GB694665A - Method of producing water-soluble products from black liquor lignin - Google Patents
Method of producing water-soluble products from black liquor ligninInfo
- Publication number
- GB694665A GB694665A GB31198/50A GB3119850A GB694665A GB 694665 A GB694665 A GB 694665A GB 31198/50 A GB31198/50 A GB 31198/50A GB 3119850 A GB3119850 A GB 3119850A GB 694665 A GB694665 A GB 694665A
- Authority
- GB
- United Kingdom
- Prior art keywords
- product
- black liquor
- lignin
- reacted
- sulphate
- 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
- 229920005610 lignin Polymers 0.000 title abstract 29
- 238000000034 method Methods 0.000 title abstract 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 18
- 235000010265 sodium sulphite Nutrition 0.000 abstract 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 12
- 229910021653 sulphate ion Inorganic materials 0.000 abstract 12
- 239000012670 alkaline solution Substances 0.000 abstract 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 6
- 239000000243 solution Substances 0.000 abstract 5
- -1 sulphite ions Chemical class 0.000 abstract 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 4
- 238000000502 dialysis Methods 0.000 abstract 4
- 229910052760 oxygen Inorganic materials 0.000 abstract 4
- 239000001301 oxygen Substances 0.000 abstract 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 abstract 4
- DXRFSTNITSDOKK-UHFFFAOYSA-N formaldehyde;sulfurous acid Chemical compound O=C.OS(O)=O DXRFSTNITSDOKK-UHFFFAOYSA-N 0.000 abstract 3
- 150000003839 salts Chemical class 0.000 abstract 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 abstract 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 2
- 239000005864 Sulphur Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 2
- 150000001340 alkali metals Chemical class 0.000 abstract 2
- 229910052788 barium Inorganic materials 0.000 abstract 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000009835 boiling Methods 0.000 abstract 2
- 159000000007 calcium salts Chemical class 0.000 abstract 2
- 150000001768 cations Chemical class 0.000 abstract 2
- 239000001913 cellulose Substances 0.000 abstract 2
- 229920002678 cellulose Polymers 0.000 abstract 2
- 239000004568 cement Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 2
- 239000010941 cobalt Substances 0.000 abstract 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229910052802 copper Inorganic materials 0.000 abstract 2
- 239000010949 copper Substances 0.000 abstract 2
- 239000002270 dispersing agent Substances 0.000 abstract 2
- 238000005553 drilling Methods 0.000 abstract 2
- 238000004043 dyeing Methods 0.000 abstract 2
- 239000003995 emulsifying agent Substances 0.000 abstract 2
- 230000001804 emulsifying effect Effects 0.000 abstract 2
- 239000000945 filler Substances 0.000 abstract 2
- 239000011121 hardwood Substances 0.000 abstract 2
- 239000000976 ink Substances 0.000 abstract 2
- 229910052742 iron Inorganic materials 0.000 abstract 2
- 238000002955 isolation Methods 0.000 abstract 2
- 239000010985 leather Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 2
- 230000007935 neutral effect Effects 0.000 abstract 2
- 239000003921 oil Substances 0.000 abstract 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 229920001195 polyisoprene Polymers 0.000 abstract 2
- 238000005185 salting out Methods 0.000 abstract 2
- 229920006395 saturated elastomer Polymers 0.000 abstract 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 abstract 2
- 235000010262 sodium metabisulphite Nutrition 0.000 abstract 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract 2
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- 239000002023 wood Substances 0.000 abstract 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 1
- 239000004291 sulphur dioxide Substances 0.000 abstract 1
- 235000010269 sulphur dioxide Nutrition 0.000 abstract 1
- 150000003573 thiols Chemical class 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Compounds Of Unknown Constitution (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
A process for converting black liquor lignin into water-soluble products is characterized in that the black liquor lignin is sulphonated at an elevated temperature (e.g. 50 DEG to 200 DEG C.) with sulphurous acid or a salt thereof, or with a substance yielding sulphurous acid. Before, during or after sulphonation the lignin may be reacted with an aldehyde. A product containing -CH2SO3H groups is produced when the aldehyde is formaldehyde. The product may then be further sulphonated in the absence of an aldehyde. The black liquor lignin may be obtained by digesting hardwood or coniferous wood or other lignocellulose containing materials according to the soda or sulphate cellulose processes. Sulphonation may be effected under acid, neutral or alkaline conditions, e.g. with alkali metal or ammonium sulphites or bisulphites. Before or during sulphonation the lignin may be oxidized, e.g. by passing air or oxygen through its solution, if desired in the presence of iron, copper or cobalt. In the oxidation, sulphate black liquor lignin which contains combined sulphur is converted to a product containing sulphonic groups. In examples: (1) black liquor lignin is reacted in alkaline solution with sodium sulphite and sulphate and sulphite ions are removed from the product by dialysis; (2) black liquor lignin, sodium sulphite and formalin are heated together, the product is treated with a hydrogen-ion-saturated cation exchanger, and evaporated to dryness. The product which contains one sulphonic acid group to about 5 methoxyl groups is converted to its barium and calcium salts; (3) a procedure similar to (2) but with isolation of the product by salting out is followed; (4) black liquor lignin, sodium hydroxide, sodium sulphite and formalin are heated together. The product is purified by dialysis; (5) the lignin is heated with sodium sulphite and sodium hydroxide. After passing sulphur dioxide through the solution, the product is reacted with formalin; (6) the product of (2) is reacted with sodium pyrosulphite; (7) sulphite process black liquor lignin in boiling alkaline solution is oxidized by passing oxygen through. The product, containing sulphonic acid groups, is reacted with sodium sulphite and dialysed; (8) sulphate black liquor lignin, sodium hydroxide and sodium sulphite are heated in solution in two batches, through only one of which air is passed; (9) the product of (1) is reacted with sodium sulphite and formalin; (10) the product of (2) is reacted with a formalin-bisulphite addition product; (11) sulphate black liquor lignin is oxidized with air in alkaline solution and the product heated with a formaldehyde-bisulphite addition compound. The products are useful in tanning leather and as emulsifying and dispersing agents, e.g. in printing inks, and cutting and drilling oils, as levelling agents in dyeing, as fillers for caoutchouc, and as dispersing, hardening promoting, and strength-increasing additives for cement.ALSO:A process for converting black liquor lignin into water-soluble products is characterized in that the black liquor lignin is sulphonated at an elevated temperature, e.g. 50 DEG to 200 DEG C. with sulphurous acid or a salt thereof or with a substance yielding sulphurous acid. The black liquor lignin may be obtained by digesting hardwood or coniferous wood or other lignocellulose-containing materials according to the soda or sulphate cellulose processes. Sulphonation may be effected under acid, neutral or alkaline conditions, e.g. with alkali metal or ammonium sulphites or bisulphites. Before or during sulphonation the lignin may be oxidized e.g. by passing air or oxygen through its solution, if desired in the presence of catalysts such as salts of iron, copper or cobalt. Before or during sulphonation the lignin may be reacted with an aldehyde, a product containing -CH2SO3H groups then being produced when the aldehyde is formaldehyde. The product may then be further sulphonated in the absence of aldehyde. Previously sulphonated lignin may also be reacted with aldehydes. The molecular weight of the products is about 1000 to 3000, being lower when sulphate liquor lignin is employed in the reaction. Sulphate black liquor lignin contains combined sulphur mainly in the form of sulphide, thiol and disulphide groups, which in the oxidation step are converted to sulphonic acid groups. In examples: (1) black liquor lignin is reacted in alkaline solution with sodium sulphite, and sulphate and sulphite ions are removed by dialysis; (2) black liquor lignin, sodium sulphite and formalin are heated together, the product is treated with a hydrogen-ion-saturated cation exchanger, and evaporated to dryness. The product, which contains one sulphonic acid group to about 5 methoxyl groups is converted to its barium and calcium salts; (3) a procedure similar to (2) but with isolation of the product by salting out is followed; (4) black liquor lignin, sodium hydroxide, sodium sulphite and formalin are heated together. The product is purified by dialysis; (5) the lignin is heated in alkaline solution with sodium sulphite and sodium hydroxide. After cooling, SO2 is passed through and the product reacted with formalin and isolated as in (1); (6) the product of (2) is reacted with sodium pyrosulphite; (7) sulphate process black liquor lignin in boiling alkaline solution is oxidized by passing oxygen through. The product, containing sulphonic groups, is reacted with sodium sulphite and dialysed to remove sulphite ions; (8) sulphate black liquor lignin, sodium hydroxide, and sodium sulphite are heated in solution while passing air through the mixture. The product is not precipitated by acetic acid. The process is repeated in the absence of air to give a product which is precipitated by acetic acid; (9) the product of (1) is reacted with sodium sulphite and formalin; (10) the product of (2) is reacted with a formaldehyde-bisulphite addition product; (11) sulphate black liquor lignin is heated in alkaline solution while passing air through. The product is heated with formaldehyde-bisulphite addition compound. The products are useful in tanning leather and as emulsifying and dispersing agents, e.g. in printing inks and cutting and drilling oils, as levelling agents in dyeing, as fillers for caoutchouc, and as dispersing, hardening-promoting and strength-increasing additives for cement.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE694665X | 1949-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB694665A true GB694665A (en) | 1953-07-22 |
Family
ID=20315299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB31198/50A Expired GB694665A (en) | 1949-12-22 | 1950-12-22 | Method of producing water-soluble products from black liquor lignin |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB694665A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088640A (en) * | 1976-06-18 | 1978-05-09 | American Can Company | Ozonated lignosulfonates |
| EP0367389A1 (en) * | 1988-10-24 | 1990-05-09 | Westvaco Corporation | Production of lignosulfonate additives |
| CN110092917A (en) * | 2019-05-29 | 2019-08-06 | 南京工业大学 | Lignin metal salt and preparation method and application thereof |
| CN114000369A (en) * | 2021-09-28 | 2022-02-01 | 山东格瑞兰德添加剂有限公司 | Method for preparing anionic surfactant from ultrafiltration sulfate pulping black liquor |
-
1950
- 1950-12-22 GB GB31198/50A patent/GB694665A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088640A (en) * | 1976-06-18 | 1978-05-09 | American Can Company | Ozonated lignosulfonates |
| EP0367389A1 (en) * | 1988-10-24 | 1990-05-09 | Westvaco Corporation | Production of lignosulfonate additives |
| CN110092917A (en) * | 2019-05-29 | 2019-08-06 | 南京工业大学 | Lignin metal salt and preparation method and application thereof |
| CN110092917B (en) * | 2019-05-29 | 2020-08-21 | 南京工业大学 | Lignin metal salt and preparation method and application thereof |
| CN114000369A (en) * | 2021-09-28 | 2022-02-01 | 山东格瑞兰德添加剂有限公司 | Method for preparing anionic surfactant from ultrafiltration sulfate pulping black liquor |
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