products, particularly methyl sulfoxide.
The present invention has for its object to provide a method of improving the yield of methyl sulfide obtained by heating waste liquors from the manufacture of cellulose, from an insignificant amount to quantities, which are sufiicient to make possible the production of methyl sulfoxide and other valuable substances in considerable quantities. This is accomplished by heating the waste liquors in the presence of metal sulfides or other substances containing inorganic sulfidic or hydrosulfidic sulfur, which has proved to be particularly capable of splitting off the methoxyl of the lignin to form methyl sulfur compounds.
According to a preferred embodiment of the invention sodium sulfide or a substance containing sodium sulfide, for instance soda smelt from sulfate cellulose production, is added to evaporated black liquor from sulfate cellulose digestion. Instead of sulfate black liquor, however, black liquor derived from cellulose digestion with soda liquor free from sulfur may be used or even sulfite waste liquor, and the waste liquors may be concentrated or unconcentrated. The sodium sulfide may be replaced by sulfides of other metals, e. g. by calcium sulfide or by ammonium hydrosulfide. Also, instead of sulfides, alkalies and sulfur may be added in another form, e. g. as sodium hydroxide and sulfur or in the form of thiosulfates of various metals. Particularly when sulfite waste liquor is treated lime and sulfur may advantageously be added.
The process may be carried out at normal or superatmospheric pressure in accordance with previously known principles (see for instance the U. S. Patents Nos. l;680,540, 1,772,216 and 1,795,557). Suitably the heating is carried to a temperature of between 150 and 500 C., preferably between 250 and 350 C.
Besides methyl sulfide a certain amount of methyl mercaptan is formed in the heat treatment. This substance may to a substantial extent be transformed into methyl sulfide by means of procedures which are known per se, for instance by passing the mercaptan over heated metal sulfide catalysts or by reaction with alkali salts of methyl sulfuric acid. After the production of the methyl sulfide the black liquor may be subjected to combustion as in the conventional sulfate process, if desired after being treated to yield other useful products such as acetone, butanone etc. in accordance with known methods.
A special advantage of the present method is that the amount of sodium sulfide required is comparatively little and may be added in the form of soda smelt of the kind that is produced in the usual sulfate cellulose process. Thus, no other chemicals are needed for the production of methyl sulfide than sodium sulfate that is always added to replace the loss of alkali and sulfur in technical sulfate cellulose production.
EXAMPLE To 1 kg. of concentrated sulfate black liquor having a solid content of 54% and an ash content of 23% there is added a quantity of sodium sulfide corresponding to 34 g. of anhydrous NazS, the mixture is heated, whereby the water is first evaporated. Thereafter the mixture is heated for 4 hours at 300 C., during which period the methyl sulfide is separated in the distillate by cooling (first fraction). The uncondensed gas, that contains among other substances methyl mercaptan is passed at 350 C. over a catalyst containing cadmium sulfide, whereby the larger part of the mercaptan is transformed into methyl sulfide (second fraction) that is condensed by cooling. The yield of methyl sulfide of first fraction is 5.9 g. and of second fraction 4.0 g. Together this corresponds to about 29 kg. per ton pulp.
Having now particularly described the nature of our invention and the manner of its operation what we claim is:
l. The method of producing methyl sulfide which comprises adding an inorganic sulfide to waste liquor from alkaline cellulose digestion, heating the mixture at a temperature between C. and 500 C., and recovering the methyl sulfide formed thereby.
2. The method of producing methyl sulfide which comprises adding an inorganic sulfide to sulfate waste liquor, heating the mixture at a temperature between 150 C. and 500 C., and recovering the methyl sulfide formed thereby.
3. The method of producing methyl sulfide which comprises adding an inorganic sulfide to concentrated waste liquor, heating the mixture at a temperature between 150" C. and 500 C., and recovering the methyl sulfide formed thereby.
4. The method of producing methyl sulfide which comprises adding sodium sulfide to waste liquor from alkaline cellulose digestion, heating the mixture at a temperature between 150 C. and 500 C., and recovering the methyl sulfide formed thereby.
5. The method of producing methyl sulfide which comprises adding sodium sulfide to sulfate waste liquor,
heating the mixture at a temperature between 150 C.
and 500 C., and recovering the methyl sulfide formed thereby.
6. The method of producing methyl sulfide which comprises adding sodium sulfide to concentrated sulfate black liquor, heating the mixture at a temperature between 150 C. and 500 C., and recovering the methyl sulfide formed thereby.
7. The method of producing methyl sulfide which comprises adding sodium sulfide to sulfate black liquor, heating the mixture at a temperature between 250 C. and 350 C., and recovering the methyl sulfide formed thereby.
8. The method of treating alkaline waste liquor from cellulose digestion which comprises reacting said liquor with a substance containing inorganic sulfidic sulfur at a temperature of from 150 C. to 500 C., and recovering methyl sulfide and methyl mercaptan formed thereby.
9. The method of treating alkaline waste liquor from cellulose digestion which comprises reacting said liquor with a substance containingjnorganic sulfidic sulfur at a temperature ofjrom 250 C. t0 350 C., and reco verin g methyl sulfide and methyl mercqptan formed thereby.
References'Cited in the file of this patent or the original patent 1,834,676 Bradley et a1. Dec. 1, 193.1
4 Lubs May 23, 1933 OTHER REFERENCES Grifien: Technical Methods of Analysis (2nd edition, 5 1927), pages 391-394.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE24293E true USRE24293E (en) | 1957-03-19 |
Family
ID=2092289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US24293D Expired USRE24293E (en) | Method of improving the yield of |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE24293E (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2976273A (en) * | 1958-09-10 | 1961-03-21 | West Virginia Pulp & Paper Co | Treatment of kraft black liquor and product |
| US5662774A (en) * | 1992-04-01 | 1997-09-02 | Tampella Power Oy | Adjusting the sulphur balance of a sulphate cellulose plant by heat treating black liquor in a last evaporation stage |
-
0
- US US24293D patent/USRE24293E/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2976273A (en) * | 1958-09-10 | 1961-03-21 | West Virginia Pulp & Paper Co | Treatment of kraft black liquor and product |
| US5662774A (en) * | 1992-04-01 | 1997-09-02 | Tampella Power Oy | Adjusting the sulphur balance of a sulphate cellulose plant by heat treating black liquor in a last evaporation stage |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2711430A (en) | Method of improving the yield of methyl sulfide obtained by heating waste liquors fro cellulose manufacture by adding inorganic sulfides | |
| US4507172A (en) | Kraft pulping process | |
| USRE24293E (en) | Method of improving the yield of | |
| US4000264A (en) | Method of recovering sodium hydroxide from sulfur free pulping or bleaching waste liquor by mixing ferric oxide with condensed waste liquor prior to burning | |
| US4127439A (en) | Pretreatment of lignocellulose with anthraquinone prior to pulping | |
| US1547907A (en) | Manufacture of wood pulp and by-products | |
| US2996540A (en) | Preparation of para-hydroxybenzoic acid | |
| RU2687986C1 (en) | Method of regenerating sodium salts from black liquor solution during production of sulphate cellulose | |
| US2840614A (en) | Process of making methyl mercaptan | |
| US1817525A (en) | Production of chemical wood pulp | |
| US1787954A (en) | Processing of raw cellulosic materials | |
| US2816832A (en) | Making dimethyl sulfide from pulp mill spent liquors | |
| US3061408A (en) | Recovery of chemicals from waste liquors | |
| US2727028A (en) | Treatment of waste sulphite liquor and products thereof | |
| US3326980A (en) | Preparation of methyl mercaptan from waste pulping liquors | |
| NO125978B (en) | ||
| US3514371A (en) | Preparation of kraft process liquor from waste soda liquor from petroleum industries | |
| US2898994A (en) | Method of making paper pulp | |
| US1802715A (en) | Process of pulping plant tissues by means of a volatile base | |
| US1469960A (en) | Process of treating black liquor produced in the manufacture of sulphate pulp | |
| US1545522A (en) | Process of making wood pulp | |
| US3008984A (en) | Manufacture of acids from ligneous materials | |
| US1742218A (en) | Process for the production of high alpha cellulose fiber | |
| RU2696636C1 (en) | Preparation of white liquor production of sulphate pulp | |
| US3451889A (en) | Method of digesting wood by the kraft process utilizing organic sulfides |